Bonding-restricted structure search for novel 2D materials with dispersed C2 dimers

PubMed Central

Zhang, Cunzhi; Zhang, Shunhong; Wang, Qian

2016-01-01

Currently, the available algorithms for unbiased structure searches are primarily atom-based, where atoms are manipulated as the elementary units, and energy is used as the target function without any restrictions on the bonding of atoms. In fact, in many cases such as nanostructure-assembled materials, the structural units are nanoclusters. We report a study of a bonding-restricted structure search method based on the particle swarm optimization (PSO) for finding the stable structures of two-dimensional (2D) materials containing dispersed C2 dimers rather than individual C atoms. The C2 dimer can be considered as a prototype of nanoclusters. Taking Si-C, B-C and Ti-C systems as test cases, our method combined with density functional theory and phonon calculations uncover new ground state geometrical structures for SiC2, Si2C2, BC2, B2C2, TiC2, and Ti2C2 sheets and their low-lying energy allotropes, as well as their electronic structures. Equally important, this method can be applied to other complex systems even containing f elements and other molecular dimers such as S2, N2, B2 and Si2, where the complex orbital orientations require extensive search for finding the optimal orientations to maximize the bonding with the dimers, predicting new 2D materials beyond MXenes (a family of transition metal carbides or nitrides) and dichalcogenide monolayers. PMID:27403589

Silicon K-edge XANES spectra of silicate minerals

NASA Astrophysics Data System (ADS)

Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

1995-03-01

Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

Electronic structure of semiconducting alkali-metal silicides and germanides

NASA Astrophysics Data System (ADS)

Tegze, M.; Hafner, J.

1989-11-01

We present self-consistent linearized-muffin-tin-orbital calculations of the electronic structure of three alkali-metal germanides and silicides (KGe, NaGe, and NaSi). Like the alkali-metal-lead compounds investigated in our earlier work [M. Tegze and J. Hafner, Phys. Rev. B 39, 8263 (1989)] the Ge and Si compounds of the alkali metals form complex structures based on the packing of tetrahedral Ge4 and Si4 clusters. Our calculations show that all three compounds are narrow-gap semiconductors. The width of the energy gap depends on two main factors: the ratio of the intracluster to the intercluster interactions between the group-IV elements (which increases from Pb to Si) and the strength of the interactions between the alkali-metal atoms (which varies with the size ratio).

Preparation, characterization and luminescence properties of core-shell ternary terbium composites SiO2(600)@Tb(MABA-Si)•L

NASA Astrophysics Data System (ADS)

Ma, Yang-Yang; Li, Wen-Xian; Zheng, Yu-Shan; Bao, Jin-Rong; Li, Yi-Lian; Feng, Li-Na; Yang, Kui-Suo; Qiao, Yan; Wu, An-Ping

2018-03-01

Two novel core-shell structure ternary terbium composites SiO2(600)@Tb(MABA-Si)·L(L:dipy/phen) nanometre luminescence materials were prepared by ternary terbium complexes Tb(MABA-Si)·L2·(ClO4)3·2H2O shell grafted onto the surface of SiO2 microspheres. And corresponding ternary terbium complexes were synthesized using (CONH(CH2)3Si(OCH2CH3)3)2 (denoted as MABA-Si) as first ligand and L as second ligand coordinated with terbium perchlorate. The as-synthesized products were characterized by means of IR spectra, 1HNMR, element analysis, molar conductivity, SEM and TEM. It was found that the first ligand MABA-Si of terbium ternary complex hydrolysed to generate the Si-OH and the Si-OH condensate with the Si-OH on the surface of SiO2 microspheres; then ligand MABA-Si grafted onto the surface of SiO2 microspheres. The diameter of SiO2 core of SiO2(600)@Tb(MABA-Si)·L was approximately 600 nm. Interestingly, the luminescence properties demonstrate that the two core-shell structure ternary terbium composites SiO2(600)Tb(MABA-Si)·L(dipy/phen) exhibit strong emission intensities, which are 2.49 and 3.35 times higher than that of the corresponding complexes Tb(MABA-Si)·L2·(ClO4)3·2H2O, respectively. Luminescence decay curves show that core-shell structure ternary terbium composites have longer lifetime. Excellent luminescence properties enable the core-shell materials to have potential applications in medicine, industry, luminescent fibres and various biomaterials fields.

Preparation, characterization and luminescence properties of core-shell ternary terbium composites SiO2(600)@Tb(MABA-Si)•L.

PubMed

Ma, Yang-Yang; Li, Wen-Xian; Zheng, Yu-Shan; Bao, Jin-Rong; Li, Yi-Lian; Feng, Li-Na; Yang, Kui-Suo; Qiao, Yan; Wu, An-Ping

2018-03-01

Two novel core-shell structure ternary terbium composites SiO 2(600) @Tb(MABA-Si)·L(L:dipy/phen) nanometre luminescence materials were prepared by ternary terbium complexes Tb(MABA-Si)·L 2 ·(ClO 4 ) 3 ·2H 2 O shell grafted onto the surface of SiO 2 microspheres. And corresponding ternary terbium complexes were synthesized using (CONH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 ) 2 (denoted as MABA-Si) as first ligand and L as second ligand coordinated with terbium perchlorate. The as-synthesized products were characterized by means of IR spectra, 1 HNMR, element analysis, molar conductivity, SEM and TEM. It was found that the first ligand MABA-Si of terbium ternary complex hydrolysed to generate the Si-OH and the Si-OH condensate with the Si-OH on the surface of SiO 2 microspheres; then ligand MABA-Si grafted onto the surface of SiO 2 microspheres. The diameter of SiO 2 core of SiO 2(600) @Tb(MABA-Si)·L was approximately 600 nm. Interestingly, the luminescence properties demonstrate that the two core-shell structure ternary terbium composites SiO 2(600) Tb(MABA-Si)·L(dipy/phen) exhibit strong emission intensities, which are 2.49 and 3.35 times higher than that of the corresponding complexes Tb(MABA-Si)·L 2 ·(ClO 4 ) 3 ·2H 2 O, respectively. Luminescence decay curves show that core-shell structure ternary terbium composites have longer lifetime. Excellent luminescence properties enable the core-shell materials to have potential applications in medicine, industry, luminescent fibres and various biomaterials fields.

Preparation, characterization and luminescence properties of core–shell ternary terbium composites SiO2(600)@Tb(MABA-Si)•L

PubMed Central

Ma, Yang-Yang; Zheng, Yu-Shan; Bao, Jin-Rong; Li, Yi-Lian; Feng, Li-Na; Yang, Kui-Suo; Qiao, Yan; Wu, An-Ping

2018-01-01

Two novel core–shell structure ternary terbium composites SiO2(600)@Tb(MABA-Si)·L(L:dipy/phen) nanometre luminescence materials were prepared by ternary terbium complexes Tb(MABA-Si)·L2·(ClO4)3·2H2O shell grafted onto the surface of SiO2 microspheres. And corresponding ternary terbium complexes were synthesized using (CONH(CH2)3Si(OCH2CH3)3)2 (denoted as MABA-Si) as first ligand and L as second ligand coordinated with terbium perchlorate. The as-synthesized products were characterized by means of IR spectra, 1HNMR, element analysis, molar conductivity, SEM and TEM. It was found that the first ligand MABA-Si of terbium ternary complex hydrolysed to generate the Si–OH and the Si–OH condensate with the Si–OH on the surface of SiO2 microspheres; then ligand MABA-Si grafted onto the surface of SiO2 microspheres. The diameter of SiO2 core of SiO2(600)@Tb(MABA-Si)·L was approximately 600 nm. Interestingly, the luminescence properties demonstrate that the two core–shell structure ternary terbium composites SiO2(600)Tb(MABA-Si)·L(dipy/phen) exhibit strong emission intensities, which are 2.49 and 3.35 times higher than that of the corresponding complexes Tb(MABA-Si)·L2·(ClO4)3·2H2O, respectively. Luminescence decay curves show that core–shell structure ternary terbium composites have longer lifetime. Excellent luminescence properties enable the core–shell materials to have potential applications in medicine, industry, luminescent fibres and various biomaterials fields. PMID:29657773

PRINCEPS: A computer-based approach to the structural description and recognition of trends within structural databases, and its application to the Ce-Ni-Si System

DOE PAGES

Guo, Yiming; Fredrickson, Daniel C.

2016-04-01

Intermetallic crystal structures offer an enormous structural diversity, with an endless array of structural motifs whose connection to stability and physical properties are often mysterious. Making sense of the often complex crystal structures that arise here, developing a clear structural description, and identifying connections to other phases can be laborious and require an encyclopedic knowledge of structure types. In this Article, we present PRINCEPS, an algorithm based on a new coordination environment projection scheme that facilitates the structural analysis and comparison of such crystal structures. We demonstrate the potential of this approach by applying it to the complex Ce-Ni-Si ternarymore » system, whose 17 binary and 21 ternary phases would present a daunting challenge to one seeking to understand the system by manual inspection (but has nonetheless been well-described through the heroic efforts of previous researchers). With the help of PRINCEPS, most of the ternary phases in this system can be rationalized as intergrowths of simple structural fragments, and grouped into a handful of structural series (with some outliers). Lastly, these results illustrate how the PRINCEPS approach can be used to organize a vast collection of crystal structures into structurally meaningful families, and guide the description of complex atomic arrangements.« less

Fabrication technology of Si face and m face on 4H-SiC (0001) epi-layer based on molten KOH etching

NASA Astrophysics Data System (ADS)

Lin, Wen-kui; Zeng, Chun-hong; Sun, Yu-hua; Zhang, Xuan; Li, Zhe; Yang, Tao-tao; Ju, Tao; Zhang, Bao-shun

2018-02-01

Additional scattering of electrons in the complex MOSFET channel caused by off-cut angle of (0001) 4H-SiC wafer, makes accurate crystal face acquisition much desired. Molten KOH was used to etch the circular grooves on the SiC wafer surface in muffle furnace, and hexagonal grooves with SiC crystal symmetry were obtained. Average etching rates at 500°C along <11-20> and <1-100> direction were about 4.826 um/min and 4.112 um/min, respectively,with a etching anisotropy ratio of 1.18. The m face was obtained by controlling the etching time and Si face was obtained by selfstopping effect. The method we developed in this paper has potential applications in the accurate crystal face acquisition of (0001) 4H-SiC epi-wafer, and the preparation of structures based on 4H-SiC.

New 3D structuring process for non-integrated circuit related technologies (Conference Presentation)

NASA Astrophysics Data System (ADS)

Nouri, Lamia; Possémé, Nicolas; Landis, Stéfan; Milesi, Frédéric; Gaillard, Frédéric-Xavier

2017-04-01

Fabrication processes that microelectronic developed for Integrated circuit (IC) technologies for decades, do not meet the new emerging structuration's requirements, in particular non-IC related technologies one, such as MEMS/NEMS, Micro-Fluidics, photovoltaics, lenses. Actually complex 3D structuration requires complex lithography patterning approaches such as gray-scale electron beam lithography, laser ablation, focused ion beam lithography, two photon polymerization. It is now challenging to find cheaper and easiest technique to achieve 3D structures. In this work, we propose a straightforward process to realize 3D structuration, intended for silicon based materials (Si, SiN, SiOCH). This structuration technique is based on nano-imprint lithography (NIL), ion implantation and selective wet etching. In a first step a pattern is performed by lithography on a substrate, then ion implantation is realized through a resist mask in order to create localized modifications in the material, thus the pattern is transferred into the subjacent layer. Finally, after the resist stripping, a selective wet etching is carried out to remove selectively the modified material regarding the non-modified one. In this paper, we will first present results achieved with simple 2D line array pattern processed either on Silicon or SiOCH samples. This step have been carried out to demonstrate the feasibility of this new structuration process. SEM pictures reveals that "infinite" selectivity between the implanted areas versus the non-implanted one could be achieved. We will show that a key combination between the type of implanted ion species and wet etching chemistries is required to obtain such results. The mechanisms understanding involved during both implantation and wet etching processes will also be presented through fine characterizations with Photoluminescence, Raman and Secondary Ion Mass Spectrometry (SIMS) for silicon samples, and ellipso-porosimetry and Fourier Transform InfraRed spectroscopy (FTIR) for SiOCH samples. Finally the benefit of this new patterning approach will be presented on 3D patterns structures.

Ultra-low Thermal Conductivity in Si/Ge Hierarchical Superlattice Nanowire.

PubMed

Mu, Xin; Wang, Lili; Yang, Xueming; Zhang, Pu; To, Albert C; Luo, Tengfei

2015-11-16

Due to interfacial phonon scattering and nanoscale size effect, silicon/germanium (Si/Ge) superlattice nanowire (SNW) can have very low thermal conductivity, which is very attractive for thermoelectrics. In this paper, we demonstrate using molecular dynamics simulations that the already low thermal conductivity of Si/Ge SNW can be further reduced by introducing hierarchical structure to form Si/Ge hierarchical superlattice nanowire (H-SNW). The structural hierarchy introduces defects to disrupt the periodicity of regular SNW and scatters coherent phonons, which are the key contributors to thermal transport in regular SNW. Our simulation results show that periodically arranged defects in Si/Ge H-SNW lead to a ~38% reduction of the already low thermal conductivity of regular Si/Ge SNW. By randomizing the arrangement of defects and imposing additional surface complexities to enhance phonon scattering, further reduction in thermal conductivity can be achieved. Compared to pure Si nanowire, the thermal conductivity reduction of Si/Ge H-SNW can be as large as ~95%. It is concluded that the hierarchical structuring is an effective way of reducing thermal conductivity significantly in SNW, which can be a promising path for improving the efficiency of Si/Ge-based SNW thermoelectrics.

Ultra-low Thermal Conductivity in Si/Ge Hierarchical Superlattice Nanowire

PubMed Central

Mu, Xin; Wang, Lili; Yang, Xueming; Zhang, Pu; To, Albert C.; Luo, Tengfei

2015-01-01

Due to interfacial phonon scattering and nanoscale size effect, silicon/germanium (Si/Ge) superlattice nanowire (SNW) can have very low thermal conductivity, which is very attractive for thermoelectrics. In this paper, we demonstrate using molecular dynamics simulations that the already low thermal conductivity of Si/Ge SNW can be further reduced by introducing hierarchical structure to form Si/Ge hierarchical superlattice nanowire (H-SNW). The structural hierarchy introduces defects to disrupt the periodicity of regular SNW and scatters coherent phonons, which are the key contributors to thermal transport in regular SNW. Our simulation results show that periodically arranged defects in Si/Ge H-SNW lead to a ~38% reduction of the already low thermal conductivity of regular Si/Ge SNW. By randomizing the arrangement of defects and imposing additional surface complexities to enhance phonon scattering, further reduction in thermal conductivity can be achieved. Compared to pure Si nanowire, the thermal conductivity reduction of Si/Ge H-SNW can be as large as ~95%. It is concluded that the hierarchical structuring is an effective way of reducing thermal conductivity significantly in SNW, which can be a promising path for improving the efficiency of Si/Ge-based SNW thermoelectrics. PMID:26568511

Structure-Based Annotation of a Novel Sugar Isomerase from the Pathogenic E. coli O157:H7

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Staalduinen, L.; Park, C; Yeom, S

2010-01-01

Prokaryotes can use a variety of sugars as carbon sources in order to provide a selective survival advantage. The gene z5688 found in the pathogenic Escherichia coli O157:H7 encodes a 'hypothetical' protein of unknown function. Sequence analysis identified the gene product as a putative member of the cupin superfamily of proteins, but no other functional information was known. We have determined the crystal structure of the Z5688 protein at 1.6 {angstrom} resolution and identified the protein as a novel E. coli sugar isomerase (EcSI) through overall fold analysis and secondary-structure matching. Extensive substrate screening revealed that EcSI is capable ofmore » acting on D-lyxose and D-mannose. The complex structure of EcSI with fructose allowed the identification of key active-site residues, and mutagenesis confirmed their importance. The structure of EcSI also suggested a novel mechanism for substrate binding and product release in a cupin sugar isomerase. Supplementation of a nonpathogenic E. coli strain with EcSI enabled cell growth on the rare pentose d-lyxose.« less

Interface Engineering for Atomic Layer Deposited Alumina Gate Dielectric on SiGe Substrates.

PubMed

Zhang, Liangliang; Guo, Yuzheng; Hassan, Vinayak Vishwanath; Tang, Kechao; Foad, Majeed A; Woicik, Joseph C; Pianetta, Piero; Robertson, John; McIntyre, Paul C

2016-07-27

Optimization of the interface between high-k dielectrics and SiGe substrates is a challenging topic due to the complexity arising from the coexistence of Si and Ge interfacial oxides. Defective high-k/SiGe interfaces limit future applications of SiGe as a channel material for electronic devices. In this paper, we identify the surface layer structure of as-received SiGe and Al2O3/SiGe structures based on soft and hard X-ray photoelectron spectroscopy. As-received SiGe substrates have native SiOx/GeOx surface layers, where the GeOx-rich layer is beneath a SiOx-rich surface. Silicon oxide regrows on the SiGe surface during Al2O3 atomic layer deposition, and both SiOx and GeOx regrow during forming gas anneal in the presence of a Pt gate metal. The resulting mixed SiOx-GeOx interface layer causes large interface trap densities (Dit) due to distorted Ge-O bonds across the interface. In contrast, we observe that oxygen-scavenging Al top gates decompose the underlying SiOx/GeOx, in a selective fashion, leaving an ultrathin SiOx interfacial layer that exhibits dramatically reduced Dit.

Polyamidoamine-Decorated Nanodiamonds as a Hybrid Gene Delivery Vector and siRNA Structural Characterization at the Charged Interfaces.

PubMed

Lim, Dae Gon; Rajasekaran, Nirmal; Lee, Dukhee; Kim, Nam Ah; Jung, Hun Soon; Hong, Sungyoul; Shin, Young Kee; Kang, Eunah; Jeong, Seong Hoon

2017-09-20

Nanodiamonds have been discovered as a new exogenous material source in biomedical applications. As a new potent form of nanodiamond (ND), polyamidoamine-decorated nanodiamonds (PAMAM-NDs) were prepared for E7 or E6 oncoprotein-suppressing siRNA gene delivery for high risk human papillomavirus-induced cervical cancer, such as types 16 and 18. It is critical to understand the physicochemical properties of siRNA complexes immobilized on cationic solid ND surfaces in the aspect of biomolecular structural and conformational changes, as the new inert carbon material can be extended into the application of a gene delivery vector. A spectral study of siRNA/PAMAM-ND complexes using differential scanning calorimetry and circular dichroism spectroscopy proved that the hydrogen bonding and electrostatic interactions between siRNA and PAMAM-NDs decreased endothermic heat capacity. Moreover, siRNA/PAMAM-ND complexes showed low cell cytotoxicity and significant suppressing effects for forward target E6 and E7 oncogenic genes, proving functional and therapeutic efficacy. The cellular uptake of siRNA/PAMAM-ND complexes at 8 h was visualized by macropinocytes and direct endosomal escape of the siRNA/PAMAM-ND complexes. It is presumed that PAMAM-NDs provided a buffering cushion to adjust the pH and hard mechanical stress to escape endosomes. siRNA/PAMAM-ND complexes provide a potential organic/inorganic hybrid material source for gene delivery carriers.

Versatile mechanical properties of novel g-SiC x monolayers from graphene to silicene: a first-principles study.

PubMed

Lu, X K; Xin, T Y; Zhang, Q; Xu, Q; Wei, T H; Wang, Y X

2018-08-03

Recently, a series of graphene-like binary monolayers (g-SiC x ), where Si partly substitutes the C positions in graphene, have been obtained by tailoring the band gaps of graphene and silicene that have made them a promising material for application in opto-electronic devices. Subsequently, evaluating the mechanical properties of g-SiC x has assumed great importance for engineering applications. In this study, we quantified the in-plane mechanical properties of g-SiC x (x = 7, 5, 3, 2 and 1) monolayers (also including graphene and silicene) based on density function theory. It was found that the mechanical parameters of g-SiC x , such as the ideal strength, Young's modulus, shear modulus, Poisson's ratio, as well as fracture toughness, are overall related to the ratio of Si-C to C-C bonds, which varies with Si concentration. However, for g-SiC 7 and g-SiC 3 , the mechanical properties seem to depend on the structure because in g-SiC 7 , the C-C bond strength is severely weakened by abnormal stretching, and in g-SiC 3 , conjugation structure is formed. The microscopic failure of g-SiC x exhibits diverse styles depending on the more complex structural deformation modes introduced by Si substitution. We elaborated the structure-properties relationship of g-SiC x during the failure process, and in particular, found that the structural transformation of g-SiC 3 and g-SiC is due to the singular symmetry of their structure. Due to the homogeneous phase, all the g-SiC x investigated in this study preserve rigorous isotropic Young's moduli and Poisson's ratios. With versatile mechanical performances, the family of g-SiC x may facilitate the design of advanced two-dimensional materials to meet the needs for practical mechanical engineering applications. The results offer a fundamental understanding of the mechanical behaviors of g-SiC x monolayers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

The Anh, Le, E-mail: letheanh@jaist.ac.jp; Lam, Pham Tien; Manoharan, Muruganathan

We present a first-principles study on the interstitial-mediated diffusion process of neutral phosphorus (P) atoms in a silicon crystal with the presence of mono-atomic hydrogen (H). By relaxing initial Si structures containing a P atom and an H atom, we derived four low-energy P-H-Si defect complexes whose formation energies are significantly lower than those of P-Si defect complexes. These four defect complexes are classified into two groups. In group A, an H atom is located near a Si atom, whereas in group B, an H atom is close to a P atom. We found that the H atom pairs withmore » P or Si atom and changes the nature bonding between P and Si atoms from out-of-phase conjugation to in-phase conjugation. This fact results in the lower formation energies compare to the cases without H atom. For the migration of defect complexes, we have found that P-H-Si defect complexes can migrate with low barrier energies if an H atom sticks to either P or Si atom. Group B complexes can migrate from one lattice site to another with an H atom staying close to a P atom. Group A complexes cannot migrate from one lattice site to another without a transfer of an H atom from one Si atom to another Si atom. A change in the structure of defect complexes between groups A and B during the migration results in a transfer of an H atom between P and Si atoms. The results for diffusion of group B complexes show that the presence of mono-atomic H significantly reduces the activation energy of P diffusion in a Si crystal, which is considered as a summation of formation energy and migration barrier energy, leading to the enhancement of diffusion of P atoms at low temperatures, which has been suggested by recent experimental studies.« less

Transition of Blast Furnace Slag from Silicate-Based to Aluminate-Based: Structure Evolution by Molecular Dynamics Simulation and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Liang, Dong; Yan, Zhiming; Lv, Xuewei; Zhang, Jie; Bai, Chenguang

2017-02-01

To determine the effect of Al2O3 content and Al2O3/SiO2 mass ratio on the structure of molten aluminosilicate systems, CaO-SiO2-Al2O3-MgO-TiO2 systems were investigated by conducting molecular dynamics (MD) simulation and Raman spectroscopy. The capabilities of different elements to attract O on the basis of bond length are ranked as follows: Si > Al > Ca. The CNSi-O (approximately 4) and the average CNAl-O (approximately 4.09) demonstrate that the [AlO4] tetrahedron is not as stable as the [SiO4] tetrahedron and that some highly coordinated Al units exist in the slags. Non-bridging oxygen prefers to be coordinated with Si, and Al tends to be localized in polymerized environments as a network intermediate phase. In addition, Ca2+ is more energetically active than Mg2+ as the charge compensation ion. MD results and Raman analysis show that an increase in Al2O3 content complicates the structure at a fixed CaO/SiO2 ratio. In addition, the viscosity of the sample may increase with increasing Al2O3 content but is also influenced by polymerization strength. The substitution of Al2O3 for SiO2 simplifies the structure of the slag at a fixed CaO concentration when Al2O3/SiO2 is less than 0.92, as indicated by the (Q4 + Q3)/(Q2 + Q1) ratio of Al and the structure complexity. The results of MD and Raman analysis agree with those of viscosity measurement.

On the interactions of nitriles and fluoro-substituted pyridines with silicon tetrafluoride: Computations and thin film IR spectroscopy

NASA Astrophysics Data System (ADS)

Hora, Nicholas J.; Wahl, Benjamin M.; Soares, Camilla; Lara, Skylee A.; Lanska, John R.; Phillips, James A.

2018-04-01

The nature of the interactions between silicon tetrafluoride and series of nitrogen bases, including nitriles (RCN, with R > CH3), pyridine, and various fluoro-substituted pyridines, has been investigated via quantum-chemical computations, low-temperature IR spectroscopy, and bulk reactivity experiments. Using (primarily) M06 with the 6-311+G(2df,2pd) basis set, we obtained equilibrium structures, binding energies, harmonic frequencies, and N-Si potentials in the gas-phase and in bulk dielectric media for an extensive series of 1:1 molecular complexes, including: C6H5CH2CN-SiF4, CH3CH2CN-SiF4, (CH3)3CCN-SiF4, C5H5N-SiF4, 4-FC5H4N-SiF4, 3,5-C5F2H3N-SiF4, 2,6-C5F2H3N-SiF4 and 3,4,5-C5F3H2N-SiF4. In addition, for the analogous 2:1 complexes of pyridine and 3,5-difluororpyridine, we obtained equilibrium structures, binding energies, and harmonic frequencies. The N-Si distances in the 1:1 nitrile complexes are fairly long, ranging from 2.84 Å to 2.88 Å, and the binding energies range from 4.0 to 4.2 kcal/mol (16.7-17.6 kJ/mol). Also, computations predict extremely anharmonic N-Si potentials, for which the inner portions of the curve are preferentially stabilized in dielectric media, which predict an enhancement of these interactions in condensed-phases. However, we see no evidence of bulk reactivity between C6H5CH2CN, CH3CH2CN, or (CH3)3CCN and SiF4, nor any significant interaction between (CH3)3CCN and SiF4 in low temperature IR spectra of solid, (CH3)3CCN/SiF4 thin films. Conversely, the interactions in four of the five 1:1, pyridine-SiF4 complexes are generally stronger; binding energies range from 5.7 to 9.6 kcal/mol (23.8-40.2 kJ/mol), and correspondingly the N-Si distances are relatively short (2.12-2.25 Å). The exception is 2,6-C5F2H3N-SiF4, for which the binding energy is only 3.6 kcal/mol (15.1 kJ/mol), and the N-Si distance is quite long (3.12 Å). In addition, both pyridine and 3,5-difluororpyridine were found to form stable reaction products with SiF4; but no analogous product was obtained with 2,6-difluororpyridine and SiF4, nor was any significant interaction indicated in low-temperature IR spectra of 2,6-difluororpyridine/SiF4 films. By contrast, low temperature spectra of pyridine/SiF4 and 3,5-difluororpyridine/SiF4 thin films are consistent with the presence of a distinct 2:1 reaction product. Moreover, the observed frequencies agree reasonably well with those predicted for the cis, octahedral coordination isomers of the 2:1 molecular complexes, in which the N-Si bonds are compressed slightly relative to those in the predicted gas-phase structures.

On Finding and Using Identifiable Parameter Combinations in Nonlinear Dynamic Systems Biology Models and COMBOS: A Novel Web Implementation

PubMed Central

DiStefano, Joseph

2014-01-01

Parameter identifiability problems can plague biomodelers when they reach the quantification stage of development, even for relatively simple models. Structural identifiability (SI) is the primary question, usually understood as knowing which of P unknown biomodel parameters p 1,…, pi,…, pP are-and which are not-quantifiable in principle from particular input-output (I-O) biodata. It is not widely appreciated that the same database also can provide quantitative information about the structurally unidentifiable (not quantifiable) subset, in the form of explicit algebraic relationships among unidentifiable pi. Importantly, this is a first step toward finding what else is needed to quantify particular unidentifiable parameters of interest from new I–O experiments. We further develop, implement and exemplify novel algorithms that address and solve the SI problem for a practical class of ordinary differential equation (ODE) systems biology models, as a user-friendly and universally-accessible web application (app)–COMBOS. Users provide the structural ODE and output measurement models in one of two standard forms to a remote server via their web browser. COMBOS provides a list of uniquely and non-uniquely SI model parameters, and–importantly-the combinations of parameters not individually SI. If non-uniquely SI, it also provides the maximum number of different solutions, with important practical implications. The behind-the-scenes symbolic differential algebra algorithms are based on computing Gröbner bases of model attributes established after some algebraic transformations, using the computer-algebra system Maxima. COMBOS was developed for facile instructional and research use as well as modeling. We use it in the classroom to illustrate SI analysis; and have simplified complex models of tumor suppressor p53 and hormone regulation, based on explicit computation of parameter combinations. It’s illustrated and validated here for models of moderate complexity, with and without initial conditions. Built-in examples include unidentifiable 2 to 4-compartment and HIV dynamics models. PMID:25350289

Electrical and optical properties of Si-doped Ga2O3

NASA Astrophysics Data System (ADS)

Li, Yin; Yang, Chuanghua; Wu, Liyuan; Zhang, Ru

2017-05-01

The charge densities, band structure, density of states, dielectric functions of Si-doped β-Ga2O3 have been investigated based on the density functional theory (DFT) within the hybrid functional HSE06. The heavy doping makes conduction band split out more bands and further influences the band structure. It decreases the band gap and changes from a direct gap to an indirect gap. After doping, the top of the valence bands is mainly composed by the O-2p states, Si-3p states and Ga-4p states and the bottom of the conduction bands is almost formed by the Si-3s, Si-3p and Ga-4s orbits. The anisotropic optical properties have been investigated by means of the complex dielectric function. After the heavy Si doping, the position of absorption band edges did not change much. The slope of the absorption curve descends and indicates that the absorption became more slow for Si-doped β-Ga2O3 than undoped one due to the indirect gap of Si-doped β-Ga2O3.

Elucidating the role of surface chemistry on cationic phosphorus dendrimer-siRNA complexation.

PubMed

Deriu, Marco A; Tsapis, Nicolas; Noiray, Magali; Grasso, Gianvito; El Brahmi, Nabil; Mignani, Serge; Majoral, Jean-Pierre; Fattal, Elias; Danani, Andrea

2018-06-14

In the field of dendrimers targeting small interfering RNA (siRNA) delivery, dendrimer structural properties, such as the flexibility/rigidity ratio, play a crucial role in the efficiency of complexation. However, advances in organic chemistry have enabled the development of dendrimers that differ only by a single atom on their surface terminals. This is the case for cationic phosphorus dendrimers functionalized with either pyrrolidinium (DP) or morpholinium (DM) terminal groups. This small change was shown to strongly affect the dendrimer-siRNA complexation, leading to more efficient anti-inflammatory effects in the case of DP. Reasons for this different behavior can hardly be inferred only by biological in vitro and in vivo experiments due to the high number of variables and complexity of the investigated biological system. However, an understanding of how small chemical surface changes may completely modify the overall dendrimer-siRNA complexation is a significant breakthrough towards the design of efficient dendrimers for nucleic acid delivery. Herein, we present experimental and computational approaches based on isothermal titration calorimetry and molecular dynamics simulations to elucidate the molecular reasons behind different efficiencies and activities of DP and DM. Results of the present research highlight how chemical surface modifications may drive the overall dendrimer-siRNA affinity by influencing enthalpic and entropic contributions of binding free energy. Moreover, this study elucidates molecular reasons related to complexation stoichiometry that may be crucial in determining the dendrimer complexation efficiency.

Mechanistic profiling of the siRNA delivery dynamics of lipid-polymer hybrid nanoparticles.

PubMed

Colombo, Stefano; Cun, Dongmei; Remaut, Katrien; Bunker, Matt; Zhang, Jianxin; Martin-Bertelsen, Birte; Yaghmur, Anan; Braeckmans, Kevin; Nielsen, Hanne M; Foged, Camilla

2015-03-10

Understanding the delivery dynamics of nucleic acid nanocarriers is fundamental to improve their design for therapeutic applications. We investigated the carrier structure-function relationship of lipid-polymer hybrid nanoparticles (LPNs) consisting of poly(DL-lactic-co-glycolic acid) (PLGA) nanocarriers modified with the cationic lipid dioleoyltrimethyl-ammoniumpropane (DOTAP). A library of siRNA-loaded LPNs was prepared by systematically varying the nitrogen-to-phosphate (N/P) ratio. Atomic force microscopy (AFM) and cryo-transmission electron microscopy (cryo-TEM) combined with small angle X-ray scattering (SAXS) and confocal laser scanning microscopy (CLSM) studies suggested that the siRNA-loaded LPNs are characterized by a core-shell structure consisting of a PLGA matrix core coated with lamellar DOTAP structures with siRNA localized both in the core and in the shell. Release studies in buffer and serum-containing medium combined with in vitro gene silencing and quantification of intracellular siRNA suggested that this self-assembling core-shell structure influences the siRNA release kinetics and the delivery dynamics. A main delivery mechanism appears to be mediated via the release of transfection-competent siRNA-DOTAP lipoplexes from the LPNs. Based on these results, we suggest a model for the nanostructural characteristics of the LPNs, in which the siRNA is organized in lamellar superficial assemblies and/or as complexes entrapped in the polymeric matrix. Copyright © 2015 Elsevier B.V. All rights reserved.

A nonviral DNA delivery system based on surface modified silica-nanoparticles can efficiently transfect cells in vitro.

PubMed

Kneuer, C; Sameti, M; Bakowsky, U; Schiestel, T; Schirra, H; Schmidt, H; Lehr, C M

2000-01-01

Diverse polycationic polymers have been used as nonviral transfection agents. Here we report the ability of colloidal silica particles with covalently attached cationic surface modifications to transfect plasmid DNA in vitro and make an attempt to describe the structure of the resulting transfection complexes. In analogy to the terms lipoplex and polyplex, we propose to describe the nanoparticle-DNA complexes by the term "nanoplex". Three batches, Si10E, Si100E, and Si26H, sized between 10 and 100 nm and with zeta potentials ranging from +7 to +31 mV at pH 7.4 were evaluated. The galactosidase expression plasmid DNA pCMVbeta was immobilized on the particle surface and efficiently transfected Cos-1 cells. The transfection activity was accompanied by very low cytotoxicity, with LD(50) values in the milligrams per milliliter range. The most active batch, Si26H, was produced by modification of commercially available silica particles with N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, yielding spherical nanoparticles with a mean diameter of 26 nm and a zeta potential of +31 mV at pH 7.4. Complexes of Si26H and pCMVbeta plasmid DNA formed at w/w ratios of 10 were most effective in promoting transfection of Cos-1 cells in the absence of serum. At this ratio, >90% of the DNA was associated with the particles, yielding nanoplexes with a net negative surface charge. When the transfection medium was supplemented with 10% serum, maximum gene expression was observed at a w/w ratio of 30, at which the resulting particle-DNA complexes possessed a positive surface charge. Transfection was strongly increased in the presence of 100 microM chloroquine in the incubation medium and reached approximately 30% of the efficiency of a 60 kDa polyethylenimine. In contrast to polyethylenimine, no toxicity was observed at the concentrations required. Atomic force microscopy of Si26H-DNA complexes revealed a spaghetti-meatball-like structure. The surface of complexes prepared at a w/w ratio of 30 was dominated by particles half-spheres. Complex sizes correlated well with those determined previously by dynamic light scattering.

Understanding lattice thermal conductivity in thermoelectric clathrates: A density functional theory study on binary Si-based type-I clathrates

NASA Astrophysics Data System (ADS)

Euchner, Holger; Pailhès, Stéphane; Giordano, Valentina M.; de Boissieu, Marc

2018-01-01

Despite their crystalline nature, thermoelectric clathrates exhibit a strongly reduced lattice thermal conductivity. While the reason for this unexpected behavior is known to lie in the peculiarities of the complex crystal structure and the interplay of the underlying guest-host framework, their respective roles are still not fully disentangled and understood. Our ab initio study of the most simple type-I clathrate phase, the binary compound Ba8Si46 and its derivatives Ba8 -xSi46 seeks to identify these mechanisms and provides insight into their origin. Indeed, the strongly decreased lattice thermal conductivity in thermoelectric clathrates is a consequence of a reduction of the acoustic phonon bandwidth, a lowering of the acoustic phonon group velocities, and the amplification of three-phonon-scattering processes. While the complexity of the crystal structure is demonstrated not to be the leading factor, the reasons are manifold. A modified Si-Si interaction causes a first decrease of the sound velocity, whereas the presence of flat Ba modes results in an additional lowering. These modes correspond to confined Bloch states that are localized on the Ba atoms and significantly increase the scattering phase space and, together with an increased anharmonicity of the interatomic interactions, strongly affect the phonon lifetimes.

Characterization of complex carbide–silicide precipitates in a Ni–Cr–Mo–Fe–Si alloy modified by welding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, D., E-mail: dhb@ansto.gov.au; Davis, J.; Drew, M.

2015-07-15

Nickel based alloys of the type Hastelloy-N™ are ideal candidate materials for molten salt reactors, as well as for applications such as pressure vessels, due to their excellent resistance to creep, oxidation and corrosion. In this work, the authors have attempted to understand the effects of welding on the morphology, chemistry and crystal structure of the precipitates in the heat affected zone (HAZ) and the weld zone of a Ni–Cr–Mo–Fe–Si alloy similar to Hastelloy-N™ in composition, by using characterization techniques such as scanning and transmission electron microscopy. Two plates of a Ni–Cr–Mo–Fe–Si alloy GH-3535 were welded together using a TiGmore » welding process without filler material to achieve a joint with a curved molten zone with dendritic structure. It is evident that the primary precipitates have melted in the HAZ and re-solidified in a eutectic-like morphology, with a chemistry and crystal structure only slightly different from the pre-existing precipitates, while the surrounding matrix grains remained unmelted, except for the zones immediately adjacent to the precipitates. In the molten zone, the primary precipitates were fully melted and dissolved in the matrix, and there was enrichment of Mo and Si in the dendrite boundaries after solidification, and re-precipitation of the complex carbides/silicides at some grain boundaries and triple points. The nature of the precipitates in the molten zone varied according to the local chemical composition. - Graphical abstract: Display Omitted - Highlights: • Ni-based alloy with Cr, Mo, Si, Fe and C was welded, examined with SEM, EBSD, and TEM. • Original Ni{sub 2}(Mo,Cr){sub 4}(Si,C) carbides changed from equiaxed to lamellar shape in HAZ. • Composition and crystal structure remained almost unchanged in HAZ. • Original carbides changed to lamellar Ni{sub 3}(Mo,Cr){sub 3}(Si,C) in some cases in weld metal. • Precipitates were mostly incoherent, but semi-coherent in some cases in weld metal.« less

Rietveld refinement, electronic structure and ionic conductivity of Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boughzala, Khaled, E-mail: khaledboughzala@gmail.com; Preparatory Institute for Engineering Studies, 5000 Monastir; Debbichi, Mourad

In this paper, we report the effect of the tunnel anions on the ionic conductivity of Strontium-Lanthanum silicate apatites. The Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics were prepared by the solid state reaction method. X-ray diffraction, NMR spectroscopy and Raman measurements were performed to investigate the crystal structure and vibrational active modes. Moreover, the electronic structures of the crystals were evaluated by the first-principles quantum mechanical calculation based on the density functional theory. Finally, the ionic conductivity was studied according to the complex impedance method. - Graphical abstract: The relaxed primitive unit cellmore » for Sr{sub 4}La{sub 6}Fap. Display Omitted.« less

Spectroscopic study on variations in illite surface properties after acid-base titration.

PubMed

Liu, Wen-xin; Coveney, R M; Tang, Hong-xiao

2003-07-01

FT-IR, Raman microscopy, XRD, 29Si and 27Al MAS NMR, were used to investigate changes in surface properties of a natural illite sample after acid-base potentiometric titration. The characteristic XRD lines indicated the presence of surface Al-Si complexes, preferable to Al(OH)3 precipitates. In the microscopic Raman spectra, the vibration peaks of Si-O and Al-O bonds diminished as a result of treatment with acid, then increased after hydroxide back titration. The varied ratio of signal intensity between (IV)Al and (VI)Al species in 27Al MAS NMR spectra, together with the stable BET surface area after acidimetric titration, suggested that edge faces and basal planes in the layer structure of illite participated in dissolution of structural components. The combined spectroscopic evidence demonstrated that the reactions between illite surfaces and acid-leaching silicic acid and aluminum ions should be considered in the model description of surface acid-base properties of the aqueous illite.

Transition of Blast Furnace Slag from Silicate Based to Aluminate Based: Density and Surface Tension

NASA Astrophysics Data System (ADS)

Yan, Zhiming; Lv, Xuewei; Pang, Zhengde; Lv, Xueming; Bai, Chenguang

2018-03-01

The effects of the Al2O3 concentration and Al2O3/SiO2 ratio on the density and surface tension of molten aluminosilicate CaO-SiO2-Al2O3-9 mass pct MgO-1 mass pct TiO2 slag were investigated at temperatures from 1723 K to 1823 K (1450 °C to 1550 °C) using the Archimedean method and the maximum bubble pressure (MBP) technique, respectively. The mechanism of the changes in density and surface tension with composition was analyzed from the viewpoint of the degree of polymerization in the structure and the types of oxygen species in the melts. At a fixed CaO/SiO2 ratio of 1.20, the density decreased with increasing Al2O3 content up to 25 mass pct, subsequently increasing. Increasing the Al2O3/SiO2 ratio from 0.47 to 0.92 caused an increase in the density at a fixed CaO content, and the density decreased slightly when the Al2O3/SiO2 ratio was greater than 0.92. Based on the structural information, the density decreased when the Al2O3 content enhanced the network structure and increased when the (Q 2 + Q 3)/(Q 0 + Q 1) ratio and structural complexity decreased. The surface tension increased with increasing Al2O3 content and Al2O3/SiO2 ratio. On the one hand, the surface-active component of SiO2 decreased; on the other hand, the concentration of [AlO4]5- tetrahedra and metal cations that act as charge compensators increased at the melt surface. A model based on the anionic and cationic radii and the Butler equation was employed to predict the surface tension, and an iso-surface tension diagram was obtained at 1773 K (1500 °C).

Transition of Blast Furnace Slag from Silicate Based to Aluminate Based: Density and Surface Tension

NASA Astrophysics Data System (ADS)

Yan, Zhiming; Lv, Xuewei; Pang, Zhengde; Lv, Xueming; Bai, Chenguang

2018-06-01

The effects of the Al2O3 concentration and Al2O3/SiO2 ratio on the density and surface tension of molten aluminosilicate CaO-SiO2-Al2O3-9 mass pct MgO-1 mass pct TiO2 slag were investigated at temperatures from 1723 K to 1823 K (1450 °C to 1550 °C) using the Archimedean method and the maximum bubble pressure (MBP) technique, respectively. The mechanism of the changes in density and surface tension with composition was analyzed from the viewpoint of the degree of polymerization in the structure and the types of oxygen species in the melts. At a fixed CaO/SiO2 ratio of 1.20, the density decreased with increasing Al2O3 content up to 25 mass pct, subsequently increasing. Increasing the Al2O3/SiO2 ratio from 0.47 to 0.92 caused an increase in the density at a fixed CaO content, and the density decreased slightly when the Al2O3/SiO2 ratio was greater than 0.92. Based on the structural information, the density decreased when the Al2O3 content enhanced the network structure and increased when the ( Q 2 + Q 3)/( Q 0 + Q 1) ratio and structural complexity decreased. The surface tension increased with increasing Al2O3 content and Al2O3/SiO2 ratio. On the one hand, the surface-active component of SiO2 decreased; on the other hand, the concentration of [AlO4]5- tetrahedra and metal cations that act as charge compensators increased at the melt surface. A model based on the anionic and cationic radii and the Butler equation was employed to predict the surface tension, and an iso-surface tension diagram was obtained at 1773 K (1500 °C).

Transformation of sludge Si to nano-Si/SiOx structure by oxygen inward diffusion as precursor for high performance anodes in lithium ion batteries

NASA Astrophysics Data System (ADS)

Hua, Qiqi; Dai, Dongyang; Zhang, Chengzhi; Han, Fei; Lv, Tiezheng; Li, Xiaoshan; Wang, Shijie; Zhu, Rui; Liao, Haojie; Zhang, Shiguo

2018-05-01

Although several Si/C composite structures have been proposed for high-performance lithium-ion batteries (LIBs), they have still suffered from expensive and complex processes of nano-Si production. Herein, a simple, controllable oxygen inward diffusion was utilized to transform Si sludge obtained from the photovoltaic (PV) industry into the nano-Si/SiOx structure as a result of the high diffusion efficiency of O inside Si and high surface area of the sludge. After further process, a yolk/shell Si/C structure was obtained as an anode material for LIBs. This composite demonstrated an excellent cycling stability, with a high reversible capacity (˜ 1250 mAh/g for 500 cycles), by void space originally left by the SiOx accommodate inner Si expansion. We believe this is a rather simple way to convert the waste Si into a valuable nano-Si for LIB applications.

Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Jie; Li, Yuan; Chen, Yingnan

Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology andmore » structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.« less

Crystal structures of η''-Cu3+xSi and η'''-Cu3+xSi.

PubMed

Corrêa, Cinthia Antunes; Perez, Olivier; Kopeček, Jaromír; Brázda, Petr; Klementová, Mariana; Palatinus, Lukáš

2017-08-01

The binary phase diagram of Cu-Si is unexpectedly complex in the vicinity of Cu 3+x Si. The low-temperature region contains three closely related incommensurately modulated phases denoted, in order of increasing temperature of stability, η''', η'' and η'. The structure analysis of η' has been reported previously [Palatinus et al. (2011). Inorg. Chem. 50, 3743]. Here the structure model for the phases η'' and η''' is reported. The structures could be solved in superspace, but no superspace structure model could be constructed due to the complexity of the modulation functions. Therefore, the structures were described in a supercell approximation, which involved a 4 × 4 × 3 supercell for the η'' phase and a 14 × 14 × 3 supercell for the η''' phase. Both structures are very similar and differ only by a subtle symmetry lowering from η'' to η'''. A comparison of the structure models of η'' and η''' with the reported structure of η' suggests that the reported structure model of η' contains an incorrect assignment of atomic types.

A Method to Predict the Structure and Stability of RNA/RNA Complexes.

PubMed

Xu, Xiaojun; Chen, Shi-Jie

2016-01-01

RNA/RNA interactions are essential for genomic RNA dimerization and regulation of gene expression. Intermolecular loop-loop base pairing is a widespread and functionally important tertiary structure motif in RNA machinery. However, computational prediction of intermolecular loop-loop base pairing is challenged by the entropy and free energy calculation due to the conformational constraint and the intermolecular interactions. In this chapter, we describe a recently developed statistical mechanics-based method for the prediction of RNA/RNA complex structures and stabilities. The method is based on the virtual bond RNA folding model (Vfold). The main emphasis in the method is placed on the evaluation of the entropy and free energy for the loops, especially tertiary kissing loops. The method also uses recursive partition function calculations and two-step screening algorithm for large, complicated structures of RNA/RNA complexes. As case studies, we use the HIV-1 Mal dimer and the siRNA/HIV-1 mutant (T4) to illustrate the method.

Application of Ce3+ single-doped complexes as solar spectral downshifters for enhancing photoelectric conversion efficiencies of a-Si-based solar cells

NASA Astrophysics Data System (ADS)

Song, Pei; Jiang, Chun

2013-05-01

The effect on photoelectric conversion efficiency of an a-Si-based solar cell by applying a solar spectral downshifter of rare earth ion Ce3+ single-doped complexes including yttrium aluminum garnet Y3Al5O12 single crystals, nanostructured ceramics, microstructured ceramics and B2O3-SiO2-Gd2O3-BaO glass is studied. The photoluminescence excitation spectra in the region 360-460 nm convert effectively into photoluminescence emission spectra in the region 450-550 nm where a-Si-based solar cells exhibit a higher spectral response. When these Ce3+ single-doped complexes are placed on the top of an a-Si-based solar cell as precursors for solar spectral downshifting, theoretical relative photoelectric conversion efficiencies of nc-Si:H and a-Si:H solar cells approach 1.09-1.13 and 1.04-1.07, respectively, by means of AMPS-1D numerical modeling, potentially benefiting an a-Si-based solar cell with a photoelectric efficiency improvement.

Molecular recognition on a cavitand-functionalized silicon surface.

PubMed

Biavardi, Elisa; Favazza, Maria; Motta, Alessandro; Fragalà, Ignazio L; Massera, Chiara; Prodi, Luca; Montalti, Marco; Melegari, Monica; Condorelli, Guglielmo G; Dalcanale, Enrico

2009-06-03

A Si(100) surface featuring molecular recognition properties was obtained by covalent functionalization with a tetraphosphonate cavitand (Tiiii), able to complex positively charged species. Tiiii cavitand was grafted onto the Si by photochemical hydrosilylation together with 1-octene as a spatial spectator. The recognition properties of the Si-Tiiii surface were demonstrated through two independent analytical techniques, namely XPS and fluorescence spectroscopy, during the course of reversible complexation-guest exchange-decomplexation cycles with specifically designed ammonium and pyridinium salts. Control experiments employing a Si(100) surface functionalized with a structurally similar, but complexation inactive, tetrathiophosphonate cavitand (TSiiii) demonstrated no recognition events. This provides evidence for the complexation properties of the Si-Tiiii surface, ruling out the possibility of nonspecific interactions between the substrate and the guests. The residual Si-O(-) terminations on the surface replace the guests' original counterions, thus stabilizing the complex ion pairs. These results represent a further step toward the control of self-assembly of complex supramolecular architectures on surfaces.

Interactions of atomic hydrogen with amorphous SiO2

NASA Astrophysics Data System (ADS)

Yue, Yunliang; Wang, Jianwei; Zhang, Yuqi; Song, Yu; Zuo, Xu

2018-03-01

Dozens of models are investigated by the first-principles calculations to simulate the interactions of an atomic hydrogen with a defect-free random network of amorphous SiO2 (a-SiO2) and oxygen vacancies. A wide variety of stable configurations are discovered due to the disorder of a-SiO2, and their structures, charges, magnetic moments, spin densities, and density of states are calculated. The atomic hydrogen interacts with the defect-free a-SiO2 in positively or negatively charged state, and produces the structures absent in crystalline SiO2. It passivates the neutral oxygen vacancies and generates two neutral hydrogenated E‧ centers with different Si dangling bond projections. Electron spin resonance parameters, including Fermi contacts, and g-tensors, are calculated for these centers. The atomic hydrogen interacts with the positive oxygen vacancies in dimer configuration, and generate four different positive hydrogenated defects, two of which are puckered like the Eγ‧ centers. This research helps to understand the interactions between an atomic hydrogen, and defect-free a-SiO2 and oxygen vacancies, which may generate the hydrogen-complexed defects that play a key role in the degeneration of silicon/silica-based microelectronic devices.

Mechanical characteristics of heterogeneous structures obtained by high-temperature brazing of corrosion-resistant steels with rapidly quenched non-boron nickel-based alloys

NASA Astrophysics Data System (ADS)

Kalin, B.; Penyaz, M.; Ivannikov, A.; Sevryukov, O.; Bachurina, D.; Fedotov, I.; Voennov, A.; Abramov, E.

2018-01-01

Recently, the use rapidly quenched boron-containing nickel filler metals for high temperature brazing corrosion resistance steels different classes is perspective. The use of these alloys leads to the formation of a complex heterogeneous structure in the diffusion zone that contains separations of intermediate phases such as silicides and borides. This structure negatively affects the strength characteristics of the joint, especially under dynamic loads and in corrosive environment. The use of non-boron filler metals based on the Ni-Si-Be system is proposed to eliminate this structure in the brazed seam. Widely used austenitic 12Cr18Ni10Ti and ferrite-martensitic 16Cr12MoSiWNiVNb reactor steels were selected for research and brazing was carried out. The mechanical characteristics of brazed joints were determined using uniaxial tensile and impact toughness tests, and fractography was investigated by electron microscopy.

Electronic structure of dense Pb overlayers on Si(111) investigated using angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Choi, W. H.; Koh, H.; Rotenberg, E.; Yeom, H. W.

2007-02-01

Dense Pb overlayers on Si(111) are important as the wetting layer for anomalous Pb island growth as well as for their own complex “devil’s-staircase” phases. The electronic structures of dense Pb overlayers on Si(111) were investigated in detail by angle-resolved photoemission. Among the series of ordered phases found recently above one monolayer, the low-coverage 7×3 and the high-coverage 14×3 phases are studied; they are well ordered and form reproducibly in large areas. The band dispersions and Fermi surfaces of the two-dimensional (2D) electronic states of these overlayers are mapped out. A number of metallic surface-state bands are identified for both phases with complex Fermi contours. The basic features of the observed Fermi contours can be explained by overlapping 2D free-electron-like Fermi circles. This analysis reveals that the 2D electrons near the Fermi level of the 7×3 and 14×3 phases are mainly governed by strong 1×1 and 3×3 potentials, respectively. The origins of the 2D electronic states and their apparent Fermi surface shapes are discussed based on recent structure models.

Structural and energetic properties of acetonitrile-Group IV (A & B) halide complexes.

PubMed

Helminiak, Heather M; Knauf, Robin R; Danforth, Samuel J; Phillips, James A

2014-06-19

We have conducted an extensive computational study of the structural and energetic properties of select acetonitrile-Group IV (A & B) tetrahalide complexes, both CH3CN-MX4 and (CH3CN)2-MX4 (M = Si, Ge, Ti; X = F, Cl). We have also examined the reactivity of CH3CN with SiF4, SiCl4, GeCl4, and TiCl4, and measured low-temperature IR spectra of thin films containing CH3CN with SiF4, GeCl4, or TiCl4. The six 1:1 complexes fall into two general structural classes. CH3CN-TiCl4, CH3CN-TiF4, and CH3CN-GeF4, exhibit relatively short M-N bonds (~2.3 Å), an intermediate degree of distortion in the MX4 subunit, and binding energies ranging from 11.0 to 13.0 kcal/mol. Conversely, CH3CN-GeCl4, CH3CN-SiF4, and CH3CN-SiCl4, are weakly bonded systems, with long M-N distances (>3.0 Å), little distortion in the MX4 subunit, and binding energies ranging from 3.0 to 4.4 kcal/mol. The structural features of analogous 2:1 systems resemble those of their 1:1 counterparts, whereas the binding energies (relative to three isolated fragments) are roughly twice as large. Calculated M-N potential curves in the gas phase and bulk, dielectric media are reported for all 1:1 complexes, and for two systems, CH3CN-GeF4 and CH3CN-SiF4, these data predict significant condensed-phase structural changes. The effect on the CH3CN-SiF4 potential is extreme; the curve becomes quite flat over a broad range in dielectric media, and at higher ε values, the global minimum shifts inward by about 1.0 Å. In bulk reactivity experiments, no reaction was observed between CH3CN and SiF4, SiCl4, or GeCl4, whereas CH3CN and TiCl4 were found to react immediately upon contact. Also, thin-film IR spectra indicate a strong interaction between CH3CN and TiCl4, yet only weak interactions between CH3CN and GeCl4 or SiF4 in the solid state.

Late-stage chemoselective functional-group manipulation of bioactive natural products with super-electrophilic silylium ions

NASA Astrophysics Data System (ADS)

Bender, Trandon A.; Payne, Philippa R.; Gagné, Michel R.

2018-01-01

The selective (and controllable) modification of complex molecules with disparate functional groups (for example, natural products) is a long-standing challenge that has been addressed using catalysts tuned to perform singular transformations (for example, C-H hydroxylation). A method whereby reactions with diverse functional groups within a single natural product are feasible depending on which catalyst or reagent is chosen would widen the possible structures one could obtain. Fluoroarylborane catalysts can heterolytically split Si-H bonds to yield an oxophilic silylium (R3Si+) equivalent along with a reducing (H-) equivalent. Together, these reactive intermediates enable the reduction of multiple functional groups. Exogenous phosphine Lewis bases further modify the catalyst speciation and attenuate aggressive silylium ions for the selective modification of complex natural products. Manipulation of the catalyst, silane reagent and the reaction conditions provides experimental control over which site is modified (and how). Applying this catalytic method to complex bioactive compounds (natural products or drugs) provides a powerful tool for studying structure-activity relationships.

Designed Single-Step Synthesis, Structure, and Derivative Textural Properties of Well-Ordered Layered Penta-Coordinate Silicon Alcoholate Complexes

PubMed Central

Li, Xiansen; Michaelis, Vladimir K.; Ong, Ta-Chung; Smith, Stacey J.; Griffin, Robert G.; Wang, Evelyn N.

2014-01-01

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. We report the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes via a novel transesterification mechanism. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building units (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+-O2− ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10ī)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counterions as a result of unique atomic arrangement in its structure. On the other hand, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7 m2 g−1 for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity. PMID:24737615

Co-delivery of doxorubicin and siRNA using octreotide-conjugated gold nanorods for targeted neuroendocrine cancer therapy

NASA Astrophysics Data System (ADS)

Xiao, Yuling; Jaskula-Sztul, Renata; Javadi, Alireza; Xu, Wenjin; Eide, Jacob; Dammalapati, Ajitha; Kunnimalaiyaan, Muthusamy; Chen, Herbert; Gong, Shaoqin

2012-10-01

A multifunctional gold (Au) nanorod (NR)-based nanocarrier capable of co-delivering small interfering RNA (siRNA) against achaete-scute complex-like 1 (ASCL1) and an anticancer drug (doxorubicin (DOX)) specifically to neuroendocrine (NE) cancer cells was developed and characterized for combined chemotherapy and siRNA-mediated gene silencing. The Au NR was conjugated with (1) DOX, an anticancer drug, via a pH-labile hydrazone linkage to enable pH-controlled drug release, (2) polyarginine, a cationic polymer for complexing siRNA, and (3) octreotide (OCT), a tumor-targeting ligand, to specifically target NE cancer cells with overexpressed somatostatin receptors. The Au NR-based nanocarriers exhibited a uniform size distribution as well as pH-sensitive drug release. The OCT-conjugated Au NR-based nanocarriers (Au-DOX-OCT, targeted) exhibited a much higher cellular uptake in a human carcinoid cell line (BON cells) than non-targeted Au NR-based nanocarriers (Au-DOX) as measured by both flow cytometry and confocal laser scanning microscopy (CLSM). Moreover, Au-DOX-OCT-ASCL1 siRNA (Au-DOX-OCT complexed with ASCL1 siRNA) resulted in significantly higher gene silencing in NE cancer cells than Au-DOX-ASCL1 siRNA (non-targeted Au-DOX complexed with ASCL1 siRNA) as measured by an immunoblot analysis. Additionally, Au-DOX-OCT-ASCL1 siRNA was the most efficient nanocarrier at altering the NE phenotype of NE cancer cells and showed the strongest anti-proliferative effect. Thus, combined chemotherapy and RNA silencing using NE tumor-targeting Au NR-based nanocarriers could potentially enhance the therapeutic outcomes in treating NE cancers.A multifunctional gold (Au) nanorod (NR)-based nanocarrier capable of co-delivering small interfering RNA (siRNA) against achaete-scute complex-like 1 (ASCL1) and an anticancer drug (doxorubicin (DOX)) specifically to neuroendocrine (NE) cancer cells was developed and characterized for combined chemotherapy and siRNA-mediated gene silencing. The Au NR was conjugated with (1) DOX, an anticancer drug, via a pH-labile hydrazone linkage to enable pH-controlled drug release, (2) polyarginine, a cationic polymer for complexing siRNA, and (3) octreotide (OCT), a tumor-targeting ligand, to specifically target NE cancer cells with overexpressed somatostatin receptors. The Au NR-based nanocarriers exhibited a uniform size distribution as well as pH-sensitive drug release. The OCT-conjugated Au NR-based nanocarriers (Au-DOX-OCT, targeted) exhibited a much higher cellular uptake in a human carcinoid cell line (BON cells) than non-targeted Au NR-based nanocarriers (Au-DOX) as measured by both flow cytometry and confocal laser scanning microscopy (CLSM). Moreover, Au-DOX-OCT-ASCL1 siRNA (Au-DOX-OCT complexed with ASCL1 siRNA) resulted in significantly higher gene silencing in NE cancer cells than Au-DOX-ASCL1 siRNA (non-targeted Au-DOX complexed with ASCL1 siRNA) as measured by an immunoblot analysis. Additionally, Au-DOX-OCT-ASCL1 siRNA was the most efficient nanocarrier at altering the NE phenotype of NE cancer cells and showed the strongest anti-proliferative effect. Thus, combined chemotherapy and RNA silencing using NE tumor-targeting Au NR-based nanocarriers could potentially enhance the therapeutic outcomes in treating NE cancers. Electronic supplementary information (ESI) available: Additional flow cytometry histogram profiles of DOX fluorescence and ASCL1 knockdown results. See DOI: 10.1039/c2nr31853a

An XPS study on the chemical bond structure at the interface between SiO{sub x}N{sub y} and N doped polyethylene terephthalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding Wanyu; Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024; Li Li

2013-03-14

The super-thin silicon oxynitride (SiO{sub x}N{sub y}) films were deposited onto the N doped polyethylene terephthalate (PET) surface. Varying the N doping parameters, the different chemical bond structures were obtained at the interface between the SiO{sub x}N{sub y} film and the PET surface. X-ray photoelectron spectra results showed that at the initial stage of SiO{sub x}N{sub y} film growth, the C=N bonds could be broken and C-N-Si crosslink bonds could be formed at the interface of SiO{sub x}N{sub y}/PET, which C=N bonds could be formed onto the PET surface during the N doping process. At these positions, the SiO{sub x}N{submore » y} film could be crosslinked well onto the PET surface. Meanwhile, the doped N could crosslink the [SiO{sub 4}] and [SiN{sub 4}] tetrahedrons, which could easily form the dense layer structure at the initial stage of SiO{sub x}N{sub y} film growth, instead of the ring and/or chain structures of [SiO{sub 4}] tetrahedrons crosslinked by O. Finally, from the point of applying SiO{sub x}N{sub y}/PET complex as the substrate, the present work reveals a simple way to crosslink them, as well as the crosslink model and physicochemical mechanism happened at the interface of complex.« less

p-n Junction Diodes Fabricated on Si-Si/Ge Heteroepitaxial Films

NASA Technical Reports Server (NTRS)

Das, K.; Mazumder, M. D. A.; Hall, H.; Alterovitz, Samuel A. (Technical Monitor)

2000-01-01

A set of photolithographic masks was designed for the fabrication of diodes in the Si-Si/Ge material system. Fabrication was performed on samples obtained from two different wafers: (1) a complete HBT structure with an n (Si emitter), p (Si/Ge base), and an n/n+ (Si collector/sub-collector) deposited epitaxially (MBE) on a high resistivity p-Si substrate, (2) an HBT structure where epitaxial growth was terminated after the p-type base (Si/Ge) layer deposition. Two different process runs were attempted for the fabrication of Si-Si/Ge (n-p) and Si/Ge-Si (p-n) junction diodes formed between the emitter-base and base-collector layers, respectively, of the Si-Si/Ge-Si HBT structure. One of the processes employed a plasma etching step to expose the p-layer in the structure (1) and to expose the e-layer in structure (2). The Contact metallization used for these diodes was a Cu-based metallization scheme that was developed during the first year of the grant. The plasma-etched base-collector diodes on structure (2) exhibited well-behaved diode-like characteristics. However, the plasma-etched emitter-base diodes demonstrated back-to-back diode characteristics. These back-to back characteristics were probably due to complete etching of the base-layer, yielding a p-n-p diode. The deep implantation process yielded rectifying diodes with asymmetric forward and reverse characteristics. The ideality factor of these diodes were between 1.6 -2.1, indicating that the quality of the MBE grown epitaxial films was not sufficiently high, and also incomplete annealing of the implantation damage. Further study will be conducted on CVD grown films, which are expected to have higher epitaxial quality.

Strong enhancement effect of silver nanowires on fluorescent property of Eu3+-ligand complexes and desired fluorescent iPP composite materials

NASA Astrophysics Data System (ADS)

Zhang, Yu; Wang, Xinzhi; Tang, Jianguo; Wang, Wei; Wang, Jinping; Belfiore, Laurence A.

2017-04-01

In this contribution, we obtained the strong enhancement effect of silver nanowires(AgNWs) on fluorescent property of Eu3+-antenna complexes through the function of the surface plasmon resonance(SPR) effect. The key structural characteristics are: (1) AgNWs are covered by the Eu3+-ligand complex and spaced by SiO2 nano-layer between AgNWs and Eu3+-ligand complex (this structure is marked as AgNWs@SiO2@EuTP), and (2) AgNWs as nano-material with large ratio of length to diameter show their good dispersion and processability in isotactic polypropylene (iPP). We obtained the important data about the optimal spacer thickness of SiO2 is 15 nm that was not found in previous publications. The enhanced intensity of fluorescence of EuTP by AgNWs in AgNWs@SiO2@EuTP is 9 times compared with that of EuTP. All of these outstanding properties and fine structures were characterized by TEM, FT-IR, XRD, and fluorescence spectrophotometer. On the other hand, the desired fluorescent iPP composite material was obtained through blending AgNWs@SiO2@EuTP into iPP host. Very importantly, the enhancement effect of AgNWs on EuTP fluorescence in AgNWs@SiO2@EuTP is refrained from the quenching caused by host polymer of iPP.

New self-limiting assembly model for Si quantum rings on Si(100).

PubMed

Yu, L W; Chen, K J; Song, J; Xu, J; Li, W; Li, X F; Wang, J M; Huang, X F

2007-04-20

We propose a new self-limiting assembly model for Si quantum rings on Si(100) where the ring's formation and evolution are driven by a growth-etching competition mechanism. The as-grown ring structure in a plasma enhanced chemical vapor deposition system has excellent rotational symmetry and superior morphology with a typical diameter, edge width, and height of 150-300, 10, and 5 nm, respectively. Based on this model, the size and morphology can be controlled well by simply tuning the timing procedure. We suggest that this growth model is not limited to certain material system, but provides a general scheme to control and tailor the self-assembly nanostructures into the desired size, shape, and complexity.

The Ba 4d-4f giant dipole resonance in complex Ba/Si compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahle, Ch. J.; Sternemann, C.; Sternemann, H.

2014-08-06

The shape of the Ba 4d–4f giant dipole resonance is studied for Ba atoms embedded inside complex Si networks covering structures consisting of Si nanocages and nanotubes, i.e. the clathrate Ba 8Si 46, the complex compound BaSi 6, and the semiconducting BaSi 2. Here, non-resonant x-ray Raman scattering is used to investigate confinement effects on the shape of the giant resonance in the vicinity of the Ba NIV, V-edge. The distinct momentum transfer dependence of the spectra is analyzed and discussed. The measurements are compared to calculations of the giant resonance within time-dependent local density approximation in the dipole limit.more » No modulation of the giant resonance's shape for Ba atoms confined in different local environments was observed, in contrast to the calculations. The absence of such shape modulation for complex Ba/Si compounds is discussed providing important implications for further studies of giant resonance phenomena utilizing both theory and experiment.« less

The Ba 4d-4f giant dipole resonance in complex Ba/Si compounds

NASA Astrophysics Data System (ADS)

Sahle, Ch J.; Sternemann, C.; Sternemann, H.; Tse, J. S.; Gordon, R. A.; Desgreniers, S.; Maekawa, S.; Yamanaka, S.; Lehmkühler, F.; Wieland, D. C. F.; Mende, K.; Huotari, S.; Tolan, M.

2014-02-01

The shape of the Ba 4d-4f giant dipole resonance is studied for Ba atoms embedded inside complex Si networks covering structures consisting of Si nanocages and nanotubes, i.e. the clathrate Ba8Si46, the complex compound BaSi6, and the semiconducting BaSi2. Here, non-resonant x-ray Raman scattering is used to investigate confinement effects on the shape of the giant resonance in the vicinity of the Ba NIV, V-edge. The distinct momentum transfer dependence of the spectra is analyzed and discussed. The measurements are compared to calculations of the giant resonance within time-dependent local density approximation in the dipole limit. No modulation of the giant resonance’s shape for Ba atoms confined in different local environments was observed, in contrast to the calculations. The absence of such shape modulation for complex Ba/Si compounds is discussed providing important implications for further studies of giant resonance phenomena utilizing both theory and experiment.

Platinum Eta 2 -Disilene Complexes: Syntheses, Reactivity, and Structures

DTIC Science & Technology

1990-01-01

CP ýsq:.Prl 25 C. 7 x, ’ .P’ NSi-...H Reaction of R 2Si(H)Si(H)R.2 with Pt Complexes. PI Ih t~ Oxidative additions of monomeric silanes to platinumPhh2...thermally to product I1 2-complexes 2a,b. The reaction of tetrasubstituted 1,2-dihydridodisi- lanes (R2SiH)2 with bis(phosphine);laitinum equivalents...e.g. (diphos)PtCl2 /Li or (diphos)-. Pt(CH2 -CH2) also yielded platinum ’? 2=disilene complexes f6a (R -i-Pr), Qb (R-He), and kc (R- Ph). Reaction of

Silicon-on-insulator with hybrid orientations for heterogeneous integration of GaN on Si (100) substrate

NASA Astrophysics Data System (ADS)

Zhang, Runchun; Zhao, Beiji; Huang, Kai; You, Tiangui; Jia, Qi; Lin, Jiajie; Zhang, Shibin; Yan, Youquan; Yi, Ailun; Zhou, Min; Ou, Xin

2018-05-01

Heterogeneous integration of materials pave a new way for the development of the microsystem with miniaturization and complex functionalities. Two types of hybrid silicon on insulator (SOI) structures, i.e., Si (100)-on-Si (111) and Si (111)-on-Si (100), were prepared by the smart-cut technique, which is consist of ion-slicing and wafer bonding. The precise calculation of the lattice strain of the transferred films without the epitaxial matching relationship to the substrate was demonstrated based on X-ray diffraction (XRD) measurements. The XRD and Raman measurement results suggest that the transferred films possess single crystalline quality. With a chemical mechanical polishing (CMP) process, the surface roughness of the transferred thin films can be reduced from 5.57 nm to 0.30 nm. The 4-inch GaN thin film epitaxially grown on the as-prepared hybrid SOI of Si (111)-on-Si (100) by metalorganic chemical vapor deposition (MOCVD) is of improved quality with a full width at half maximum (FWHM) of 672.54 arcsec extracted from the XRD rocking curve and small surface roughness of 0.40 nm. The wafer-scale GaN on Si (111)-on-Si (100) can serve as a potential platform for the one chip integration of GaN-based high electron mobility transistors (HEMT) or photonics with the Si (100)-based complementary metal oxide semiconductor (CMOS).

Characterization of electronic structures from CdS/Si nanoheterostructure array based on silicon nanoporous pillar array

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yong, E-mail: liyong@pdsu.edu.cn; Song, Xiao Yan; Song, Yue Li

2016-02-15

Highlights: • CdS/Si nanoheterostructure array has been fabricated through a CBD method. • The electronic properties have been investigated by the I–V and C–V techniques. • The onset voltages, characteristic frequency and built-in potential are investigated. • The electronic structures can be tuned through the annealing treatments. - Abstract: The electronic properties of heterostructures are very important to its applications in the field of optoelectronic devices. Understanding and control of electronic properties are very necessary. CdS/Si nanoheterostructure array have been fabricated through growing CdS nanocrystals on the silicon nanoporous pillar array using a chemical bath deposition method. The electronic propertiesmore » of CdS nanoheterostructure array have been investigated by the current–voltage, complex impedance spectroscopy and capacitance–voltage techniques. The onset voltages, characteristic frequency and built-in potential are gradually increased with increasing the annealing temperature. It is indicated that the electronic structures of CdS/Si nanoheterostructure array can be tuned through the annealing treatments.« less

The Developmental Toxicity of Complex Silica-Embedded Nickel Nanoparticles Is Determined by Their Physicochemical Properties

PubMed Central

Mahoney, Sharlee; Najera, Michelle; Bai, Qing; Burton, Edward A.; Veser, Götz

2016-01-01

Complex engineered nanomaterials (CENs) are a rapidly developing class of structurally and compositionally complex materials that are expected to dominate the next generation of functional nanomaterials. The development of methods enabling rapid assessment of the toxicity risk associated with this type of nanomaterial is therefore critically important. We evaluated the toxicity of three differently structured nickel-silica nanomaterials as prototypical CENs: simple, surface-deposited Ni-SiO2 and hollow and non-hollow core-shell Ni@SiO2 materials (i.e., ~1–2 nm Ni nanoparticles embedded into porous silica shells with and without a central cavity, respectively). Zebrafish embryos were exposed to these CENs, and morphological (survival and malformations) and physiological (larval motility) endpoints were coupled with thorough characterization of physiochemical characteristics (including agglomeration, settling and nickel ion dissolution) to determine how toxicity differed between these CENs and equivalent quantities of Ni2+ salt (based on total Ni). Exposure to Ni2+ ions strongly compromised zebrafish larva viability, and surviving larvae showed severe malformations. In contrast, exposure to the equivalent amount of Ni CEN did not result in these abnormalities. Interestingly, exposure to Ni-SiO2 and hollow Ni@SiO2 provoked abnormalities of zebrafish larval motor function, indicating developmental toxicity, while non-hollow Ni@SiO2 showed no toxicity. Correlating these observations with physicochemical characterization of the CENs suggests that the toxicity of the Ni-SiO2 and hollow Ni@SiO2 material may result partly from an increased effective exposure at the bottom of the well due to rapid settling. Overall, our data suggest that embedding nickel NPs in a porous silica matrix may be a straightforward way to mitigate their toxicity without compromising their functional properties. At the same time, our results also indicate that it is critical to consider modification of the effective exposure when comparing different nanomaterial configurations, because effective exposure might influence NP toxicity more than specific “nano-chemistry” effects. PMID:27031643

Tricolor microcavity OLEDs based on P-nc-Si:H films as the complex anodes

NASA Astrophysics Data System (ADS)

Yang, Li; Xingyuan, Liu; Chunya, Wu; Zhiguo, Meng; Yi, Wang; Shaozhen, Xiong

2009-06-01

A P+-nc-Si:H film (boron-doped nc-Si:H thin film) was used as a complex anode of an OLED. As an ideal candidate for the composite anode, the P+-nc-Si:H thin film has a good conductivity with a high work function (~ 5.7 eV) and outstanding optical properties of high reflectivity, transmission, and a very low absorption. As a result, the combination of the relatively high reflectivity of a P+-nc-Si:H film/ITO complex anode with the very high reflectivity of an Al cathode could form a micro-cavity structure with a certain Q to improve the efficiency of the OLED fabricated on it. An RGB pixel generated by microcavity OLEDs is beneficial for both the reduction of the light loss and the improvement of the color purity and the efficiency. The small molecule Alq would be useful for the emitting light layer (EML) of the MOLED, and the P+-nc-Si film would be used as a complex anode of the MOLED, whose configuration can be constructed as Glass/LTO/P+-nc-Si:H/ITO/MoO3/NPB/Alq/LiF/Al. By adjusting the thickness of the organic layer NPB/Alq, the optical length of the microcavity and the REB colors of the device can be obtained. The peak wavelengths of an OLED are located at 486, 550, and 608 nm, respectively. The CIE coordinates are (0.21, 0.45), (0.33, 0.63), and (0.54, 0.54), and the full widths at half maximum (FWHM) are 35, 32, and 39 nm for red, green, and blue, respectively.

Stabilization of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} through Si–Ti substitution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Weiwei, E-mail: weiweix@princeton.edu; Fuccillo, M.K.; Phelan, B.F.

2015-07-15

We report a route for designing and synthesizing Ti{sub 3}Co{sub 5}B{sub 2}-type compounds in the Ti–Ru–B system by using chemical substitution of Si for Ti to decrease the d-electron-based antibonding interactions that it is argued would otherwise drive an instability in this structure for unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2}. Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} with x=0.75, 1.00 and 1.25 nominal compositions crystalizes in the Ti{sub 3}Co{sub 5}B{sub 2} structure type using arc melting methods, whereas at lower doping levels (x=0.0, 0.25 and 0.50) the more complex Zn{sub 11}Rh{sub 18}B{sub 8}-type structure is stable. Electronic structure calculations show that in hypothetical,more » unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2} with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure, the antibonding interactions are strong around the Fermi level between the Ti and Ru in the structure that form tetragonal prisms. We propose that weakening these strong interactions through the partial substitution of isovalent Si for Ti leads to the observed stability of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} for x≈1. - Graphical abstract: We present the designing and synthesizing of Ti{sub 3}Co{sub 5}B{sub 2}-type compounds in the Ti–Ru–B system by using chemical substitution of Si for Ti to decrease the d-electron-based antibonding interactions that would otherwise drive an instability in this structure for unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2}. Electronic structure calculations show that in hypothetical, unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2} with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure, the antibonding interactions are strong around the Fermi level between the Ti and Ru in the structure that form tetragonal prisms. We propose that weakening these strong interactions through the partial substitution of isovalent Si for Ti leads to the observed stability of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} for x≈1. - Highlights: • New quaternary phase Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} in Ti{sub 3}Co{sub 5}B{sub 2}-type structure is reported. • Chemical substitution of isovalent Si for Ti is used to stabilize the phase. • Decreasing the d-electron-based antibonding interactions is proved by calculation. • Physical properties of Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} are presented down to 0.4 K.« less

Low-temperature photoluminescence study of thin epitaxial GaAs films on Ge substrates

NASA Astrophysics Data System (ADS)

Brammertz, Guy; Mols, Yves; Degroote, Stefan; Motsnyi, Vasyl; Leys, Maarten; Borghs, Gustaaf; Caymax, Matty

2006-05-01

Thin epitaxial GaAs films, with thickness varying from 140 to 1000 nm and different Si doping levels, were grown at 650 °C by organometallic vapor phase epitaxy on Ge substrates and analyzed by low-temperature photoluminescence (PL) spectroscopy. All spectra of thin GaAs on Ge show two different structures, one narrow band-to-band (B2B) structure at an energy of ~1.5 eV and a broad inner-band-gap (IB) structure at an energy of ~1.1 eV. Small strain in the thin GaAs films causes the B2B structure to be separated into a light-hole and a heavy-hole peak. At 2.5 K the good structural quality of the thin GaAs films on Ge can be observed from the narrow excitonic peaks. Peak widths of less than 1 meV are measured. GaAs films with thickness smaller than 200 nm show B2B PL spectra with characteristics of an n-type doping level of approximately 1018 at./cm3. This is caused by heavy Ge diffusion from the substrate into the GaAs at the heterointerface between the two materials. The IB structure observed in all films consists of two Gaussian peaks with energies of 1.04 and 1.17 eV. These deep trapping states arise from Ge-based complexes formed within the GaAs at the Ge-GaAs heterointerface, due to strong diffusion of Ge atoms into the GaAs. Because of similarities with Si-based complexes, the peak at 1.04 eV was identified to be due to a GeGa-GeAs complex, whereas the peak at 1.17 eV was attributed to the GeGa-VGa complex. The intensity of the IB structure decreases strongly as the GaAs film thickness is increased. PL intensity of undoped GaAs films containing antiphase domains (APDs) is four orders of magnitude lower than for similar films without APDs. This reduction in intensity is due to the electrically active Ga-Ga and As-As bonds at the boundaries between the different APDs. When the Si doping level is increased, the PL intensity of the APD-containing films is increased again as well. A film containing APDs with a Si doping level of ~1018 at./cm3 has only a factor 10 reduced intensity. We tentatively explain this observation by Si or Ge clustering at antiphase boundaries, which eliminates the effects of the Ga-Ga and As-As bonds. This assumption is confirmed by the fact that, at 77 K, the ratio between the intensity of the IB peak at 1.17 eV to the intensity of the peak at 1.04 eV is smaller than 1.4 for all films containing APDs, whereas it is larger than 1.4 for all films without APDs. This shows stronger clustering of Si or Ge in the material with APDs. For future electronic applications, Ge diffusion into the GaAs will have to be reduced. PL analysis will be a rapid tool for studying the Ge diffusion into the GaAs thin films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, XS; Michaelis, VK; Ong, TC

The controllable synthesis of well-ordered layered materials with specific nanoarchitecture poses a grand challenge in materials chemistry. Here the solvothermal synthesis of two structurally analogous 5-coordinate organosilicate complexes through a novel transesterification mechanism is reported. Since the polycrystalline nature of the intrinsic hypervalent Si complex thwarts the endeavor in determining its structure, a novel strategy concerning the elegant addition of a small fraction of B species as an effective crystal growth mediator and a sacrificial agent is proposed to directly prepare diffraction-quality single crystals without disrupting the intrinsic elemental type. In the determined crystal structure, two monomeric primary building unitsmore » (PBUs) self-assemble into a dimeric asymmetric secondary BU via strong Na+O2- ionic bonds. The designed one-pot synthesis is straightforward, robust, and efficient, leading to a well-ordered (10)-parallel layered Si complex with its principal interlayers intercalated with extensive van der Waals gaps in spite of the presence of substantial Na+ counter-ions as a result of unique atomic arrangement in its structure. However, upon fast pyrolysis, followed by acid leaching, both complexes are converted into two SiO2 composites bearing BET surface areas of 163.3 and 254.7m(2)g(-1) for the pyrolyzed intrinsic and B-assisted Si complexes, respectively. The transesterification methodology merely involving alcoholysis but without any hydrolysis side reaction is designed to have generalized applicability for use in synthesizing new layered metal-organic compounds with tailored PBUs and corresponding metal oxide particles with hierarchical porosity.« less

The impact of target site accessibility on the design of effective siRNAs.

PubMed

Tafer, Hakim; Ameres, Stefan L; Obernosterer, Gregor; Gebeshuber, Christoph A; Schroeder, Renée; Martinez, Javier; Hofacker, Ivo L

2008-05-01

Small-interfering RNAs (siRNAs) assemble into RISC, the RNA-induced silencing complex, which cleaves complementary mRNAs. Despite their fluctuating efficacy, siRNAs are widely used to assess gene function. Although this limitation could be ascribed, in part, to variations in the assembly and activation of RISC, downstream events in the RNA interference (RNAi) pathway, such as target site accessibility, have so far not been investigated extensively. In this study we present a comprehensive analysis of target RNA structure effects on RNAi by computing the accessibility of the target site for interaction with the siRNA. Based on our observations, we developed a novel siRNA design tool, RNAxs, by combining known siRNA functionality criteria with target site accessibility. We calibrated our method on two data sets comprising 573 siRNAs for 38 genes, and tested it on an independent set of 360 siRNAs targeting four additional genes. Overall, RNAxs proves to be a robust siRNA selection tool that substantially improves the prediction of highly efficient siRNAs.

Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions.

PubMed

Izod, Keith; Bowman, Lyndsey J; Wills, Corinne; Clegg, William; Harrington, Ross W

2009-05-07

A straightforward Peterson olefination reaction between either [{(Me(2)PhSi)(3)C}Li(THF)] or in situ-generated [(Me(3)Si)(2){Ph(2)P(BH(3))}CLi(THF)(n)] and paraformaldehyde gives the alkenes (Me(2)PhSi)(2)C[double bond, length as m-dash]CH(2) () and (Me(3)Si){Ph(2)P(BH(3))}C[double bond, length as m-dash]CH(2) (), respectively, in good yield. Ultrasonic treatment of with lithium in THF yields the lithium complex [{(Me(2)PhSi)(2)C(CH(2))}Li(THF)(n)](2) (), which reacts in situ with one equivalent of KOBu(t) in diethyl ether to give the potassium salt [{(Me(2)PhSi)(2)C(CH(2))}K(THF)](2) (). Similarly, ultrasonic treatment of with lithium in THF yields the lithium complex [[{Ph(2)P(BH(3))}(Me(3)Si)C(CH(2))]Li(THF)(3)](2).2THF (). The bis(phosphine-borane) [(Me(3)Si){Me(2)(H(3)B)P}CH(Me(2)Si)(CH(2))](2) () may be prepared by the reaction of [Me(2)P(BH(3))CH(SiMe(3))]Li with half an equivalent of ClSiMe(2)CH(2)CH(2)SiMe(2)Cl in refluxing THF. Metalation of with two equivalents of MeLi in refluxing THF yields the lithium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}]Li(THF)(3)](2) (), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}](2)K(2)(THF)(4)](infinity) () after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex crystallises as a discrete molecular species, the potassium complexes and crystallise as sheet and chain polymers, respectively.

Structural and functional analyses reveal the contributions of the C- and N-lobes of Argonaute protein to selectivity of RNA target cleavage.

PubMed

Dayeh, Daniel M; Kruithoff, Bradley C; Nakanishi, Kotaro

2018-04-27

Some gene transcripts have cellular functions as regulatory noncoding RNAs. For example, ∼23-nucleotide (nt)-long siRNAs are loaded into Argonaute proteins. The resultant ribonucleoprotein assembly, the RNA-induced silencing complex (RISC), cleaves RNAs that are extensively base-paired with the loaded siRNA. To date, base complementarity is recognized as the major determinant of specific target cleavage (or slicing), but little is known about how Argonaute inspects base pairing before cleavage. A hallmark of Argonaute proteins is their bilobal structure, but despite the significance of this structure for curtailing slicing activity against mismatched targets, the molecular mechanism remains elusive. Here, our structural and functional studies of a bilobed yeast Argonaute protein and its isolated catalytic C-terminal lobe (C-lobe) revealed that the C-lobe alone retains almost all properties of bilobed Argonaute: siRNA-duplex loading, passenger cleavage/ejection, and siRNA-dependent RNA cleavage. A 2.1 Å-resolution crystal structure revealed that the catalytic C-lobe mirrors the bilobed Argonaute in terms of guide-RNA recognition and that all requirements for transitioning to the catalytically active conformation reside in the C-lobe. Nevertheless, we found that in the absence of the N-terminal lobe (N-lobe), target RNAs are scanned for complementarity only at positions 5-14 on a 23-nt guide RNA before endonucleolytic cleavage, thereby allowing for some off-target cleavage. Of note, acquisition of an N-lobe expanded the range of the guide RNA strand used for inspecting target complementarity to positions 2-23. These findings offer clues to the evolution of the bilobal structure of catalytically active Argonaute proteins. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Optimization of a growth process for as-grown 2D materials-based devices

NASA Astrophysics Data System (ADS)

Lindquist, Miles; Khadka, Sudiksha; Aleithan, Shrouq; Blumer, Ari; Wickramasinghe, Thushan; Thorat, Ruhi; Kordesch, Martin; Stinaff, Eric

We will present the effects of varying key parameters of a deterministic growth method for producing self-contacted 2D transition metal dichalcogenides. Chemical vapor deposition is used to grow a film of 2D material nucleated around and seeded from metallic features prepared by photolithography and sputtering on a Si/SiO2 substrate prior to growth. We will focus on a particular method of growing variable MoS2 based device structures. The goal of this work is to arrive at robust platform for growing a variety of device structures by systematically altering parameters such as the amount of reactants used, the heat of the substrate and oxide powder, and the flow rate of argon gas used. These results will help advance a comprehensive process for the scalable production of as-grown, complex, 2D materials-based device architectures.

Pentacoordinate silicon(IV): cationic, anionic and neutral complexes derived from the reaction of NHC→SiCl4 with highly Lewis acidic (C2F5)2SiH2.

PubMed

Böttcher, T; Steinhauer, S; Neumann, B; Stammler, H-G; Röschenthaler, G-V; Hoge, B

2014-06-14

Addition of NHC→SiCl4 to the highly Lewis acidic bis(pentafluoroethyl)silane ((C2F5)2SiH2) afforded the salt [(NHC)2SiCl2H][(C2F5)2SiCl3] with pentacoordinate silicon in the cation and the anion. The anion represents the first example of a chlorosilicate structurally characterized in the solid state. In this reaction, the long sought pentacoordinate NHC-adduct of silicochloroform was identified as an intermediate and its crystal structure is presented.

Phonon transport control by nanoarchitecture including epitaxial Ge nanodots for Si-based thermoelectric materials

PubMed Central

Yamasaka, Shuto; Nakamura, Yoshiaki; Ueda, Tomohiro; Takeuchi, Shotaro; Sakai, Akira

2015-01-01

Phonon transport in Si films was controlled using epitaxially-grown ultrasmall Ge nanodots (NDs) with ultrahigh density for the purpose of developing Si-based thermoelectric materials. The Si/Ge ND stacked structures, which were formed by the ultrathin SiO2 film technique, exhibited lower thermal conductivities than those of the conventional nanostructured SiGe bulk alloys, despite the stacked structures having a smaller Ge fraction. This came from the large thermal resistance caused by phonon scattering at the Si/Ge ND interfaces. The phonon scattering can be controlled by the Ge ND structure, which was independent of Si layer structure for carrier transport. These results demonstrate the effectiveness of ultrasmall epitaxial Ge NDs as phonon scattering sources, opening up a route for the realisation of Si-based thermoelectric materials. PMID:26434678

Electrochemical Deposition of Conformal and Functional Layers on High Aspect Ratio Silicon Micro/Nanowires.

PubMed

Ozel, Tuncay; Zhang, Benjamin A; Gao, Ruixuan; Day, Robert W; Lieber, Charles M; Nocera, Daniel G

2017-07-12

Development of new synthetic methods for the modification of nanostructures has accelerated materials design advances to furnish complex architectures. Structures based on one-dimensional (1D) silicon (Si) structures synthesized using top-down and bottom-up methods are especially prominent for diverse applications in chemistry, physics, and medicine. Yet further elaboration of these structures with distinct metal-based and polymeric materials, which could open up new opportunities, has been difficult. We present a general electrochemical method for the deposition of conformal layers of various materials onto high aspect ratio Si micro- and nanowire arrays. The electrochemical deposition of a library of coaxial layers comprising metals, metal oxides, and organic/inorganic semiconductors demonstrate the materials generality of the synthesis technique. Depositions may be performed on wire arrays with varying diameter (70 nm to 4 μm), pitch (5 μ to 15 μ), aspect ratio (4:1 to 75:1), shape (cylindrical, conical, hourglass), resistivity (0.001-0.01 to 1-10 ohm/cm 2 ), and substrate orientation. Anisotropic physical etching of wires with one or more coaxial shells yields 1D structures with exposed tips that can be further site-specifically modified by an electrochemical deposition approach. The electrochemical deposition methodology described herein features a wafer-scale synthesis platform for the preparation of multifunctional nanoscale devices based on a 1D Si substrate.

The HSOB GAIA: a cryogenic high stability cesic optical bench for missions requiring sub-nanometric optical stability

NASA Astrophysics Data System (ADS)

Courteau, Pascal; Poupinet, Anne; Kroedel, Mathias; Sarri, Giuseppe

2017-11-01

Global astrometry, very demanding in term of stability, requires extremely stable material for optical bench. CeSiC developed by ECM and Alcatel Alenia Space for mirrors and high stability structures, offers the best compromise in term of structural strength, stability and very high lightweight capability, with characteristics leading to be insensitive to thermo-elastic at cryogenic T°. The HSOB GAIA study realised by Alcatel Alenia Space under ESA contract aimed to design, develop and test a full scale representative High Stability Optical Bench in CeSiC. The bench has been equipped with SAGEIS-CSO laser metrology system MOUSE1, Michelson interferometer composed of integrated optics with a nm resolution. The HSOB bench has been submitted to an homogeneous T° step under vacuum to characterise the homothetic behaviour of its two arms. The quite negligible inter-arms differential measured with a nm range reproducibility, demonstrates that a complete 3D structure in CeSiC has the same CTE homogeneity as characterisation samples, fully in line with the GAIA need (1pm at 120K). This participates to the demonstration that CeSiC properties at cryogenic T° is fully appropriate to the manufacturing of complex highly stable optical structures. This successful study confirms ECM and Alcatel Alenia Space ability to define and manufacture monolithic lightweight highly stable optical structures, based on inner cells triangular design made only possible by the unique CeSiC manufacturing process.

Spectroscopic Ellipsometry Studies of n-i-p Hydrogenated Amorphous Silicon Based Photovoltaic Devices

PubMed Central

Karki Gautam, Laxmi; Junda, Maxwell M.; Haneef, Hamna F.; Collins, Robert W.; Podraza, Nikolas J.

2016-01-01

Optimization of thin film photovoltaics (PV) relies on characterizing the optoelectronic and structural properties of each layer and correlating these properties with device performance. Growth evolution diagrams have been used to guide production of materials with good optoelectronic properties in the full hydrogenated amorphous silicon (a-Si:H) PV device configuration. The nucleation and evolution of crystallites forming from the amorphous phase were studied using in situ near-infrared to ultraviolet spectroscopic ellipsometry during growth of films prepared as a function of hydrogen to reactive gas flow ratio R = [H2]/[SiH4]. In conjunction with higher photon energy measurements, the presence and relative absorption strength of silicon-hydrogen infrared modes were measured by infrared extended ellipsometry measurements to gain insight into chemical bonding. Structural and optical models have been developed for the back reflector (BR) structure consisting of sputtered undoped zinc oxide (ZnO) on top of silver (Ag) coated glass substrates. Characterization of the free-carrier absorption properties in Ag and the ZnO + Ag interface as well as phonon modes in ZnO were also studied by spectroscopic ellipsometry. Measurements ranging from 0.04 to 5 eV were used to extract layer thicknesses, composition, and optical response in the form of complex dielectric function spectra (ε = ε1 + iε2) for Ag, ZnO, the ZnO + Ag interface, and undoped a-Si:H layer in a substrate n-i-p a-Si:H based PV device structure. PMID:28773255

Improving Turbine Performance with Ceramic Matrix Composites

NASA Technical Reports Server (NTRS)

DiCarlo, James A.

2007-01-01

Under the new NASA Fundamental Aeronautics Program, efforts are on-going within the Supersonics Project aimed at the implementation of advanced SiC/SiC ceramic composites into hot section components of future gas turbine engines. Due to recent NASA advancements in SiC-based fibers and matrices, these composites are lighter and capable of much higher service temperatures than current metallic superalloys, which in turn will allow the engines to operate at higher efficiencies and reduced emissions. This presentation briefly reviews studies within Task 6.3.3 that are primarily aimed at developing physics-based concepts, tools, and process/property models for micro- and macro-structural design, fabrication, and lifing of SiC/SiC turbine components in general and airfoils in particular. Particular emphasis is currently being placed on understanding and modeling (1) creep effects on residual stress development within the component, (2) fiber architecture effects on key composite properties such as design strength, and (3) preform formation processes so that the optimum architectures can be implemented into complex-shaped components, such as turbine vanes and blades.

Silver nanoparticle deposition on inverse opal SiO2 films embedded in protective polypropylene micropits for SERS applications

NASA Astrophysics Data System (ADS)

Ammosova, Lena; Ankudze, Bright; Philip, Anish; Jiang, Yu; Pakkanen, Tuula T.; Pakkanen, Tapani A.

2018-01-01

Common methods to fabricate surface enhanced Raman scattering (SERS) substrates with controlled micro-nanohierarchy are often complex and expensive. In this study, we demonstrate a simple and cost effective method to fabricate SERS substrates with complex geometries. Microworking robot structuration is used to pattern a polypropylene (PP) substrate with micropits, facilitating protective microenvironment for brittle SiO2 inverse opal (IO) structure. Hierarchical SiO2 IO patterns were obtained using polystyrene (PS) spheres as a sacrificial template, and were selectively embedded into the hydrophilized PP micropits. The same microworking robot technique was subsequently used to deposit silver nanoparticle ink into the SiO2 IO cavities. The fabricated multi-level micro-nanohierarchy surface was studied to enhance Raman scattering of the 4-aminothiophenol (4-ATP) analyte molecule. The results show that the SERS performance of the micro-nanohierarchical substrate increases significantly the Raman scattering intensity compared to substrates with structured 2D surface geometries.

Inter-molecular β-sheet structure facilitates lung-targeting siRNA delivery

NASA Astrophysics Data System (ADS)

Zhou, Jihan; Li, Dong; Wen, Hao; Zheng, Shuquan; Su, Cuicui; Yi, Fan; Wang, Jue; Liang, Zicai; Tang, Tao; Zhou, Demin; Zhang, Li-He; Liang, Dehai; Du, Quan

2016-03-01

Size-dependent passive targeting based on the characteristics of tissues is a basic mechanism of drug delivery. While the nanometer-sized particles are efficiently captured by the liver and spleen, the micron-sized particles are most likely entrapped within the lung owing to its unique capillary structure and physiological features. To exploit this property in lung-targeting siRNA delivery, we designed and studied a multi-domain peptide named K-β, which was able to form inter-molecular β-sheet structures. Results showed that K-β peptides and siRNAs formed stable complex particles of 60 nm when mixed together. A critical property of such particles was that, after being intravenously injected into mice, they further associated into loose and micron-sized aggregates, and thus effectively entrapped within the capillaries of the lung, leading to a passive accumulation and gene-silencing. The large size aggregates can dissociate or break down by the shear stress generated by blood flow, alleviating the pulmonary embolism. Besides the lung, siRNA enrichment and targeted gene silencing were also observed in the liver. This drug delivery strategy, together with the low toxicity, biodegradability, and programmability of peptide carriers, show great potentials in vivo applications.

Alkyl complexes of strontium and barium: synthesis and structural characterization of [(Me3Si)2(MeOMe2Si)C]2Sr(THF) and [(Me3Si)2(MeOMe2Si)C]2Ba(MeOCH2CH2OMe).

PubMed

Izod, Keith; Liddle, Stephen T; Clegg, William

2003-06-25

Metathesis between either SrI2 or BaI2 and 2 equiv of {(Me3Si)2(MeOMe2Si)C}K in THF yields the novel heavier alkali metal dialkyls {(Me3Si)2(MeOMe2Si)C}2M(L) [M(L) = Sr(THF) (2), Ba(DME) (3) (DME = 1,2-dimethoxyethane)] after recrystallization.

Tubular and Spherical SiO₂ Obtained by Sol Gel Method for Lipase Immobilization and Enzymatic Activity.

PubMed

Anastasescu, Crina; Preda, Silviu; Rusu, Adriana; Culita, Dana; Plavan, Gabriel; Strungaru, Stefan; Calderon-Moreno, Jose Maria; Munteanu, Cornel; Gifu, Catalina; Enache, Mirela; Socoteanu, Radu; Angelescu, Daniel; Anastasescu, Mihai; Gartner, Mariuca; Balint, Ioan; Zaharescu, Maria

2018-06-05

A wide range of hybrid biomaterials has been designed in order to sustain bioremediation processes by associating sol-gel SiO₂ matrices with various biologically active compounds (enzymes, antibodies). SiO₂ is a widespread, chemically stable and non-toxic material; thus, the immobilization of enzymes on silica may lead to improving the efficiency of biocatalysts in terms of endurance and economic costs. Our present work explores the potential of different hybrid morphologies, based on hollow tubes and solid spheres of amorphous SiO₂, for enzyme immobilization and the development of competitive biocatalysts. The synthesis protocol and structural characterization of spherical and tubular SiO₂ obtained by the sol gel method were fully investigated in connection with the subsequent immobilization of lipase from Rhizopus orizae . The immobilization is conducted at pH 6, lower than the isoelectric point of lipase and higher than the isoelectric point of silica, which is meant to sustain the physical interactions of the enzyme with the SiO₂ matrix. The morphological, textural and surface properties of spherical and tubular SiO₂ were investigated by SEM, nitrogen sorption, and electrokinetic potential measurements, while the formation and characterization of hybrid organic-inorganic complexes were studied by UV-VIS, FTIR-ATR and fluorescence spectroscopy. The highest degree of enzyme immobilization (as depicted from total organic carbon) was achieved for tubular morphology and the hydrolysis of p-nitrophenyl acetate was used as an enzymatic model reaction conducted in the presence of hybrid lipase⁻SiO₂ complex.

Solid-State Synthesized Nanostructured Au Dendritic Aggregates Towards Surface-Enhanced Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Gentile, A.; Ruffino, F.; D'Andrea, C.; Gucciardi, P. G.; Reitano, R.; Grimaldi, M. G.

2016-06-01

Micrometric Au structures, presenting a dendritic nano-structure, have been fabricated on a Si-based substrate. The fabrication method involves the deposition of a thin Au film on the substrate and a high-temperature annealing (1100°C) using fast heating and cooling ramps. The thermal process produces the growth, from the substrate, of Si micro-pillars whose top surfaces, covered by a crystalline Au layer, present a nanodendritic morphology. In addition to the micro-pillars, the sample surface presents a complex structural and chemical composition including Si3N4 regions due to the silicon-nitrogen intermixing during the heating stage. By studying the kinetic processes at the Au-Si interface during the thermal treatment, we describe the stages involved in the micro-pillars growth, in the dendritic morphology development, and in the Au atoms entrapment at the top of the dendritic surfaces. Finally, we present the analyses of the optical and surface enhanced Raman scattering properties of the Au dendritic aggregates. We show, in particular, that: (1) the Au dendrites aggregates act as effective scattering elements for the electromagnetic radiation in the infrared spectral region; and (2) the higher surface area due to the branched dendritic structure is responsible for the improvement in the sensitivity of the surface enhanced Raman scattering activity.

Advances in SiC/SiC Composites for Aerospace Applications

NASA Technical Reports Server (NTRS)

DiCarlo, James A.

2006-01-01

In recent years, supported by a variety of materials development programs, NASA Glenn Research Center has significantly increased the thermostructural capability of SiC/SiC composite materials for high-temperature aerospace applications. These state-of-the-art advances have occurred in every key constituent of the composite: fiber, fiber coating, matrix, and environmental barrier coating, as well as processes for forming the fiber architectures needed for complex-shaped components such as turbine vanes for gas turbine engines. This presentation will briefly elaborate on the nature of these advances in terms of performance data and underlying mechanisms. Based on a list of first-order property goals for typical high-temperature applications, key data from a variety of laboratory tests are presented which demonstrate that the NASA-developed constituent materials and processes do indeed result in SiC/SiC systems with the desired thermal and structural capabilities. Remaining process and microstructural issues for further property enhancement are discussed, as well as on-going approaches at NASA to solve these issues. NASA efforts to develop physics-based property models that can be used not only for component design and life modeling, but also for constituent material and process improvement will also be discussed.

Laser characterization of the depth profile of complex refractive index of PMMA implanted with 50 keV silicon ions

NASA Astrophysics Data System (ADS)

Stefanov, Ivan L.; Stoyanov, Hristiyan Y.; Petrova, Elitza; Russev, Stoyan C.; Tsutsumanova, Gichka G.; Hadjichristov, Georgi B.

2013-03-01

The depth profile of the complex refractive index of silicon ion (Si+) implanted polymethylmethacrylate (PMMA) is studied, in particular PMMA implanted with Si+ ions accelerated to a relatively low energy of 50 keV and at a fluence of 3.2 × 1015 cm-2. The ion-modified material with nano-clustered structure formed in the near(sub)surface layer of a thickness of about 100 nm is optically characterized by simulation based on reflection ellipsometry measurements at a wavelength of 632.8 nm (He-Ne laser). Being of importance for applications of ion-implanted PMMA in integrated optics, optoelectronics and optical communications, the effect of the index depth profile of Si+-implanted PMMA on the profile of the reflected laser beam due to laser-induced thermo-lensing in reflection is also analyzed upon illumination with a low power cw laser (wavelength 532 nm, optical power 10 - 50 mW).

[Components and assembly of RNA-induced silencing complex].

PubMed

Song, Xue-Mei; Yan, Fei; Du, Li-Xin

2006-06-01

Degradation of homologous RNA in RNA interference is carried out by functional RNA-induced silencing complex (RISC). RISC contains Dicer, Argonaute proein, siRNA and other components. Researching structures and functions of these components is primary important for understanding assembly and functional mechanism of RISC, as well as the whole RNAi pathway. Recent research works showed that Dicer, containing RNaseIII domain, is responsible for production of siRNA at the beginning of RNAi, and guarantees the stability of RISC intermediate in assembly process. As the core component of RISC, Argonaute protein functions as slicer to cleave target RNA and offers the binding site of siRNA in RISC assembly, which are depended on PIWI domain and PAZ domain separately. Although there is only one strand of siRNA that is the guider of RISC, the double stranded structural character of siRNA is determinant of RNAi. Except those, there are still other components with unknown functions in RISC. The knowledge about RISC components and assembly now, is basis of a presumed RISC assembly model.

Iron(II) cage complexes of N-heterocyclic amide and bis(trimethylsilyl)amide ligands: synthesis, structure, and magnetic properties.

PubMed

Sulway, Scott A; Collison, David; McDouall, Joseph J W; Tuna, Floriana; Layfield, Richard A

2011-03-21

Metallation of hexahydropyrimidopyrimidine (hppH) by [Fe{N(SiMe(3))(2)}(2)] (1) produces the trimetallic iron(II) amide cage complex [{(Me(3)Si)(2)NFe}(2)(hpp)(4)Fe] (2), which contains three iron(II) centers, each of which resides in a distorted tetrahedral environment. An alternative, one-pot route that avoids use of the highly air-sensitive complex 1 is described for the synthesis of the iron(II)-lithium complex [{(Me(3)Si)(2)N}(2)Fe{Li(bta)}](2) (3) (where btaH = benzotriazole), in which both iron(II) centers reside in 3-coordinated pyramidal environments. The structure of 3 is also interpreted in terms of the ring laddering principle developed for alkali metal amides. Magnetic susceptibility measurements reveal that both compounds display very weak antiferromagnetic exchange between the iron(II) centers, and that the iron(II) centers in 2 and 3 possess large negative axial zero-field splittings.

The Paralinear Oxidation of SiC in Combustion Environments

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Greenbauer-Seng, Leslie (Technical Monitor)

2000-01-01

SiC is proposed for structural applications in high pressure, high temperature. high gas velocity environments of turbine and rocket engines. These environments are typically composed of complex gas mixtures containing carbon dioxide, oxygen, water vapor, and nitrogen. It is known that the primary oxidant for SiC in these environments is water vapor.

A combined interfacial and in-situ polymerization strategy to construct well-defined core-shell epoxy-containing SiO2-based microcapsules with high encapsulation loading, super thermal stability and nonpolar solvent tolerance

NASA Astrophysics Data System (ADS)

Jia; Wang; Tian; Li; Xu; Jiao; Cao; Wu

2016-10-01

SiO2-based microcapsules containing hydrophobic molecules exhibited potential applications such as extrinsic self-healing, drug delivery, due to outstanding thermal and chemical stability of SiO2. However, to construct SiO2-based microcapsules with both high encapsulation loading and long-term structural stability is still a troublesome issue, limiting their further utilization. We herein design a single-batch route, a combined interfacial and in-situ polymerization strategy, to fabricate epoxy-containing SiO2-based microcapsules with both high encapsulation loading and long-term structural stability. The final SiO2-based microcapsules preserve high encapsulation loading of 85.7 wt% by controlling exclusively hydrolysis and condensed polymerization at oil/water interface in the initial interfacial polymerization step. In the subsequent in-situ polymerization step, the initial SiO2-based microcapsules as seeds could efficiently harvest SiO2 precursors and primary SiO2 particles to finely tune the SiO2 wall thickness, thereby enhancing long-term structural stability of the final SiO2-based microcapsules including high thermal stability with almost no any weight loss until 250°C, and strong tolerance against nonpolar solvents such as CCl4 with almost unchanged core-shell structure and unchanged core weight after immersing into strong solvents for up to 5 days. These SiO2-based microcapsules are extremely suited for processing them into anticorrosive coating in the presence of nonpolar solvents for self-healing application.

Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton.

PubMed

Baus, Johannes A; Tacke, Reinhold

2017-07-11

Treatment of SiCl 4 with lithium dithiocarbamates of the formula type Li[R 2 NCS 2 ] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(iv) complexes [Ph 2 NCS 2 ] 2 SiCl 2 (3) and [iPr 2 NCS 2 ] 2 SiCl 2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(iv) complexes with an SiCl 2 S 4 skeleton.

Targeting the Blind Spot of Polycationic Nanocarrier-Based siRNA Delivery

PubMed Central

Zheng, Mengyao; Pavan, Giovanni M.; Neeb, Manuel; Schaper, Andreas K.; Danani, Andrea; Klebe, Gerhard; Merkel, Olivia M.; Kissel, Thomas

2013-01-01

Polycationic nanocarriers attract increasing attention to the field of siRNA delivery. We investigated the self-assembly of siRNA vs pDNA with polycations, which are broadly used for nonviral gene and siRNA delivery. Although polyethyleneimine (PEI) was routinely adopted as siRNA carrier based on its efficacy in delivering pDNA, it has not been investigated yet why PEI efficiently delivers pDNA to cells but is controversially discussed in terms of efficacy for siRNA delivery. We are the first to investigate the self-assembly of PEI/siRNA vs PEI/pDNA and the steps of complexation and aggregation through different levels of hierarchy on the atomic and molecular scale with the novel synergistic use of molecular modeling, molecular dynamics simulation, isothermal titration calorimetry, and other characterization techniques. We are also the fist to elucidate atomic interactions, size, shape, stoichiometry, and association dynamics for polyplexes containing siRNA vs pDNA. Our investigation highlights differences in the hierarchical mechanism of formation of related polycation–siRNA and polycation–pDNA complexes. The results of fluorescence quenching assays indicated a biphasic behavior of siRNA binding with polycations where molecular reorganization of the siRNA within the polycations occurred at lower N/P ratios (nitrogen/phosphorus). Our results, for the first time, emphasize a biphasic behavior in siRNA complexation and the importance of low N/P ratios, which allow for excellent siRNA delivery efficiency. Our investigation highlights the formulation of siRNA complexes from a thermodynamic point of view and opens new perspectives to advance the rational design of new siRNA delivery systems. PMID:23036046

An albumin-mediated cholesterol design-based strategy for tuning siRNA pharmacokinetics and gene silencing.

PubMed

Bienk, Konrad; Hvam, Michael Lykke; Pakula, Malgorzata Maria; Dagnæs-Hansen, Frederik; Wengel, Jesper; Malle, Birgitte Mølholm; Kragh-Hansen, Ulrich; Cameron, Jason; Bukrinski, Jens Thostrup; Howard, Kenneth A

2016-06-28

Major challenges for the clinical translation of small interfering RNA (siRNA) include overcoming the poor plasma half-life, site-specific delivery and modulation of gene silencing. In this work, we exploit the intrinsic transport properties of human serum albumin to tune the blood circulatory half-life, hepatic accumulation and gene silencing; based on the number of siRNA cholesteryl modifications. We demonstrate by a gel shift assay a strong and specific affinity of recombinant human serum albumin (rHSA) towards cholesteryl-modified siRNA (Kd>1×10(-7)M) dependent on number of modifications. The rHSA/siRNA complex exhibited reduced nuclease degradation and reduced induction of TNF-α production by human peripheral blood mononuclear cells. The increased solubility of heavily cholesteryl modified siRNA in the presence of rHSA facilitated duplex annealing and consequent interaction that allowed in vivo studies using multiple cholesteryl modifications. A structural-activity-based screen of in vitro EGFP-silencing was used to select optimal siRNA designs containing cholesteryl modifications within the sense strand that were used for in vivo studies. We demonstrate plasma half-life extension in NMRI mice from t1/2 12min (naked) to t1/2 45min (single cholesteryl) and t1/2 71min (double cholesteryl) using fluorescent live bioimaging. The biodistribution showed increased accumulation in the liver for the double cholesteryl modified siRNA that correlated with an increase in hepatic Factor VII gene silencing of 28% (rHSA/siRNA) compared to 4% (naked siRNA) 6days post-injection. This work presents a novel albumin-mediated cholesteryl design-based strategy for tuning pharmacokinetics and systemic gene silencing. Copyright © 2016 Elsevier B.V. All rights reserved.

The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

PubMed

Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina

2014-07-01

Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cationic aza-macrocyclic complexes of germanium(II) and silicon(IV).

PubMed

Everett, Matthew; Jolleys, Andrew; Levason, William; Light, Mark E; Pugh, David; Reid, Gillian

2015-12-28

[GeCl2(dioxane)] reacts with the neutral aza-macrocyclic ligands L, L = Me3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane), Me4cyclen (1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) or Me4cyclam (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and two mol. equiv. of Me3SiO3SCF3 in thf solution to yield the unusual and hydrolytically very sensitive [Ge(L)][O3SCF3]2 as white solids in moderate yield. Using shorter reaction times [Ge(Me3tacn)]Cl2 and [Ge(Me3tacn)]Cl[O3SCF3] were also isolated; the preparation of [Ge(Me4cyclen)][GeCl3]2 is also described. The structures of the Me3tacn complexes show κ(3)-coordination of the macrocycle, with the anions interacting only weakly to produce very distorted five- or six-coordination at germanium. In contrast, the structure of [Ge(Me4cyclen)][O3SCF3]2 shows no anion interactions, and a distorted square planar geometry at germanium from coordination to the tetra-aza macrocycle. Crystal structures of the Si(iv) complexes, [SiCl3(Me3tacn)]Y (Y = O3SCF3, BAr(F); [B{3,5-(CF3)2C6H3}4]) and [SiHCl2(Me3tacn)][BAr(F)], obtained from reaction of SiCl4 or SiHCl3 with Me3tacn, followed by addition of either Me3SiO3SCF3 or Na[BAr(F)], contain distorted octahedral cations, with facialκ(3)-coordinated Me3tacn. The open-chain triamine, Me2NCH2CH2N(Me)CH2CH2NMe2 (pmdta), forms [SiCl3(pmdta)][BAr(F)] and [SiBr3(pmdta)][BAr(F)] under similar conditions, containing mer-octahedral cations.

Structure of 5-hydroxymethylcytosine-specific restriction enzyme, AbaSI, in complex with DNA.

PubMed

Horton, John R; Borgaro, Janine G; Griggs, Rose M; Quimby, Aine; Guan, Shengxi; Zhang, Xing; Wilson, Geoffrey G; Zheng, Yu; Zhu, Zhenyu; Cheng, Xiaodong

2014-07-01

AbaSI, a member of the PvuRts1I-family of modification-dependent restriction endonucleases, cleaves deoxyribonucleic acid (DNA) containing 5-hydroxymethylctosine (5hmC) and glucosylated 5hmC (g5hmC), but not DNA containing unmodified cytosine. AbaSI has been used as a tool for mapping the genomic locations of 5hmC, an important epigenetic modification in the DNA of higher organisms. Here we report the crystal structures of AbaSI in the presence and absence of DNA. These structures provide considerable, although incomplete, insight into how this enzyme acts. AbaSI appears to be mainly a homodimer in solution, but interacts with DNA in our structures as a homotetramer. Each AbaSI subunit comprises an N-terminal, Vsr-like, cleavage domain containing a single catalytic site, and a C-terminal, SRA-like, 5hmC-binding domain. Two N-terminal helices mediate most of the homodimer interface. Dimerization brings together the two catalytic sites required for double-strand cleavage, and separates the 5hmC binding-domains by ∼70 Å, consistent with the known activity of AbaSI which cleaves DNA optimally between symmetrically modified cytosines ∼22 bp apart. The eukaryotic SET and RING-associated (SRA) domains bind to DNA containing 5-methylcytosine (5mC) in the hemi-methylated CpG sequence. They make contacts in both the major and minor DNA grooves, and flip the modified cytosine out of the helix into a conserved binding pocket. In contrast, the SRA-like domain of AbaSI, which has no sequence specificity, contacts only the minor DNA groove, and in our current structures the 5hmC remains intra-helical. A conserved, binding pocket is nevertheless present in this domain, suitable for accommodating 5hmC and g5hmC. We consider it likely, therefore, that base-flipping is part of the recognition and cleavage mechanism of AbaSI, but that our structures represent an earlier, pre-flipped stage, prior to actual recognition. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

Structure of 5-hydroxymethylcytosine-specific restriction enzyme, AbaSI, in complex with DNA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horton, John R.; Borgaro, Janine G.; Griggs, Rose M.

2014-07-03

AbaSI, a member of the PvuRts1I-family of modification-dependent restriction endonucleases, cleaves DNA containing 5-hydroxymethylctosine (5hmC) and glucosylated 5hmC (g5hmC), but not DNA containing unmodified cytosine. AbaSI has been used as a tool for mapping the genomic locations of 5hmC, an important epigenetic modification in the DNA of higher organisms. Here we report the crystal structures of AbaSI in the presence and absence of DNA. These structures provide considerable, although incomplete, insight into how this enzyme acts. AbaSI appears to be mainly a homodimer in solution, but interacts with DNA in our structures as a homotetramer. Each AbaSI subunit comprises anmore » N-terminal, Vsr-like, cleavage domain containing a single catalytic site, and a C-terminal, SRA-like, 5hmC-binding domain. Two N-terminal helices mediate most of the homodimer interface. Dimerization brings together the two catalytic sites required for double-strand cleavage, and separates the 5hmC binding-domains by ~ 70 Å, consistent with the known activity of AbaSI which cleaves DNA optimally between symmetrically modified cytosines ~ 22 bp apart. The eukaryotic SET and RING-associated (SRA) domains bind to DNA containing 5-methylcytosine (5mC) in the hemi-methylated CpG sequence. They make contacts in both the major and minor DNA grooves, and flip the modified cytosine out of the helix into a conserved binding pocket. In contrast, the SRA-like domain of AbaSI, which has no sequence specificity, contacts only the minor DNA groove, and in our current structures the 5hmC remains intra-helical. A conserved, binding pocket is nevertheless present in this domain, suitable for accommodating 5hmC and g5hmC. We consider it likely, therefore, that base-flipping is part of the recognition and cleavage mechanism of AbaSI, but that our structures represent an earlier, pre-flipped stage, prior to actual recognition.« less

Electromagnetic resonance modes on a two-dimensional tandem grating and its application for broadband absorption in the visible spectrum.

PubMed

Han, Sunwoo; Lee, Bong Jae

2016-01-25

In this work, we numerically investigate the electromagnetic resonances on two-dimensional tandem grating structures. The base of a tandem grating consists of an opaque Au substrate, a SiO(2) spacer, and a Au grating (concave type); that is, a well-known fishnet structure forming Au/SiO(2)/Au stack. A convex-type Au grating (i.e., topmost grating) is then attached on top of the base fishnet structure with or without additional SiO(2) spacer, resulting in two types of tandem grating structures. In order to calculate the spectral reflectance and local magnetic field distribution, the finite-difference time-domain method is employed. When the topmost Au grating is directly added onto the base fishnet structure, the surface plasmon and magnetic polariton in the base structure are branched out due to the geometric asymmetry with respect to the SiO(2) spacer. If additional SiO(2) spacer is added between the topmost Au grating and the base fishnet structure, new magnetic resonance modes appear due to coupling between two vertically aligned Au/SiO(2)/Au stacks. With the understanding of multiple electromagnetic resonance modes on the proposed tandem grating structures, we successfully design a broadband absorber made of Au and SiO(2) in the visible spectrum.

Designing novel Sn-Bi, Si-C and Ge-C nanostructures, using simple theoretical chemical similarities

NASA Astrophysics Data System (ADS)

Zdetsis, Aristides D.

2011-04-01

A framework of simple, transparent and powerful concepts is presented which is based on isoelectronic (or isovalent) principles, analogies, regularities and similarities. These analogies could be considered as conceptual extensions of the periodical table of the elements, assuming that two atoms or molecules having the same number of valence electrons would be expected to have similar or homologous properties. In addition, such similar moieties should be able, in principle, to replace each other in more complex structures and nanocomposites. This is only partly true and only occurs under certain conditions which are investigated and reviewed here. When successful, these concepts are very powerful and transparent, leading to a large variety of nanomaterials based on Si and other group 14 elements, similar to well known and well studied analogous materials based on boron and carbon. Such nanomaterias designed in silico include, among many others, Si-C, Sn-Bi, Si-C and Ge-C clusters, rings, nanowheels, nanorodes, nanocages and multidecker sandwiches, as well as silicon planar rings and fullerenes similar to the analogous sp2 bonding carbon structures. It is shown that this pedagogically simple and transparent framework can lead to an endless variety of novel and functional nanomaterials with important potential applications in nanotechnology, nanomedicine and nanobiology. Some of the so called predicted structures have been already synthesized, not necessarily with the same rational and motivation. Finally, it is anticipated that such powerful and transparent rules and analogies, in addition to their predictive power, could also lead to far-reaching interpretations and a deeper understanding of already known results and information.

Designing novel Sn-Bi, Si-C and Ge-C nanostructures, using simple theoretical chemical similarities.

PubMed

Zdetsis, Aristides D

2011-04-27

A framework of simple, transparent and powerful concepts is presented which is based on isoelectronic (or isovalent) principles, analogies, regularities and similarities. These analogies could be considered as conceptual extensions of the periodical table of the elements, assuming that two atoms or molecules having the same number of valence electrons would be expected to have similar or homologous properties. In addition, such similar moieties should be able, in principle, to replace each other in more complex structures and nanocomposites. This is only partly true and only occurs under certain conditions which are investigated and reviewed here. When successful, these concepts are very powerful and transparent, leading to a large variety of nanomaterials based on Si and other group 14 elements, similar to well known and well studied analogous materials based on boron and carbon. Such nanomaterias designed in silico include, among many others, Si-C, Sn-Bi, Si-C and Ge-C clusters, rings, nanowheels, nanorodes, nanocages and multidecker sandwiches, as well as silicon planar rings and fullerenes similar to the analogous sp2 bonding carbon structures. It is shown that this pedagogically simple and transparent framework can lead to an endless variety of novel and functional nanomaterials with important potential applications in nanotechnology, nanomedicine and nanobiology. Some of the so called predicted structures have been already synthesized, not necessarily with the same rational and motivation. Finally, it is anticipated that such powerful and transparent rules and analogies, in addition to their predictive power, could also lead to far-reaching interpretations and a deeper understanding of already known results and information.

Processing and Structural Advantages of the Sylramic-iBN SiC Fiber for SiC/SiC Components

NASA Technical Reports Server (NTRS)

Yun, H. M.; Dicarlo, J. A.; Bhatt, R. T.; Hurst, J. B.

2008-01-01

The successful high-temperature application of complex-shaped SiC/SiC components will depend on achieving as high a fraction of the as-produced fiber strength as possible during component fabrication and service. Key issues center on a variety of component architecture, processing, and service-related factors that can reduce fiber strength, such as fiber-fiber abrasion during architecture shaping, surface chemical attack during interphase deposition and service, and intrinsic flaw growth during high-temperature matrix formation and composite creep. The objective of this paper is to show that the NASA-developed Sylramic-iBN SiC fiber minimizes many of these issues for state-of-the-art melt-infiltrated (MI) SiC/BN/SiC composites. To accomplish this, data from various mechanical tests are presented that compare how different high performance SiC fiber types retain strength during formation of complex architectures, during processing of BN interphases and MI matrices, and during simulated composite service at high temperatures.

Oxime Ether Lipids as Transfection Agents: Assembly and Complexation with siRNA.

PubMed

Puri, Anu; Zampino, Serena; Viard, Mathias; Shapiro, Bruce A

2017-01-01

RNAi-based therapeutic approaches to combat cancer and other diseases are currently an area of great interest. However, practical applications of this approach rely on optimal tools to carry and deliver siRNA to the desired site. Oxime ether lipids (OELs) are a class of molecules among other various carriers being examined for siRNA delivery. OELs, relatively new candidates, belong to a class of non-glycerol based lipids and have begun to claim their place as an siRNA delivery carrier in the field of RNAi therapy. Chemical synthesis steps of OELs are considered relatively simple with the ability to modify the functionalities as desired. OEL-siRNA complexes can be assembled in the presence of serum-containing buffers (or cell culture media) and recent data from our and other groups have demonstrated that OELs are viable carriers for siRNA delivery in the cell culture systems. In this chapter, we provide the details of experimental protocols routinely used in our laboratory to examine OEL-siRNA complexes including their assembly, stability, and transfection efficiencies.

Gene silencing activity of siRNA polyplexes based on thiolated N,N,N-trimethylated chitosan.

PubMed

Varkouhi, Amir K; Verheul, Rolf J; Schiffelers, Raymond M; Lammers, Twan; Storm, Gert; Hennink, Wim E

2010-12-15

N,N,N-Trimethylated chitosan (TMC) is a biodegradable polymer emerging as a promising nonviral vector for nucleic acid and protein delivery. In the present study, we investigated whether the introduction of thiol groups in TMC enhances the extracellular stability of the complexes based on this polymer and promotes the intracellular release of siRNA. The gene silencing activity and the cellular cytotoxicity of polyplexes based on thiolated TMC were compared with those based on the nonthiolated counterpart and the regularly used lipidic transfection agent Lipofectamine. Incubation of H1299 human lung cancer cells expressing firefly luciferase with siRNA/thiolated TMC polyplexes resulted in 60-80% gene silencing activity, whereas complexes based on nonthiolated TMC showed less silencing (40%). The silencing activity of the complexes based on Lipofectamine 2000 was about 60-70%. Importantly, the TMC-SH polyplexes retained their silencing activity in the presence of hyaluronic acid, while nonthiolated TMC polyplexes hardly showed any silencing activity, demonstrating their stability against competing anionic macromolecules. Under the experimental conditions tested, the cytotoxicity of the thiolated and nonthiolated siRNA complexes was lower than those based on Lipofectamine. Given the good extracellular stability and good silencing activity, it is concluded that polyplexes based on TMC-SH are attractive systems for further in vivo evaluations.

2-Acylpyrroles as mono-anionic O,N-chelating ligands in silicon coordination chemistry.

PubMed

Kämpfe, Alexander; Brendler, Erica; Kroke, Edwin; Wagler, Jörg

2014-07-21

Kryptopyrrole (2,4-dimethyl-3-ethylpyrrole) was acylated with, for example, benzoyl chloride to afford 2-benzoyl-3,5-dimethyl-4-ethylpyrrole (L(1)H). With SiCl4 this ligand reacts under liberation of HCl and formation of the complex L(1)2SiCl2. In related reactions with HSiCl3 or H2SiCl2, the same chlorosilicon complex is formed under liberation of HCl and H2 or liberation of H2, respectively. The chlorine atoms of L(1)2SiCl2 can be replaced by fluoride and triflate using ZnF2 and Me3Si-OTf, respectively. The use of a supporting base (triethylamine) is required for the complexation of phenyltrichlorosilane and diphenyldichlorosilane. The complexes L(1)2SiCl2, L(1)2SiF2, L(1)2Si(OTf)2, L(1)2SiPhCl, and L(1)2SiPh2 exhibit various configurations of the octahedral silicon coordination spheres (i.e. cis or trans configuration of the monodentate substituents, different orientations of the bidentate chelating ligands relative to each other). Furthermore, cationic silicon complexes L(1)3Si(+) and L(1) SiPh(+) were synthesized by chloride abstraction with GaCl3. In contrast, reaction of L(1)2SiCl2 with a third equivalent of L(1)H in the presence of excess triethylamine produced a charge-neutral hexacoordinate Si complex with a new tetradentate chelating ligand which formed by Si-templated C-C coupling of two ligands L(1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of the nanoformulation of siRNA-lipid assemblies on their cellular uptake and immune stimulation.

PubMed

Kubota, Kohei; Onishi, Kohei; Sawaki, Kazuaki; Li, Tianshu; Mitsuoka, Kaoru; Sato, Takaaki; Takeoka, Shinji

2017-01-01

Two lipid-based nanoformulations have been used to date in clinical studies: lipoplexes and lipid nanoparticles (LNPs). In this study, we prepared small interfering RNA (siRNA)-loaded carriers using lipid components of the same composition to form molecular assemblies of differing structures, and evaluated the impact of structure on cellular uptake and immune stimulation. Lipoplexes are electrostatic complexes formed by mixing preformed cationic lipid liposomes with anionic siRNA in an aqueous environment, whereas LNPs are nanoparticles embedding siRNA prepared by mixing an alcoholic lipid solution with an aqueous siRNA solution in one step. Although the physicochemical properties of lipoplexes and LNPs were similar except for small increases in apparent size of lipoplexes and zeta potential of LNPs, siRNA uptake efficiency of LNPs was significantly higher than that of lipoplexes. Furthermore, in the case of LNPs, both siRNA and lipid were effectively incorporated into cells in a co-assembled state; however, in the case of lipoplexes, the amount of siRNA internalized into cells was small in comparison with lipid. siRNAs in lipoplexes were thought to be more likely to localize on the particle surface and thereby undergo dissociation into the medium. Inflammatory cytokine responses also appeared to differ between lipoplexes and LNPs. For tumor necrosis factor-α, release was mainly caused by siRNA. On the other hand, the release of interleukin-1β was mainly due to the cationic nature of particles. LNPs released lower amounts of tumor necrosis factor-α and interleukin-1β than lipoplexes and were thus considered to be better tolerated with respect to cytokine release. In conclusion, siRNA-loaded nanoformulations effect their cellular uptake and immune stimulation in a manner that depends on the structure of the molecular assembly; therefore, nanoformulations should be optimized before extending studies into the in vivo environment.

Effect of the nanoformulation of siRNA-lipid assemblies on their cellular uptake and immune stimulation

PubMed Central

Kubota, Kohei; Onishi, Kohei; Sawaki, Kazuaki; Li, Tianshu; Mitsuoka, Kaoru; Sato, Takaaki; Takeoka, Shinji

2017-01-01

Two lipid-based nanoformulations have been used to date in clinical studies: lipoplexes and lipid nanoparticles (LNPs). In this study, we prepared small interfering RNA (siRNA)-loaded carriers using lipid components of the same composition to form molecular assemblies of differing structures, and evaluated the impact of structure on cellular uptake and immune stimulation. Lipoplexes are electrostatic complexes formed by mixing preformed cationic lipid liposomes with anionic siRNA in an aqueous environment, whereas LNPs are nanoparticles embedding siRNA prepared by mixing an alcoholic lipid solution with an aqueous siRNA solution in one step. Although the physicochemical properties of lipoplexes and LNPs were similar except for small increases in apparent size of lipoplexes and zeta potential of LNPs, siRNA uptake efficiency of LNPs was significantly higher than that of lipoplexes. Furthermore, in the case of LNPs, both siRNA and lipid were effectively incorporated into cells in a co-assembled state; however, in the case of lipoplexes, the amount of siRNA internalized into cells was small in comparison with lipid. siRNAs in lipoplexes were thought to be more likely to localize on the particle surface and thereby undergo dissociation into the medium. Inflammatory cytokine responses also appeared to differ between lipoplexes and LNPs. For tumor necrosis factor-α, release was mainly caused by siRNA. On the other hand, the release of interleukin-1β was mainly due to the cationic nature of particles. LNPs released lower amounts of tumor necrosis factor-α and interleukin-1β than lipoplexes and were thus considered to be better tolerated with respect to cytokine release. In conclusion, siRNA-loaded nanoformulations effect their cellular uptake and immune stimulation in a manner that depends on the structure of the molecular assembly; therefore, nanoformulations should be optimized before extending studies into the in vivo environment. PMID:28790820

Lanthanide luminescence enhancements in porous silicon resonant microcavities.

PubMed

Jenie, S N Aisyiyah; Pace, Stephanie; Sciacca, Beniamino; Brooks, Robert D; Plush, Sally E; Voelcker, Nicolas H

2014-08-13

In this paper, the covalent immobilization and luminescence enhancement of a europium (Eu(III)) complex in a porous silicon (pSi) layer with a microcavity (pSiMC) structure are demonstrated. The alkyne-pendant arm of the Eu(III) complex was covalently immobilized on the azide-modified surface via ligand-assisted "click" chemistry. The design parameters of the microcavity were optimized to obtain an efficient luminescence-enhancing device. Luminescence enhancements by a factor of 9.5 and 3.0 were observed for Eu(III) complex bound inside the pSiMC as compared to a single layer and Bragg reflector of identical thickness, respectively, confirming the increased interaction between the immobilized molecules and the electric field in the spacer of the microcavity. When comparing pSiMCs with different resonance wavelength position, luminescence was enhanced when the resonance wavelength overlapped with the maximum emission wavelength of the Eu(III) complex at 614 nm, allowing for effective coupling between the confined light and the emitting molecules. The pSiMC also improved the spectral color purity of the Eu(III) complex luminescence. The ability of a pSiMC to act as an efficient Eu(III) luminescence enhancer, combined with the resulting sharp linelike emission, can be exploited for the development of ultrasensitive optical biosensors.

Kinetic analysis of the effects of target structure on siRNA efficiency

NASA Astrophysics Data System (ADS)

Chen, Jiawen; Zhang, Wenbing

2012-12-01

RNAi efficiency for target cleavage and protein expression is related to the target structure. Considering the RNA-induced silencing complex (RISC) as a multiple turnover enzyme, we investigated the effect of target mRNA structure on siRNA efficiency with kinetic analysis. The 4-step model was used to study the target cleavage kinetic process: hybridization nucleation at an accessible target site, RISC-mRNA hybrid elongation along with mRNA target structure melting, target cleavage, and enzyme reactivation. At this model, the terms accounting for the target accessibility, stability, and the seed and the nucleation site effects are all included. The results are in good agreement with that of experiments which show different arguments about the structure effects on siRNA efficiency. It shows that the siRNA efficiency is influenced by the integrated factors of target's accessibility, stability, and the seed effects. To study the off-target effects, a simple model of one siRNA binding to two mRNA targets was designed. By using this model, the possibility for diminishing the off-target effects by the concentration of siRNA was discussed.

Steric restrictions of RISC in RNA interference identified with size-expanded RNA nucleobases.

PubMed

Hernández, Armando R; Peterson, Larryn W; Kool, Eric T

2012-08-17

Understanding the interactions between small interfering RNAs (siRNAs) and the RNA-induced silencing complex (RISC), the key protein complex of RNA interference (RNAi), is of great importance to the development of siRNAs with improved biological and potentially therapeutic function. Although various chemically modified siRNAs have been reported, relatively few studies with modified nucleobases exist. Here we describe the synthesis and hybridization properties of siRNAs bearing size-expanded RNA (xRNA) nucleobases and their use as a novel and systematic set of steric probes in RNAi. xRNA nucleobases are expanded by 2.4 Å using benzo-homologation and retain canonical Watson-Crick base-pairing groups. Our data show that the modified siRNA duplexes display small changes in melting temperature (+1.4 to -5.0 °C); substitutions near the center are somewhat destabilizing to the RNA duplex, while substitutions near the ends are stabilizing. RNAi studies in a dual-reporter luciferase assay in HeLa cells revealed that xRNA nucleobases in the antisense strand reduce activity at some central positions near the seed region but are generally well tolerated near the ends. Most importantly, we observed that xRNA substitutions near the 3'-end increased activity over that of wild-type siRNAs. The data are analyzed in terms of site-dependent steric effects in RISC. Circular dichroism experiments show that single xRNA substitutions do not significantly distort the native A-form helical structure of the siRNA duplex, and serum stability studies demonstrated that xRNA substitutions protect siRNAs against nuclease degradation.

Steric Restrictions of RISC in RNA Interference Identified with Size-Expanded RNA Nucleobases

PubMed Central

Hernández, Armando R.; Peterson, Larryn W.; Kool, Eric T.

2012-01-01

Understanding the interactions between small interfering RNAs (siRNAs) and the RNA-induced silencing complex (RISC) – the key protein complex of RNA interference (RNAi) – is of great importance to the development of siRNAs with improved biological, and potentially therapeutic, function. Although various chemically modified siRNAs have been reported, relatively few studies with modified nucleobases exist. Here we describe the synthesis and hybridization properties of siRNAs bearing size-expanded RNA (xRNA) nucleobases, and their use as a novel and systematic set of steric probes in RNAi. xRNA nucleobases are expanded by 2.4 Å using benzo-homologation and retain canonical Watson-Crick base-pairing groups. Our data show that the modified siRNA duplexes display small changes in melting temperature (+1.4 to −5.0 °C); substitutions near the center are somewhat destabilizing to the RNA duplex, while substitutions near the ends are stabilizing. RNAi studies in a dual-reporter luciferase assay in HeLa cells revealed that xRNA nucleobases in the antisense strand reduce activity at some central positions near the seed region, but are generally well tolerated near the ends. Most importantly, we observed that xRNA substitutions near the 3′-end increased activity over wild-type siRNAs. The data are analyzed in terms of site-dependent steric effects in RISC. Circular dichroism experiments show that single xRNA substitutions do not significantly distort the native A-form helical structure of the siRNA duplex, and serum stability studies demonstrated that xRNA substitutions protect siRNAs against nuclease degradation. PMID:22646660

Structural study of Na2O-B2O3-SiO2 glasses from molecular simulations using a polarizable force field.

PubMed

Pacaud, Fabien; Delaye, Jean-Marc; Charpentier, Thibault; Cormier, Laurent; Salanne, Mathieu

2017-10-28

Sodium borosilicate glasses Na 2 O-B 2 O 3 -SiO 2 (NBS) are complex systems from a structural point of view. Three main building units are present: tetrahedral SiO 4 and BO 4 (B IV ) and triangular BO 3 (B III ). One of the salient features of these compounds is the change of the B III /B IV ratio with the alkali concentration, which is very difficult to capture in force fields-based molecular dynamics simulations. In this work, we develop a polarizable force field that is able to reproduce the boron coordination and more generally the structure of several NBS systems in the glass and in the melt. The parameters of the potential are fitted from density functional theory calculations only, in contrast with the existing empirical potentials for NBS systems. This ensures a strong improvement on the transferability of the parameters from one composition to another. Using this new force field, the structure of NBS systems is validated against neutron diffraction and nuclear magnetic resonance experiments. A special focus is given to the distribution of B III /B IV with respect to the composition and the temperature.

Synthesis, spectroscopic characterization, and determination of the solution association energy of the dimer [Co{N(SiMe3)2}2]2: magnetic studies of low-coordinate Co(II) silylamides [Co{N(SiMe3)2}2L] (L = PMe3, pyridine, and THF) and related species that reveal evidence of very large zero-field splittings.

PubMed

Bryan, Aimee M; Long, Gary J; Grandjean, Fernande; Power, Philip P

2013-10-21

The synthesis, magnetic, and spectroscopic characteristics of the synthetically useful dimeric cobalt(II) silylamide complex [Co{N(SiMe3)2}2]2 (1) and several of its Lewis base complexes have been investigated. Variable-temperature nuclear magnetic resonance (NMR) spectroscopy of 1 showed that it exists in a monomer-dimer equilibrium in benzene solution and has an association energy (ΔGreacn) of -0.30(20) kcal mol(-1) at 300 K. Magnetic data for the polycrystalline, red-brown [Co{N(SiMe3)2}2]2 (1) showed that it displays strong antiferromagnetic exchange coupling, expressed as -2JexS1S2, between the two S = (3)/2 cobalt(II) centers with a Jex value of -215(5) cm(-1), which is consistent with its bridged dimeric structure in the solid state. The electronic spectrum of 1 in solution is reported for the first time, and it is shown that earlier reports of the melting point, synthesis, electronic spectrum, and magnetic studies of the monomer "Co{N(SiMe3)2}2" are consistent with those of the bright green-colored tetrahydrofuran (THF) complex [Co{N(SiMe3)2}2(THF)] (4). Treatment of 1 with various Lewis bases yielded monomeric three-coordinated species-[Co{N(SiMe3)2}2(PMe3)] (2), and [Co{N(SiMe3)2}2(THF)] (4), as well as the previously reported [Co{N(SiMe3)2}2(py)] (3)-and the four-coordinated species [Co{N(SiMe3)2}2(py)2] (5) in good yields. The paramagnetic complexes 2-4 were characterized by electronic and (1)H NMR spectroscopy, and by X-ray crystallography in the case of 2 and 4. Magnetic studies of 2-5 and of the known three-coordinated cobalt(II) species [Na(12-crown-4)2][Co{N(SiMe3)2}3] (6) showed that they have considerably larger χMT products and, hence, magnetic moments, than the spin-only values of 1.875 emu K mol(-1) and 3.87 μB, which is indicative of a significant zero-field splitting and g-tensor anisotropy resulting from the pseudo-trigonal crystal field. A fit of χMT for 2-6 yields a large g-tensor anisotropy, large negative D-values (between -62 cm(-1) and -82 cm(-1)), and E-values between ±10 cm(-1) and ±21 cm(-1).

Structural, thermal, dielectric spectroscopic and AC impedance properties of SiC nanoparticles doped PVK/PVC blend

NASA Astrophysics Data System (ADS)

Alghunaim, Naziha Suliman

2018-06-01

Nanocomposite films based on poly (N-vinylcarbazole)/polyvinylchloride (PVK/PVC) blend doped with different concentrations of Silicon Carbide (SiC) nanoparticles have been prepared. The X-ray diffraction, Ultra violet-visible spectroscopy, thermogravimetric analysis and electrical spectroscopic has been used to characterize these nanocomposites. The X-ray analysis confirms the semi-crystalline nature of the films. The intensity of the main X-ray peak is decreased due to the interaction between the PVK/PVC and SiC. The main SiC peaks are absent due to complete dissolution of SiC in polymeric matrices. The UV-Vis spectra indicated that the band gap optical energy is affected by adding SiC nanoparticles because the charges transfer complexes between PVK/PVC with amount of SiC. The thermal stability is improved and the estimated values of ε‧ and ε″ are increased with increasing for SiC content due to the free charge carriers which in turn increase the ionic conductivity of the doped samples. The plots of tan δ with frequency are studied. A single peak from the plot between tan δ and Log (f) is appeared and shifted towards the higher frequency confirmed the presence of relaxing dipoles moment.

Nanostructured gold and platinum electrodes on silicon structures for biosensing

NASA Astrophysics Data System (ADS)

Ogurtsov, V. I.; Sheehan, M. M.

2005-01-01

Gold and platinum metal electrodes on Si/SiO2 having undergone anisotropic potassium hydroxide (KOH) etch treatment are considered. This treatment etches at different rates and directions in the material resulting in creation of numerous pyramid shaped holes in the silicon substrate. This surface is used to make metal electrodes with increased electrode efficiency. The electrodes can serve as the sensors or as the sensor substrates (for surface polymer modification) and because both gold and platinum are inert they have applications for food safety biosensing. Wine, an economically significant food product, was chosen as a matrix, and impedance spectroscopy (EIS) was selected as a method of investigation of electrode behaviour. Based on results of EIS, different complexity equivalent circuits were determined by applying fitting mean square root optimisation of sensor complex impedance measurements.

Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

PubMed

Lorenz, Volker; Ehle, Sophie; Liebing, Phil; Engelhardt, Felix; Hashemi-Haeri, Haleh; Oehler, Florian; Hinderberger, Dariush; Busse, Sabine; Urbaschok, Jens; Edelmann, Frank T

2017-12-19

A unique trivalent manganese siloxide complex, blue-violet Mn III Li 2 Cl[(Ph 2 SiO) 2 O] 2 (THF) 4 ·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph 2 SiOH) 2 O (1) followed by reaction with MnCl 2 (THF) 2 gave the structurally remarkable Mn(ii) precursor Mn II Li 4 Cl 2 [(Ph 2 SiO) 2 O] 2 (THF) 5 ·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO 4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

Defect charge states in Si doped hexagonal boron-nitride monolayer

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Andrew, R. C.; Chetty, N.

2016-02-01

We perform ab initio density functional theory calculations to investigate the energetics, electronic and magnetic properties of isolated stoichiometric and non-stoichiometric substitutional Si complexes in a hexagonal boron-nitride monolayer. The Si impurity atoms substituting the boron atom sites SiB giving non-stoichiometric complexes are found to be the most energetically favourable, and are half-metallic and order ferromagnetically in the neutral charge state. We find that the magnetic moments and magnetization energies increase monotonically when Si defects form a cluster. Partial density of states and standard Mulliken population analysis indicate that the half-metallic character and magnetic moments mainly arise from the Si 3p impurity states. The stoichiometric Si complexes are energetically unfavorable and non-magnetic. When charging the energetically favourable non-stoichiometric Si complexes, we find that the formation energies strongly depend on the impurity charge states and Fermi level position. We also find that the magnetic moments and orderings are tunable by charge state modulation q  =  -2, -1, 0, +1, +2. The induced half-metallic character is lost (retained) when charging isolated (clustered) Si defect(s). This underlines the potential of a Si doped hexagonal boron-nitride monolayer for novel spin-based applications.

In-silico analysis for RNA-interference mechanism of α-synuclein to treat Parkinson's disease.

PubMed

Seema, S; Seenivasagam, R; Hemavathi, K

2013-01-01

Parkinson's Disease (PD) causing mutations in α-synuclein gene are ALA30PRO, GLU46LYS and ALA53THR. The conformational changes in proteins with respect to all the three mutations were analysed. These were used to predict the structures of Short Interfering RNA (siRNA) antisense strand and siRNA region. The siRNA binds with the argonaute protein forming RNA Induced Silencing Complex (RISC). Then, siRNA antisense-strand was attached to RISC. The structure of dicer (RNase-III-enzyme) cleaves double-stranded RNA (dsRNA) into two siRNA-strands. Incorporation of single siRNA-strand into RISC guides to pair with the complementary α-synuclein target-messenger RNA (mRNA) thereby enabling it to cleave the target.

Single Image Super-Resolution Using Global Regression Based on Multiple Local Linear Mappings.

PubMed

Choi, Jae-Seok; Kim, Munchurl

2017-03-01

Super-resolution (SR) has become more vital, because of its capability to generate high-quality ultra-high definition (UHD) high-resolution (HR) images from low-resolution (LR) input images. Conventional SR methods entail high computational complexity, which makes them difficult to be implemented for up-scaling of full-high-definition input images into UHD-resolution images. Nevertheless, our previous super-interpolation (SI) method showed a good compromise between Peak-Signal-to-Noise Ratio (PSNR) performances and computational complexity. However, since SI only utilizes simple linear mappings, it may fail to precisely reconstruct HR patches with complex texture. In this paper, we present a novel SR method, which inherits the large-to-small patch conversion scheme from SI but uses global regression based on local linear mappings (GLM). Thus, our new SR method is called GLM-SI. In GLM-SI, each LR input patch is divided into 25 overlapped subpatches. Next, based on the local properties of these subpatches, 25 different local linear mappings are applied to the current LR input patch to generate 25 HR patch candidates, which are then regressed into one final HR patch using a global regressor. The local linear mappings are learned cluster-wise in our off-line training phase. The main contribution of this paper is as follows: Previously, linear-mapping-based conventional SR methods, including SI only used one simple yet coarse linear mapping to each patch to reconstruct its HR version. On the contrary, for each LR input patch, our GLM-SI is the first to apply a combination of multiple local linear mappings, where each local linear mapping is found according to local properties of the current LR patch. Therefore, it can better approximate nonlinear LR-to-HR mappings for HR patches with complex texture. Experiment results show that the proposed GLM-SI method outperforms most of the state-of-the-art methods, and shows comparable PSNR performance with much lower computational complexity when compared with a super-resolution method based on convolutional neural nets (SRCNN15). Compared with the previous SI method that is limited with a scale factor of 2, GLM-SI shows superior performance with average 0.79 dB higher in PSNR, and can be used for scale factors of 3 or higher.

Theoretical predictions of a bucky-diamond SiC cluster.

PubMed

Yu, Ming; Jayanthi, C S; Wu, S Y

2012-06-15

A study of structural relaxations of Si(n)C(m) clusters corresponding to different compositions, different relative arrangements of Si/C atoms, and different types of initial structure, reveals that the Si(n)C(m) bucky-diamond structure can be obtained for an initial network structure constructed from a truncated bulk 3C-SiC for a magic composition corresponding to n = 68 and m = 79. This study was performed using a semi-empirical Hamiltonian (SCED-LCAO) since it allowed an extensive search of different types of initial structures. However, the bucky-diamond structure predicted by this method was also confirmed by a more accurate density functional theory (DFT) based method. The bucky-diamond structure exhibited by a SiC-based system represents an interesting paradigm where a Si atom can form three-coordinated as well as four-coordinated networks with carbon atoms and vice versa and with both types of network co-existing in the same structure. Specifically, the bucky-diamond structure of the Si(68)C(79) cluster consists of a 35-atom diamond-like inner core (four-atom coordinations) suspended inside a 112-atom fullerene-like shell (three-atom coordinations).

Ab initio modeling of complex amorphous transition-metal-based ceramics.

PubMed

Houska, J; Kos, S

2011-01-19

Binary and ternary amorphous transition metal (TM) nitrides and oxides are of great interest because of their suitability for diverse applications ranging from high-temperature machining to the production of optical filters or electrochromic devices. However, understanding of bonding in, and electronic structure of, these materials represents a challenge mainly due to the d electrons in their valence band. In the present work, we report ab initio calculations of the structure and electronic structure of ZrSiN materials. We focus on the methodology needed for the interpretation and automatic analysis of the bonding structure, on the effect of the length of the calculation on the convergence of individual quantities of interest and on the electronic structure of materials. We show that the traditional form of the Wannier function center-based algorithm fails due to the presence of d electrons in the valence band. We propose a modified algorithm, which allows one to analyze bonding structure in TM-based systems. We observe an appearance of valence p states of TM atoms in the electronic spectra of such systems (not only ZrSiN but also NbO(x) and WAuO), and examine the importance of the p states for the character of the bonding as well as for facilitating the bonding analysis. The results show both the physical phenomena and the computational methodology valid for a wide range of TM-based ceramics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warren, W.L.; Vanheusden, K.; Fleetwood, D.M.

Recently, the authors have demonstrated that annealing Si/SiO{sub 2}/Si structures in a hydrogen containing ambient introduces mobile H{sup +} ions into the buried SiO{sub 2} layer. Changes in the H{sup +} spatial distribution within the SiO{sub 2} layer were electrically monitored by current-voltage (I-V) measurements. The ability to directly probe reversible protonic motion in Si/SiO{sub 2}/Si structures makes this an exemplar system to explore the physics and chemistry of hydrogen in the technologically relevant Si/SiO{sub 2} structure. In this work, they illustrate that this effect can be used as the basis for a programmable nonvolatile field effect transistor (NVFET) memorymore » that may compete with other Si-based memory devices. The power of this novel device is its simplicity; it is based upon standard Si/SiO{sub 2}/Si technology and forming gas annealing, a common treatment used in integrated circuit processing. They also briefly discuss the effects of radiation on its retention properties.« less

Self-transducing silicon nanowire electromechanical systems at room temperature.

PubMed

He, Rongrui; Feng, X L; Roukes, M L; Yang, Peidong

2008-06-01

Electronic readout of the motions of genuinely nanoscale mechanical devices at room temperature imposes an important challenge for the integration and application of nanoelectromechanical systems (NEMS). Here, we report the first experiments on piezoresistively transduced very high frequency Si nanowire (SiNW) resonators with on-chip electronic actuation at room temperature. We have demonstrated that, for very thin (~90 nm down to ~30 nm) SiNWs, their time-varying strain can be exploited for self-transducing the devices' resonant motions at frequencies as high as approximately 100 MHz. The strain of wire elongation, which is only second-order in doubly clamped structures, enables efficient displacement transducer because of the enhanced piezoresistance effect in these SiNWs. This intrinsically integrated transducer is uniquely suited for a class of very thin wires and beams where metallization and multilayer complex patterning on devices become impractical. The 30 nm thin SiNW NEMS offer exceptional mass sensitivities in the subzeptogram range. This demonstration makes it promising to advance toward NEMS sensors based on ultrathin and even molecular-scale SiNWs, and their monolithic integration with microelectronics on the same chip.

Contributions of 3'-overhang to the dissociation of small interfering RNAs from the PAZ domain: molecular dynamics simulation study.

PubMed

Lee, Hui Sun; Lee, Soo Nam; Joo, Chul Hyun; Lee, Heuiran; Lee, Han Saem; Yoon, Seung Yong; Kim, Yoo Kyum; Choe, Han

2007-03-01

RNA interference (RNAi) is a 'knock-down' reaction to reduce expression of a specific gene through highly regulated, enzyme-mediated processes. Small interfering RNAs (siRNAs) are RNA molecules that play an effector role in RNAi and can bind the PAZ domains present in Dicer and RISC. We investigated the interaction between the PAZ domain and the siRNA-like duplexes through dissociation molecular dynamics (DMD) simulations. Specifically, we focused on the response of the PAZ domain to various 3'-overhang structures of the siRNA-like duplexes. We found that the siRNA-like duplex with the 3' UU-overhang made relatively more stable complex with the PAZ domain compared to those with 3' CC-, AA-, and GG-overhangs. The siRNA-like duplex with UU-overhang was easily dissociated from the PAZ domain once the structural stability of the complex is impaired. Interestingly, the 3' UU-overhang spent the least time at the periphery region of the binding pocket during the dissociation process, which can be mainly attributable to UU-overhang's smallest number of hydrogen bonds.

Vision-based system identification technique for building structures using a motion capture system

NASA Astrophysics Data System (ADS)

Oh, Byung Kwan; Hwang, Jin Woo; Kim, Yousok; Cho, Tongjun; Park, Hyo Seon

2015-11-01

This paper presents a new vision-based system identification (SI) technique for building structures by using a motion capture system (MCS). The MCS with outstanding capabilities for dynamic response measurements can provide gage-free measurements of vibrations through the convenient installation of multiple markers. In this technique, from the dynamic displacement responses measured by MCS, the dynamic characteristics (natural frequency, mode shape, and damping ratio) of building structures are extracted after the processes of converting the displacement from MCS to acceleration and conducting SI by frequency domain decomposition. A free vibration experiment on a three-story shear frame was conducted to validate the proposed technique. The SI results from the conventional accelerometer-based method were compared with those from the proposed technique and showed good agreement, which confirms the validity and applicability of the proposed vision-based SI technique for building structures. Furthermore, SI directly employing MCS measured displacements to FDD was performed and showed identical results to those of conventional SI method.

Facile synthesis, microstructure and photophysical properties of core-shell nanostructured (SiCN)/BN nanocomposites

PubMed Central

Zhang, Qian; Jia, Dechang; Yang, Zhihua; Cai, Delong; Laine, Richard M.; Li, Qian; Zhou, Yu

2017-01-01

Increasing structural complexity at nanoscale can permit superior control over photophysical properties in the precursor-derived semiconductors. We demonstrate here the synthesis of silicon carbonitride (SiCN)/boron nitride (BN) nanocomposites via a polymer precursor route wherein the cobalt polyamine complexes used as the catalyst, exhibiting novel composite structures and photophysical properties. High Resolution Transmission Electron Microscopy (HRTEM) analysis shows that the diameters of SiCN−BN core−shell nanocomposites and BN shells are 50‒400 nm and 5‒25 nm, respectively. BN nanosheets (BNNSs) are also observed with an average sheet size of 5‒15 nm. The photophysical properties of these nanocomposites are characterized using the UV-Vis and photoluminescence (PL) analyses. The as-produced composites have emission behavior including an emission lifetime of 2.5 ns (±20 ps) longer observed in BN doped SiCN than that seen for SiC nanoparticles. Our results suggest that the SiCN/BN nanocomposites act as semiconductor displaying superior width photoluminescence at wavelengths spanning the visible to near-infrared (NIR) spectral range (400‒700 nm), owing to the heterojunction of the interface between the SiC(N) nanowire core and the BN nanosheet shell. PMID:28084300

Possibilities for LWIR detectors using MBE-grown Si(/Si(1-x)Ge(x) structures

NASA Technical Reports Server (NTRS)

Hauenstein, Robert J.; Miles, Richard H.; Young, Mary H.

1990-01-01

Traditionally, long wavelength infrared (LWIR) detection in Si-based structures has involved either extrinsic Si or Si/metal Schottky barrier devices. Molecular beam epitaxially (MBE) grown Si and Si/Si(1-x)Ge(x) heterostructures offer new possibilities for LWIR detection, including sensors based on intersubband transitions as well as improved conventional devices. The improvement in doping profile control of MBE in comparison with conventional chemical vapor deposited (CVD) Si films has resulted in the successful growth of extrinsic Si:Ga, blocked impurity-band conduction detectors. These structures exhibit a highly abrupt step change in dopant profile between detecting and blocking layers which is extremely difficult or impossible to achieve through conventional epitaxial growth techniques. Through alloying Si with Ge, Schottky barrier infrared detectors are possible, with barrier height values between those involving pure Si or Ge semiconducting materials alone. For both n-type and p-type structures, strain effects can split the band edges, thereby splitting the Schottky threshold and altering the spectral response. Measurements of photoresponse of n-type Au/Si(1-x)Ge(x) Schottky barriers demonstrate this effect. For intersubband multiquntum well (MQW) LWIR detection, Si(1-x)Ge(x)/Si detectors grown on Si substrates promise comparable absorption coefficients to that of the Ga(Al)As system while in addition offering the fundamental advantage of response to normally incident light as well as the practical advantage of Si-compatibility. Researchers grew Si(1-x)Ge(x)/Si MQW structures aimed at sensitivity to IR in the 8 to 12 micron region and longer, guided by recent theoretical work. Preliminary measurements of n- and p-type Si(1-x)Ge(x)/Si MQW structures are given.

Learning Complex Grammar in the Virtual Classroom: A Comparison of Processing Instruction, Structured Input, Computerized Visual Input Enhancement, and Traditional Instruction

ERIC Educational Resources Information Center

Russell, Victoria

2012-01-01

This study investigated the effects of processing instruction (PI) and structured input (SI) on the acquisition of the subjunctive in adjectival clauses by 92 second-semester distance learners of Spanish. Computerized visual input enhancement (VIE) was combined with PI and SI in an attempt to increase the salience of the targeted grammatical form…

Silylene-Nickel Promoted Cleavage of B-O Bonds: From Catechol Borane to the Hydroborylene Ligand.

PubMed

Hadlington, Terrance J; Szilvási, Tibor; Driess, Matthias

2017-06-19

The first 16 valence electron [bis(NHC)](silylene)Ni 0 complex 1, [( TMS L)ClSi:→Ni(NHC) 2 ], bearing the acyclic amido-chlorosilylene ( TMS L)ClSi: ( TMS L=N(SiMe 3 )Dipp; Dipp=2,6-Pr i 2 C 6 H 4 ) and two NHC ligands (N-heterocyclic carbene=:C[(Pr i )NC(Me)] 2 ) was synthesized in high yield and structurally characterized. Compound 1 is capable of facile dihydrogen activation under ambient conditions to give the corresponding HSi-NiH complex 2. Most notably, 1 reacts with catechol borane to afford the unprecedented hydroborylene-coordinated (chloro)(silyl)nickel(II) complex 3, {[cat( TMS L)Si](Cl)Ni←:BH(NHC) 2 }, via the cleavage of two B-O bonds and simultaneous formation of two Si-O bonds. The mechanism for the formation of 3 was rationalized by means of DFT calculations, which highlight the powerful synergistic effects of the Si:→Ni moiety in the breaking of incredibly strong B-O bonds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced thermal conductivity of nanotwinned random layer structures: a promising nanostructuring towards efficient Si and Si/Ge thermoelectric materials

NASA Astrophysics Data System (ADS)

Samaraweera, Nalaka; Chan, Kin L.; Mithraratne, Kumar

2018-05-01

Si and Si/Ge based nanostructures of reduced lattice thermal conductivity are widely attractive for developing efficient thermoelectric materials. In this study, we demonstrate the reduced thermal conductivity of Si nanotwinned random layer (NTRL) structures over corresponding superlattice and twin-free counterparts. The participation ratio analysis of vibrational modes shows that a possible cause of thermal conductivity reduction is phonon localization due to the random arrangement of twin boundaries. Via non-equilibrium molecular dynamic simulations, it is shown that ~23 and ~27% reductions over superlattice counterparts and ~55 and 53% over twin-free counterparts can be attained for the structures of total lengths of 90 and 170 nm, respectively. Furthermore, a random twin boundary distribution is applied for Si/Ge random layer structures seeking further reduction of thermal conductivity. A significant reduction in thermal conductivity of Si/Ge structures exceeding the thermal insulating performance of the corresponding amorphous Si structure by ~31% for a total length of 90 nm can be achieved. This reduction is as high as ~98% compared to the twin-free Si counterpart. It is demonstrated that application of randomly organised nanoscale twin boundaries is a promising nanostructuring strategy towards developing efficient Si and Si/Ge based thermoelectric materials in the future.

A high-performance ternary Si composite anode material with crystal graphite core and amorphous carbon shell

NASA Astrophysics Data System (ADS)

Sui, Dong; Xie, Yuqing; Zhao, Weimin; Zhang, Hongtao; Zhou, Ying; Qin, Xiting; Ma, Yanfeng; Yang, Yong; Chen, Yongsheng

2018-04-01

Si is a promising anode material for lithium-ion batteries, but suffers from sophisticated engineering structures and complex fabrication processes that pose challenges for commercial application. Herein, a ternary Si/graphite/pyrolytic carbon (SiGC) anode material with a structure of crystal core and amorphous shell using low-cost raw materials is developed. In this ternary SiGC composite, Si component exists as nanoparticles and is spread on the surface of the core graphite flakes while the sucrose-derived pyrolytic carbon further covers the graphite/Si components as the amorphous shell. With this structure, Si together with the graphite contributes to the high specific capacity of this Si ternary material. Also the graphite serves as the supporting and conducting matrix and the amorphous shell carbon could accommodate the volume change effect of Si, reinforces the integrity of the composite architecture, and prevents the graphite and Si from direct exposing to the electrolyte. The optimized ternary SiGC composite displays high reversible specific capacity of 818 mAh g-1 at 0.1 A g-1, initial Coulombic efficiency (CE) over 80%, and excellent cycling stability at 0.5 A g-1 with 83.6% capacity retention (∼610 mAh g-1) after 300 cycles.

Amylose-Based Cationic Star Polymers for siRNA Delivery.

PubMed

Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials.

Narrow absorption lines complex I: one form of broad absorption line

NASA Astrophysics Data System (ADS)

Lu, Wei-Jian; Lin, Ying-Ru

2018-03-01

We discover that some of the broad absorption lines (BALs) are actually a complex of narrow absorption lines (NALs). As a pilot study of this type of BAL, we show this discovery through a typical example in this paper. Utilizing the two-epoch observations of J002710.06-094435.3 (hereafter J0027-0944) from the Sloan Digital Sky Survey (SDSS), we find that each of the C IV and Si IV BAL troughs contains at least four NAL doublets. By resolving the Si IV BAL into multiple NALs, we present the following main results and conclusions. First, all these NALs show coordinated variations between the two-epoch SDSS observations, suggesting that they all originate in the quasar outflow, and that their variations are due to global changes in the ionization condition of the absorbing gas. Secondly, a BAL consisting of a number of NAL components indicates that this type of BAL is basically the same as the intrinsic NAL, which tends to support the inclination model rather than the evolution model. Thirdly, although both the C IV and Si IV BALs originate from the same clumpy substructures of the outflow, they show different profile shapes: multiple absorption troughs for the Si IV BAL in a wider velocity range, while P-Cygni for the C IV BAL in a narrower velocity range. This can be interpreted by the substantial differences in fine structure and oscillator strength between the Si IVλλ1393, 1402 and C IVλλ1548, 1551 doublets. Based on the above conclusions, we consider that the decomposition of a BAL into NALs can serve as a way to resolve the clumpy structure for outflows, and it can be used to learn more about characteristics of the clumpy structure and to test the outflow model, when utilizing high-resolution spectra and photoionization model.

Strained multilayer structures with pseudomorphic GeSiSn layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timofeev, V. A., E-mail: Vyacheslav.t@isp.nsc.ru; Nikiforov, A. I.; Tuktamyshev, A. R.

2016-12-15

The temperature and composition dependences of the critical thickness of the 2D–3D transition for a GeSiSn film on Si(100) have been studied. The regularities of the formation of multilayer structures with pseudomorphic GeSiSn layers directly on a Si substrate, without relaxed buffer layers, were investigated for the first time. The possibility of forming multilayer structures based on pseudomorphic GeSiSn layers has been shown and the lattice parameters have been determined using transmission electron microscopy. The grown structures demonstrate photoluminescence for Sn contents from 3.5 to 5% in GeSiSn layers.

Organosilylated complex [Eu(TTA)3(Bpy-Si)]: a bifunctional moiety for the engeneering of luminescent silica-based nanoparticles for bioimaging.

PubMed

Duarte, Adriana P; Mauline, Léïla; Gressier, Marie; Dexpert-Ghys, Jeannette; Roques, Christine; Caiut, José Maurício A; Deffune, Elenice; Maia, Danielle C G; Carlos, Iracilda Z; Ferreira, Antonio A P; Ribeiro, Sidney J L; Menu, Marie-Joëlle

2013-05-14

A new highly luminescent europium complex with the formula [Eu(TTA)3(Bpy-Si)], where TTA stands for the thenoyltrifluoroacetone, (C4H3S)COCH2COCF3, chelating ligand and Bpy-Si, Bpy-CH2NH(CH2)3Si(OEt)3, is an organosilyldipyridine ligand displaying a triethoxysilyl group as a grafting function has been synthesized and fully characterized. This bifunctional complex has been grafted onto the surface of dense silica nanoparticles (NPs) and on mesoporous silica microparticles as well. The covalent bonding of [Eu(TTA)3(Bpy-Si)] inside uniform Stöber silica nanoparticles was also achieved. The general methodology proposed could be applied to any silica matrix, allowed high grafting ratios that overcome chelate release and the tendency to agglomerate. Luminescent silica-based nanoparticles SiO2-[Eu(TTA)3(Bpy-Si)], with a diameter of 28 ± 2 nm, were successfully tested as a luminescent labels for the imaging of Pseudomonas aeruginosa biofilms. They were also functionalized by a specific monoclonal antibody and subsequently employed for the selective imaging of Escherichia coli bacteria.

A Theoretical Simulation of the Radiation Responses of Si, Ge, and Si/Ge Superlattice to Low-Energy Irradiation.

PubMed

Jiang, Ming; Xiao, Haiyan; Peng, Shuming; Yang, Guixia; Liu, Zijiang; Qiao, Liang; Zu, Xiaotao

2018-05-02

In this study, the low-energy radiation responses of Si, Ge, and Si/Ge superlattice are investigated by an ab initio molecular dynamics method and the origins of their different radiation behaviors are explored. It is found that the radiation resistance of the Ge atoms that are around the interface of Si/Ge superlattice is comparable to bulk Ge, whereas the Si atoms around the interface are more difficult to be displaced than the bulk Si, showing enhanced radiation tolerance as compared with the bulk Si. The mechanisms for defect generation in the bulk and superlattice structures show somewhat different character, and the associated defects in the superlattice are more complex. Defect formation and migration calculations show that in the superlattice structure, the point defects are more difficult to form and the vacancies are less mobile. The enhanced radiation tolerance of the Si/Ge superlattice will benefit for its applications as electronic and optoelectronic devices under radiation environment.

A Theoretical Simulation of the Radiation Responses of Si, Ge, and Si/Ge Superlattice to Low-Energy Irradiation

NASA Astrophysics Data System (ADS)

Jiang, Ming; Xiao, Haiyan; Peng, Shuming; Yang, Guixia; Liu, Zijiang; Qiao, Liang; Zu, Xiaotao

2018-05-01

In this study, the low-energy radiation responses of Si, Ge, and Si/Ge superlattice are investigated by an ab initio molecular dynamics method and the origins of their different radiation behaviors are explored. It is found that the radiation resistance of the Ge atoms that are around the interface of Si/Ge superlattice is comparable to bulk Ge, whereas the Si atoms around the interface are more difficult to be displaced than the bulk Si, showing enhanced radiation tolerance as compared with the bulk Si. The mechanisms for defect generation in the bulk and superlattice structures show somewhat different character, and the associated defects in the superlattice are more complex. Defect formation and migration calculations show that in the superlattice structure, the point defects are more difficult to form and the vacancies are less mobile. The enhanced radiation tolerance of the Si/Ge superlattice will benefit for its applications as electronic and optoelectronic devices under radiation environment.

Monometallic Ni(0) and Heterobimetallic Ni(0) /Au(I) Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis.

PubMed

Cluff, Kyle J; Bhuvanesh, Nattamai; Blümel, Janet

2015-07-06

The tridentate chelate nickel complexes [(CO)Ni{(PPh2 CH2 )3 CMe}] (2), [(CO)Ni{(PPh2 CH2 CH2 )3 SiMe}] (6), and [Ph3 PNi{(PPh2 CH2 CH2 )3 SiMe}] (7), as well as the bidentate complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 PPh2 }] (3) and the heterobimetallic complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 Ph2 PAuCl}] (4), have been synthesized and fully characterized in solution. All (1) H and (13) C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their (31) P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zircon solubility and of Zr species in subduction zone fluids

NASA Astrophysics Data System (ADS)

Wilke, M.; Schmidt, C.; Rickers, K.; Pascarelli, S.; Manning, C. E.; Stechern, A.

2009-12-01

The geochemical signature of igneous rocks at convergent plate margins is thought to result from complex melt formation processes involving aqueous solutions derived from dehydration of the subducted slab. In these processes, the depletion of high-field-strength elements (HFSE) may be controlled by the presence of accessory phases such as zircon and rutile, which can strongly fractionate these elements; however, the stability and solubility of these phases depends strongly on the fluid composition, including concentration and stoichiometry of Na-Al silicate components. Here we present new data on the influence of the fluid composition on zircon solubility as well as data on the Zr complexation in these fluids at P&T. Experiments were conducted using a modified hydrothermal diamond-anvil cell (HDAC). Zr contents at P&T were determined using SR-µXRF spectra. Zr K-edge X-ray Absorption Fine Structure (XAFS) spectra were acquired to investigate the Zr complexation in-situ at P&T. A grain of synthetic crystalline zircon was equilibrated with an aqueous fluid containing Na2Si2O5 or Na2Si2O5 + Al2O3 components. XAFS and SR-µXRF spectra were taken at the dispersive beamline ID24 of the ESRF, Grenoble, France. Some additional SR-µXRF spectra were taken at HASYLAB, Hamburg, beamline L. The observed Zr concentrations in fluids containing 7-33 wt% Na2Si2O5 and variable Al contents were between 75 and 720 ppm at 500 to 750°C and ~300 MPa to ~700 MPa. These values match expected solubilities calculated from linear interpolation of the maximum solubility in pure H2O (from the detection limit) and the solubility in the most alkaline high-silica melts reported by Ellison and Hess (1986, CMP, 94, 343). The high Zr solubility in sodium silicate-bearing solutions signifies that aqueous fluids with alkali silicates offer an efficient mechanism for HFSE transport. This can be explained by complexation of HFSE with Si, Na, and perhaps also Al, via formation of polymerized solutes. The XAFS results show clear differences between spectra of Zr in an HCl solution and in H2O-Na2Si2O5 (±Al2O3) aqueous fluid, implying considerable differences in Zr complexation. The latter spectra display similarities to spectra of Zr in Na2Si2O5 glass. This may indicate a similar structural environment for the two examined states, and thus point to Zr in (alumino)-silicate-based polymeric units in the aqueous solutions.

Thermo-mechanical performance of precision C/SiC mounts

NASA Astrophysics Data System (ADS)

Goodman, William A.; Mueller, Claus E.; Jacoby, Marc T.; Wells, Jim D.

2001-12-01

For complex shaped, lightweight, high precision opto- mechanical structures that must operate in adverse environments and over wide ranges of temperature, we consider IABG's optical grade silicon carbide composite ceramic (C/SiC) as the material of choice. C/SiC employs conventional NC machining/milling equipment to rapidly fabricate near-net shape parts, providing substantial schedule, cost, and risk savings for high precision components. Unlike powder based SiC ceramics, C/SiC does not experience significant shrinkage during processing, nor does it suffer from incomplete densification. If required, e.g. for large-size components, a fully-monolithic ceramic joining technique can be applied. Generally, the thermal and mechanical properties of C/SiC are tunable in certain ranges by modifying certain process steps. This paper focuses on the thermo-mechanical performance of new, high precision mounts designed by Schafer Corporation and manufactured by IABG. The mounts were manufactured using standard optical grade C/SiC (formulation internally called A-3). The A-3 formulation has a near-perfect CTE match with silicon, making it the ideal material to athermally support Schafer produced Silicon Lightweight Mirrors (SLMs) that will operate in a cryogenic environment. Corresponding thermo- mechanical testing and analysis is presented in this manuscript.

2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid as linker for Co(II)/Ni(II)/Cu(II) coordination polymers: Synthesis, structures and properties

NASA Astrophysics Data System (ADS)

Wang, Duo-Zhi; Wang, Xin-Fang; Du, Jia-Qiang; Dong, Jun-Liang; Xie, Fei

2018-02-01

We report the synthesis and characterization of five transition metal coordination polymers (CPs) based on M(II) (M: Co, Ni and Cu), 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid (H2L) ligand. They are formulated as {[Co2(HL)2(H2O)3(SO4)]·H2O}n (1), {[Co2(HL)2(H2O)2]·SiF6}n (2), {[Ni2(HL)2(H2O)3(SO4)]·2H2O}n (3), {[Ni2(HL)2(H2O)4]·H2O·SiF6}n (4), {[Cu2(HL)2(H2O)2]·SiF6}n (5). The complexes 1-5 structure were characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Complexes 1-5 are two-dimensional (2D) network type coordination polymers that 1-3, 5 crystallize in monoclinic system within the centrosymmetric space group P2(1)/c, and 4 in triclinic system P-1 space group, they show the same coordination modes (κ1-κ1)-(κ1)-(κ1)-μ3 in coordination polymers. Complexes 1 and 3 expand to three-dimensional framework by means of hydrogen bond interactions, and can be rationalized to be three-connected {63} topological network, while 2, 4, 5 exhibit the topological network with a four-connected {44·62} topological sql network. The luminescent properties (for complexes 1, 2) and UV diffuse reflectance (for complexes 1-5) in the solid state at room temperature were also investigated and discussed. Complexes 1-5 act as effective heterogeneous catalysts, under mild conditions, for the homocoupling reaction of 4-substituted aryl iodides bearing electron-donating groups (-CH3, -OCH3).

Biomorphous SiC ceramics prepared from cork oak as precursor

NASA Astrophysics Data System (ADS)

Yukhymchuk, V. O.; Kiselov, V. S.; Valakh, M. Ya.; Tryus, M. P.; Skoryk, M. A.; Rozhin, A. G.; Kulinich, S. A.; Belyaev, A. E.

2016-04-01

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material's porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:C:Si, SiC:C, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.

Polycrystalline silicon carbide dopant profiles obtained through a scanning nano-Schottky contact

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golt, M. C.; Strawhecker, K. E.; Bratcher, M. S.

2016-07-14

The unique thermo-electro-mechanical properties of polycrystalline silicon carbide (poly-SiC) make it a desirable candidate for structural and electronic materials for operation in extreme environments. Necessitated by the need to understand how processing additives influence poly-SiC structure and electrical properties, the distribution of lattice defects and impurities across a specimen of hot-pressed 6H poly-SiC processed with p-type additives was visualized with high spatial resolution using a conductive atomic force microscopy approach in which a contact forming a nano-Schottky interface is scanned across the sample. The results reveal very intricate structures within poly-SiC, with each grain having a complex core-rim structure. Thismore » complexity results from the influence the additives have on the evolution of the microstructure during processing. It was found that the highest conductivities localized at rims as well as at the interface between the rim and the core. The conductivity of the cores is less than the conductivity of the rims due to a lower concentration of dopant. Analysis of the observed conductivities and current-voltage curves is presented in the context of nano-Schottky contact regimes where the conventional understanding of charge transport to diode operation is no longer valid.« less

Polycrystalline silicon carbide dopant profiles obtained through a scanning nano-Schottky contact

NASA Astrophysics Data System (ADS)

Golt, M. C.; Strawhecker, K. E.; Bratcher, M. S.; Shanholtz, E. R.

2016-07-01

The unique thermo-electro-mechanical properties of polycrystalline silicon carbide (poly-SiC) make it a desirable candidate for structural and electronic materials for operation in extreme environments. Necessitated by the need to understand how processing additives influence poly-SiC structure and electrical properties, the distribution of lattice defects and impurities across a specimen of hot-pressed 6H poly-SiC processed with p-type additives was visualized with high spatial resolution using a conductive atomic force microscopy approach in which a contact forming a nano-Schottky interface is scanned across the sample. The results reveal very intricate structures within poly-SiC, with each grain having a complex core-rim structure. This complexity results from the influence the additives have on the evolution of the microstructure during processing. It was found that the highest conductivities localized at rims as well as at the interface between the rim and the core. The conductivity of the cores is less than the conductivity of the rims due to a lower concentration of dopant. Analysis of the observed conductivities and current-voltage curves is presented in the context of nano-Schottky contact regimes where the conventional understanding of charge transport to diode operation is no longer valid.

Hydrogen-impurity complexes in III V semiconductors

NASA Astrophysics Data System (ADS)

Ulrici, W.

2004-12-01

This review summarizes the presently available knowledge concerning hydrogen-impurity complexes in III-V compounds. The impurities form shallow acceptors on group III sites (Be, Zn, Cd) and on group V sites (C, Si, Ge) as well as shallow donors on group V sites (S, Se, Te) and on group III sites (Si, Sn). These complexes are mainly revealed by their hydrogen stretching modes. Therefore, nearly all information about their structure and dynamic properties is derived from vibrational spectroscopy. The complexes of shallow impurities with hydrogen have been most extensively investigated in GaAs, GaP and InP. This holds also for Mg-H in GaN. The complexes exhibit a different microscopic structure, which is discussed in detail. The isoelectronic impurity nitrogen, complexed with one hydrogen atom, is investigated in detail in GaAs and GaP. Those complexes can exist in different charge states. The experimental results such as vibrational frequencies, the microscopic structure and the activation energy for reorientation for many of these complexes are in very good agreement with results of ab initio calculations. Different types of oxygen-hydrogen complexes in GaAs and GaP are described, with one hydrogen atom or two hydrogen atoms bonded to oxygen. Three of these complexes in GaAs were found to be electrically active.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Yiming; Fredrickson, Daniel C.

Intermetallic crystal structures offer an enormous structural diversity, with an endless array of structural motifs whose connection to stability and physical properties are often mysterious. Making sense of the often complex crystal structures that arise here, developing a clear structural description, and identifying connections to other phases can be laborious and require an encyclopedic knowledge of structure types. In this Article, we present PRINCEPS, an algorithm based on a new coordination environment projection scheme that facilitates the structural analysis and comparison of such crystal structures. We demonstrate the potential of this approach by applying it to the complex Ce-Ni-Si ternarymore » system, whose 17 binary and 21 ternary phases would present a daunting challenge to one seeking to understand the system by manual inspection (but has nonetheless been well-described through the heroic efforts of previous researchers). With the help of PRINCEPS, most of the ternary phases in this system can be rationalized as intergrowths of simple structural fragments, and grouped into a handful of structural series (with some outliers). Lastly, these results illustrate how the PRINCEPS approach can be used to organize a vast collection of crystal structures into structurally meaningful families, and guide the description of complex atomic arrangements.« less

Synthesis, structures and stabilities of thioanisole-functionalised phosphido-borane complexes of the alkali metals.

PubMed

Izod, Keith; Watson, James M; Clegg, William; Harrington, Ross W

2011-11-28

Treatment of the secondary phosphine {(Me(3)Si)(2)CH}PH(C(6)H(4)-2-SMe) with BH(3)·SMe(2) gives the corresponding phosphine-borane {(Me(3)Si)(2)CH}PH(BH(3))(C(6)H(4)-2-SMe) (9) as a colourless solid. Deprotonation of 9 with n-BuLi, PhCH(2)Na or PhCH(2)K proceeds cleanly to give the corresponding alkali metal complexes [[{(Me(3)Si)(2)CH}P(BH(3))(C(6)H(4)-2-SMe)]ML](n) [ML = Li(THF), n = 2 (10); ML = Na(tmeda), n = ∞ (11); ML = K(pmdeta), n = 2 (12)] as yellow/orange crystalline solids. X-ray crystallography reveals that the phosphido-borane ligands bind the metal centres through their sulfur and phosphorus atoms and through the hydrogen atoms of the BH(3) group in each case, leading to dimeric or polymeric structures. Compounds 10-12 are stable towards both heat and ambient light; however, on heating in toluene solution in the presence of 10, traces of free phosphine-borane 9 are slowly converted to the free phosphine {(Me(3)Si)(2)CH}PH(C(6)H(4)-2-SMe) (5) with concomitant formation of the corresponding phosphido-bis(borane) complex [{(Me(3)Si)(2)CH}P(BH(3))(2)(C(6)H(4)-2-SMe)]Li (14).

A Monte Carlo modeling on charging effect for structures with arbitrary geometries

NASA Astrophysics Data System (ADS)

Li, C.; Mao, S. F.; Zou, Y. B.; Li, Yong Gang; Zhang, P.; Li, H. M.; Ding, Z. J.

2018-04-01

Insulating materials usually suffer charging effects when irradiated by charged particles. In this paper, we present a Monte Carlo study on the charging effect caused by electron beam irradiation for sample structures with any complex geometry. When transporting in an insulating solid, electrons encounter elastic and inelastic scattering events; the Mott cross section and a Lorentz-type dielectric function are respectively employed to describe such scatterings. In addition, the band gap and the electron–long optical phonon interaction are taken into account. The electronic excitation in inelastic scattering causes generation of electron–hole pairs; these negative and positive charges establish an inner electric field, which in turn induces the drift of charges to be trapped by impurities, defects, vacancies etc in the solid, where the distributions of trapping sites are assumed to have uniform density. Under charging conditions, the inner electric field distorts electron trajectories, and the surface electric potential dynamically alters secondary electron emission. We present, in this work, an iterative modeling method for a self-consistent calculation of electric potential; the method has advantages in treating any structure with arbitrary complex geometry, in comparison with the image charge method—which is limited to a quite simple boundary geometry. Our modeling is based on: the combination of the finite triangle mesh method for an arbitrary geometry construction; a self-consistent method for the spatial potential calculation; and a full dynamic description for the motion of deposited charges. Example calculations have been done to simulate secondary electron yield of SiO2 for a semi-infinite solid, the charging for a heterostructure of SiO2 film grown on an Au substrate, and SEM imaging of a SiO2 line structure with rough surfaces and SiO2 nanoparticles with irregular shapes. The simulations have explored interesting interlaced charge layer distribution underneath the nanoparticle surface and the mechanism by which it is produced.

Capillary electrophoresis method to determine siRNA complexation with cationic liposomes.

PubMed

Furst, Tania; Bettonville, Virginie; Farcas, Elena; Frere, Antoine; Lechanteur, Anna; Evrard, Brigitte; Fillet, Marianne; Piel, Géraldine; Servais, Anne-Catherine

2016-10-01

Small interfering RNA (siRNA) inducing gene silencing has great potential to treat many human diseases. To ensure effective siRNA delivery, it must be complexed with an appropriate vector, generally nanoparticles. The nanoparticulate complex requires an optimal physiochemical characterization and the complexation efficiency has to be precisely determined. The methods usually used to measure complexation in gel electrophoresis and RiboGreen ® fluorescence-based assay. However, those approaches are not automated and present some drawbacks such as the low throughput and the use of carcinogenic reagents. The aim of this study is to develop a new simple and fast method to accurately quantify the complexation efficiency. In this study, capillary electrophoresis (CE) was used to determine the siRNA complexation with cationic liposomes. The short-end injection mode applied enabled siRNA detection in less than 5 min. Moreover, the CE technique offers many advantages compared with the other classical methods. It is automated, does not require sample preparation and expensive reagents. Moreover, no mutagenic risk is associated with the CE approach since no carcinogenic product is used. Finally, this methodology can also be extended for the characterization of other types of nanoparticles encapsulating siRNA, such as cationic polymeric nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot spots based gold nanostar@SiO2@CdSe/ZnS quantum dots complex with strong fluorescence enhancement

NASA Astrophysics Data System (ADS)

Shan, Feng; Su, Dan; Li, Wei; Hu, Wei; Zhang, Tong

2018-02-01

In this paper, a novel gold nanostar (NS)@SiO2@CdSe/ZnS quantum dots (QDs) complex with plasmon-enhanced fluorescence synthesized using a step-by-step surface linkage method was presented. The gold NS was synthesized by the seed growth method. The synthesized gold NS with the apexes structure has a hot-spot effect due to the strong electric field distributed at its sharp apexes, which leads to a plasmon resonance enhancement. Because the distance between QDs and metal nanostructures can be precisely controlled by this method, the relationship between enhancement and distance was revealed. The thickness of SiO2 shell was also optimized and the optimum distance of about 21 nm was obtained. The highest fluorescence enhancement of 4.8-fold accompanied by a minimum fluorescence lifetime of 2.3 ns were achieved. This strong enhancement comes from the hot spots distributed at the sharp tip of our constructed nanostructure. Through the finite element method, we calculated the field distribution on the surface of NS and found that gold NS with the sharpest apexes exhibited the highest field enhancement, which matches well with our experiment result. This complex shows tremendous potential applications for liquid-dependent biometric imaging systems.

Structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 phases from first-principles calculations

NASA Astrophysics Data System (ADS)

Li, X. D.; Li, K.; Wei, C. H.; Han, W. D.; Zhou, N. G.

2018-06-01

The structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 are systematically investigated by using first-principles calculations method based on density functional theory (DFT). The calculated formation enthalpies and cohesive energies show that CaSi2 possesses the greatest structural stability and CaSi has the strongest alloying ability. The structural stability of the three phases is compared according to electronic structures. Further analysis on electronic structures indicates that the bonding of these phases exhibits the combinations of metallic, covalent, and ionic bonds. The elastic constants are calculated, and the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and anisotropy factor of polycrystalline materials are deduced. Additionally, the thermodynamic properties were theoretically predicted and discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, K.M.; Al-Jassim, M.M.; Williamson, D.L.

Over the last two decades extensive studies on the optical and electrical properties of hydrogenated amorphous Si (a-Si:H) have been reported. However, less attention was given to the structural characterization of this material partly due to the insensitivity to hydrogen of structural probes such as x-rays and electron diffraction. From a recent set of experiments, results on the solubility limit of hydrogen in a special type of a-Si:H and the characterization of hydrogen induced complexes or nanobubbles has been reported. In this study, we report TEM observations of the structural morphology of hydrogen related defects that support these recent measurementsmore » obtained by secondary ion mass spectrometry (SIMS) and small-angle x-ray scattering (SAXS).« less

Amylose-Based Cationic Star Polymers for siRNA Delivery

PubMed Central

Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials. PMID:26539548

Continuum simulation of heat transfer and solidification behavior of AlSi10Mg in Direct Metal Laser Sintering Process

NASA Astrophysics Data System (ADS)

Ojha, Akash; Samantaray, Mihir; Nath Thatoi, Dhirendra; Sahoo, Seshadev

2018-03-01

Direct Metal Laser Sintering (DMLS) process is a laser based additive manufacturing process, which built complex structures from powder materials. Using high intensity laser beam, the process melts and fuse the powder particles makes dense structures. In this process, the laser beam in terms of heat flux strikes the powder bed and instantaneously melts and joins the powder particles. The partial solidification and temperature distribution on the powder bed endows a high cooling rate and rapid solidification which affects the microstructure of the build part. During the interaction of the laser beam with the powder bed, multiple modes of heat transfer takes place in this process, that make the process very complex. In the present research, a comprehensive heat transfer and solidification model of AlSi10Mg in direct metal laser sintering process has been developed on ANSYS 17.1.0 platform. The model helps to understand the flow phenomena, temperature distribution and densification mechanism on the powder bed. The numerical model takes into account the flow, heat transfer and solidification phenomena. Simulations were carried out for sintering of AlSi10Mg powders in the powder bed having dimension 3 mm × 1 mm × 0.08 mm. The solidification phenomena are incorporated by using enthalpy-porosity approach. The simulation results give the fundamental understanding of the densification of powder particles in DMLS process.

Adsorption of bovine serum albumin on silicon dioxide nanoparticles: Impact of pH on nanoparticle-protein interactions.

PubMed

Givens, Brittany E; Diklich, Nina D; Fiegel, Jennifer; Grassian, Vicki H

2017-05-03

Bovine serum albumin (BSA) adsorbed on amorphous silicon dioxide (SiO 2 ) nanoparticles was studied as a function of pH across the range of 2 to 8. Aggregation, surface charge, surface coverage, and protein structure were investigated over this entire pH range. SiO 2 nanoparticle aggregation is found to depend upon pH and differs in the presence of adsorbed BSA. For SiO 2 nanoparticles truncated with hydroxyl groups, the largest aggregates were observed at pH 3, close to the isoelectric point of SiO 2 nanoparticles, whereas for SiO 2 nanoparticles with adsorbed BSA, the aggregate size was the greatest at pH 3.7, close to the isoelectric point of the BSA-SiO 2 complex. Surface coverage of BSA was also the greatest at the isoelectric point of the BSA-SiO 2 complex with a value of ca. 3 ±   1 × 10 11 molecules cm -2 . Furthermore, the secondary protein structure was modified when compared to the solution phase at all pH values, but the most significant differences were seen at pH 7.4 and below. It is concluded that protein-nanoparticle interactions vary with solution pH, which may have implications for nanoparticles in different biological fluids (e.g., blood, stomach, and lungs).

A structural and electronic comparison of armchair and zigzag epitaxial graphene sidewall nanoribbons

NASA Astrophysics Data System (ADS)

Nevius, Meredith; Wang, F.; Palacio, I.; Celis, A.; Tejeda, A.; Taleb-Ibrahimi, A.; de Heer, W.; Berger, C.; Conrad, E.

2014-03-01

Graphene grown on sidewalls of trenches etched in SiC shows particular promise as a candidate for post-Si CMOS electronics because of its ballistic transport, exceptional mobilities, low intrinsic doping, and the opening of a large band gap. However, before definitive progress can be made toward epitaxial graphene-based transistors, we must fully understand the nuances of graphene ribbon growth on different SiC facets. We have now confirmed that sidewall ribbons grown in graphene's two primary crystallographic directions (``armchair'' and ``zigzag'') differ greatly in both structure and electronic band-structure. We present data from both geometries obtained using low-energy electron microscopy (LEEM), low-energy electron diffraction (LEED), angle-resolved photoemission spectroscopy (ARPES), photoemission electron microscopy (PEEM), micro-ARPES and dark-field micro-ARPES. We demonstrate that while graphene grows on stable facets of trenches oriented for armchair edge growth, trenches oriented for zigzag edge growth prefer narrow ribbons of graphene on the (0001) surface near the trench edge. The structure of these zigzag edge graphene ribbons is complex and paramount to understanding their transport. This work was supported by the NSF under grants DMR-1005880 and DMR-0820382, the W. M. Keck Foundation and the Partner University Fund from the Embassy of France

In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

PubMed

Lee, Sang Yun; Ko, Young Soo

2018-02-01

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Silicon as a potential anode material for Li-ion batteries: where size, geometry and structure matter.

PubMed

Ashuri, Maziar; He, Qianran; Shaw, Leon L

2016-01-07

Silicon has attracted huge attention in the last decade because it has a theoretical capacity ∼10 times that of graphite. However, the practical application of Si is hindered by three major challenges: large volume expansion during cycling (∼300%), low electrical conductivity, and instability of the SEI layer caused by repeated volume changes of the Si material. Significant research efforts have been devoted to addressing these challenges, and significant breakthroughs have been made particularly in the last two years (2014 and 2015). In this review, we have focused on the principles of Si material design, novel synthesis methods to achieve such structural designs, and the synthesis-structure-performance relationships to enhance the properties of Si anodes. To provide a systematic overview of the Si material design strategies, we have grouped the design strategies into several categories: (i) particle-based structures (containing nanoparticles, solid core-shell structures, hollow core-shell structures, and yolk-shell structures), (ii) porous Si designs, (iii) nanowires, nanotubes and nanofibers, (iv) Si-based composites, and (v) unusual designs. Finally, our personal perspectives on outlook are offered with an aim to stimulate further discussion and ideas on the rational design of durable and high performance Si anodes for the next generation Li-ion batteries in the near future.

About complex refractive index of black Si

NASA Astrophysics Data System (ADS)

Pinčík, Emil; Brunner, Robert; Kobayashi, Hikaru; Mikula, Milan

2017-12-01

The paper deals with the complex refractive index in the IR light region of two types of samples (i) as prepared black silicon, and (ii) thermally oxidized black silicon (BSi) nano-crystalline specimens produced both by the surface structure chemical transfer method using catalytic Ag evaporated spots (as prepared sample) and by the catalytic Pt catalytic mesh (thermally oxidized sample). We present, compare, and discuss the values of the IR complex refractive index obtained by calculation using the Kramers-Krönig transformation. Results indicate that small differences between optical properties of as prepared black Si and thermally oxidized BSi are given by: (i) - oxidation procedure, (ii) - thickness of the formed black Si layer, mainly, not by utilization of different catalytic metals, and by iii) the different thickness. Contamination of the surface by different catalytic metals contributes almost equally to the calculated values of the corresponding complex refractive index.

Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries.

PubMed

Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin

2016-03-02

In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat.

Dielectric response of crystalline tris(acetylacetonato)cobalt(III) films grown on Si substrate for low- k dielectric applications

NASA Astrophysics Data System (ADS)

Dakhel, A. A.; Ali-Mohamed, A. Y.

2008-01-01

Thin films of the complex tris(acetylacetonato)cobalt(III) [abb. Co(acac) 3] were deposited in vacuum on glass and p-Si substrates for optical and dielectric studies. The samples were characterised by X-ray diffraction and fluorescence methods as well as optical absorption spectroscopy. The prepared films show a polycrystalline of monoclinic P2 1/ c structure. The optical absorption spectrum of the prepared film was not exactly fit to that of the molecular one. The energy of the optical absorption onset of the Co(acac) 3 film was calculated by using usual solid-state methods. For electrical measurements on the complex as insulator, samples in the form of metal-insulator-semiconductor (MIS) structure were prepared and characterised by measurement of the capacitance as a function of gate voltage at 1 MHz. The frequency dependence of the complex dielectric constant of the complex was studied in the frequency range (1-1000 kHz) in the temperature range (294-323 K). The experimental results were analysed in the framework of Debye single relaxation model. Generally, the present study shows that a film of complex Co(acac) 3 grown on Si substrate is a promising candidate for low- k dielectric applications, it displays low- k value around 1.7 at high frequencies.

Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to-allene rearrangement, and the electronic transition relevant to the back-bonding interaction.

PubMed

Pinkas, Jiří; Gyepes, Róbert; Císařová, Ivana; Kubišta, Jiří; Horáček, Michal; Mach, Karel

2015-04-28

The titanocene-ethene complex [Ti(II)(η(2)-C2H4)(η(5)-C5Me5)2] (1) with simple internal alkynes R(1)C≡CR(2) gives complexes [Ti(II)(η(2)-R(1)C≡CR(2))(η(5)-C5Me5)2] {R(1), R(2): Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R(1) = Me and R(2) = t-Bu or i-Pr afford allene complexes [Ti(II)(η(2)-CH2=C=CHR(2))(η(5)-C5Me5)2] (11) and (12), whereas for R(2) = Et a mixture of alkyne complex (13A) and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC≡CSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R(1), R(2): Me), not obtainable from 1, together with compounds 3–6 and 10 (R(1), R(2): Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3–9 display the longest-wavelength electronic absorption band in the range 670-940 nm due to the HOMO → LUMO transition. The assignment of the first excitation to be of predominantly a b2 → a1 transition was confirmed by DFT calculations. The calculated first excitation energies for 3–9 followed the order of hypsochromic shifts of the absorption band relative to 8 that were induced by acetylene substituents: Me > Ph ≫ SiMe3. Computational results have also affirmed the back-bonding nature in the alkyne-to-metal coordination.

Ab initio study of point defects near stacking faults in 3C-SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xi, Jianqi; Liu, Bin; Zhang, Yanwen

Interactions between point defects and stacking faults in 3C-SiC are studied using an ab initio method based on density functional theory. The results show that the discontinuity of the stacking sequence considerably affects the configurations and behavior of intrinsic defects, especially in the case of silicon interstitials. The existence of an intrinsic stacking fault (missing a C-Si bilayer) shortens the distance between the tetrahedral-center site and its second-nearest-neighboring silicon layer, making the tetrahedral silicon interstitial unstable. Instead of a tetrahedral configuration with four C neighbors, a pyramid-like interstitial structure with a defect state within the band gap becomes a stablemore » configuration. In addition, orientation rotation occurs in the split interstitials that has diverse effects on the energy landscape of silicon and carbon split interstitials in the stacking fault region. Moreover, our analyses of ionic relaxation and electronic structure of vacancies show that the built-in strain field, owing to the existence of the stacking fault, makes the local environment around vacancies more complex than that in the bulk.« less

Ab initio study of point defects near stacking faults in 3C-SiC

DOE PAGES

Xi, Jianqi; Liu, Bin; Zhang, Yanwen; ...

2016-07-02

Interactions between point defects and stacking faults in 3C-SiC are studied using an ab initio method based on density functional theory. The results show that the discontinuity of the stacking sequence considerably affects the configurations and behavior of intrinsic defects, especially in the case of silicon interstitials. The existence of an intrinsic stacking fault (missing a C-Si bilayer) shortens the distance between the tetrahedral-center site and its second-nearest-neighboring silicon layer, making the tetrahedral silicon interstitial unstable. Instead of a tetrahedral configuration with four C neighbors, a pyramid-like interstitial structure with a defect state within the band gap becomes a stablemore » configuration. In addition, orientation rotation occurs in the split interstitials that has diverse effects on the energy landscape of silicon and carbon split interstitials in the stacking fault region. Moreover, our analyses of ionic relaxation and electronic structure of vacancies show that the built-in strain field, owing to the existence of the stacking fault, makes the local environment around vacancies more complex than that in the bulk.« less

Recent Advances on Luminescent Enhancement-Based Porous Silicon Biosensors.

PubMed

Jenie, S N Aisyiyah; Plush, Sally E; Voelcker, Nicolas H

2016-10-01

Luminescence-based detection paradigms have key advantages over other optical platforms such as absorbance, reflectance or interferometric based detection. However, autofluorescence, low quantum yield and lack of photostability of the fluorophore or emitting molecule are still performance-limiting factors. Recent research has shown the need for enhanced luminescence-based detection to overcome these drawbacks while at the same time improving the sensitivity, selectivity and reducing the detection limits of optical sensors and biosensors. Nanostructures have been reported to significantly improve the spectral properties of the emitting molecules. These structures offer unique electrical, optic and magnetic properties which may be used to tailor the surrounding electrical field of the emitter. Here, the main principles behind luminescence and luminescence enhancement-based detections are reviewed, with an emphasis on europium complexes as the emitting molecule. An overview of the optical porous silicon microcavity (pSiMC) as a biosensing platform and recent proof-of-concept examples on enhanced luminescence-based detection using pSiMCs are provided and discussed.

Advances in SiC/SiC Composites for Aero-Propulsion

NASA Technical Reports Server (NTRS)

DiCarlo, James A.

2013-01-01

In the last decade, considerable progress has been made in the development and application of ceramic matrix composites consisting of silicon carbide (SiC) based matrices reinforced by small-diameter continuous-length SiC-based fibers. For example, these SiC/SiC composites are now in the early stages of implementation into hot-section components of civil aero-propulsion gas turbine engines, where in comparison to current metallic components they offer multiple advantages due to their lighter weight and higher temperature structural capability. For current production-ready SiC/SiC, this temperature capability for long time structural applications is 1250 degC, which is better than 1100 degC for the best metallic superalloys. Foreseeing that even higher structural reliability and temperature capability would continue to increase the advantages of SiC/SiC composites, progress in recent years has also been made at NASA toward improving the properties of SiC/SiC composites by optimizing the various constituent materials and geometries within composite microstructures. The primary objective of this chapter is to detail this latter progress, both fundamentally and practically, with particular emphasis on recent advancements in the materials and processes for the fiber, fiber coating, fiber architecture, and matrix, and in the design methods for incorporating these constituents into SiC/SiC microstructures with improved thermo-structural performance.

Lifetimes of the Vibrational States of DNA Molecules in Functionalized Complexes of Semiconductor Quantum Dots

NASA Astrophysics Data System (ADS)

Bayramov, F. B.; Poloskin, E. D.; Chernev, A. L.; Toporov, V. V.; Dubina, M. V.; Sprung, C.; Lipsanen, H. K.; Bairamov, B. Kh.

2018-01-01

Results of studying nanocrystalline nc-Si/SiO2 quantum dots (QDs) functionalized by short oligonucleotides show that complexes of isolated crystalline semiconductor QDs are unique objects for detecting the manifestation of new quantum confinement phenomena. It is established that narrow lines observed in high-resolution spectra of inelastic light scattering can be used for determining the characteristic time scale of vibrational excitations of separate nucleotide molecules and for studying structural-dynamic properties of fast oscillatory processes in biomacromolecules.

Production of three-dimensional quantum dot lattice of Ge/Si core-shell quantum dots and Si/Ge layers in an alumina glass matrix.

PubMed

Buljan, M; Radić, N; Sancho-Paramon, J; Janicki, V; Grenzer, J; Bogdanović-Radović, I; Siketić, Z; Ivanda, M; Utrobičić, A; Hübner, R; Weidauer, R; Valeš, V; Endres, J; Car, T; Jerčinović, M; Roško, J; Bernstorff, S; Holy, V

2015-02-13

We report on the formation of Ge/Si quantum dots with core/shell structure that are arranged in a three-dimensional body centered tetragonal quantum dot lattice in an amorphous alumina matrix. The material is prepared by magnetron sputtering deposition of Al2O3/Ge/Si multilayer. The inversion of Ge and Si in the deposition sequence results in the formation of thin Si/Ge layers instead of the dots. Both materials show an atomically sharp interface between the Ge and Si parts of the dots and layers. They have an amorphous internal structure that can be crystallized by an annealing treatment. The light absorption properties of these complex materials are significantly different compared to films that form quantum dot lattices of the pure Ge, Si or a solid solution of GeSi. They show a strong narrow absorption peak that characterizes a type II confinement in accordance with theoretical predictions. The prepared materials are promising for application in quantum dot solar cells.

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

NASA Astrophysics Data System (ADS)

Łuczak, Teresa; Pankiewicz, Radosław; Łęska, Bogusława; Schroeder, Grzegorz; Bełtowska-Brzezinska, Maria; Brzezinski, Bogumil

2006-12-01

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li + cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.

Synthesis, spectroscopic properties, molecular docking, anti-colon cancer and anti-microbial studies of some novel metal complexes for 2-amino-4-phenylthiazole derivative

NASA Astrophysics Data System (ADS)

Al-Harbi, Sami A.; Bashandy, Mahmoud S.; Al-Saidi, Hammed M.; Emara, Adel A. A.; Mousa, Tarek A. A.

2015-06-01

This article describes the synthesis of novel bidentate Schiff base (H2L) from condensation of 2-amino-4-phenylthiazole (APT) with 4,6-diacetylresorcinol (DAR) in the molar ratio 2:1. We studied interaction of ligand (H2L) with transition metal ions such as Cr(III), Fe(III), Cu(II), Zn(II) and Cd(II). The ligand (H2L) has two bidentate sets of (N-O) units which can coordinate with two metal ions to afford novel binuclear metal complexes. The directions of coordinate bonds are from nitrogen atoms of azomethine groups and oxygen atoms of the phenolic groups. Structures of the newly synthesized complexes were confirmed by elemental analysis, IR, UV, 1H NMR, ESR, TGA and mass spectral data. All of the newly synthesized complexes were evaluated for their antibacterial and anti-fungal activities. They were also evaluated for their in vitro anticancer activity against human colon carcinoma cells (HCT-116) and mammalian cells of African green monkey kidney (VERO). The Cu(II) complex with selectivity index (S.I.) = 21.26 exhibited better activity than methotrexate (MTX) as a reference drug with S.I. value = 13.30, while Zn(II) complex with S.I. value = 10.24 was found to be nearly as active as MTX. Molecular docking studies further helped in understanding the mode of action of the compounds through their various interactions with active sites of dihydrofolate reductase (DHFR) enzyme. The observed activity of Fe(III) and Cu(II) complexes gave rise to the conclusion that they might exert their action through inhibition of the DHFR enzyme.

Synthesis, spectroscopic properties, molecular docking, anti-colon cancer and anti-microbial studies of some novel metal complexes for 2-amino-4-phenylthiazole derivative.

PubMed

Al-Harbi, Sami A; Bashandy, Mahmoud S; Al-Saidi, Hammed M; Emara, Adel A A; Mousa, Tarek A A

2015-06-15

This article describes the synthesis of novel bidentate Schiff base (H2L) from condensation of 2-amino-4-phenylthiazole (APT) with 4,6-diacetylresorcinol (DAR) in the molar ratio 2:1. We studied interaction of ligand (H2L) with transition metal ions such as Cr(III), Fe(III), Cu(II), Zn(II) and Cd(II). The ligand (H2L) has two bidentate sets of (N-O) units which can coordinate with two metal ions to afford novel binuclear metal complexes. The directions of coordinate bonds are from nitrogen atoms of azomethine groups and oxygen atoms of the phenolic groups. Structures of the newly synthesized complexes were confirmed by elemental analysis, IR, UV, (1)H NMR, ESR, TGA and mass spectral data. All of the newly synthesized complexes were evaluated for their antibacterial and anti-fungal activities. They were also evaluated for their in vitro anticancer activity against human colon carcinoma cells (HCT-116) and mammalian cells of African green monkey kidney (VERO). The Cu(II) complex with selectivity index (S.I.)=21.26 exhibited better activity than methotrexate (MTX) as a reference drug with S.I. value=13.30, while Zn(II) complex with S.I. value=10.24 was found to be nearly as active as MTX. Molecular docking studies further helped in understanding the mode of action of the compounds through their various interactions with active sites of dihydrofolate reductase (DHFR) enzyme. The observed activity of Fe(III) and Cu(II) complexes gave rise to the conclusion that they might exert their action through inhibition of the DHFR enzyme. Copyright © 2015 Elsevier B.V. All rights reserved.

Advances in stable isotope assisted labeling strategies with information science.

PubMed

Kigawa, Takanori

2017-08-15

Stable-isotope (SI) labeling of proteins is an essential technique to investigate their structures, interactions or dynamics by nuclear magnetic resonance (NMR) spectroscopy. The assignment of the main-chain signals, which is the fundamental first step in these analyses, is usually achieved by a sequential assignment method based on triple resonance experiments. Independently of the triple resonance experiment-based sequential assignment, amino acid-selective SI labeling is beneficial for discriminating the amino acid type of each signal; therefore, it is especially useful for the signal assignment of difficult targets. Various combinatorial selective labeling schemes have been developed as more sophisticated labeling strategies. In these strategies, amino acids are represented by combinations of SI labeled samples, rather than simply assigning one amino acid to one SI labeled sample as in the case of conventional amino acid-selective labeling. These strategies have proven to be useful for NMR analyses of difficult proteins, such as those in large complex systems, in living cells, attached or integrated into membranes, or with poor solubility. In this review, recent advances in stable isotope assisted labeling strategies will be discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

Simulation and experimental study of a novel bifacial structure of silicon heterojunction solar cell for high efficiency and low cost

NASA Astrophysics Data System (ADS)

Huang, Haibin; Tian, Gangyu; Zhou, Lang; Yuan, Jiren; Fahrner, Wolfgang R.; Zhang, Wenbin; Li, Xingbing; Chen, Wenhao; Liu, Renzhong

2018-03-01

A novel structure of Ag grid/SiN x /n+-c-Si/n-c-Si/i-a-Si:H/p+-a-Si:H/TCO/Ag grid was designed to increase the efficiency of bifacial amorphous/crystalline silicon-based solar cells and reduce the rear material consumption and production cost. The simulation results show that the new structure obtains higher efficiency compared with the typical bifacial amorphous/crystalline silicon-based solar cell because of an increase in the short-circuit current (J sc), while retaining the advantages of a high open-circuit voltage, low temperature coefficient, and good weak-light performance. Moreover, real cells composed of the novel structure with dimensions of 75 mm ×75 mm were fabricated by a special fabrication recipe based on industrial processes. Without parameter optimization, the cell efficiency reached 21.1% with the J sc of 41.7 mA/cm2. In addition, the novel structure attained 28.55% potential conversion efficiency under an illumination of AM 1.5 G, 100 mW/cm2. We conclude that the configuration of the Ag grid/SiN x /n+-c-Si/n-c-Si/i-a-Si:H/p+-a-Si:H/TCO/Ag grid is a promising structure for high efficiency and low cost. Project supported by the Jiangxi Provincial Key Research and Development Foundation, China (Grant No. 2016BBH80043), the Open Fund of Jiangsu Key Laboratory of Materials and Technology for Energy Conversion, China (Grant No. NJ20160032), and the National Natural Science Foundation of China (Grant Nos. 61741404, 61464007, and 51561022).

Impact of target mRNA structure on siRNA silencing efficiency: A large-scale study.

PubMed

Gredell, Joseph A; Berger, Angela K; Walton, S Patrick

2008-07-01

The selection of active siRNAs is generally based on identifying siRNAs with certain sequence and structural properties. However, the efficiency of RNA interference has also been shown to depend on the structure of the target mRNA, primarily through studies using exogenous transcripts with well-defined secondary structures in the vicinity of the target sequence. While these studies provide a means for examining the impact of target sequence and structure independently, the predicted secondary structures for these transcripts are often not reflective of structures that form in full-length, native mRNAs where interactions can occur between relatively remote segments of the mRNAs. Here, using a combination of experimental results and analysis of a large dataset, we demonstrate that the accessibility of certain local target structures on the mRNA is an important determinant in the gene silencing ability of siRNAs. siRNAs targeting the enhanced green fluorescent protein were chosen using a minimal siRNA selection algorithm followed by classification based on the predicted minimum free energy structures of the target transcripts. Transfection into HeLa and HepG2 cells revealed that siRNAs targeting regions of the mRNA predicted to have unpaired 5'- and 3'-ends resulted in greater gene silencing than regions predicted to have other types of secondary structure. These results were confirmed by analysis of gene silencing data from previously published siRNAs, which showed that mRNA target regions unpaired at either the 5'-end or 3'-end were silenced, on average, approximately 10% more strongly than target regions unpaired in the center or primarily paired throughout. We found this effect to be independent of the structure of the siRNA guide strand. Taken together, these results suggest minimal requirements for nucleation of hybridization between the siRNA guide strand and mRNA and that both mRNA and guide strand structure should be considered when choosing candidate siRNAs. (c) 2008 Wiley Periodicals, Inc.

Impact of target mRNA structure on siRNA silencing efficiency: a large-scale study

PubMed Central

Gredell, Joseph A.; Berger, Angela K.; Walton, S. Patrick

2009-01-01

The selection of active siRNAs is generally based on identifying siRNAs with certain sequence and structural properties. However, the efficiency of RNA interference has also been shown to depend on the structure of the target mRNA, primarily through studies using exogenous transcripts with well-defined secondary structures in the vicinity of the target sequence. While these studies provide a means for examining the impact of target sequence and structure independently, the predicted secondary structures for these transcripts are often not reflective of structures that form in full-length, native mRNAs where interactions can occur between relatively remote segments of the mRNAs. Here, using a combination of experimental results and analysis of a large dataset, we demonstrate that the accessibility of certain local target structures on the mRNA is an important determinant in the gene silencing ability of siRNAs. siRNAs targeting the enhanced green fluorescent protein were chosen using a minimal siRNA selection algorithm followed by classification based on the predicted minimum free energy structures of the target transcripts. Transfection into HeLa and HepG2 cells revealed that siRNAs targeting regions of the mRNA predicted to have unpaired 5’- and 3’-ends resulted in greater gene silencing than regions predicted to have other types of secondary structure. These results were confirmed by analysis of gene silencing data from previously published siRNAs, which showed that mRNA target regions unpaired at either the 5’-end or 3’-end were silenced, on average, ~10% more strongly than target regions unpaired in the center or primarily paired throughout. We found this effect to be independent of the structure of the siRNA guide strand. Taken together, these results suggest minimal requirements for nucleation of hybridization between the siRNA guide strand and mRNA and that both mRNA and guide strand structure should be considered when choosing candidate siRNAs. PMID:18306428

Glycogen-nucleic acid constructs for gene silencing in multicellular tumor spheroids.

PubMed

Wojnilowicz, Marcin; Besford, Quinn A; Wu, Yun-Long; Loh, Xian Jun; Braunger, Julia A; Glab, Agata; Cortez-Jugo, Christina; Caruso, Frank; Cavalieri, Francesca

2018-05-20

The poor penetration of nanocarrier-siRNA constructs into tumor tissue is a major hurdle for the in vivo efficacy of siRNA therapeutics, where the ability of the constructs to permeate the 3D multicellular matrix is determined by their physicochemical properties. Herein, we optimized the use of soft glycogen nanoparticles for the engineering of glycogen-siRNA constructs that can efficiently penetrate multicellular tumor spheroids and exert a significant gene silencing effect. Glycogen nanoparticles from different bio-sources and with different structural features were investigated. We show that larger glycogen nanoparticles ranging from 50 to 80 nm are suboptimal systems for complexation of nucleic acids if fine control of the size of constructs is required. Our studies suggest that 20 nm glycogen nanoparticles are optimal for complexation and efficient delivery of siRNA. The chemical composition, surface charge, and size of glycogen-siRNA constructs were finely controlled to minimize interactions with serum proteins and allow penetration into 3D multicellular spheroids of human kidney epithelial cells and human prostate cancer cells. We introduced pH sensitive moieties within the construct to enhance early endosome escape and efficiently improve the silencing effect in vitro. Glycogen-siRNA constructs were found to mediate gene silencing in 3D multicellular spheroids causing ∼60% specific gene silencing. The optimized construct exhibited an in vivo circulation lifetime of 8 h in mice, with preferential accumulation in the liver. No accumulation in the kidney, lung, spleen, heart or brain, or signs of toxicity in mice were observed. Our results highlight the potential for screening siRNA nanocarriers in 3D cultured prostate tumor models, thereby improving the predictive therapeutic efficacy of glycogen-based platforms in human physiological conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pressure-controlled terahertz filter based on 1D photonic crystal with a defective semiconductor

NASA Astrophysics Data System (ADS)

Qinwen, XUE; Xiaohua, WANG; Chenglin, LIU; Youwen, LIU

2018-03-01

The tunable terahertz (THz) filter has been designed and studied, which is composed of 1D photonic crystal (PC) containing a defect layer of semiconductor GaAs. The analytical solution of 1D defective PC (1DDPC) is deduced based on the transfer matrix method, and the electromagnetic plane wave numerical simulation of this 1DDPC is performed by using the finite element method. The calculated and simulated results have confirmed that the filtering transmittance of this 1DDPC in symmetric structure of air/(Si/SiO2) N /GaAs/(SiO2/Si) N /air is far higher than in asymmetric structure of air/(Si/SiO2) N /GaAs/(Si/SiO2) N /air, where the filtering frequency can be tuned by the external pressure. It can provide a feasible route to design the external pressure-controlled THz filter based on 1DPC with a defective semiconductor.

Uniform Si nano-dot fabrication using reconstructed structure of Si(110)

NASA Astrophysics Data System (ADS)

Yano, Masahiro; Uozumi, Yuki; Yasuda, Satoshi; Asaoka, Hidehito

2018-06-01

Si nano-dot (ND) formation on Si(110) is observed by means of a scanning tunneling microscope (STM). The initial Si-NDs are Si crystals that are continuous from the substrate and grow during the oxide layer desorption. The NDs fabricated on the flat surface of Si(110)-1 × 1 are surrounded by four types of facets with almost identical appearance probabilities. An increase in the size of the NDs increases the variety of its morphology. In contrast, most Si-NDs fabricated on straight-stepped surface of Si(110)-16 × 2 reconstructed structure are surrounded by only a single type of facet, namely the \\text{Si}(17,15,1)-2 × 1 plane. An appearance probability of the facet in which the base line is along the step of Si(110)-16 × 2 exceeds 75%. This finding provides a fabrication technique of uniformed structural Si-NDs by using the reconstructed structure of Si(110).

Impact of distributions on the archetypes and prototypes in heterogeneous nanoparticle ensembles.

PubMed

Fernandez, Michael; Wilson, Hugh F; Barnard, Amanda S

2017-01-05

The magnitude and complexity of the structural and functional data available on nanomaterials requires data analytics, statistical analysis and information technology to drive discovery. We demonstrate that multivariate statistical analysis can recognise the sets of truly significant nanostructures and their most relevant properties in heterogeneous ensembles with different probability distributions. The prototypical and archetypal nanostructures of five virtual ensembles of Si quantum dots (SiQDs) with Boltzmann, frequency, normal, Poisson and random distributions are identified using clustering and archetypal analysis, where we find that their diversity is defined by size and shape, regardless of the type of distribution. At the complex hull of the SiQD ensembles, simple configuration archetypes can efficiently describe a large number of SiQDs, whereas more complex shapes are needed to represent the average ordering of the ensembles. This approach provides a route towards the characterisation of computationally intractable virtual nanomaterial spaces, which can convert big data into smart data, and significantly reduce the workload to simulate experimentally relevant virtual samples.

Design guideline for Si/organic hybrid solar cell with interdigitated back contact structure

NASA Astrophysics Data System (ADS)

Bimo Prakoso, Ari; Rusli; Li, Zeyu; Lu, Chenjin; Jiang, Changyun

2018-03-01

We study the design of Si/organic hybrid (SOH) solar cells with interdigitated back contact (IBC) structure. SOH solar cells formed between n-Si and poly(3,4-ethylenedioxythiophene): polystyrenesulphonate (PEDOT:PSS) is a promising concept that combines the excellent electronic properties of Si with the solution-based processing advantage of an organic polymer. The IBC cell structure is employed to minimize parasitic absorption losses in the organic polymer, eliminate grid shadowing losses, and allow excellent passivation of the front Si surface in one step over a large area. The influence of Si thickness, doping concentration and contact geometry are simulated in this study to optimize the performance of the SOH-IBC solar cell. We found that a high power conversion efficiency of >20% can be achieved for optimized SOH-IBC cell based on a thin c-Si substrate of 40 μm thickness.

The Effect of SiC Polytypes on the Heat Distribution Efficiency of a Phase Change Memory.

NASA Astrophysics Data System (ADS)

Aziz, M. S.; Mohammed, Z.; Alip, R. I.

2018-03-01

The amorphous to crystalline transition of germanium-antimony-tellurium (GST) using three types of silicon carbide’s structure as a heating element was investigated. Simulation was done using COMSOL Multiphysic 5.0 software with separate heater structure. Silicon carbide (SiC) has three types of structure; 3C-SiC, 4H-SiC and 6H-SiC. These structures have a different thermal conductivity. The temperature of GST and phase transition of GST can be obtained from the simulation. The temperature of GST when using 3C-SiC, 4H-SiC and 6H-SiC are 467K, 466K and 460K, respectively. The phase transition of GST from amorphous to crystalline state for three type of SiC’s structure can be determined in this simulation. Based on the result, the thermal conductivity of SiC can affecting the temperature of GST and changed of phase change memory (PCM).

Solving complex band structure problems with the FEAST eigenvalue algorithm

NASA Astrophysics Data System (ADS)

Laux, S. E.

2012-08-01

With straightforward extension, the FEAST eigenvalue algorithm [Polizzi, Phys. Rev. B 79, 115112 (2009)] is capable of solving the generalized eigenvalue problems representing traveling-wave problems—as exemplified by the complex band-structure problem—even though the matrices involved are complex, non-Hermitian, and singular, and hence outside the originally stated range of applicability of the algorithm. The obtained eigenvalues/eigenvectors, however, contain spurious solutions which must be detected and removed. The efficiency and parallel structure of the original algorithm are unaltered. The complex band structures of Si layers of varying thicknesses and InAs nanowires of varying radii are computed as test problems.

Structural and optical modification in 4H-SiC following 30 keV silver ion irradiation

NASA Astrophysics Data System (ADS)

Kaushik, Priya Darshni; Aziz, Anver; Siddiqui, Azher M.; Lakshmi, G. B. V. S.; Syväjärvi, Mikael; Yakimova, Rositsa; Yazdi, G. Reza

2018-05-01

The market of high power, high frequency and high temperature based electronic devices is captured by SiC due to its superior properties like high thermal conductivity and high sublimation temperature and also due to the limitation of silicon based electronics in this area. There is a need to investigate effect of ion irradiation on SiC due to its application in outer space as outer space is surrounded both by low and high energy ion irradiations. In this work, effect of low energy ion irradiation on structural and optical property of 4H-SiC is investigated. ATR-FTIR is used to study structural modification and UV-Visible spectroscopy is used to study optical modifications in 4H-SiC following 30 keV Ag ion irradiation. FTIR showed decrease in bond density of SiC along the ion path (track) due to the creation of point defects. UV-Visible absorption spectra showed decrease in optical band gap from 3.26 eV to 2.9 eV. The study showed degradation of SiC crystallity and change in optical band gap following low energy ion irradiation and should be addressed while fabricationg devices based on SiC for outer space application. Additionally, this study provides a platform for introducing structural and optical modification in 4H-SiC using ion beam technology in a controlled manner.

Monochloro non-bridged half-metallocene-type zirconium complexes containing phosphine oxide-(thio)phenolate chelating ligands as efficient ethylene polymerization catalysts.

PubMed

Tang, Xiao-Yan; Wang, Yong-Xia; Liu, San-Rong; Liu, Jing-Yu; Li, Yue-Sheng

2013-01-14

A series of novel monochloro half-zirconocene complexes containing phosphine oxide-(thio)phenolate chelating ligands of the type, ClCp'Zr[X-2-R(1)-4-R(2)-6-(Ph(2)P=O)C(6)H(2)](2) (Cp' = C(5)H(5), 2a: X = O, R(1) = Ph, R(2) = H; 2b: X = O, R(1) = F, R(2) = H; 2c: X = O, R(1) = (t)Bu, R(2) = H; 2d: X = O, R(1) = R(2) = (t)Bu; 2e: X = O, R(1) = SiMe(3), R(2) = H; 2f: X = S, R(1) = SiMe(3), R(2) = H; Cp' = C(5)Me(5), 2g: X = O, R(1) = SiMe(3), R(2) = H), have been synthesized in high yields. These complexes were identified by (1)H {(13)C} NMR and elemental analyses. Structures for 2b, 2c and 2f were further confirmed by X-ray crystallography. Structural characterization of these complexes reveals crowded environments around the zirconium. Complexes 2b and 2c adopt six-coordinate, distorted octahedral geometry around the zirconium center, in which the equatorial positions are occupied by three oxygen atoms of two chelating phosphine oxide-bridged phenolate ligands and a chlorine atom. The cyclopentadienyl ring and one oxygen atom of the ligand are coordinated on the axial position. Complex 2f also folds a six-coordinate, distorted octahedral geometry around the Zr center, consisting of a Cp-Zr-O (in P=O) axis [177.16°] and a distorted plane of two sulfur atoms and one oxygen atom of two chelating phosphine oxide-bridged thiophenolate ligands as well as a chlorine atom. When activated by modified methylaluminoxane (MMAO), all the complexes exhibited high activities towards ethylene polymerization at high temperature (75 °C), giving high molecular weight polymers with unimodal molecular weight distribution. The formation of 14-electron, cationic metal alkyl species might come from the Zr-O (in phenol ring) bond cleavage based on the DFT calculations study.

A mechanism of charge transport in electroluminescent structures consisting of porous silicon and single-crystal silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evtukh, A. A., E-mail: dept_5@isp.kiev.ua; Kaganovich, E. B.; Manoilov, E. G.

2006-02-15

Electroluminescent structures that emit in the visible region of the spectrum and are based on porous silicon (por-Si) formed on the p-Si substrate electrolytically using an internal current source are fabricated. The photoluminescent and electroluminescent properties, as well as the current-and capacitance-voltage characteristics of the structures are studied. Electroluminescence is observed only if the forward bias voltage is applied to the structure; the electroluminescence mechanism is based on the injection and is related to the radiative recombination of electrons and holes in quantum-dimensional Si nanocrystals. The injection of holes is controlled by the condition of their accumulation in the space-chargemore » region of p-Si and by a comparatively low concentration of electronic states at the por-Si/p-Si interface. The charge transport in por-Si is caused by the direct tunneling of charge carriers between the quantum-mechanical levels, which is ensured by an appreciable number of quantum-dimensional Si nanocrystals. The leakage currents are low as a result of a small variance in the sizes of Si nanocrystals and the absence of comparatively large nanocrystals.« less

Nanocrystalline coating design for extreme applications based on the concept of complex adaptive behavior

NASA Astrophysics Data System (ADS)

Fox-Rabinovich, G. S.; Veldhuis, S. C.; Dosbaeva, G. K.; Yamamoto, K.; Kovalev, A. I.; Wainstein, D. L.; Gershman, I. S.; Shuster, L. S.; Beake, B. D.

2008-04-01

The development of effective hard coatings for high performance dry machining, which is associated with high stress/temperatures during friction, is a major challenge. Newly developed synergistically alloyed nanocrystalline adaptive Ti0.2Al0.55Cr0.2Si0.03Y0.02N plasma vapor deposited hard coatings exhibit excellent tool life under conditions of high performance dry machining of hardened steel, especially under severe and extreme cutting conditions. The coating is capable of sustaining cutting speeds as high as 600 m/min. Comprehensive investigation of the microstructure and properties of the coating was performed. The structure of the coating before and after service has been characterized by high resolution transmission electron microscopy. Micromechanical characteristics of the coating have been investigated at elevated temperatures. Oxidation resistance of the coating has been studied by using thermogravimetry within a temperature range of 25-1100 °C in air. The coefficient of friction of the coatings was studied within a temperature range of 25-1200 °C. To determine the causes of excellent tool life and improved wear behavior of the TiAlCrSiYN coatings, its surface structure characteristics after service have been investigated by using x-ray photoelectron spectroscopy and extended energy-loss fine spectroscopy. One of the major features of this coating is the dynamic formation of the protective tribo-oxide films (dissipative structures) on the surface during friction with a sapphire and mullite crystal structure. Aluminum- and silicon-rich tribofilms with dangling bonds form on the surface as well. These tribofilms act in synergy and protect the surface so efficiently that it is able to sustain extreme operating conditions. Moreover, the Ti0.2Al0.55Cr0.2Si0.03Y0.02N coating possesses some features of a complex adaptive behavior because it has a number of improved characteristics (tribological adaptability, ultrafine nanocrystalline structure, hot hardness and plasticity, and oxidation stability) that work synergistically as a whole. Due to the complex adaptive behavior, this coating represents a higher ordered system that has an ability to achieve unattainable wear resistance under strongly intensifying and extreme tribological conditions.

First-principles calculations of orientation dependence of Si thermal oxidation based on Si emission model

NASA Astrophysics Data System (ADS)

Nagura, Takuya; Kawachi, Shingo; Chokawa, Kenta; Shirakawa, Hiroki; Araidai, Masaaki; Kageshima, Hiroyuki; Endoh, Tetsuo; Shiraishi, Kenji

2018-04-01

It is expected that the off-state leakage current of MOSFETs can be reduced by employing vertical body channel MOSFETs (V-MOSFETs). However, in fabricating these devices, the structure of the Si pillars sometimes cannot be maintained during oxidation, since Si atoms sometimes disappear from the Si/oxide interface (Si missing). Thus, in this study, we used first-principles calculations based on the density functional theory, and investigated the Si emission behavior at the various interfaces on the basis of the Si emission model including its atomistic structure and dependence on Si crystal orientation. The results show that the order in which Si atoms are more likely to be emitted during thermal oxidation is (111) > (110) > (310) > (100). Moreover, the emission of Si atoms is enhanced as the compressive strain increases. Therefore, the emission of Si atoms occurs more easily in V-MOSFETs than in planar MOSFETs. To reduce Si missing in V-MOSFETs, oxidation processes that induce less strain, such as wet or pyrogenic oxidation, are necessary.

Fabrication of the replica templated from butterfly wing scales with complex light trapping structures

NASA Astrophysics Data System (ADS)

Han, Zhiwu; Li, Bo; Mu, Zhengzhi; Yang, Meng; Niu, Shichao; Zhang, Junqiu; Ren, Luquan

2015-11-01

The polydimethylsiloxane (PDMS) positive replica templated twice from the excellent light trapping surface of butterfly Trogonoptera brookiana wing scales was fabricated by a simple and promising route. The exact SiO2 negative replica was fabricated by using a synthesis method combining a sol-gel process and subsequent selective etching. Afterwards, a vacuum-aided process was introduced to make PDMS gel fill into the SiO2 negative replica, and the PDMS gel was solidified in an oven. Then, the SiO2 negative replica was used as secondary template and the structures in its surface was transcribed onto the surface of PDMS. At last, the PDMS positive replica was obtained. After comparing the PDMS positive replica and the original bio-template in terms of morphology, dimensions and reflectance spectra and so on, it is evident that the excellent light trapping structures of butterfly wing scales were inherited by the PDMS positive replica faithfully. This bio-inspired route could facilitate the preparation of complex light trapping nanostructure surfaces without any assistance from other power-wasting and expensive nanofabrication technologies.

Six complexes based on bis(imidazole/benzimidazole-1-yl)pyridazine ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Wang, Xin-Fang; Du, Ceng-Ceng; Zhou, Sheng-Bin; Wang, Duo-Zhi

2017-01-01

Herein we reported six new Ni(II)/Cu(II)/Zn(II) complexes, namely, [Ni(L1)4(OH)2] (1), [Cu(L1)4(OH)2] (2), [Cu(L1)2(SiF6)]n (3), {[Cu(L2)(HCOO)2]·H2O·CH3OH}n (4), [Ni(L2)2(NO3)2]n (5) and {[Zn(L2)Cl2]·DMF}n (6) (L1 = 3,6-bis(imidazole-1-yl)pyridazine, L2 = 3,6-bis(benzimidazole-1-yl)pyridazine), which were characterized by single-crystal X-ray diffraction, elemental analysis, IR, PXRD. These complexes have been successfully constructed under interface diffusion process, heating reflux or hydrothermal conditions. The structures of 1 and 2 are mononuclear complexes. Complex 3 exhibits a 6-connected 3D topology network with the Schläfli symbol of (412·63). In complex 4, two Cu(II) were connected through two HCOO- anions to form dinuclear structure unit, which is arranged into a 1D ladder-like structure by μ2-L2 ligands. Complexes 5 and 6 are 1D zigzag chains connected by L2 ligands, but the Ni(II) ion is six-coordinated in 5 and the Zn(II) ion is four-coordinated in 6. Moreover, the solid-state luminescence property and UV-vis diffuse reflection spectrum of complex 6 have been investigated and discussed.

Impurity-doped Si10 cluster: Understanding the structural and electronic properties from first-principles calculations

NASA Astrophysics Data System (ADS)

Majumder, Chiranjib; Kulshreshtha, S. K.

2004-12-01

Structural and electronic properties of metal-doped silicon clusters ( MSi10 , M=Li , Be, B, C, Na, Mg, Al, and Si) have been investigated via ab initio molecular dynamics simulation under the formalism of the density functional theory. The exchange-correlation energy has been calculated using the generalized gradient approximation method. Several stable isomers of MSi10 clusters have been identified based on different initial configurations and their relative stabilities have been analyzed. From the results it is revealed that the location of the impurity atom depends on the nature of interaction between the impurity atom and the host cluster and the size of the impurty atom. Whereas Be and B atoms form stable isomers, the impurity atom being placed at the center of the bicapped tetragonal antiprism structure of the Si10 cluster, all other elements diffuse outside the cage of Si10 cluster. Further, to understand the stability and the chemical bonding, the LCAO-MO based all electron calculations have been carried out for the lowest energy isomers using the hybrid B3LYP energy functional. Based on the interaction energy of the M atoms with Si10 clusters it is found that p-p interaction dominates over the s-p interaction and smaller size atoms interact more strongly. Based on the binding energy, the relative stability of MSi10 clusters is found to follow the order of CSi10>BSi10>BeSi10>Si11>AlSi10>LiSi10>NaSi10>MgSi10 , leading one to infer that while the substitution of C, B and Be enhances the stability of the Si11 cluster, others have an opposite effect. The extra stability of the BeSi10 clusters is due to its encapsulated close packed structure and large energy gap between the HOMO and LUMO energy levels.

Geometry- and QTAIM-Based Comparison of Intramolecular Charge-Inverted Hydrogen Bonds, M···(H-Si) "Agostic Bond", and M···(η(2)-SiH) σ Interactions.

PubMed

Jabłoński, Mirosław

2015-11-19

Using large sets of systems having an intramolecular charge-inverted hydrogen bond (IMCIHB), M···(Ha-Si) "agostic bond" or M···(η(2)-SiH) σ interaction, we have compared both geometric and QTAIM-based topological parameters characterizing all these three types of interactions. It is shown that IMCIHBs can be distinguished from the other relevant interactions by the significantly less elongated Si-H bond. The other geometric parameters are not characteristic because they accept wide ranges of values in systems having either an M···(Ha-Si) "agostic bond" or M···(η(2)-SiH) σ interaction. If QTAIM-based results are investigated, then it is shown that an IMCIHB can be characterized by the position of the BCPH···M that is closer to the metal atom, whereas, quite the contrary, this BCP has been found to be closer to the agostic hydrogen in complexes having either M···(Ha-Si) or M···(η(2)-SiH) interactions. Another difference is in the curvature of the M···H bond path. If the M···H bond path tracing the M···(H-E) (E = Si, C) interaction is curved, then this curvature appears near the agostic hydrogen-a property particularly pronounced in M···(Ha-C) agostic bonds. Moreover, it has also been shown that an IMCIHB can be characterized by lower curvatures and, in general, lower values of the electron density computed at BCPH···Al than at BCPs of either M···(Ha-Si) or M···(η(2)-SiH) interactions. Importantly, IMCIHBs can be distinguished from the other two types of interactions on the basis of values of delocalization index, which are significantly lower for IMCIHBs. Other QTAIM-based parameters have occurred to be not characteristic for IMCIHBs due to wide ranges of their values obtained for M···(Ha-Si) and M···(η(2)-SiH) interactions. It has also been shown that the PBE0 functional gives the best molecular structure in comparison with experimental data.

High-performance silicon nanowire bipolar phototransistors

NASA Astrophysics Data System (ADS)

Tan, Siew Li; Zhao, Xingyan; Chen, Kaixiang; Crozier, Kenneth B.; Dan, Yaping

2016-07-01

Silicon nanowires (SiNWs) have emerged as sensitive absorbing materials for photodetection at wavelengths ranging from ultraviolet (UV) to the near infrared. Most of the reports on SiNW photodetectors are based on photoconductor, photodiode, or field-effect transistor device structures. These SiNW devices each have their own advantages and trade-offs in optical gain, response time, operating voltage, and dark current noise. Here, we report on the experimental realization of single SiNW bipolar phototransistors on silicon-on-insulator substrates. Our SiNW devices are based on bipolar transistor structures with an optically injected base region and are fabricated using CMOS-compatible processes. The experimentally measured optoelectronic characteristics of the SiNW phototransistors are in good agreement with simulation results. The SiNW phototransistors exhibit significantly enhanced response to UV and visible light, compared with typical Si p-i-n photodiodes. The near infrared responsivities of the SiNW phototransistors are comparable to those of Si avalanche photodiodes but are achieved at much lower operating voltages. Compared with other reported SiNW photodetectors as well as conventional bulk Si photodiodes and phototransistors, the SiNW phototransistors in this work demonstrate the combined advantages of high gain, high photoresponse, low dark current, and low operating voltage.

Phosphine and diphosphine complexes of silicon(IV) halides.

PubMed

Levason, William; Pugh, David; Reid, Gillian

2013-05-06

The reaction of SiX4 (X = Cl or Br) with PMe3 in anhydrous CH2Cl2 forms trans-[SiX4(PMe3)2], while the diphosphines, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2, and o-C6H4(PMe2)2 form cis-[SiX4(diphosphine)], all containing six-coordinate silicon centers. With Me2PCH2PMe2 the product was trans-[SiCl4(κ(1)-Me2PCH2PMe2)2]. The complexes have been characterized by X-ray crystallography, microanalysis, IR, and multinuclear ((1)H, (13)C{(1)H}, and (31)P{(1)H}) NMR spectroscopies. The complexes are stable solids and not significantly dissociated in nondonor solvents, although they are very moisture and oxygen sensitive. This stability conflicts with the predictions of recent density functional theory (DFT) calculations (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) which suggested six-coordinate silicon phosphines would be unstable, and also contrasts with the failure to isolate complexes with SiF4 (George et al. Dalton Trans. 2011, 40, 1584-1593). No reaction occurred between phosphines and SiI4, or with SiX4 and arsine ligands including AsMe3 and o-C6H4(AsMe2)2. Attempts to make five-coordinate [SiX4(PR3)] using the sterically bulky phosphines, P(t)Bu3, P(i)Pr3, or PCy3 failed, with no apparent reaction occurring, consistent with predictions (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) that such compounds would be very endothermic, while the large cone angles of the phosphines presumably preclude formation of six-coordination at the small silicon center. The reaction of Si2Cl6 with PMe3 or the diphosphines in CH2Cl2 results in instant disproportionation to the SiCl4 adducts and polychlorosilanes, but from hexane solution very unstable white [Si2Cl6(PMe3)2] and [Si2Cl6(diphosphine)] (diphosphine = Me2P(CH2)2PMe2 or o-C6H4(PMe2)2) precipitate. The reactions of SiHCl3 with PMe3 and Me2P(CH2)2PMe2 also produce the SiCl4 adducts, but using Et2P(CH2)2PEt2, colorless [SiHCl3{Et2P(CH2)2PEt2}] was isolated, which was characterized by an X-ray structure which showed a pseudo-octahedral complex with the Si-H trans to P. Attempts to reduce the silicon(IV) phosphine complexes to silicon(II) were unsuccessful, contrasting with the isolation of stable N-heterocyclic carbene adducts of Si(II).

Oxidation of ZrB2 SiC TaSi2 Materials at Ultra High Temperatures

NASA Technical Reports Server (NTRS)

Opila, E.; Smith, J.; Levine, S.; Lorincz, J.; Reigel, M.

2008-01-01

ZrB2 - 20v% SiC - 20v% TaSi2 was oxidized in stagnant air for ten minute cycles for times up to 100 minutes at 1627 C and 1927 C. The sample oxidized at 1627 C showed oxidation resistance better than that of the standard ZrB2 - 20v% SiC. The sample oxidized at 1927 C, however, showed evidence of liquid phase formation and complex oxidation products. The sample exposed at 1927 C was analyzed in detail by scanning electron microprobe and wavelength dispersive spectroscopy to understand the complex oxidation and melting reactions occurring during exposure. The as hot-pressed material shows the formation of a Zr(Ta)B2 phase in addition to the three phases in the nominal composition already noted. After oxidation, the TaSi2 in the matrix was completely reacted to form Ta(Zr)C. The layered oxidation products included SiO2, ZrO2, Ta2O5, and a complex oxide containing both Zr and Ta. Likely reactions are proposed based on thermodynamic phase stability and phase morphology.

Structural effects in the interstitial solid solution system (La,Ce)(Fe,Si)13Cx-H: Correlation with hydrogenation kinetics

NASA Astrophysics Data System (ADS)

Hai, X.; Porcher, F.; Mayer, C.; Miraglia, S.

2018-02-01

Steady state and in-situ neutron powder diffraction on selected compositions of the magneto-caloric (La,Ce)(Fe,Si)13CxHy compounds has been used to locate the sites accommodated by the interstitial species and to reveal the structural modifications (breathing) that occur upon metal substitution and/or interstitial insertion. The latter type of measurement in which the sequential filling of interstitial sites is followed allows one to extract some useful hydrogenation kinetics data. This structural investigation has allowed to precise the deformations undergone by the complex metallic alloys La(Fe,Si)13 when subjected to light interstitial insertion or rare earth substitution at the cation site of the NaZn13-structure type. We attempt to correlate hydrogenation kinetics variations (depression or enhancement of the hydrogen absorption rate) with a particular inhomogeneous cell variation (breathing) and bonding of the NaZn13 structure-type.

The effects of Bi4Ti3O12 interfacial ferroelectric layer on the dielectric properties of Au/n-Si structures

NASA Astrophysics Data System (ADS)

Gökçen, Muharrem; Yıldırım, Mert

2015-06-01

Au/n-Si metal-semiconductor (MS) and Au/Bi4Ti3O12/n-Si metal-ferroelectric-semiconductor (MFS) structures were fabricated and admittance measurements were held between 5 kHz and 1 MHz at room temperature so that dielectric properties of these structures could be investigated. The ferroelectric interfacial layer Bi4Ti3O12 decreased the polarization voltage by providing permanent dipoles at metal/semiconductor interface. Depending on different mechanisms, dispersion behavior was observed in dielectric constant, dielectric loss and loss tangent versus bias voltage plots of both MS and MFS structures. The real and imaginary parts of complex modulus of MFS structure take smaller values than those of MS structure, because permanent dipoles in ferroelectric layer cause a large spontaneous polarization mechanism. While the dispersion in AC conductivity versus frequency plots of MS structure was observed at high frequencies, for MFS structure it was observed at lower frequencies.

High ink absorption performance of inkjet printing based on SiO2@Al13 core-shell composites

NASA Astrophysics Data System (ADS)

Chen, YiFan; Jiang, Bo; Liu, Li; Du, Yunzhe; Zhang, Tong; Zhao, LiWei; Huang, YuDong

2018-04-01

The increasing growth of the inkjet market makes the inkjet printing more necessary. A composite material based on core-shell structure has been developed and applied to prepare inkjet printing layer. In this contribution, the ink printing record layers based on SiO2@Al13 core-shell composite was elaborated. The prepared core-shell composite materials were characterized by X-ray photoelectron spectroscopy (XPS), zeta potential, X-ray diffraction (XRD), scanning electron microscopy (SEM). The results proved the presence of electrostatic adsorption between SiO2 molecules and Al13 molecules with the formation of the well-dispersed system. In addition, based on the adsorption and the liquid permeability analysis, SiO2@Al13 ink printing record layer achieved a relatively high ink uptake (2.5 gmm-1) and permeability (87%), respectively. The smoothness and glossiness of SiO2@Al13 record layers were higher than SiO2 record layers. The core-shell structure facilitated the dispersion of the silica, thereby improved its ink absorption performance and made the clear printed image. Thus, the proposed procedure based on SiO2@Al13 core-shell structure of dye particles could be applied as a promising strategy for inkjet printing.

More complete gene silencing by fewer siRNAs: transparent optimized design and biophysical signature

PubMed Central

Ladunga, Istvan

2007-01-01

Highly accurate knockdown functional analyses based on RNA interference (RNAi) require the possible most complete hydrolysis of the targeted mRNA while avoiding the degradation of untargeted genes (off-target effects). This in turn requires significant improvements to target selection for two reasons. First, the average silencing activity of randomly selected siRNAs is as low as 62%. Second, applying more than five different siRNAs may lead to saturation of the RNA-induced silencing complex (RISC) and to the degradation of untargeted genes. Therefore, selecting a small number of highly active siRNAs is critical for maximizing knockdown and minimizing off-target effects. To satisfy these needs, a publicly available and transparent machine learning tool is presented that ranks all possible siRNAs for each targeted gene. Support vector machines (SVMs) with polynomial kernels and constrained optimization models select and utilize the most predictive effective combinations from 572 sequence, thermodynamic, accessibility and self-hairpin features over 2200 published siRNAs. This tool reaches an accuracy of 92.3% in cross-validation experiments. We fully present the underlying biophysical signature that involves free energy, accessibility and dinucleotide characteristics. We show that while complete silencing is possible at certain structured target sites, accessibility information improves the prediction of the 90% active siRNA target sites. Fast siRNA activity predictions can be performed on our web server at . PMID:17169992

Shattuckite and plancheite: A crystal chemical study

USGS Publications Warehouse

Evans, Howard T.; Mrose, Mary E.

1966-01-01

The orthorhombic crystal structures of shattuckite, Cu5( SiO3)4(OH)2 and planchétite, Cu8(Si4011)2(OH)4 H2O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.

Cobalt(II) complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine: Structures, photoluminescent and photocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jin-Ping; Fan, Jian-Zhong; Wang, Duo-Zhi, E-mail: wangdz@xju.edu.cn

2016-07-15

Six new Co{sup II} complexes [Co(L{sup 1}){sub 4}(OH){sub 2}] (1), {[Co(L"1)(H_2O)_4]·2ClO_4}{sub ∞} (2), {[Co(L"1)(H_2O)_4]·SiF_6}{sub ∞} (3), {[Co(L"1)_3]·2ClO_4}{sub ∞} (4), [Co(L{sup 2})Cl{sub 2}]{sub ∞} (5) and {[Co(L"2)_2]·SiF_6}{sub ∞} (6) [L{sup 1}=3,6-bis(N-imidazolyl) pyridazine, L{sup 2}=3,6-bis (N-benzimidazolyl) pyridazine] have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 has a mononuclear structure, while complexes 2 and 3 have 1-D chain structures. Considering the Co{sup II} centers were linked by the L{sup 1} ligands, the 3-D framework of complex 4 can be rationalized to be a {4^12.6^3} 6-c topological net with the stoichiometry uninodal net. 5 revealsmore » a coordination 1-D zigzag chain structure consisting of a neutral chain [Co(L{sup 2})Cl{sub 2}]{sub n} with the Co{sup II} centers. Complex 6 has a rhombohedral grid with a (4, 4) topology. The TGA property, fluorescent property and photocatalytic activity of complexes 1–6 have been investigated and discussed. - Graphical abstract: Six Co{sup II} complexes of bis(N-imidazolyl/benzimidazolyl)pyridazine were synthesized and structurally characterized. The fluorescence properties and photocatalytic activity for dye degradation under UV light of all complexes have been investigated and discussed. Display Omitted - Highlights: • Six new Co{sup II} complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine. • Structural analysis of all complexes. • Fluorescent property of all complexes. • Photocatalytic activity for dye degradation under UV light of all complexes.« less

Simulation and characterization of silicon nanopillar-based nanoparticle sensors

NASA Astrophysics Data System (ADS)

Wasisto, Hutomo Suryo; Merzsch, Stephan; Huang, Kai; Stranz, Andrej; Waag, Andreas; Peiner, Erwin

2013-05-01

Nanopillar-based structures hold promise as highly sensitive resonant mass sensors for a new generation of aerosol nanoparticle (NP) detecting devices because of their very small masses. In this work, the possible use of a silicon nanopillar (SiNPL) array as a nanoparticle sensor is investigated. The sensor structures are created and simulated using a finite element modeling (FEM) tool of COMSOL Multiphysics 4.3 to study the resonant characteristics and the sensitivity of the SiNPL for femtogram NP mass detection. Instead of using 2D plate models or simple single 3D cylindrical pillar models, FEM is performed with SiNPLs in 3D structures based on the real geometry of experimental SiNPL arrays employing a piezoelectric stack for resonant excitation. In order to achieve an optimal structure and investigate the etching effect on the fabricated resonators, SiNPLs with different designs of meshes, sidewall profiles, lengths, and diameters are simulated and analyzed. To validate the FEM results, fabricated SiNPLs with a high aspect ratio of ~60 are employed and characterized in resonant frequency measurements. SiNPLs are mounted onto a piezoactuator inside a scanning electron microscope (SEM) chamber which can excite SiNPLs into lateral vibration. The measured resonant frequencies of the SiNPLs with diameters about 650 nm and heights about 40 μm range from 434.63 kHz to 458.21 kHz, which agree well with those simulated by FEM. Furthermore, the deflection of a SiNPL can be enhanced by increasing the applied piezoactuator voltage. By depositing different NPs (i.e., carbon, TiO2, SiO2, Ag, and Au NPs) on the SiNPLs, the decrease of the resonant frequency is clearly shown confirming their potential to be used as airborne NP mass sensor with femtogram resolution level.

Atomic and electronic structures of Si(1 1 1)-(√3 x √3)R30°-Au and (6 × 6)-Au surfaces.

PubMed

Patterson, C H

2015-12-02

Si(1 1 1)-Au surfaces with around one monolayer of Au exhibit many ordered structures and structures containing disordered domain walls. Hybrid density functional theory (DFT) calculations presented here reveal the origin of these complex structures and tendency to form domain walls. The conjugate honeycomb chain trimer (CHCT) structure of the [Formula: see text]-Au phase contains Si atoms with non-bonding surface states which can bind Au atoms in pairs in interstices of the CHCT structure and make this surface metallic. Si adatoms adsorbed on the [Formula: see text]-Au surface induce a gapped surface through interaction with the non-bonding states. Adsorption of extra Au atoms in interstitial sites of the [Formula: see text]-Au surface is stabilized by interaction with the non-bonding orbitals and leads to higher coverage ordered structures including the [Formula: see text]-Au phase. Extra Au atoms bound in interstitial sites of the [Formula: see text]-Au surface result in top layer Si atoms with an SiAu4 butterfly wing configuration. The structure of a [Formula: see text]-Au phase, whose in-plane top atomic layer positions were previously determined by an electron holography technique (Grozea et al 1998 Surf. Sci. 418 32), is calculated using total energy minimization. The Patterson function for this structure is calculated and is in good agreement with data from an in-plane x-ray diffraction study (Dornisch et al 1991 Phys. Rev. B 44 11221). Filled and empty state scanning tunneling microscopy (STM) images are calculated for domain walls and the [Formula: see text]-Au structure. The [Formula: see text]-Au phase is 2D chiral and this is evident in computed and actual STM images. [Formula: see text]-Au and domain wall structures contain the SiAu4 motif with a butterfly wing shape. Chemical bonding within the Si-Au top layers of the [Formula: see text]-Au and [Formula: see text]-Au surfaces is analyzed and an explanation for the SiAu4 motif structure is given.

Improving the opto-microwave performance of SiGe/Si phototransistor through edge-illuminated structure

NASA Astrophysics Data System (ADS)

Tegegne, Z. G.; Viana, C.; Polleux, J. L.; Grzeskowiak, M.; Richalot, E.

2016-03-01

This paper demonstrates the experimental study of edge and top illuminated SiGe phototransistors (HPT) implemented using the existing industrial SiGe2RF Telefunken GmbH BiCMOS technology for opto-microwave (OM) applications using 850nm Multi-Mode Fibers (MMF). Its technology and structure are described. Two different optical window size HPTs with top illumination (5x5μm2, 10x10μm2) and an edge illuminated HPTs having 5μm x5μm size are presented and compared. A two-step post fabrication process was used to create an optical access on the edge of the HPT for lateral illumination with a lensed MMF through simple polishing and dicing techniques. We perform Opto-microwave Scanning Near-field Optical Microscopy (OM-SNOM) analysis on edge and top illuminated HPTs in order to observe the fastest and the highest sensitive regions of the HPTs. This analysis also allows understanding the parasitic effect from the substrate, and thus draws a conclusion on the design aspect of SiGe/Si HPT. A low frequency OM responsivity of 0.45A/W and a cutoff frequency, f-3dB, of 890MHz were measured for edge illuminated HPT. Compared to the top illuminated HPT of the same size, the edge illuminated HPT improves the f-3dB by a factor of more than two and also improves the low frequency responsivity by a factor of more than four. These results demonstrate that a simple etched HPT is still enough to achieve performance improvements compared to the top illuminated HPT without requiring a complex coupling structure. Indeed, it also proves the potential of edge coupled SiGe HPT in the ultra-low-cost silicon based optoelectronics circuits with a new approach of the optical packaging and system integration to 850nm MMF.

Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization.

PubMed

Lyubov, Dmitry M; Cherkasov, Anton V; Fukin, Georgy K; Ketkov, Sergey Yu; Shavyrin, Andrey S; Trifonov, Alexander A

2014-10-14

The reaction of Ap(9Me)Lu(CH2SiMe3)2(thf) (Ap(9Me) = (2,4,6-trimethylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) with two molar equivalents of PhSiH3 affords a trinuclear alkyl-hydrido cluster [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2]. The analogous reactions with Ap(9Me)Ln(CH2SiMe3)2(thf) (Ln = Y, Yb) are more complex and result in the formation of mixtures of two types of trinuclear alkyl-hydrido complexes [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiH2Ph)(thf)2] differing in the alkyl group. The DFT calculations of [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] (Ap* = (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) confirm localization of the HOMO on the Ap*-Y(1A)-CH2SiMe3 fragment, thus explaining its enhanced reactivity. Analysis of the electron density distribution reveals the Y-H and H-H bonding interactions in the (Y)3(μ(2)-H)3(μ(3)-H)2 moiety. The NMR studies of diamagnetic complexes [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] demonstrated that the trinuclear cores are retained in the solution and revealed exchange between μ(3)- and μ(2)-bridging hydrido ligands. Complexes [(Ap*Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2], the cationic yttrium hydrido cluster [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(thf)3](+)[B(C6F5)4](-) as well as [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] proved to be active in catalysis of ethylene polymerization under mild conditions.

Hybrid silicon honeycomb/organic solar cells with enhanced efficiency using surface etching.

PubMed

Liu, Ruiyuan; Sun, Teng; Liu, Jiawei; Wu, Shan; Sun, Baoquan

2016-06-24

Silicon (Si) nanostructure-based photovoltaic devices are attractive for their excellent optical and electrical performance, but show lower efficiency than their planar counterparts due to the increased surface recombination associated with the high surface area and roughness. Here, we demonstrate an efficiency enhancement for hybrid nanostructured Si/polymer solar cells based on a novel Si honeycomb (SiHC) structure using a simple etching method. SiHC structures are fabricated using a combination of nanosphere lithography and plasma treatment followed by a wet chemical post-etching. SiHC has shown superior light-trapping ability in comparison with the other Si nanostructures, along with a robust structure. Anisotropic tetramethylammonium hydroxide etching not only tunes the final surface morphologies of the nanostructures, but also reduces the surface roughness leading to a lower recombination rate in the hybrid solar cells. The suppressed recombination loss, benefiting from the reduced surface-to-volume ratio and roughness, has resulted in a high open-circuit voltage of 600 mV, a short-circuit current of 31.46 mA cm(-2) due to the light-trapping ability of the SiHCs, and yields a power conversion efficiency of 12.79% without any other device structure optimization.

A series of transition metal-organic frameworks based on a bipyridinium carboxylate ligand: Syntheses, structures and photoluminescent properties

NASA Astrophysics Data System (ADS)

Pei, Ru-Bo; Cao, Ming-Yang; Li, Lin-Ke; Dong, Xi-Yan; Zang, Shuang-Quan

2017-09-01

Based on a bipyridinium carboxylate ligand 1-(3,5-dicarboxy)-benzyl-1,2-di(pyridine-4-yl)ethylene chloride (H2L+Cl-), eight transition metal coordination polymers, namely, {[Zn(L)Cl]ṡ4H2O}n (1), {[Zn(L)H2O]ṡNO3ṡ2H2O}n (2), {[Zn(L) (H2O)]ṡ(NO3)0.5ṡ(Cl)0.5ṡ2H2O}n (3), {[Cd(L)(H2O)(NO3)]ṡ2H2O}n (4), {[Cd1.5(L) (Cl)2]ṡ2H2O}n (5), {[Cu(L)(H2O)]ṡNO3ṡH2O}n (6), {[Cu(HL)2(H2O)2]·Cl2·6H2O}n (7) and {[Ni(L)(H2O)Cl]ṡ4H2O}n (8) have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complexes 1 and 8 display 2D wave-like layer structures with a 3-connected 63 topology. Complexes 2 and 6 demonstrate 3D 2-fold interpenetrating frameworks with uninodal, 3-connected (10,3)-d utp-topology. Another pair of 3D 2-fold interpenetrating frameworks 3 and 4 possess 3-connected, uninodal 103ThSi2 (ths)-topology. Complex 5 shows a 2D layer structure based on the extending of trinuclear Cd(II) subunits. Complex 7 presents 1D double-chain structure, in which the central Cu(II) ions are connected by the partially deprotonated ligand HL. Additionally, powder X-ray diffractions (PXRD) and thermogravimetric analyses of complexes 1-8, as well as the solid-state luminescent properties of d10 metal complexes 1-4 at room temperature have also been discussed.

Helical coil buckling mechanism for a stiff nanowire on an elastomeric substrate

NASA Astrophysics Data System (ADS)

Chen, Youlong; Liu, Yilun; Yan, Yuan; Zhu, Yong; Chen, Xi

2016-10-01

When a stiff nanowire is deposited on a compliant soft substrate, it may buckle into a helical coil form when the system is compressed. Using theoretical and finite element method (FEM) analyses, the detailed three-dimensional coil buckling mechanism for a silicon nanowire (SiNW) on a polydimethylsiloxane (PDMS) substrate is studied. A continuum mechanics approach based on the minimization of the strain energy in the SiNW and elastomeric substrate is developed. Due to the helical buckling, the bending strain in SiNW is significantly reduced and the maximum local strain is almost uniformly distributed along SiNW. Based on the theoretical model, the energy landscape for different buckling modes of SiNW on PDMS substrate is given, which shows that both the in-plane and out-of-plane buckling modes have the local minimum potential energy, whereas the helical buckling model has the global minimum potential energy. Furthermore, the helical buckling spacing and amplitudes are deduced, taking into account the influences of the elastic properties and dimensions of SiNWs. These features are verified by systematic FEM simulations and parallel experiments. As the effective compressive strain in elastomeric substrate increases, the buckling profile evolves from a vertical ellipse to a lateral ellipse, and then approaches to a circle when the effective compressive strain is larger than 30%. The study may shed useful insights on the design and optimization of high-performance stretchable electronics and 3D complex nano-structures.

Infrared studies of the evolution of the C{sub i}O{sub i}(Si{sub I}) defect in irradiated Si upon isothermal anneals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Angeletos, T.; Londos, C. A., E-mail: hlontos@phys.uoa.gr; Chroneos, A., E-mail: alexander.chroneos@imperial.ac.uk

2016-03-28

Carbon-oxygen-self-interstitial complexes were investigated in silicon by means of Fourier transform infrared spectroscopy. Upon irradiation, the C{sub i}O{sub i} defect (C{sub 3}) forms which for high doses attract self-interstitials (Si{sub I}s) leading to the formation of the C{sub i}O{sub i}(Si{sub I}) defect (C{sub 4}) with two well-known related bands at 939.6 and 1024 cm{sup −1}. The bands are detectable in the spectra both in room temperature (RT) and liquid helium (LH) temperature. Upon annealing at 150 °C, these bands were transformed to three bands at 725, 952, and 973 cm{sup −1}, detectable only at LH temperatures. Upon annealing at 220 °C, these bands weremore » transformed to three bands at 951, 969.5, and 977 cm{sup −1}, detectable both at RT and LH temperatures. Annealing at 280 °C resulted in the transformation of these bands to two new bands at 973 and 1024 cm{sup −1}. The latter bands disappear from the spectra upon annealing at 315 °C without the emergence of other bands in the spectra. Considering reaction kinetics and defect metastability, we developed a model to describe the experimental results. Annealing at 150 °C triggers the capturing of Si{sub I}s by the C{sub 4} defect leading to the formation of the C{sub i}O{sub i}(Si{sub I}){sub 2} complex. The latter structure appears to be bistable: measuring at LH, the defect is in configuration C{sub i}O{sub i}(Si{sub I}){sub 2} giving rise to the bands at 725, 952, and 973 cm{sup −1}, whereas on measurements at RT, the defect converts to another configuration C{sub i}O{sub i}(Si{sub I}){sub 2}{sup *} without detectable bands in the spectra. Possible structures of the two C{sub i}O{sub i}(Si{sub I}){sub 2} configurations are considered and discussed. Upon annealing at 220 °C, additional Si{sub I}s are captured by the C{sub i}O{sub i}(Si{sub I}){sub 2} defect leading to the formation of the C{sub i}O{sub i}(Si{sub I}){sub 3} complex, which in turn on annealing at 280 °C converts to the C{sub i}O{sub i}(Si{sub I}){sub 4} complex. The latter defect anneals out at 315 °C, without being accompanied in the spectra by the growth of new bands.« less

Optimization of Silicon parameters as a betavoltaic battery: Comparison of Si p-n and Ni/Si Schottky barrier

NASA Astrophysics Data System (ADS)

Rahmani, Faezeh; Khosravinia, Hossein

2016-08-01

Theoretical studies on the optimization of Silicon (Si) parameters as the base of betavoltaic battery have been presented using Monte Carlo simulations and the state equations in semiconductor to obtain maximum power. Si with active area of 1 cm2 has been considered in p-n junction and Schottky barrier structure to collect the radiation induced-charge from 10 mCi cm-2 of Nickle-63 (63Ni) Source. The results show that the betavoltaic conversion efficiency in the Si p-n structure is about 2.7 times higher than that in the Ni/Si Schottky barrier structure.

Towards rhombohedral SiGe epitaxy on 150mm c-plane sapphire substrates

NASA Astrophysics Data System (ADS)

Duzik, Adam J.; Park, Yeonjoon; Choi, Sang H.

2015-04-01

Previous work demonstrated for the first time the ability to epitaxially grow uniform single crystal diamond cubic SiGe (111) films on trigonal sapphire (0001) substrates. While SiGe (111) forms two possible crystallographic twins on sapphire (0001), films consisting primarily of one twin were produced on up to 99.95% of the total wafer area. This permits new bandgap engineering possibilities and improved group IV based devices that can exploit the higher carrier mobility in Ge compared to Si. Models are proposed on the epitaxy of such dissimilar crystal structures based on the energetic favorability of crystallographic twins and surface reconstructions. This new method permits Ge (111) on sapphire (0001) epitaxy, rendering Ge an economically feasible replacement for Si in some applications, including higher efficiency Si/Ge/Si quantum well solar cells. Epitaxial SiGe films on sapphire showed a 280% increase in electron mobility and a 500% increase in hole mobility over single crystal Si. Moreover, Ge possesses a wider bandgap for solar spectrum conversion than Si, while the transparent sapphire substrate permits an inverted device structure, increasing the total efficiency to an estimated 30-40%, much higher than traditional Si solar cells. Hall Effect mobility measurements of the Ge layer in the Si/Ge/Si quantum well structure were performed to demonstrate the advantage in carrier mobility over a pure Si solar cell. Another application comes in the use of microelectromechanical devices technology, where high-resistivity Si is currently used as a substrate. Sapphire is a more resistive substrate and offers better performance via lower parasitic capacitance and higher film carrier mobility over the current Si-based technology.

MAS-NMR investigations of the crystallization behaviour of lithium aluminum silicate (LAS) glasses containing P 2O 5 and TiO 2 nucleants

NASA Astrophysics Data System (ADS)

Ananthanarayanan, A.; Kothiyal, G. P.; Montagne, L.; Revel, B.

2010-06-01

Lithium aluminum silicate (LAS) glass of composition (mol%) 20.4Li 2O-4.0Al 2O 3-68.6SiO 2-3.0K 2O-2.6B 2O 3-0.5P 2O 5-0.9TiO 2 was prepared by melt quenching. The glass was then nucleated and crystallized based on differential thermal analysis (DTA) data and was characterized by 29Si, 31P, 11B and 27Al MAS-NMR. XRD and 29Si NMR showed that lithium metasilicate (Li 2SiO 3) is the first phase to c form followed by cristobalite (SiO 2) and lithium disilicate (Li 2Si 2O 5). 29Si MAS-NMR revealed a change in the network structure already for the glasses nucleated at 550 °C. Since crystalline Li 3PO 4, as observed by 31P MAS-NMR, forms concurrently with the silicate phases, we conclude that crystalline Li 3PO 4 does not act as a nucleating agent for lithium silicate phases. Moreover, 31P NMR indicates the formation of M-PO 4 ( M=B, Al or Ti) complexes. The presence of BO 3 and BO 4 structural units in all the glass/glass-ceramic samples is revealed through 11B MAS-NMR. B remains in the residual glass and the crystallization of silicate phases causes a reduction in the number of alkali ions available for charge compensation. As a result, the number of trigonally coordinated B (BO 3) increases at the expense of tetrahedrally coordinated B (BO 4). The 27Al MAS-NMR spectra indicate the presence of tetrahedrally coordinated Al species, which are only slightly perturbed by the crystallization.

Electronic structure and optical properties of Si, Ge and diamond in the lonsdaleite phase.

PubMed

De, Amrit; Pryor, Craig E

2014-01-29

Crystalline semiconductors may exist in different polytypic phases with significantly different electronic and optical properties. In this paper, we calculate the electronic structure and optical properties of diamond, Si and Ge in the lonsdaleite (hexagonal diamond) phase using a transferable model empirical pseudopotential method with spin–orbit interactions. We calculate their band structures and extract various relevant parameters. Differences between the cubic and hexagonal phases are highlighted by comparing their densities of states. While diamond and Si remain indirect gap semiconductors in the lonsdaleite phase, Ge transforms into a direct gap semiconductor with a much smaller bandgap. We also calculate complex dielectric functions for different optical polarizations and find strong optical anisotropy. We further provide expansion parameters for the dielectric functions in terms of Lorentz oscillators.

Detection of intra-brain cytoplasmic 1 (BC1) long noncoding RNA using graphene oxide-fluorescence beacon detector.

PubMed

Kim, Mee Young; Hwang, Do Won; Li, Fangyuan; Choi, Yoori; Byun, Jung Woo; Kim, Dongho; Kim, Jee-Eun; Char, Kookheon; Lee, Dong Soo

2016-03-21

Detection of cellular expression of long noncoding RNAs (lncRNAs) was elusive due to the ambiguity of exposure of their reactive sequences associated with their secondary/tertiary structures and dynamic binding of proteins around lncRNAs. Herein, we developed graphene-based detection techniques exploiting the quenching capability of graphene oxide (GO) flakes for fluorescent dye (FAM)-labeled single-stranded siRNAs and consequent un-quenching by their detachment from GO by matching lncRNAs. A brain cytoplasmic 1 (BC1) lncRNA expression was significantly decreased by a siRNA, siBC1-1. GO quenched the FAM-labeled siBC1-1 peptide nucleic acid (PNA) probe, and this quenching was recovered by BC1. While FAM-siBC1-1-PNA-GO complex transfected spontaneously mouse or human neural stem cells, fluorescence was recovered only in mouse cells having high BC1 expression. Fluorescent dye-labeled single-stranded RNA-GO probe could detect the reactive exposed nucleic acid sequence of a cytoplasmic lncRNA expressing in the cytoplasm, which strategy can be used as a detection method of lncRNA expression.

Amorphous SiC as a structural layer in microbridge-based RF MEMS switches for use in software-defined radio

NASA Astrophysics Data System (ADS)

Parro, Rocco J.; Scardelletti, Maximilian C.; Varaljay, Nicholas C.; Zimmerman, Sloan; Zorman, Christian A.

2008-10-01

This paper reports an effort to develop amorphous silicon carbide (a-SiC) films for use in shunt capacitor RF MEMS microbridge-based switches. The films were deposited using methane and silane as the precursor gases. Switches were fabricated using 500 nm and 300 nm-thick a-SiC films to form the microbridges. Switches made from metallized 500 nm-thick SiC films exhibited favorable mechanical performance but poor RF performance. In contrast, switches made from metallized 300 nm-thick SiC films exhibited excellent RF performance but poor mechanical performance. Load-deflection testing of unmetallized and metallized bulk micromachined SiC membranes indicates that the metal layers have a small effect on the Young's modulus of the 500 nm and 300 nm-thick SiC MEMS. As for residual stress, the metal layers have a modest effect on the 500 nm-thick structures, but a significant affect on the residual stress in the 300 nm-thick structures.

Principles of water oxidation and O2-based hydrocarbon transformation by multinuclear catalytic sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Musaev, Djamaladdin G; Hill, Craig L; Morokuma, Keiji

Abstract The central thrust of this integrated experimental and computational research program was to obtain an atomistic-level understanding of the structural and dynamic factors underlying the design of catalysts for water oxidation and selective reductant-free O2-based transformations. The focus was on oxidatively robust polyoxometalate (POM) complexes in which a catalytic active site interacts with proximal metal centers in a synergistic manner. Thirty five publications in high-impact journals arose from this grant. I. Developing an oxidatively and hydrolytically stable and fast water oxidation catalyst (WOC), a central need in the production of green fuels using water as a reductant, has provenmore » particularly challenging. During this grant period we have designed and investigated several carbon-free, molecular (homogenous), oxidatively and hydrolytically stable WOCs, including the Rb8K2[{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]·25H2O (1) and [Co4(H2O)2(α-PW9O34)2]10- (2). Although complex 1 is fast, oxidatively and hydrolytically stable WOC, Ru is neither abundant nor inexpensive. Therefore, development of a stable and fast carbon-free homogenous WOC, based on earth-abundant elements became our highest priority. In 2010, we reported the first such catalyst, complex 2. This complex is substantially faster than 1 and stable under homogeneous conditions. Recently, we have extended our efforts and reported a V2-analog of the complex 2, i.e. [Co4(H2O)2(α-VW9O34)2]10- (3), which shows an even greater stability and reactivity. We succeeded in: (a) immobilizing catalysts 1 and 2 on the surface of various electrodes, and (b) elucidating the mechanism of O2 formation and release from complex 1, as well as the Mn4O4L6 “cubane” cluster. We have shown that the direct O-O bond formation is the most likely pathway for O2 formation during water oxidation catalyzed by 1. II. Oxo transfer catalysts that contain two proximal and synergistically interacting redox active metal centers in the active site form another part of considerable interest of our grant because species with such sites [including methane monooxygenase (MMO) and more] are some of the most effective oxygenase catalysts known. Our team conducted the following research on γ-M2-Keggin complexes: (a) investigated stability of the trimer [{Fe3(OH)3(H2O)2}3(γ-SiW10O36)3]15-, 4, in water, and developed the chemistry and catalysis of the di-iron centered POM, [γ(1,2)-SiW10{Fe(OH)}2O38]6-, 5, in organic solvents (Figure 2). We also study the thermodynamic and structural stability of γ-M2-Keggin in aqueous media for different M’s (d-electron metals). We have defined two structural classes of POMs with proximally bound d-electron metal centers. We refer to these structural isomers of the {γ-M2SiW10} family of POMs as “in-pocket” and “out-of pocket”. We have elucidated the factors controlling the structure and stability of the V, Fe, Ru, Tc, Mo and Rh derivatives of [(SiO4)M2(OH)2W10O32]4- using a range of computational tools. We have: (a) demonstrated that heteroatom X in these polyanions may function as an “internal switch” for defining the ground electronic states and, consequently, the reactivity of the γ-M2-Keggin POM complexes; (b) elucidated reactivity of divacant lacunary species and polyperoxotungstates (PPTs), {Xn+O4[WO(O2)2]4}n-, which could be degradation products of γ-M2-Keggin complexes in aqueous media; (c) elucidated the role of the POM ligand in stabilization of {Ru2} and {(Ru-oxo)2} fragments in the reactant and product of the reaction of {γ-[(Xn+O4)Ru2(OH)2W10O32]}(8-n)- (where X = Si4+, P5+ and S6+) with O2, and (d) the mechanisms of olefin epoxidation catalyzed by these di-d-transition metal substituted and divacant lacunary γ-M2-Keggin complexes. III. Complementing the efforts presented above was the development of less time-consuming but reasonably accurate computational methods allowing one to explore more deeply large catalytic systems. We developed Reactive Force Field (ReaxFF) to study interaction of the targeted POMs with water, proton and hydroxide ions in the liquid phase. We tested our ReaxFF parameters on the Lindqvist POMs, M6O19n-, where M = Nb and Ta. These parameters are made available as part of the ReaxFF code. In addition, we have developed parameters for Sc, Ti, Fe, Co and Ni in combination with H, C, N, O, as well as the same metal (M-M) for the spin-polarized self-consistent-charge density-functional tight-binding (DFTB) method. Test calculations showed that the DFTB method with the present parameters in most cases reproduces structural properties very well. These parameters are made available as part of the DFTB code. Thus, this DOE BES funded research project has clarified several key areas impacting (a) water oxidation and O2-based hydrocarbon transformation, (b) stabilization of key structures and catalytic intermediates in such processes, (c) immobilization of molecular catalysts on metal oxide surfaces, and (d) application of optimal computational methods to study reaction dynamics in large systems.« less

Practical synchronization on complex dynamical networks via optimal pinning control

NASA Astrophysics Data System (ADS)

Li, Kezan; Sun, Weigang; Small, Michael; Fu, Xinchu

2015-07-01

We consider practical synchronization on complex dynamical networks under linear feedback control designed by optimal control theory. The control goal is to minimize global synchronization error and control strength over a given finite time interval, and synchronization error at terminal time. By utilizing the Pontryagin's minimum principle, and based on a general complex dynamical network, we obtain an optimal system to achieve the control goal. The result is verified by performing some numerical simulations on Star networks, Watts-Strogatz networks, and Barabási-Albert networks. Moreover, by combining optimal control and traditional pinning control, we propose an optimal pinning control strategy which depends on the network's topological structure. Obtained results show that optimal pinning control is very effective for synchronization control in real applications.

Stable Dispersions of Covalently Tethered Polymer Improved Graphene Oxide Nanoconjugates as an Effective Vector for siRNA Delivery.

PubMed

Yadav, Nisha; Kumar, Naveen; Prasad, Peeyush; Shirbhate, Shivani; Sehrawat, Seema; Lochab, Bimlesh

2018-05-02

Conjugates of poly(amidoamine) (PAMAM) with modified graphene oxide (GO) are attractive nonviral vectors for gene-based cancer therapeutics. GO protects siRNA from enzymatic cleavage and showed reasonable transfection efficiency along with simultaneous benefits of low cost and large scale production. PAMAM is highly effective in siRNA delivery but suffers from high toxicity with poor in vivo efficacy. Co-reaction of GO and PAMAM led to aggregation and more importantly, have detrimental effect on stability of dispersion at physiological pH preventing their exploration at clinical level. In the current work, we have designed, synthesized, characterized and explored a new type of hybrid vector (GPD), using GO synthesized via improved method which was covalently tethered with poly(ethylene glycol) (PEG) and PAMAM. The existence of covalent linkage, relative structural changes and properties of GPD is well supported by Fourier transform infrared (FTIR), UV-visible (UV-vis), Raman, X-ray photoelectron (XPS), elemental analysis, powder X-ray diffraction (XRD), thermogravimetry analysis (TGA), dynamic light scattering (DLS), and zeta potential. Scanning electron microscopy (SEM), and transmission electron microscopy (TEM) of GPD showed longitudinally aligned columnar self-assembled ∼10 nm thick polymeric nanoarchitectures onto the GO surface accounting to an average size reduction to ∼20 nm. GPD revealed an outstanding stability in both phosphate buffer saline (PBS) and serum containing cell medium. The binding efficiency of EPAC1 siRNA to GPD was supported by gel retardation assay, DLS, zeta potential and photoluminescence (PL) studies. A lower cytotoxicity with enhanced cellular uptake and homogeneous intracellular distribution of GPD/siRNA complex is confirmed by imaging studies. GPD exhibited a higher transfection efficiency with remarkable inhibition of cell migration and lower invasion than PAMAM and Lipofectamine 2000 suggesting its role in prevention of breast cancer progression and metastasis. A significant reduction in the expression of the specific protein against which siRNA was delivered is revealed by Western blot assay. Furthermore, a pH-triggered release of siRNA from the GPD/siRNA complex was studied to provide a mechanistic insight toward unloading of siRNA from the vector. Current strategy is a way forward for designing effective therapeutic vectors for gene-based antitumor therapy.

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

PubMed

Armitt, David J; Bruce, Michael I; Gaudio, Maryka; Zaitseva, Natasha N; Skelton, Brian W; White, Allan H; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A; Roberts, Rachel L; Hartl, Frantisek; Low, Paul J

2008-12-21

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp (); Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes , , , and .

Structural and magnetic studies of half-metallic Heusler alloy Cr2CoSi nanoparticle synthesized by mechanical-alloying method

NASA Astrophysics Data System (ADS)

Saravanan, G.; Asvini, V.; Kalaiezhily, R. K.; Ravichandran, K.

2018-05-01

Heusler Alloy based Cr2CoSi nanoparticles were synthesized by using ball milling. X-ray diffractions studies were used to characterize the crystal structure of Cr2CoSi nanoparticles and magnetic properties were studied using VSM. XRD data analysis confirms the Heusler alloy phase showing the L21 structure. Magnetic properties are measured for synthesized samples having coercivity Hc = 389 Oe, with high saturation magnetization value Ms = 8.64 emu/g and remenance value Mr = 2.93 emu/g. Synthesized Heusler alloy Cr2CoSi nanoparticles can be potential materials for use in Spin polarized based spin sensors, spin devices, magnetic sensors and transducer applications.

Efficiency Improvement of HIT Solar Cells on p-Type Si Wafers.

PubMed

Wei, Chun-You; Lin, Chu-Hsuan; Hsiao, Hao-Tse; Yang, Po-Chuan; Wang, Chih-Ming; Pan, Yen-Chih

2013-11-22

Single crystal silicon solar cells are still predominant in the market due to the abundance of silicon on earth and their acceptable efficiency. Different solar-cell structures of single crystalline Si have been investigated to boost efficiency; the heterojunction with intrinsic thin layer (HIT) structure is currently the leading technology. The record efficiency values of state-of-the art HIT solar cells have always been based on n-type single-crystalline Si wafers. Improving the efficiency of cells based on p-type single-crystalline Si wafers could provide broader options for the development of HIT solar cells. In this study, we varied the thickness of intrinsic hydrogenated amorphous Si layer to improve the efficiency of HIT solar cells on p-type Si wafers.

Self-organized patterns along sidewalls of iron silicide nanowires on Si(110) and their origin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Debolina; Mahato, J. C.; Bisi, Bhaskar

Iron silicide (cubic FeSi{sub 2}) nanowires have been grown on Si(110) by reactive deposition epitaxy and investigated by scanning tunneling microscopy and scanning/transmission electron microscopy. On an otherwise uniform nanowire, a semi-periodic pattern along the edges of FeSi{sub 2} nanowires has been discovered. The origin of such growth patterns has been traced to initial growth of silicide nanodots with a pyramidal Si base at the chevron-like atomic arrangement of a clean reconstructed Si(110) surface. The pyramidal base evolves into a comb-like structure along the edges of the nanowires. This causes the semi-periodic structure of the iron silicide nanowires along theirmore » edges.« less

Cationic liquid crystalline nanoparticles for the delivery of synthetic RNAi-based therapeutics.

PubMed

Gentile, Emanuela; Oba, Taro; Lin, Jing; Shao, Ruping; Meng, Feng; Cao, Xiaobo; Lin, Heather Y; Mourad, Majidi; Pataer, Apar; Baladandayuthapani, Veerabhadran; Cai, Dong; Roth, Jack A; Ji, Lin

2017-07-18

RNA interference (RNAi)-based therapeutics have been used to silence the expression of targeted pathological genes. Small interfering RNA (siRNAs) and microRNA (miRNAs) inhibitor have performed this function. However, short half-life, poor cellular uptake, and nonspecific distribution of small RNAs call for the development of novel delivery systems to facilitate the use of RNAi. We developed a novel cationic liquid crystalline nanoparticle (CLCN) to efficiently deliver synthetic siRNAs and miRNAs. CLCNs were prepared by using high-speed homogenization and assembled with synthetic siRNA or miRNA molecules in nuclease-free water to create CLCN/siRNA or miRNA complexes. The homogeneous and stable CLCNs and CLCN-siRNA complexes were about 100 nm in diameter, with positively charged surfaces. CLCNs are nontoxic and are taken up by human cells though endocytosis. Significant inhibition of gene expression was detected in transiently transfected lung cancer H1299 cells treated with CLCNs/anti-GFP complexes 24 hours after transfection. Biodistribution analysis showed that the CLCNs and CLCNs-RNAi complexes were successfully delivered to various organs and into the subcutaneous human lung cancer H1299 tumor xenografts in mice 24 hours after systemic administration. These results suggest that CLCNs are a unique and advanced delivery system capable of protecting RNAi from degradation and of efficiently delivering RNAi in vitro and in vivo.

Cationic liquid crystalline nanoparticles for the delivery of synthetic RNAi-based therapeutics

PubMed Central

Gentile, Emanuela; Oba, Taro; Lin, Jing; Shao, Ruping; Meng, Feng; Cao, Xiaobo; Lin, Heather Y.; Mourad, Majidi; Pataer, Apar; Baladandayuthapani, Veerabhadran; Cai, Dong; Roth, Jack A.; Ji, Lin

2017-01-01

RNA interference (RNAi)-based therapeutics have been used to silence the expression of targeted pathological genes. Small interfering RNA (siRNAs) and microRNA (miRNAs) inhibitor have performed this function. However, short half-life, poor cellular uptake, and nonspecific distribution of small RNAs call for the development of novel delivery systems to facilitate the use of RNAi. We developed a novel cationic liquid crystalline nanoparticle (CLCN) to efficiently deliver synthetic siRNAs and miRNAs. CLCNs were prepared by using high-speed homogenization and assembled with synthetic siRNA or miRNA molecules in nuclease-free water to create CLCN/siRNA or miRNA complexes. The homogeneous and stable CLCNs and CLCN-siRNA complexes were about 100 nm in diameter, with positively charged surfaces. CLCNs are nontoxic and are taken up by human cells though endocytosis. Significant inhibition of gene expression was detected in transiently transfected lung cancer H1299 cells treated with CLCNs/anti-GFP complexes 24 hours after transfection. Biodistribution analysis showed that the CLCNs and CLCNs-RNAi complexes were successfully delivered to various organs and into the subcutaneous human lung cancer H1299 tumor xenografts in mice 24 hours after systemic administration. These results suggest that CLCNs are a unique and advanced delivery system capable of protecting RNAi from degradation and of efficiently delivering RNAi in vitro and in vivo. PMID:28637023

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals.

PubMed

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-01-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF 3 @CeF 3 and TbF 3 @CeF 3 @SiO 2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO 2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF 3 @CeF 3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, 'the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb 3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO 2 shell. .

Structural, spectroscopic and cytotoxicity studies of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals

NASA Astrophysics Data System (ADS)

Grzyb, Tomasz; Runowski, Marcin; Dąbrowska, Krystyna; Giersig, Michael; Lis, Stefan

2013-10-01

Terbium fluoride nanocrystals, covered by a shell, composed of cerium fluoride were synthesized by a co-precipitation method. Their complex structure was formed spontaneously during the synthesis. The surface of these core/shell nanocrystals was additionally modified by silica. The properties of TbF3@CeF3 and TbF3@CeF3@SiO2 nanocrystals, formed in this way, were investigated. Spectroscopic studies showed that the differences between these two groups of products resulted from the presence of the SiO2 shell. X-ray diffraction patterns confirmed the trigonal crystal structure of TbF3@CeF3 nanocrystals. High resolution transmission electron microscopy in connection with energy-dispersive X-ray spectroscopy showed a complex structure of the formed nanocrystals. Crystallized as small discs, `the products', with an average diameter around 10 nm, showed an increase in the concentration of Tb3+ ions from surface to the core of nanocrystals. In addition to photo-physical analyses, cytotoxicity studies were performed on HSkMEC (Human Skin Microvascular Endothelial Cells) and B16F0 mouse melanoma cancer cells. The cytotoxicity of the nanomaterials was neutral for the investigated cells with no toxic or antiproliferative effect in the cell cultures, either for normal or for cancer cells. This fact makes the obtained nanocrystals good candidates for biological applications and further modifications of the SiO2 shell.

Effect of mixed Ge/Si cross-linking on the physical properties of amorphous Ge-Si-Te networks

NASA Astrophysics Data System (ADS)

Gunasekera, K.; Boolchand, P.; Micoulaut, M.

2014-04-01

Amorphous GexSixTe1-2x glasses are studied as a function of composition by a combination of experimental and theoretical methods, allowing for a full description of the network structure in relationship with physico-chemical properties. Calorimetric and thermal measurements reveal that such glasses display an anomalous behavior across a range of compositions xc1=7.5% and

Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? The Silicon (Si(3P))-Dimethylacetylene (C4H6(X1A1g)) System as a Case Study.

PubMed

Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H

2018-06-06

The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.

A Combined Precipitation, Yield Stress, and Work Hardening Model for Al-Mg-Si Alloys Incorporating the Effects of Strain Rate and Temperature

NASA Astrophysics Data System (ADS)

Myhr, Ole Runar; Hopperstad, Odd Sture; Børvik, Tore

2018-05-01

In this study, a combined precipitation, yield strength, and work hardening model for Al-Mg-Si alloys known as NaMo has been further developed to include the effects of strain rate and temperature on the resulting stress-strain behavior. The extension of the model is based on a comprehensive experimental database, where thermomechanical data for three different Al-Mg-Si alloys are available. In the tests, the temperature was varied between 20 °C and 350 °C with strain rates ranging from 10-6 to 750 s-1 using ordinary tension tests for low strain rates and a split-Hopkinson tension bar system for high strain rates, respectively. This large span in temperatures and strain rates covers a broad range of industrial relevant problems from creep to impact loading. Based on the experimental data, a procedure for calibrating the different physical parameters of the model has been developed, starting with the simplest case of a stable precipitate structure and small plastic strains, from which basic kinetic data for obstacle limited dislocation glide were extracted. For larger strains, when work hardening becomes significant, the dynamic recovery was linked to the Zener-Hollomon parameter, again using a stable precipitate structure as a basis for calibration. Finally, the complex situation of concurrent work hardening and dynamic evolution of the precipitate structure was analyzed using a stepwise numerical solution algorithm where parameters representing the instantaneous state of the structure were used to calculate the corresponding instantaneous yield strength and work hardening rate. The model was demonstrated to exhibit a high degree of predictive power as documented by a good agreement between predictions and measurements, and it is deemed well suited for simulations of thermomechanical processing of Al-Mg-Si alloys where plastic deformation is carried out at various strain rates and temperatures.

The effect of millisecond flash lamp annealing on electrical and structural properties of ZnO:Al/Si structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindberg, P. F.; Riise, H. N.; Vines, L.

2016-05-14

The effect of millisecond flash lamp annealing (FLA) on aluminum doped ZnO (AZO) films and their interface with Si have been studied. The AZO films were deposited by magnetron sputtering on Si (100) substrates. The electrical and structural properties of the film and AZO/Si structures were characterized by current–voltage, capacitance–voltage, and deep level transient spectroscopy measurements, X-ray diffraction, and secondary ion mass spectrometry. The resistivity of the AZO film is reduced to a close to state-of-the-art value of 2 × 10{sup −4} Ω cm after FLA for 3 ms with an average energy density of 29 J/cm{sup 2}. In addition, most of the interfacial defects energymore » levels are simultaneously annealed out, except for one persisting shallow level, tentatively assigned to the vacancy-oxygen complex in Si, which was not affected by FLA. Subsequent to the FLA, the samples were treated in N{sub 2} or forming gas (FG) (N{sub 2}/H{sub 2}, 90/10%{sub mole}) ambient at 200–500 °C. The latter samples maintained the low resistivity achieved after the FLA, but not the former ones. The interfacial defect level persisting after the FLA is removed by the FG treatment, concurrently as another level emerges at ∼0.18 eV below the conduction band. The electrical data of the AZO films are discussed in term of point defects controlling the resistivity, and it is argued that the FLA promotes formation of electrically neutral clusters of Zink vacancies (V{sub Zn}'s) rather than passivating/compensating complexes between the Al donors and V{sub Zn}'s.« less

The CiCs(SiI)n Defect in Silicon from a Density Functional Theory Perspective.

PubMed

Christopoulos, Stavros-Richard G; Sgourou, Efstratia N; Vovk, Ruslan V; Chroneos, Alexander; Londos, Charalampos A

2018-04-16

Carbon constitutes a significant defect in silicon (Si) as it can interact with intrinsic point defects and affect the operation of devices. In heavily irradiated Si containing carbon the initially produced carbon interstitial-carbon substitutional (C i C s ) defect can associate with self-interstitials (Si I 's) to form, in the course of irradiation, the C i C s (Si I ) defect and further form larger complexes namely, C i C s (Si I ) n defects, by the sequential trapping of self-interstitials defects. In the present study, we use density functional theory to clarify the structure and energetics of the C i C s (Si I ) n defects. We report that the lowest energy C i C s (Si I ) and C i C s (Si I )₂ defects are strongly bound with -2.77 and -5.30 eV, respectively.

Formation of equiaxed crystal structures in directionally solidified Al-Si alloys using Nb-based heterogeneous nuclei

PubMed Central

Bolzoni, Leandro; Xia, Mingxu; Babu, Nadendla Hari

2016-01-01

The design of chemical compositions containing potent nuclei for the enhancement of heterogeneous nucleation in aluminium, especially cast alloys such as Al-Si alloys, is a matter of importance in order to achieve homogeneous properties in castings with complex geometries. We identified that Al3Nb/NbB2 compounds are effective heterogeneous nuclei and are successfully produced in the form of Al-2Nb-xB (x = 0.5, 1 and 2) master alloys. Our study shows that the inoculation of Al-10Si braze alloy with these compounds effectively promotes the heterogeneous nucleation of primary α-Al crystals and reduces the undercooling needed for solidification to take place. Moreover, we present evidences that these Nb-based compounds prevent the growth of columnar crystals and permit to obtain, for the first time, fine and equiaxed crystals in directionally solidified Al-10Si braze alloy. As a consequence of the potent heterogeneous particles, the size of the α-Al crystals was found to be less dependent on the processing conditions, especially the thermal gradient. Finally, we also demonstrate that the enhanced nucleation leads to the refinement of secondary phases such as eutectic silicon and primary silicon particles. PMID:28008967

HfO2 and SiO2 as barriers in magnetic tunneling junctions

NASA Astrophysics Data System (ADS)

Shukla, Gokaran; Archer, Thomas; Sanvito, Stefano

2017-05-01

SiO2 and HfO2 are both high-k, wide-gap semiconductors, currently used in the microelectronic industry as gate barriers. Here we investigate whether the same materials can be employed to make magnetic tunnel junctions, which in principle can be amenable for integration in conventional Si technology. By using a combination of density functional theory and the nonequilibrium Green's functions method for quantum transport we have studied the transport properties of Co [0001 ] /SiO2[001 ] /Co [0001 ] and Fe [001 ] /HfO2[001 ] /Fe [001 ] junctions. In both cases we found a quite large magnetoresistance, which is explained through the analysis of the real band structure of the magnets and the complex one of the insulator. We find that there is no symmetry spin filtering for the Co-based junction since the high transmission Δ2' band crosses the Fermi level, EF, for both spin directions. However, the fact that Co is a strong ferromagnet makes the orbital contribution to the two Δ2' spin subbands different, yielding magnetoresistance. In contrast for the Fe-based junction symmetry filtering is active for an energy window spanning between the Fermi level and 1 eV below EF, with Δ1 symmetry contributing to the transmission.

Stable divalent germanium, tin and lead amino(ether)-phenolate monomeric complexes: structural features, inclusion heterobimetallic complexes, and ROP catalysis.

PubMed

Wang, Lingfang; Roşca, Sorin-Claudiu; Poirier, Valentin; Sinbandhit, Sourisak; Dorcet, Vincent; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann

2014-03-21

Stable germanium(II) and lead(II) amido complexes {LO(i)}M(N(SiMe3)2) (M = Ge(II), Pb(II)) bearing amino(ether)phenolate ligands are readily available using the proteo-ligands {LO(i)}H of general formula 2-CH2NR2-4,6-tBu2-C6H2OH (i = 1, NR2 = N((CH2)2OCH3)2; i = 2, NR2 = NEt2; i = 3, NR2 = aza-15-crown-5) and M(N(SiMe3)2)2 precursors. The molecular structures of these germylenes and plumbylenes, as well as those of {LO(3)}GeCl, {LO(3)}SnCl and of the congeneric {LO(4)}Sn(II)(N(SiMe3)2) where NR2 = aza-12-crown-4, have been determined crystallographically. All complexes are monomeric, with 3-coordinate metal centres. The phenolate systematically acts as a N^O(phenolate) bidentate ligand, with no interactions between the metal and the O(side-arm) atoms in these cases (for {LO(1)}(-), {LO(3)}(-) and {LO(4)}(-)) where they could potentially arise. For each family, the lone pair of electrons essentially features ns(2) character, and there is little, if any, hybridization of the valence orbitals. Heterobimetallic complexes {LO(3)}M(N(SiMe3)2)·LiOTf, where the Li(+) cation sits inside the tethered crown-ether, were prepared by reaction of {LO(3)}M(N(SiMe3)2) and LiOTf (M = Ge(II), Sn(II)). The inclusion of Li(+) (featuring a close contact with the triflate anion) in the macrocycle bears no influence on the coordination sphere of the divalent tetrel element. In association with iPrOH, the amido germylenes, stannylenes and plumbylenes catalyse the controlled polymerisation of L- and racemic lactide. The activity increases linearly according to Ge(II) ≪ Sn(II) ≪ Pb(II). The simple germylenes generate very sluggish catalysts, but the activity is significantly boosted if the heterobimetallic complex {LO(3)}Ge(N(SiMe3)2)·LiOTf is used instead. On the other hand, with 10-25 equiv. of iPrOH, the plumbylenes afford highly active binary catalysts, converting 1000 or 5000 equiv. of monomer at 60 °C within 3 or 45 min, respectively, in a controlled fashion.

Si/Ti2O3/Reduced Graphene Oxide Nanocomposite Anodes for Lithium-Ion Batteries with Highly Enhanced Cyclic Stability.

PubMed

Park, A Reum; Son, Dae-Yong; Kim, Jung Sub; Lee, Jun Young; Park, Nam-Gyu; Park, Juhyun; Lee, Joong Kee; Yoo, Pil J

2015-08-26

Silicon (Si) has attracted tremendous attention as a high-capacity anode material for next generation Li-ion batteries (LIBs); unfortunately, it suffers from poor cyclic stability due to excessive volume expansion and reduced electrical conductivity after repeated cycles. To circumvent these issues, we propose that Si can be complexed with electrically conductive Ti2O3 to significantly enhance the reversible capacity and cyclic stability of Si-based anodes. We prepared a ternary nanocomposite of Si/Ti2O3/reduced graphene oxide (rGO) using mechanical blending and subsequent thermal reduction of the Si, TiO2 nanoparticles, and rGO nanosheets. As a result, the obtained ternary nanocomposite exhibited a specific capacity of 985 mAh/g and a Coulombic efficiency of 98.4% after 100 cycles at a current density of 100 mA/g. Furthermore, these ternary nanocomposite anodes exhibited outstanding rate capability characteristics, even with an increased current density of 10 A/g. This excellent electrochemical performance can be ascribed to the improved electron and ion transport provided by the Ti2O3 phase within the Si domains and the structurally reinforced conductive framework comprised of the rGO nanosheets. Therefore, it is expected that our approach can also be applied to other anode materials to enable large reversible capacity, excellent cyclic stability, and good rate capability for high-performance LIBs.

Tribological Behavior of Aluminum Alloy AlSi10Mg-TiB2 Composites Produced by Direct Metal Laser Sintering (DMLS)

NASA Astrophysics Data System (ADS)

Lorusso, Massimo; Aversa, Alberta; Manfredi, Diego; Calignano, Flaviana; Ambrosio, Elisa Paola; Ugues, Daniele; Pavese, Matteo

2016-08-01

Direct metal laser sintering (DMLS) is an additive manufacturing technique for the production of parts with complex geometry and it is especially appropriate for structural applications in aircraft and automotive industries. Aluminum-based metal matrix composites (MMCs) are promising materials for these applications because they are lightweight, ductile, and have a good strength-to-weight ratio This paper presents an investigation of microstructure, hardness, and tribological properties of AlSi10Mg alloy and AlSi10Mg alloy/TiB2 composites prepared by DMLS. MMCs were realized with two different compositions: 10% wt. of microsize TiB2, 1% wt. of nanosize TiB2. Wear tests were performed using a pin-on-disk apparatus on the prepared samples. Performances of AlSi10Mg samples manufactured by DMLS were also compared with the results obtained on AlSi10Mg alloy samples made by casting. It was found that the composites displayed a lower coefficient of friction (COF), but in the case of microsize TiB2 reinforcement the wear rate was higher than with nanosize reinforcements and aluminum alloy without reinforcement. AlSi10Mg obtained by DMLS showed a higher COF than AlSi10Mg obtained by casting, but the wear rate was higher in the latter case.

Effects of the c-Si/a-SiO2 interfacial atomic structure on its band alignment: an ab initio study.

PubMed

Zheng, Fan; Pham, Hieu H; Wang, Lin-Wang

2017-12-13

The crystalline-Si/amorphous-SiO 2 (c-Si/a-SiO 2 ) interface is an important system used in many applications, ranging from transistors to solar cells. The transition region of the c-Si/a-SiO 2 interface plays a critical role in determining the band alignment between the two regions. However, the question of how this interface band offset is affected by the transition region thickness and its local atomic arrangement is yet to be fully investigated. Here, by controlling the parameters of the classical Monte Carlo bond switching algorithm, we have generated the atomic structures of the interfaces with various thicknesses, as well as containing Si at different oxidation states. A hybrid functional method, as shown by our calculations to reproduce the GW and experimental results for bulk Si and SiO 2 , was used to calculate the electronic structure of the heterojunction. This allowed us to study the correlation between the interface band characterization and its atomic structures. We found that although the systems with different thicknesses showed quite different atomic structures near the transition region, the calculated band offset tended to be the same, unaffected by the details of the interfacial structure. Our band offset calculation agrees well with the experimental measurements. This robustness of the interfacial electronic structure to its interfacial atomic details could be another reason for the success of the c-Si/a-SiO 2 interface in Si-based electronic applications. Nevertheless, when a reactive force field is used to generate the a-SiO 2 and c-Si/a-SiO 2 interfaces, the band offset significantly deviates from the experimental values by about 1 eV.

Effects of the c-Si/a-SiO 2 interfacial atomic structure on its band alignment: an ab initio study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Fan; Pham, Hieu H.; Wang, Lin-Wang

The crystalline-Si/amorphous-SiO 2 (c-Si/a-SiO 2) interface is an important system used in many applications, ranging from transistors to solar cells. The transition region of the c-Si/a-SiO 2 interface plays a critical role in determining the band alignment between the two regions. However, the question of how this interface band offset is affected by the transition region thickness and its local atomic arrangement is yet to be fully investigated. Here in this study, by controlling the parameters of the classical Monte Carlo bond switching algorithm, we have generated the atomic structures of the interfaces with various thicknesses, as well as containingmore » Si at different oxidation states. A hybrid functional method, as shown by our calculations to reproduce the GW and experimental results for bulk Si and SiO 2, was used to calculate the electronic structure of the heterojunction. This allowed us to study the correlation between the interface band characterization and its atomic structures. We found that although the systems with different thicknesses showed quite different atomic structures near the transition region, the calculated band offset tended to be the same, unaffected by the details of the interfacial structure. Our band offset calculation agrees well with the experimental measurements. This robustness of the interfacial electronic structure to its interfacial atomic details could be another reason for the success of the c-Si/a-SiO 2 interface in Si-based electronic applications. Nevertheless, when a reactive force field is used to generate the a-SiO 2 and c-Si/a-SiO 2 interfaces, the band offset significantly deviates from the experimental values by about 1 eV« less

Effects of the c-Si/a-SiO 2 interfacial atomic structure on its band alignment: an ab initio study

DOE PAGES

Zheng, Fan; Pham, Hieu H.; Wang, Lin-Wang

2017-11-13

The crystalline-Si/amorphous-SiO 2 (c-Si/a-SiO 2) interface is an important system used in many applications, ranging from transistors to solar cells. The transition region of the c-Si/a-SiO 2 interface plays a critical role in determining the band alignment between the two regions. However, the question of how this interface band offset is affected by the transition region thickness and its local atomic arrangement is yet to be fully investigated. Here in this study, by controlling the parameters of the classical Monte Carlo bond switching algorithm, we have generated the atomic structures of the interfaces with various thicknesses, as well as containingmore » Si at different oxidation states. A hybrid functional method, as shown by our calculations to reproduce the GW and experimental results for bulk Si and SiO 2, was used to calculate the electronic structure of the heterojunction. This allowed us to study the correlation between the interface band characterization and its atomic structures. We found that although the systems with different thicknesses showed quite different atomic structures near the transition region, the calculated band offset tended to be the same, unaffected by the details of the interfacial structure. Our band offset calculation agrees well with the experimental measurements. This robustness of the interfacial electronic structure to its interfacial atomic details could be another reason for the success of the c-Si/a-SiO 2 interface in Si-based electronic applications. Nevertheless, when a reactive force field is used to generate the a-SiO 2 and c-Si/a-SiO 2 interfaces, the band offset significantly deviates from the experimental values by about 1 eV« less

Resistive switching behaviors of Au/pentacene/Si-nanowire arrays/heavily doped n-type Si devices for memory applications

NASA Astrophysics Data System (ADS)

Tsao, Hou-Yen; Lin, Yow-Jon

2014-02-01

The fabrication of memory devices based on the Au/pentacene/heavily doped n-type Si (n+-Si), Au/pentacene/Si nanowires (SiNWs)/n+-Si, and Au/pentacene/H2O2-treated SiNWs/n+-Si structures and their resistive switching characteristics were reported. A pentacene memory structure using SiNW arrays as charge storage nodes was demonstrated. The Au/pentacene/SiNWs/n+-Si devices show hysteresis behavior. H2O2 treatment may lead to the hysteresis degradation. However, no hysteresis-type current-voltage characteristics were observed for Au/pentacene/n+-Si devices, indicating that the resistive switching characteristic is sensitive to SiNWs and the charge trapping effect originates from SiNWs. The concept of nanowires within the organic layer opens a promising direction for organic memory devices.

Multifunctional nanocarrier based on clay nanotubes for efficient intracellular siRNA delivery and gene silencing.

PubMed

Wu, Hui; Shi, Yinfeng; Huang, Chusen; Zhang, Yang; Wu, Jiahui; Shen, Hebai; Jia, Nengqin

2014-04-01

RNA interference-mediated gene silencing relating to disease has recently emerged as a powerful method in gene therapy. Despite the promises, effective transport of siRNA with minimal side effects remains a challenge. Halloysites are cheap and naturally available aluminosilicate clay nanotubes with high mechanical strength and biocompatibility. In this study, a novel multifunctional nanocarrier based on functionalized halloysite nanotubes (f-HNTs) has been developed via electrostatic layer-by-layer assembling approach for loading and intracellular delivery of therapeutic antisurvivin siRNA and simultaneously tracking their intracellular transport, in which PEI-modified HNTs are used as gene vector, antisurvivin siRNA as gene therapeutic agent, and mercaptoacetic acid-capped CdSe quantum dots as fluorescent labeling probes. The successful assembly of the f-HNTs-siRNA complexes was systematically characterized by transmission electron microscopy (TEM), UV-visible spectrophotometry, Zeta potential measurement, fluorescence spectrophotometry, and electrochemical impedance spectroscopy. Confocal microscopy, biological TEM, and flow cytometry studies revealed that the complexes enabled the efficient intracellular delivery of siRNA for cell-specific gene silencing. MTT assays exhibited that the complexes can enhance antitumor activity. Furthermore, Western blot analysis showed that f-HNTs-mediated siRNA delivery effectively knocked down gene expression of survivin and thereby decreased the levels of target proteins of PANC-1 cells. Therefore, this study suggested that the synthesized f-HNTs were a new effective drug delivery system for potential application in cancer gene therapy.

A spot laser modulated resistance switching effect observed on n-type Mn-doped ZnO/SiO2/Si structure.

PubMed

Lu, Jing; Tu, Xinglong; Yin, Guilin; Wang, Hui; He, Dannong

2017-11-09

In this work, a spot laser modulated resistance switching (RS) effect is firstly observed on n-type Mn-doped ZnO/SiO 2 /Si structure by growing n-type Mn-doped ZnO film on Si wafer covered with a 1.2 nm native SiO 2 , which has a resistivity in the range of 50-80 Ω∙cm. The I-V curve obtained in dark condition evidences the structure a rectifying junction, which is further confirmed by placing external bias. Compared to the resistance state modulated by electric field only in dark (without illumination), the switching voltage driving the resistance state of the structure from one state to the other, shows clear shift under a spot laser illumination. Remarkably, the switching voltage shift shows a dual dependence on the illumination position and power of the spot laser. We ascribe this dual dependence to the electric filed produced by the redistribution of photo-generated carriers, which enhance the internal barrier of the hetero-junction. A complete theoretical analysis based on junction current and diffusion equation is presented. The dependence of the switching voltage on spot laser illumination makes the n-type Mn-doped ZnO/SiO 2 /Si structure sensitive to light, which thus allows for the integration of an extra functionality in the ZnO-based photoelectric device.

The Effect of Input-Based Instruction Type on the Acquisition of Spanish Accusative Clitics

ERIC Educational Resources Information Center

White, Justin

2015-01-01

The purpose of this paper is to compare structured input (SI) with other input-based instructional treatments. The input-based instructional types include: input flood (IF), text enhancement (TE), SI activities, and focused input (FI; SI without implicit negative feedback). Participants included 145 adult learners enrolled in an intermediate…

Boron doped Si rich oxide/SiO{sub 2} and silicon rich nitride/SiN{sub x} bilayers on molybdenum-fused silica substrates for vertically structured Si quantum dot solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Ziyun, E-mail: z.lin@unsw.edu.au; Wu, Lingfeng; Jia, Xuguang

2015-07-28

Vertically structured Si quantum dots (QDs) solar cells with molybdenum (Mo) interlayer on quartz substrates would overcome current crowding effects found in mesa-structured cells. This study investigates the compatibility between boron (B) doped Si QDs bilayers and Mo-fused silica substrate. Both Si/SiO{sub 2} and Si/SiN{sub x} based QDs bilayers were studied. The material compatibility under high temperature treatment was assessed by examining Si crystallinity, microstress, thin film adhesion, and Mo oxidation. It was observed that the presence of Mo interlayer enhanced the Si QDs size confinement, crystalline fraction, and QDs size uniformity. The use of B doping was preferred comparedmore » to phosphine (PH{sub 3}) doping studied previously in terms of better surface and interface properties by reducing oxidized spots on the film. Though crack formation due to thermal mismatch after annealing remained, methods to overcome this problem were proposed in this paper. Schematic diagram to fabricate full vertical structured Si QDs solar cells was also suggested.« less

Solid oxide membrane-assisted controllable electrolytic fabrication of metal carbides in molten salt.

PubMed

Zou, Xingli; Zheng, Kai; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu

2016-08-15

Silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and tantalum carbide (TaC) have been electrochemically produced directly from their corresponding stoichiometric metal oxides/carbon (MOx/C) precursors by electrodeoxidation in molten calcium chloride (CaCl2). An assembled yttria stabilized zirconia solid oxide membrane (SOM)-based anode was employed to control the electrodeoxidation process. The SOM-assisted controllable electrochemical process was carried out in molten CaCl2 at 1000 °C with a potential of 3.5 to 4.0 V. The reaction mechanism of the electrochemical production process and the characteristics of these produced metal carbides (MCs) were systematically investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses clearly identify that SiC, TiC, ZrC, and TaC carbides can be facilely fabricated. SiC carbide can be controlled to form a homogeneous nanowire structure, while the morphologies of TiC, ZrC, and TaC carbides exhibit porous nodular structures with micro/nanoscale particles. The complex chemical/electrochemical reaction processes including the compounding, electrodeoxidation, dissolution-electrodeposition, and in situ carbonization processes in molten CaCl2 are also discussed. The present results preliminarily demonstrate that the molten salt-based SOM-assisted electrodeoxidation process has the potential to be used for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs, which can potentially be used for various applications.

Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ-η5:η1 bonding indolyl and μ3-oxo groups.

PubMed

Yang, Song; Zhu, Xiancui; Zhou, Shuangliu; Wang, Shaowu; Feng, Zhijun; Wei, Yun; Miao, Hui; Guo, Liping; Wang, Fenhua; Zhang, Guangchao; Gu, Xiaoxia; Mu, Xiaolong

2014-02-14

The reactions of different pyrrolyl-functionalized indoles with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) produced different kinds of rare-earth metal amido complexes. Reactions of N-((1H-pyrrol-2-yl)methylene)-2-(1H-indol-3-yl)ethanamine with rare-earth metal amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) in toluene or THF at temperatures of 75-80 °C afforded the novel trinuclear rare-earth metal amido complexes incorporating the indolyl ligand in μ-η(5):η(1) bonding modes and a μ3-O group, which is believed to originate from cleavage of the THF ring based on experimental results. Reactions of 2-(1H-indol-3-yl)-N-((1-methyl-1H-pyrrol-2-yl)methylene)ethanamine with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Dy) produced mononuclear ytterbium and dysprosium amides having the indolyl ligand in an η(1) bonding fashion. The results indicate that substituents not only have an influence on reactivity, but also have an influence on the bonding of the indolyl ligands with metals. The catalytic activities of the novel lanthanide amido complexes for the hydrophosphonylation of both aromatic and aliphatic aldehydes and ketones were explored. The results indicate that these complexes display a high catalytic activity for the C-P bond formation under mild conditions when using low catalyst loadings (0.1 mol% for aldehydes and ketones). Thus, it provides a potential way to prepare α-hydroxy phosphonates.

Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand.

PubMed

Zhu, Xiancui; Li, Yang; Guo, Dianjun; Wang, Shaowu; Wei, Yun; Zhou, Shuangliu

2018-03-12

Herein, rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized β-diketiminato ligand with the formula LRE(CH 2 SiMe 3 ) 2 (thf) (RE = Y (1a), Dy (1b), Er (1c), Yb (1d); L = MeC(NDipp)CHC(Me)NCH 2 CH 2 NC 4 H 2 -2,5-Me 2 , Dipp = 2,6- i Pr 2 C 6 H 3 ) were synthesized via the reactions of the β-diketimine HL with the rare-earth metal trialkyl complexes RE(CH 2 SiMe 3 ) 3 (thf) 2 in high yields. The reactivities of 1 with pyridine derivatives, unsaturated substrates, and elemental sulfur were investigated, and some interesting chemical transformations were observed. Ligand exchange and activation of sp 2 and sp 3 C-H bonds occurred during the reactions with pyridine derivatives to afford different types of mononuclear rare-earth metal pyridyl complexes, namely, LEr(CH 2 SiMe 3 ) 2 (η 1 -NC 5 H 4 ) (2c), LRE(η 3 -CH 2 -2-NC 5 H 2 -4,6-Me 2 ) 2 (RE = Y (3a), Er (3c)), and LRE(CH 2 SiMe 3 )(η 2 -(C,N)-2-(2-C 6 H 4 NC 5 H 4 )) (RE = Er (4c), Yb = (4d)). Similarly, activation of the sp C-H bond occurred during the reaction of phenylacetylene with 1c to produce the dinuclear erbium alkynyl complex [LEr(CH 2 SiMe 3 )(μ-C[triple bond, length as m-dash]CPh)] 2 (5c). The mixed amidinate-β-diketiminato ytterbium complex LYb[(Dipp)NC(CH 2 SiMe 3 )N(Dipp)](CH 2 SiMe 3 ) (6d) was obtained by the insertion of bis(2,6-diisopropylphenyl)carbodiimide into a Yb-alkyl bond, as well as via the direct alkane elimination of a CH 2 SiMe 3 moiety with bis(2,6-diisopropylphenyl)formamidine to afford the erbium complex LEr(DippNCHNDipp)(CH 2 SiMe 3 ) (7c). A rare sp 2 C-H bond oxidation of the β-diketiminato backbone with elemental sulfur insertion was detected to provide the unprecedented dinuclear rare-earth metal thiolate complexes (LRE) 2 (μ-SCH 2 SiMe 3 ) 2 (μ-SCC(Me)(NDipp)C(Me)NCH 2 CH 2 NC 4 H 2 Me 2 -2,5) (RE = Y (8a), Er (8c)) in the reactions of S 8 with 1a and 1c, respectively. The molecular structures of the complexes 1-8 were determined by single-crystal X-ray diffraction analyses.

Aluminum acceptor four particle bound exciton complex in 4H, 6H, and 3C SiC

NASA Technical Reports Server (NTRS)

Clemen, L. L.; Devaty, R. P.; Macmillan, M. F.; Yoganathan, M.; Choyke, W. J.; Larkin, D. J.; Powell, J. A.; Edmond, J. A.; Kong, H. S.

1993-01-01

Evidence is presented for a four particle acceptor complex in 3C, 6H, and 4H SiC, obtained in low-temperature photoluminescence and cathodoluminescence experiments. The new lines were observed in p-type films lightly doped with aluminum, of 6H, 4H, and 3C SiC grown on the silicon (0001) face of 6H SiC under special conditions. The lines increase in intensity as more aluminum is added during growth. The multiplicity of observed lines is consistent with symmetry-based models similar to those which have been proposed to describe 4A centers in p-type zincblende semiconductors.

Dynamics of Defects and Dopants in Complex Systems: Si and Oxide Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

Kirichenko, Taras; Yu, Decai; Banarjee, Sanjay; Hwang, Gyeong

2004-10-01

Fabrication of forthcoming nanometer scale electronic devices faces many difficulties including formation of extremely shallow and highly doped junctions. At present, ultra-low-energy ion implantation followed by high-temperature thermal annealing is most widely used to fabricate such ultra-shallow junctions. In the process, a great challenge lies in achieving precise control of redistribution and electrical activation of dopant impurities. Native defects (such as vacancies and interstitials) generated during implantation are known to be mainly responsible for the TED and also influence significantly the electrical activation/deactivation. Defect-dopant dynamics is rather well understood in crystalline Si and SiO2. However, little is known about their diffusion and annihilation (or precipitation) at the surfaces and interfaces, despite its growing importance in determining junction profiles as device dimensions get smaller. In this talk, we will present our density functional theory calculation results on the atomic and electronic structure and dynamical behavior of native defects and dopant-defect complexes in disordered/strained Si and oxide systems, such as i) clean and absorbent-modified Si(100) surface and subsurface layers, ii) amorphous-crystalline Si interfaces and iii) amorphous SiO2/Si interfaces. The fundamental understanding and data is essential in developing a comprehensive kinetic model for junction formation, which would contribute greatly in improving current process technologies.

Examination of the Atomic Pair Distribution Function (PDF) of SiC Nanocrystals by In-situ High Pressure Diffraction

NASA Technical Reports Server (NTRS)

Grzanka, E.; Stelmakh, S.; Gierlotka, S.; Zhao, Y.; Palosz, B.; Palosz, W.

2003-01-01

Key properties of nanocrystals are determined by their real atomic structure, therefore a reasonable understanding and meaningful interpretation of their properties requires a realistic model of the structure. In this paper we present an evidence of a complex response of the lattice distances to external pressure indicating a presence of a complex structure of Sic nanopowders. The experiments were performed on nanocrystalline Sic subjected to hydrostatic or isostatic pressure using synchrotron and neutron powder diffraction. Elastic properties of the samples were examined based on X-ray diffraction data using a Diamond Anvil Cell (DAC) in HASYLAB at DESY. The dependence'of the lattice parameters and of the Bragg reflections width with pressure exhibits a ha1 nature of the properties (compressibilities) of the powders and indicates a complex structure of the grains. We interpreted tws behaviour as originating from different elastic properties of the grain interior and surface. Analysis of the dependence of individual interatomic distances on pressure was based on in-situ neutron diffraction measurements done with HbD diffractometer at LANSCE in Los Alamos National Laboratory with the Paris-Edinburgh cell under pressures up to 8 GPa (Qmax = 26/A). Interatomic distances were obtained by PDF analysis using the PDFgetN program. We have found that the interatomic distances undergo a complex, non-monotonic changes. Even under substantial pressures a considerable relaxation of the lattice may take place: some interatomic distances increase with an increase in pressure. We relate this phenomenon to: (1), changes of the microstructure of the densified material, in particular breaking of its fractal chain structure and, (2), its complex structure resembling that of a material composed of two phases, each with its distinct elastic properties.

Thousands of Stellar SiO masers in the Galactic center: The Bulge Asymmetries and Dynamic Evolution (BAaDE) survey

NASA Astrophysics Data System (ADS)

Sjouwerman, Loránt O.; Pihlström, Ylva M.; Rich, R. Michael; Morris, Mark R.; Claussen, Mark J.

2017-01-01

A radio survey of red giant SiO sources in the inner Galaxy and bulge is not hindered by extinction. Accurate stellar velocities (<1 km/s) are obtained with minimal observing time (<1 min) per source. Detecting over 20,000 SiO maser sources yields data comparable to optical surveys with the additional strength of a much more thorough coverage of the highly obscured inner Galaxy. Modeling of such a large sample would reveal dynamical structures and minority populations; the velocity structure can be compared to kinematic structures seen in molecular gas, complex orbit structure in the bar, or stellar streams resulting from recently infallen systems. Our Bulge Asymmetries and Dynamic Evolution (BAaDE) survey yields bright SiO masers suitable for follow-up Galactic orbit and parallax determination using VLBI. Here we outline our early VLA observations at 43 GHz in the northern bulge and Galactic plane (0

Quasi-2D silicon structures based on ultrathin Me2Si (Me = Mg, Ca, Sr, Ba) films

NASA Astrophysics Data System (ADS)

Migas, D. B.; Bogorodz, V. O.; Filonov, A. B.; Borisenko, V. E.; Skorodumova, N. V.

2018-04-01

By means of ab initio calculations with hybrid functionals we show a possibility for quasi-2D silicon structures originated from semiconducting Mg2Si, Ca2Si, Sr2Si and Ba2Si silicides to exist. Such a 2D structure is similar to the one of transition metal chalcogenides where silicon atoms form a layer in between of metal atoms aligned in surface layers. These metal surface atoms act as pseudo passivation species stabilizing crystal structure and providing semiconducting properties. Considered 2D Mg2Si, Ca2Si, Sr2Si and Ba2Si have band gaps of 1.14 eV, 0.69 eV, 0.33 eV and 0.19 eV, respectively, while the former one is also characterized by a direct transition with appreciable oscillator strength. Electronic states of the surface atoms are found to suppress an influence of the quantum confinement on the band gaps. Additionally, we report Sr2Si bulk in the cubic structure to have a direct band gap of 0.85 eV as well as sizable oscillator strength of the first direct transition.

Field electron emission based on resonant tunneling in diamond/CoSi2/Si quantum well nanostructures

PubMed Central

Gu, Changzhi; Jiang, Xin; Lu, Wengang; Li, Junjie; Mantl, Siegfried

2012-01-01

Excellent field electron emission properties of a diamond/CoSi2/Si quantum well nanostructure are observed. The novel quantum well structure consists of high quality diamond emitters grown on bulk Si substrate with a nanosized epitaxial CoSi2 conducting interlayer. The results show that the main emission properties were modified by varying the CoSi2 thickness and that stable, low-field, high emission current and controlled electron emission can be obtained by using a high quality diamond film and a thicker CoSi2 interlayer. An electron resonant tunneling mechanism in this quantum well structure is suggested, and the tunneling is due to the long electron mean free path in the nanosized CoSi2 layer. This structure meets most of the requirements for development of vacuum micro/nanoelectronic devices and large-area cold cathodes for flat-panel displays. PMID:23082241

Field electron emission based on resonant tunneling in diamond/CoSi2/Si quantum well nanostructures.

PubMed

Gu, Changzhi; Jiang, Xin; Lu, Wengang; Li, Junjie; Mantl, Siegfried

2012-01-01

Excellent field electron emission properties of a diamond/CoSi(2)/Si quantum well nanostructure are observed. The novel quantum well structure consists of high quality diamond emitters grown on bulk Si substrate with a nanosized epitaxial CoSi(2) conducting interlayer. The results show that the main emission properties were modified by varying the CoSi(2) thickness and that stable, low-field, high emission current and controlled electron emission can be obtained by using a high quality diamond film and a thicker CoSi(2) interlayer. An electron resonant tunneling mechanism in this quantum well structure is suggested, and the tunneling is due to the long electron mean free path in the nanosized CoSi(2) layer. This structure meets most of the requirements for development of vacuum micro/nanoelectronic devices and large-area cold cathodes for flat-panel displays.

Strain-free Ge/GeSiSn Quantum Cascade Lasers Based on L-Valley Intersubband Transitions

DTIC Science & Technology

2007-01-01

found in III-V quantum cascade lasers QCLs. Various groups have obtained electroluminescence from Si-rich Si/SiGe quantum cascade structures,2–4 but...Ge/GeSiSn quantum cascade lasers based on L-valley intersubband transitions 5c. PROGRAM ELEMENT NUMBER 612305 6. AUTHOR(S) 5d. PROJECT NUMBER...ABSTRACT The authors propose a Ge/Ge0.76Si0.19Sn0.05 quantum cascade laser using intersubband transitions at L valleys of the conduction band

Putting Humpty-Dumpty Together: Clustering the Functional Dynamics of Single Biomolecular Machines Such as the Spliceosome.

PubMed

Rohlman, C E; Blanco, M R; Walter, N G

2016-01-01

The spliceosome is a biomolecular machine that, in all eukaryotes, accomplishes site-specific splicing of introns from precursor messenger RNAs (pre-mRNAs) with high fidelity. Operating at the nanometer scale, where inertia and friction have lost the dominant role they play in the macroscopic realm, the spliceosome is highly dynamic and assembles its active site around each pre-mRNA anew. To understand the structural dynamics underlying the molecular motors, clocks, and ratchets that achieve functional accuracy in the yeast spliceosome (a long-standing model system), we have developed single-molecule fluorescence resonance energy transfer (smFRET) approaches that report changes in intra- and intermolecular interactions in real time. Building on our work using hidden Markov models (HMMs) to extract kinetic and conformational state information from smFRET time trajectories, we recognized that HMM analysis of individual state transitions as independent stochastic events is insufficient for a biomolecular machine as complex as the spliceosome. In this chapter, we elaborate on the recently developed smFRET-based Single-Molecule Cluster Analysis (SiMCAn) that dissects the intricate conformational dynamics of a pre-mRNA through the splicing cycle in a model-free fashion. By leveraging hierarchical clustering techniques developed for Bioinformatics, SiMCAn efficiently analyzes large datasets to first identify common molecular behaviors. Through a second level of clustering based on the abundance of dynamic behaviors exhibited by defined functional intermediates that have been stalled by biochemical or genetic tools, SiMCAn then efficiently assigns pre-mRNA FRET states and transitions to specific splicing complexes, with the potential to find heretofore undescribed conformations. SiMCAn thus arises as a general tool to analyze dynamic cellular machines more broadly. © 2016 Elsevier Inc. All rights reserved.

Confined Li ion migration in the silicon-graphene complex system: An ab initio investigation

NASA Astrophysics Data System (ADS)

Wang, Guoqing; Xu, Bo; Shi, Jing; Lei, Xueling; Ouyang, Chuying

2018-04-01

Silicon-Carbon complex systems play an important role in enhancing the performance of Si-based anode materials for Li ion batteries. In this work, the Li migration property of the Silicon-Graphene (Si-Gr) complex systems are investigated by using first-principles calculations. Especially, the effects of graphene coating on the migration of Li ions are discussed in detail. The distance between Si surface and graphene in the Si-Gr system significantly affects the lateral migration of Li ions. With the decrease of the distance from 4.715 to 3.844 Å, the energy barrier of Li ion migration also decreases from 0.115 to 0.067 eV, which are all lower than that of the case without graphene d(0.135 eV). However, smaller distance (3.586 Å) brings the high energy barrier (0.237 eV). Through AIMD calculations, it is found that the graphene coating in the Si-Gr complex system would result in the larger intercalation depths, more uniform distributions, and higher migration coefficients of Li ions. Further calculations of migration coefficients of Li ions at different temperature are used to obtained the activation energy for Li ions migration in the Si-Gr system, which is as low as 0.028 eV. This low activation energy shows that it is easy for Li ions migrating in the Si-Gr system. Our study provided the basically information to understand the migration mechanism of Li ions in Si-C system.

Luminal Starch Substrate "Brake" on Maltase-Glucoamylase Activity Is Located within the Glucoamylase Subunit

USDA-ARS?s Scientific Manuscript database

The detailed mechanistic aspects for the final starch digestion process leading to effective alpha-glucogenesis by the 2 mucosal alpha-glucosidases, human sucrase-isomaltase complex (SI) and human maltase-glucoamylase (MGAM), are poorly understood. This is due to the structural complexity and vast v...

Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry

NASA Astrophysics Data System (ADS)

Brieva, A. C.; Jenkins, T. E.; Jones, D. G.; Strössner, F.; Evans, D. A.; Clark, G. F.

2006-04-01

The internal structure of copper(II)-phthalocyanine (CuPc) thin films grown on SiO2/Si by organic molecular beam deposition has been studied by grazing incidence x-ray reflectometry (GIXR) and atomic force microscopy. The electronic density profile is consistent with a structure formed by successive monolayers of molecules in the α form with the b axis lying in the substrate surface plane. The authors present an electronic density profile model of CuPc films grown on SiO2/Si. The excellent agreement between the model and experimental data allows postdeposition monitoring of the internal structure of the CuPc films with the nondestructive GIXR technique, providing a tool for accurate control of CuPc growth on silicon-based substrates. In addition, since the experiments have been carried out ex situ, they show that these structures can endure ambient conditions.

Active pixel imagers incorporating pixel-level amplifiers based on polycrystalline-silicon thin-film transistors

PubMed Central

El-Mohri, Youcef; Antonuk, Larry E.; Koniczek, Martin; Zhao, Qihua; Li, Yixin; Street, Robert A.; Lu, Jeng-Ping

2009-01-01

Active matrix, flat-panel imagers (AMFPIs) employing a 2D matrix of a-Si addressing TFTs have become ubiquitous in many x-ray imaging applications due to their numerous advantages. However, under conditions of low exposures and∕or high spatial resolution, their signal-to-noise performance is constrained by the modest system gain relative to the electronic additive noise. In this article, a strategy for overcoming this limitation through the incorporation of in-pixel amplification circuits, referred to as active pixel (AP) architectures, using polycrystalline-silicon (poly-Si) TFTs is reported. Compared to a-Si, poly-Si offers substantially higher mobilities, enabling higher TFT currents and the possibility of sophisticated AP designs based on both n- and p-channel TFTs. Three prototype indirect detection arrays employing poly-Si TFTs and a continuous a-Si photodiode structure were characterized. The prototypes consist of an array (PSI-1) that employs a pixel architecture with a single TFT, as well as two arrays (PSI-2 and PSI-3) that employ AP architectures based on three and five TFTs, respectively. While PSI-1 serves as a reference with a design similar to that of conventional AMFPI arrays, PSI-2 and PSI-3 incorporate additional in-pixel amplification circuitry. Compared to PSI-1, results of x-ray sensitivity demonstrate signal gains of ∼10.7 and 20.9 for PSI-2 and PSI-3, respectively. These values are in reasonable agreement with design expectations, demonstrating that poly-Si AP circuits can be tailored to provide a desired level of signal gain. PSI-2 exhibits the same high levels of charge trapping as those observed for PSI-1 and other conventional arrays employing a continuous photodiode structure. For PSI-3, charge trapping was found to be significantly lower and largely independent of the bias voltage applied across the photodiode. MTF results indicate that the use of a continuous photodiode structure in PSI-1, PSI-2, and PSI-3 results in optical fill factors that are close to unity. In addition, the greater complexity of PSI-2 and PSI-3 pixel circuits, compared to that of PSI-1, has no observable effect on spatial resolution. Both PSI-2 and PSI-3 exhibit high levels of additive noise, resulting in no net improvement in the signal-to-noise performance of these early prototypes compared to conventional AMFPIs. However, faster readout rates, coupled with implementation of multiple sampling protocols allowed by the nondestructive nature of pixel readout, resulted in a significantly lower noise level of ∼560 e (rms) for PSI-3. PMID:19673229

Active pixel imagers incorporating pixel-level amplifiers based on polycrystalline-silicon thin-film transistors.

PubMed

El-Mohri, Youcef; Antonuk, Larry E; Koniczek, Martin; Zhao, Qihua; Li, Yixin; Street, Robert A; Lu, Jeng-Ping

2009-07-01

Active matrix, flat-panel imagers (AMFPIs) employing a 2D matrix of a-Si addressing TFTs have become ubiquitous in many x-ray imaging applications due to their numerous advantages. However, under conditions of low exposures and/or high spatial resolution, their signal-to-noise performance is constrained by the modest system gain relative to the electronic additive noise. In this article, a strategy for overcoming this limitation through the incorporation of in-pixel amplification circuits, referred to as active pixel (AP) architectures, using polycrystalline-silicon (poly-Si) TFTs is reported. Compared to a-Si, poly-Si offers substantially higher mobilities, enabling higher TFT currents and the possibility of sophisticated AP designs based on both n- and p-channel TFTs. Three prototype indirect detection arrays employing poly-Si TFTs and a continuous a-Si photodiode structure were characterized. The prototypes consist of an array (PSI-1) that employs a pixel architecture with a single TFT, as well as two arrays (PSI-2 and PSI-3) that employ AP architectures based on three and five TFTs, respectively. While PSI-1 serves as a reference with a design similar to that of conventional AMFPI arrays, PSI-2 and PSI-3 incorporate additional in-pixel amplification circuitry. Compared to PSI-1, results of x-ray sensitivity demonstrate signal gains of approximately 10.7 and 20.9 for PSI-2 and PSI-3, respectively. These values are in reasonable agreement with design expectations, demonstrating that poly-Si AP circuits can be tailored to provide a desired level of signal gain. PSI-2 exhibits the same high levels of charge trapping as those observed for PSI-1 and other conventional arrays employing a continuous photodiode structure. For PSI-3, charge trapping was found to be significantly lower and largely independent of the bias voltage applied across the photodiode. MTF results indicate that the use of a continuous photodiode structure in PSI-1, PSI-2, and PSI-3 results in optical fill factors that are close to unity. In addition, the greater complexity of PSI-2 and PSI-3 pixel circuits, compared to that of PSI-1, has no observable effect on spatial resolution. Both PSI-2 and PSI-3 exhibit high levels of additive noise, resulting in no net improvement in the signal-to-noise performance of these early prototypes compared to conventional AMFPIs. However, faster readout rates, coupled with implementation of multiple sampling protocols allowed by the nondestructive nature of pixel readout, resulted in a significantly lower noise level of approximately 560 e (rms) for PSI-3.

Positron annihilation spectroscopy: Applications to Si, ZnO, and multilayer semiconductor structures

NASA Astrophysics Data System (ADS)

Schaffer, J. P.; Rohatgi, A.; Dewald, A. B.; Frost, R. L.; Pang, S. K.

1989-11-01

The potential of positron annihilation spectroscopy (PAS) for defect characterization at the atomic scale in semiconductors is demonstrated for Si, ZnO, and multilayer structures, such as an AlGaAs/GaAs solar cell. The types of defects discussed include: i) vacancy complexes, oxygen impurities and dopants, ii) the influence of cooling rates on spatial non-uniformities in defects, and iii) characterization of buried interfaces. In sev-eral instances, the results of the PAS investigations are correlated with data from other established semiconductor characterization techniques.

Giant crystal-electric-field effect and complex magnetic behavior in single-crystalline CeRh3Si2

NASA Astrophysics Data System (ADS)

Pikul, A. P.; Kaczorowski, D.; Gajek, Z.; Stȩpień-Damm, J.; Ślebarski, A.; Werwiński, M.; Szajek, A.

2010-05-01

Single-crystalline CeRh3Si2 was investigated by means of x-ray diffraction, magnetic susceptibility, magnetization, electrical resistivity, and specific-heat measurements carried out in wide temperature and magnetic field ranges. Moreover, the electronic structure of the compound was studied at room temperature by cerium core-level x-ray photoemission spectroscopy (XPS). The physical properties were analyzed in terms of crystalline electric field and compared with results of ab initio band-structure calculations performed within the density-functional theory approach. The compound was found to crystallize in the orthorhombic unit cell of the ErRh3Si2 type (space group Imma No.74, Pearson symbol: oI24 ) with the lattice parameters a=7.1330(14)Å , b=9.7340(19)Å , and c=5.6040(11)Å . Analysis of the magnetic and XPS data revealed the presence of well-localized magnetic moments of trivalent cerium ions. All the physical properties were found to be highly anisotropic over the whole temperature range studied and influenced by exceptionally strong crystalline electric field with the overall splitting of the 4f1 ground multiplet exceeding 5700 K. Antiferromagnetic order of the cerium magnetic moments at TN=4.70(1)K and their subsequent spin rearrangement at Tt=4.48(1)K manifest themselves as distinct anomalies in the temperature characteristic of all the physical properties investigated and exhibit complex evolution in an external magnetic field. A tentative magnetic B-T phase diagram, constructed for B parallel to the b axis being the easy magnetization direction, shows very complex magnetic behavior of CeRh3Si2 , similar to that recently reported for an isostructural compound CeIr3Si2 . The electronic band-structure calculations corroborated the antiferromagnetic ordering of the cerium magnetic moments and well-reproduced the experimental XPS valence-band spectrum.

Method for improving the toughness of silicon carbide-based ceramics

DOEpatents

Tein, Tseng-Ying; Hilmas, Gregory E.

1996-01-01

Method of improving the toughness of SiC-based ceramics. SiC, , AlN, Al.sub.2 O.sub.3 and optionally .alpha.-Si.sub.3 N.sub.4 are hot pressed to form a material which includes AlN polytypoids within its structure.

Magneto-transport phenomena in metal/SiO2/n(p)-Si hybrid structures

NASA Astrophysics Data System (ADS)

Volkov, N. V.; Tarasov, A. S.; Rautskii, M. V.; Lukyanenko, A. V.; Bondarev, I. A.; Varnakov, S. N.; Ovchinnikov, S. G.

2018-04-01

Present review touches upon a subject of magnetotransport phenomena in hybrid structures which consist of ferromagnetic or nonmagnetic metal layer, layer of silicon oxide and silicon substrate with n- or p-type conductivity. Main attention will be paid to a number gigantic magnetotransport effects discovered in the devices fabricated on the base of the M/SiO2/n(p)-Si (M is ferromagnetic or paramagnetic metal) hybrid structures. These effects include bias induced dc magnetoresistance, gigantic magnetoimpedance, dc magnetoresistance induced by an optical irradiation and lateral magneto-photo-voltaic effect. The magnetoresistance ratio in ac and dc modes for some of our devices can exceed 106% in a magnetic field below 1 T. For lateral magneto-photo-voltaic effect, the relative change of photo-voltage in magnetic field can reach 103% at low temperature. Two types of mechanisms are responsible for sensitivity of the transport properties of the silicon based hybrid structures to magnetic field. One is related to transformation of the energy structure of the (donor) acceptor states including states near SiO2/n(p)-Si interface in magnetic field. Other mechanism is caused by the Lorentz force action. The features in behaviour of magnetotransport effects in concrete device depend on composition of the used structure, device topology and experimental conditions (bias voltage, optical radiation and others). Obtained results can be base for design of some electronic devices driven by a magnetic field. They can also provide an enhancement of the functionality for existing sensors.

Atomic Structure of Interface States in Silicon Heterojunction Solar Cells

NASA Astrophysics Data System (ADS)

George, B. M.; Behrends, J.; Schnegg, A.; Schulze, T. F.; Fehr, M.; Korte, L.; Rech, B.; Lips, K.; Rohrmüller, M.; Rauls, E.; Schmidt, W. G.; Gerstmann, U.

2013-03-01

Combining orientation dependent electrically detected magnetic resonance and g tensor calculations based on density functional theory we assign microscopic structures to paramagnetic states involved in spin-dependent recombination at the interface of hydrogenated amorphous silicon crystalline silicon (a-Si:H/c-Si) heterojunction solar cells. We find that (i) the interface exhibits microscopic roughness, (ii) the electronic structure of the interface defects is mainly determined by c-Si, (iii) we identify the microscopic origin of the conduction band tail state in the a-Si:H layer, and (iv) present a detailed recombination mechanism.

Inverse problems in complex material design: Applications to non-crystalline solids

NASA Astrophysics Data System (ADS)

Biswas, Parthapratim; Drabold, David; Elliott, Stephen

The design of complex amorphous materials is one of the fundamental problems in disordered condensed-matter science. While impressive developments of ab-initio simulation methods during the past several decades have brought tremendous success in understanding materials property from micro- to mesoscopic length scales, a major drawback is that they fail to incorporate existing knowledge of the materials in simulation methodologies. Since an essential feature of materials design is the synergy between experiment and theory, a properly developed approach to design materials should be able to exploit all available knowledge of the materials from measured experimental data. In this talk, we will address the design of complex disordered materials as an inverse problem involving experimental data and available empirical information. We show that the problem can be posed as a multi-objective non-convex optimization program, which can be addressed using a number of recently-developed bio-inspired global optimization techniques. In particular, we will discuss how a population-based stochastic search procedure can be used to determine the structure of non-crystalline solids (e.g. a-SiH, a-SiO2, amorphous graphene, and Fe and Ni clusters). The work is partially supported by NSF under Grant Nos. DMR 1507166 and 1507670.

Effect of Composite Substrates on the Mechanical Behavior of Brazed Joints in Metal-Composite System

NASA Technical Reports Server (NTRS)

Singh, M.; Morscher, Gregory N.; Shpargel, Tarah; Asthana, Rajiv

2006-01-01

Advanced composite components are being considered for a wide variety of demanding applications in aerospace, space exploration, and ground based systems. A number of these applications require robust integration technologies to join dissimilar materials (metalcomposites) into complex structural components. In this study, three types of composites (C-C, C-SiC, and SiC-SiC) were vacuum brazed to commercially pure Ti using the active metal braze alloy Cusil-ABA (63Ag-35.3Cu-1.75Ti). Composite substrates with as fabricated and polished surfaces were used for brazing. The microstructure and composition of the joint, examined using scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), showed sound metallurgical bonding in all systems. The butt strap tensile (BST) test was performed on bonded specimens at room and elevated temperatures. Effect of substrate composition, interlaminar properties, and surface roughness on the mechanical properties and failure behavior of joints will be discussed.

Processing, Structure and High Temperature Oxidation Properties of Polymer-Derived and Hafnium Oxide Based Ceramic Systems

NASA Astrophysics Data System (ADS)

Terauds, Kalvis

Demands for hypersonic aircraft are driving the development of ultra-high temperature structural materials. These aircraft, envisioned to sustain Mach 5+, are expected to experience continuous temperatures of 1200--1800°C on the aircraft surface and temperatures as high as 2800°C in combustion zones. Breakthroughs in the development of fiber based ceramic matrix composites (CMCs) are opening the door to a new class of high-tech UHT structures for aerospace applications. One limitation with current carbon fiber or silicon carbide fiber based CMC technology is the inherent problem of material oxidation, requiring new approaches for protective environmental barrier coatings (EBC) in extreme environments. This thesis focuses on the development and characterization of SiCN-HfO2 based ceramic composite EBC systems to be used as a protective layer for silicon carbide fiber based CMCs. The presented work covers three main architectures for protection (i) multilayer films, (ii) polymer-derived HfSiCNO, and (iii) composite SiCN-HfO 2 infiltration. The scope of this thesis covers processing development, material characterization, and high temperature oxidation behavior of these three SiCN-HfO2 based systems. This work shows that the SiCN-HfO 2 composite materials react upon oxidation to form HfSiO4, offering a stable EBC in streaming air and water vapor at 1600°C.

Rheological principles of development hetero-modulus and hetero-viscous complex materials with extreme dynamic strength

NASA Astrophysics Data System (ADS)

Gömze, L. A.; Gömze, L. N.

2017-02-01

Materials with different crystalline and morphological compositions have different chemical, physical, mechanical and rheological properties, including wear protection, melting temperature, module of elasticity and viscosity. Examining the material structures and behaviors of differentceramic bodies and CMCs under high speed collisions in several years the authors have understood the advantages of hetero-modulus and hetero-viscous complex material systems to absorb and dissipate the kinetic energy of objects during high speed collisions. Applying the rheo-mechanical principles the authors successfully developed a new family of hetero-modulus and hetero-viscous alumina matrix composite materials with extreme mechanical properties including dynamic strength. These new corundum-matrix composite materials reinforced with Si2ON 2, Si3N4 , SiAlON and AlN submicron and nanoparticles have excellent dynamic strength during collisions with high density metallic bodies with speeds about 1000 m/sec or more. At the same time in the alumina matrix composites can be observed a phase transformation of submicron and nanoparticles of alpha and beta silicone-nitride crystals into cubicc-Si3N4 diamond-like particles can be observed, when the high speed collision processes are taken place in vacuum or oxygen-free atmosphere. Using the rheological principles and the energy engorgement by fractures, heating and melting of components the authors successfully developed several new hetero-modulus, hetero-viscous and hetero-plastic complex materials. These materials generally are based on ceramic matrixes and components having different melting temperatures and modules of elasticity from low values like carbon and light metals (Mg, Al, Ti, Si) up to very high values like boride, nitride and carbide ceramics. Analytical methods applied in this research were scanning electron microscopy, X-ray diffractions and energy dispersive spectrometry. Digital image analysis was applied to microscopy results to enhance the results of transformations.

Work function characterization of solution-processed cobalt silicide

DOE PAGES

Ullah, Syed Shihab; Robinson, Matt; Hoey, Justin; ...

2012-05-08

Cobalt silicide thin films were prepared by spin-coating Si6H12-based inks onto various substrates followed by a thermal treatment. The work function of the solution processed Co-Si was determined by both capacitance-voltage (C-V) measurements of metal-oxide-semiconductor (MOS) structures as well as by ultraviolet photoelectron spectroscopy (UPS). The UPS-derived work function was 4.80 eV for a Co-Si film on Si (100) while C-V of MOS structures yielded a work function of 4.36 eV where the metal was solution-processed Co-Si, the oxide was SiO2 and the semiconductor was a B-doped Si wafer.

The role of chemical structure on the magnetic and electronic properties of Co{sub 2}FeAl{sub 0.5}Si{sub 0.5}/Si(111) interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuerbanjiang, Balati; Nedelkoski, Zlatko; Ghasemi, Arsham

2016-04-25

We show that Co{sub 2}FeAl{sub 0.5}Si{sub 0.5} film deposited on Si(111) has a single crystal structure and twin related epitaxial relationship with the substrate. Sub-nanometer electron energy loss spectroscopy shows that in a narrow interface region there is a mutual inter-diffusion dominated by Si and Co. Atomic resolution aberration-corrected scanning transmission electron microscopy reveals that the film has B2 ordering. The film lattice structure is unaltered even at the interface due to the substitutional nature of the intermixing. First-principles calculations performed using structural models based on the aberration corrected electron microscopy show that the increased Si incorporation in the filmmore » leads to a gradual decrease of the magnetic moment as well as significant spin-polarization reduction. These effects can have significant detrimental role on the spin injection from the Co{sub 2}FeAl{sub 0.5}Si{sub 0.5} film into the Si substrate, besides the structural integrity of this junction.« less

Study of a SiGeSn/GeSn/SiGeSn structure toward direct bandgap type-I quantum well for all group-IV optoelectronics.

PubMed

Ghetmiri, Seyed Amir; Zhou, Yiyin; Margetis, Joe; Al-Kabi, Sattar; Dou, Wei; Mosleh, Aboozar; Du, Wei; Kuchuk, Andrian; Liu, Jifeng; Sun, Greg; Soref, Richard A; Tolle, John; Naseem, Hameed A; Li, Baohua; Mortazavi, Mansour; Yu, Shui-Qing

2017-02-01

A SiGeSn/GeSn/SiGeSn single quantum well structure was grown using an industry standard chemical vapor deposition reactor with low-cost commercially available precursors. The material characterization revealed the precisely controlled material growth process. Temperature-dependent photoluminescence spectra were correlated with band structure calculation for a structure accurately determined by high-resolution x-ray diffraction and transmission electron microscopy. Based on the result, a systematic study of SiGeSn and GeSn bandgap energy separation and barrier heights versus material compositions and strain was conducted, leading to a practical design of a type-I direct bandgap quantum well.

Atomic and electronic structures of Si(1 1 1)-\\left(\\sqrt{\\mathbf{3}}\\times\\sqrt{\\mathbf{3}}\\right)\\text{R}\\mathbf{3}{{\\mathbf{0}}^{\\circ}} -Au and (6 × 6)-Au surfaces

NASA Astrophysics Data System (ADS)

Patterson, C. H.

2015-12-01

Si(1 1 1)-Au surfaces with around one monolayer of Au exhibit many ordered structures and structures containing disordered domain walls. Hybrid density functional theory (DFT) calculations presented here reveal the origin of these complex structures and tendency to form domain walls. The conjugate honeycomb chain trimer (CHCT) structure of the \\sqrt{3} -Au phase contains Si atoms with non-bonding surface states which can bind Au atoms in pairs in interstices of the CHCT structure and make this surface metallic. Si adatoms adsorbed on the \\sqrt{3} -Au surface induce a gapped surface through interaction with the non-bonding states. Adsorption of extra Au atoms in interstitial sites of the \\sqrt{3} -Au surface is stabilized by interaction with the non-bonding orbitals and leads to higher coverage ordered structures including the ≤ft(6× 6\\right) -Au phase. Extra Au atoms bound in interstitial sites of the \\sqrt{3} -Au surface result in top layer Si atoms with an SiAu4 butterfly wing configuration. The structure of a ≤ft(6× 6\\right) -Au phase, whose in-plane top atomic layer positions were previously determined by an electron holography technique (Grozea et al 1998 Surf. Sci. 418 32), is calculated using total energy minimization. The Patterson function for this structure is calculated and is in good agreement with data from an in-plane x-ray diffraction study (Dornisch et al 1991 Phys. Rev. B 44 11221). Filled and empty state scanning tunneling microscopy (STM) images are calculated for domain walls and the ≤ft(6× 6\\right) -Au structure. The ≤ft(6× 6\\right) -Au phase is 2D chiral and this is evident in computed and actual STM images. ≤ft(6× 6\\right) -Au and domain wall structures contain the SiAu4 motif with a butterfly wing shape. Chemical bonding within the Si-Au top layers of the \\sqrt{3} -Au and ≤ft(6× 6\\right) -Au surfaces is analyzed and an explanation for the SiAu4 motif structure is given.

Influence of annealing temperature on optical properties of the photonic-crystal structures obtained by self-organization of colloidal microspheres of polystyrene and silica

NASA Astrophysics Data System (ADS)

Mikhnev, L. V.; Bondarenko, E. A.; Chapura, O. M.; Skomorokhov, A. A.; Kravtsov, A. A.

2018-01-01

The influence of annealing temperature on the transmission spectra of photonic crystals composed of polystyrene and silicon dioxide microspheres was studied. It was found that annealing of photonic crystals based on polystyrene and silica leads to a shift in the photonic band gap to the short-wavelength region. Based on the results of optical studies, the dependences of the structural parameters of the obtained opal-like crystals on annealing temperature were obtained. In the case of polystyrene photonic crystals, the displacement of the photonic band gap is observed in a narrow temperature range above the glass transition temperature. For SiO2 photonic crystals, it was found that the process of microspheres sintering is complex and involves three stages of structural modification.

DICER-ARGONAUTE2 Complex in Continuous Fluorogenic Assays of RNA Interference Enzymes

PubMed Central

Bernard, Mark A.; Wang, Leyu; Tachado, Souvenir D.

2015-01-01

Mechanistic studies of RNA processing in the RNA-Induced Silencing Complex (RISC) have been hindered by lack of methods for continuous monitoring of enzymatic activity. “Quencherless” fluorogenic substrates of RNAi enzymes enable continuous monitoring of enzymatic reactions for detailed kinetics studies. Recombinant RISC enzymes cleave the fluorogenic substrates targeting human thymidylate synthase (TYMS) and hypoxia-inducible factor 1-α subunit (HIF1A). Using fluorogenic dsRNA DICER substrates and fluorogenic siRNA, DICER+ARGONAUTE2 mixtures exhibit synergistic enzymatic activity relative to either enzyme alone, and addition of TRBP does not enhance the apparent activity. Titration of AGO2 and DICER in enzyme assays suggests that AGO2 and DICER form a functional high-affinity complex in equimolar ratio. DICER and DICER+AGO2 exhibit Michaelis-Menten kinetics with DICER substrates. However, AGO2 cannot process the fluorogenic siRNA without DICER enzyme, suggesting that AGO2 cannot self-load siRNA into its active site. The DICER+AGO2 combination processes the fluorogenic siRNA substrate (K m=74 nM) with substrate inhibition kinetics (K i=105 nM), demonstrating experimentally that siRNA binds two different sites that affect Dicing and AGO2-loading reactions in RISC. This result suggests that siRNA (product of DICER) bound in the active site of DICER may undergo direct transfer (as AGO2 substrate) to the active site of AGO2 in the DICER+AGO2 complex. Competitive substrate assays indicate that DICER+AGO2 cleavage of fluorogenic siRNA is specific, since unlabeled siRNA and DICER substrates serve as competing substrates that cause a concentration-dependent decrease in fluorescent rates. Competitive substrate assays of a series of DICER substrates in vitro were correlated with cell-based assays of HIF1A mRNA knockdown (log-log slope=0.29), suggesting that improved DICER substrate designs with 10-fold greater processing by the DICER+AGO2 complex can provide a strong (~2800-fold) improvement in potency for mRNA knockdown. This study lays the foundation of a systematic biochemical approach to optimize nucleic acid-based therapeutics for Dicing and ARGONAUTE2-loading for improving efficacy. PMID:25793518

Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles.

PubMed

Givaja, Gonzalo; Volpe, Manuel; Leeland, James W; Edwards, Michael A; Young, Thomas K; Darby, S Barnie; Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Wolowska, Joanna; McInnes, Eric J L; Schröder, Martin; Love, Jason B

2007-01-01

The syntheses, characterisation and complexation reactions of a series of binucleating Schiff-base calixpyrrole macrocycles are described. The acid-templated [2+2] condensations between meso-disubstituted diformyldipyrromethanes and o-phenylenediamines generate the Schiff-base pyrrolic macrocycles H(4)L(1) to H(4)L(6) upon basic workup. The single-crystal X-ray structures of both H(4)L(3).2 EtOH and H(4)L(6).H2O confirm that [2+2] cyclisation has occurred, with either EtOH or H2O hydrogen-bonded within the macrocyclic cleft. A series of complexation reactions generate the dipalladium [Pd2(L)] (L=L(1) to L(5)), dinickel [Ni2(L(1))] and dicopper [Cu2(L)] (L=L(1) to L(3)) complexes. All of these complexes have been structurally characterised in the solid state and are found to adopt wedged structures that are enforced by the rigidity of the aryl backbone to give a cleft reminiscent of the structures of Pacman porphyrins. The binuclear nickel complexes [Ni2(mu-OMe)2Cl2(HOMe)2(H(4)L(1))] and [Ni2(mu-OH)2Cl2(HOMe)(H(4)L(5))] have also been prepared, although in these cases the solid-state structures show that the macrocyclic ligand remains protonated at the pyrrolic nitrogen atoms, and the Ni(II) cations are therefore co-ordinated by the imine nitrogen atoms only to give an open conformation for the complex. The dicopper complex [Cu2(L(3))] was crystallised in the presence of pyridine to form the adduct [Cu2(py)(L(3))], in which, in the solid state, the pyridine ligand is bound within the binuclear molecular cleft. Reaction between H(4)L(1) and [Mn(thf){N(SiMe(3))2}2] results in clean formation of the dimanganese complex [Mn2(L(1))], which, upon crystallisation, formed the mixed-valent complex [Mn2(mu-OH)(L(1))] in which the hydroxo ligand bridges the metal centres within the molecular cleft.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

PubMed

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

Method for improving the toughness of silicon carbide-based ceramics

DOEpatents

Tein, T.Y.; Hilmas, G.E.

1996-12-03

Method of improving the toughness of SiC-based ceramics is disclosed. SiC, , AlN, Al{sub 2}O{sub 3} and optionally {alpha}-Si{sub 3}N{sub 4} are hot pressed to form a material which includes AlN polytypoids within its structure. 1 fig.

Structure-based design, synthesis, and biological evaluation of novel pyrrolyl aryl sulfones: HIV-1 non-nucleoside reverse transcriptase inhibitors active at nanomolar concentrations.

PubMed

Artico, M; Silvestri, R; Pagnozzi, E; Bruno, B; Novellino, E; Greco, G; Massa, S; Ettorre, A; Loi, A G; Scintu, F; La Colla, P

2000-05-04

Pyrrolyl aryl sulfones (PASs) have been recently reported as a new class of human immunodeficiency virus type 1 (HIV-1) reverse transcriptase (RT) inhibitors acting at the non-nucleoside binding site of this enzyme (Artico, M.; et al. J. Med. Chem. 1996, 39, 522-530). Compound 3, the most potent inhibitor within the series (EC(50) = 0.14 microM, IC(50) = 0.4 microM, and SI > 1429), was then selected as a lead compound for a synthetic project based on molecular modeling studies. Using the three-dimensional structure of RT cocrystallized with the alpha-APA derivative R95845, we derived a model of the RT/3 complex by taking into account previously developed structure-activity relationships. Inspection of this model and docking calculations on virtual compounds prompted the design of novel PAS derivatives and related analogues. Our computational approach proved to be effective in making qualitative predictions, that is in discriminating active versus inactive compounds. Among the compounds synthesized and tested, 20 was the most active one, with EC(50) = 0.045 microM, IC(50) = 0.05 microM, and SI = 5333. Compared with the lead 3, these values represent a 3- and 8-fold improvement in the cell-based and enzyme assays, respectively, together with the highest selectivity achieved so far in the PAS series.

The Nanometer-Sized Eutectic Structure of Si/CrSi2 Thermoelectric Materials Fabricated by Rapid Solidification

NASA Astrophysics Data System (ADS)

Norizan, Mohd Natashah; Miyazaki, Yoshinobu; Ohishi, Yuji; Muta, Hiroaki; Kurosaki, Ken; Yamanaka, Shinsuke

2018-04-01

Nanostructuring is known to be an effective method to improve thermoelectric performance but, generally, it requires complex procedures and much labor. In the present study, self-assembled nanometer-sized composite structures of silicon (Si) and chromium disilicide (CrSi2) were easily fabricated by the rapid solidification of a melt with a eutectic composition. Ribbon-like samples were obtained with a dominant nanostructure of fine aligned lamellae with a spacing range of 20-35 nm. The thermoelectric power factor of the ribbon was observed to be 1.2 mW/mK2 at room temperature and reached 3.0 mW/mK2 at 773 K. The thermal conductivity was 65% lower than that of a bulk eutectic sample. The results suggest that this method is promising for fabricating an effective nanostructure for thermoelectric performance.

Templated assembly of albumin-based nanoparticles for simultaneous gene silencing and magnetic resonance imaging

NASA Astrophysics Data System (ADS)

Mertz, Damien; Affolter-Zbaraszczuk, Christine; Barthès, Julien; Cui, Jiwei; Caruso, Frank; Baumert, Thomas F.; Voegel, Jean-Claude; Ogier, Joelle; Meyer, Florent

2014-09-01

In this article, we address the design of innovative human serum albumin (HSA)-based nanoparticles loaded with silencing RNA and grafted with gadolinium complexes having average sizes ranging from ca. 50 to 150 nm according to the siRNA/HSA composition. The non-covalent siRNA/HSA assembly is formed on isobutyramide-modified mesoporous silica and the self-supported HSA-based nanoparticles are obtained following the silica template dissolution. These original protein particles provide simultaneous magnetic resonance imaging contrast enhancement and cellular in vitro gene silencing.In this article, we address the design of innovative human serum albumin (HSA)-based nanoparticles loaded with silencing RNA and grafted with gadolinium complexes having average sizes ranging from ca. 50 to 150 nm according to the siRNA/HSA composition. The non-covalent siRNA/HSA assembly is formed on isobutyramide-modified mesoporous silica and the self-supported HSA-based nanoparticles are obtained following the silica template dissolution. These original protein particles provide simultaneous magnetic resonance imaging contrast enhancement and cellular in vitro gene silencing. Electronic supplementary information (ESI) available: Experimental details and supporting Fig. S1-S4. See DOI: 10.1039/c4nr02623c

A galactose-functionalized dendritic siRNA-nanovector to potentiate hepatitis C inhibition in liver cells

NASA Astrophysics Data System (ADS)

Lakshminarayanan, Abirami; Reddy, B. Uma; Raghav, Nallani; Ravi, Vijay Kumar; Kumar, Anuj; Maiti, Prabal K.; Sood, A. K.; Jayaraman, N.; Das, Saumitra

2015-10-01

A RNAi based antiviral strategy holds the promise to impede hepatitis C viral (HCV) infection overcoming the problem of emergence of drug resistant variants, usually encountered in the interferon free direct-acting antiviral therapy. Targeted delivery of siRNA helps minimize adverse `off-target' effects and maximize the efficacy of therapeutic response. Herein, we report the delivery of siRNA against the conserved 5'-untranslated region (UTR) of HCV RNA using a liver-targeted dendritic nano-vector functionalized with a galactopyranoside ligand (DG). Physico-chemical characterization revealed finer details of complexation of DG with siRNA, whereas molecular dynamic simulations demonstrated sugar moieties projecting ``out'' in the complex. Preferential delivery of siRNA to the liver was achieved through a highly specific ligand-receptor interaction between dendritic galactose and the asialoglycoprotein receptor. The siRNA-DG complex exhibited perinuclear localization in liver cells and co-localization with viral proteins. The histopathological studies showed the systemic tolerance and biocompatibility of DG. Further, whole body imaging and immunohistochemistry studies confirmed the preferential delivery of the nucleic acid to mice liver. Significant decrease in HCV RNA levels (up to 75%) was achieved in HCV subgenomic replicon and full length HCV-JFH1 infectious cell culture systems. The multidisciplinary approach provides the `proof of concept' for restricted delivery of therapeutic siRNAs using a target oriented dendritic nano-vector.A RNAi based antiviral strategy holds the promise to impede hepatitis C viral (HCV) infection overcoming the problem of emergence of drug resistant variants, usually encountered in the interferon free direct-acting antiviral therapy. Targeted delivery of siRNA helps minimize adverse `off-target' effects and maximize the efficacy of therapeutic response. Herein, we report the delivery of siRNA against the conserved 5'-untranslated region (UTR) of HCV RNA using a liver-targeted dendritic nano-vector functionalized with a galactopyranoside ligand (DG). Physico-chemical characterization revealed finer details of complexation of DG with siRNA, whereas molecular dynamic simulations demonstrated sugar moieties projecting ``out'' in the complex. Preferential delivery of siRNA to the liver was achieved through a highly specific ligand-receptor interaction between dendritic galactose and the asialoglycoprotein receptor. The siRNA-DG complex exhibited perinuclear localization in liver cells and co-localization with viral proteins. The histopathological studies showed the systemic tolerance and biocompatibility of DG. Further, whole body imaging and immunohistochemistry studies confirmed the preferential delivery of the nucleic acid to mice liver. Significant decrease in HCV RNA levels (up to 75%) was achieved in HCV subgenomic replicon and full length HCV-JFH1 infectious cell culture systems. The multidisciplinary approach provides the `proof of concept' for restricted delivery of therapeutic siRNAs using a target oriented dendritic nano-vector. Electronic supplementary information (ESI) available: Spectral data and experimental details. See DOI: 10.1039/c5nr02898a

Ge/graded-SiGe multiplication layers for low-voltage and low-noise Ge avalanche photodiodes on Si

NASA Astrophysics Data System (ADS)

Miyasaka, Yuji; Hiraki, Tatsurou; Okazaki, Kota; Takeda, Kotaro; Tsuchizawa, Tai; Yamada, Koji; Wada, Kazumi; Ishikawa, Yasuhiko

2016-04-01

A new structure is examined for low-voltage and low-noise Ge-based avalanche photodiodes (APDs) on Si, where a Ge/graded-SiGe heterostructure is used as the multiplication layer of a separate-absorption-carrier-multiplication structure. The Ge/SiGe heterojunction multiplication layer is theoretically shown to be useful for preferentially enhancing impact ionization for photogenerated holes injected from the Ge optical-absorption layer via the graded SiGe, reflecting the valence band discontinuity at the Ge/SiGe interface. This property is effective not only for the reduction of operation voltage/electric field strength in Ge-based APDs but also for the reduction of excess noise resulting from the ratio of the ionization coefficients between electrons and holes being far from unity. Such Ge/graded-SiGe heterostructures are successfully fabricated by ultrahigh-vacuum chemical vapor deposition. Preliminary pin diodes having a Ge/graded-SiGe multiplication layer act reasonably as photodetectors, showing a multiplication gain larger than those for diodes without the Ge/SiGe heterojunction.

Crystal structure of tricarbon­yl(μ-di­phenyl­phosphido-κ2 P:P)(methyl­diphenyl­silyl-κSi)bis(tri­phenyl­phosphane-κP)iron(II)platinum(0)(Fe—Pt)

PubMed Central

Mohamed, Ahmed Said; Jourdain, Isabelle; Knorr, Michael; Rousselin, Yoann; Kubicki, Marek M.

2015-01-01

The title compound, [FePt(C12H10P)(C13H13Si)(C18H15P)2(CO)3]·0.5CH2Cl2, represents an example of a phosphido-bridged heterobimetallic silyl complex; these are inter­esting precursors for the coordination and activation of small unsaturated organic mol­ecules. The μ2-PPh2 ligand spans the iron and platinum atoms, which are connected via a metal–metal bond of 2.7738 (4) Å. In contrast to most other complexes of the [(OC)3Fe(SiR 3)(μ-PR 2)PtL 2] family, where the iron-bound SiR 3 group is trans-arranged with respect to the μ2-PPh2 ligand, the SiPh2Me ligand is roughly collinear with the Fe–Pt vector [Si—Fe—Pt = 169.07 (3)°]. PMID:25878830

Colloidal and electrochemical aspects of copper-CMP

NASA Astrophysics Data System (ADS)

Sun, Yuxia

Copper based interconnects with low dielectric constant layers are currently used to increase interconnect densities and reduce interconnect time delays in integrated circuits. The technology used to develop copper interconnects involves Chemical Mechanical Planarization (CMP) of copper films deposited on low-k layers (silica or silica based films), which is carried out using slurries containing abrasive particles. One issue using such a structure is copper contamination over dielectric layers (SiO2 film), if not reduced, this contamination will cause current leakage. In this study, the conditions conducive to copper contamination onto SiO2 films during Cu-CMP process were studied, and a post-CMP cleaning technique was discussed based on experimental results. It was found that the adsorption of copper onto a silica surface is kinetically fast (<0.5 minute). The amount of copper absorbed is pH and concentration dependent and affected by presence of H2O2, complexing agents, and copper corrosion inhibitor Benzotrazole. Based on de-sorption results, DI water alone was unable to reduce adsorbed copper to an acceptable level, especially for adsorption that takes place at a higher pH condition. The addition of complex agent, citric acid, proved effective in suppressing copper adsorption onto oxide silica during polishing or post-CMP cleaning by forming stable copper-CA complexes. Surface Complexation Modeling was used to simulate copper adsorption isotherms and predict the copper contamination levels on SiO2 surfaces. Another issue with the application of copper CMP is its environmental impact. CMP is a costly process due to its huge consumption of pure water and slurry. Additionally, Cu-CMP processing generates a waste stream containing certain amounts of copper and abrasive slurry particles. In this study, the separation technique electrocoagulation was investigated to remove both copper and abrasive slurry particles simultaneously. For effluent containing ˜40 ppm dissolved copper, it was found that ˜90% dissolved copper was removed from the waste streams through electroplating and in-situ chemical precipitation. The amount of copper removed through plating is impacted by membrane surface charge, type/amount of complexing agents, and solid content in the slurry suspension. The slurry particles can be removed ˜90% within 2 hours of EC through multiple mechanisms.

Structural and electronic properties of the transition layer at the SiO{sub 2}/4H-SiC interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wenbo; Wang, Dejun, E-mail: dwang121@dlut.edu.cn; Zhao, Jijun

Using first-principles methods, we generate an amorphous SiO{sub 2}/4H-SiC interface with a transition layer. Based this interface model, we investigate the structural and electronic properties of the interfacial transition layer. The calculated Si 2p core-level shifts for this interface are comparable to the experimental data, indicating that various SiC{sub x}O{sub y} species should be present in this interface transition layer. The analysis of the electronic structures reveals that the tetrahedral SiC{sub x}O{sub y} structures cannot introduce any of the defect states at the interface. Interestingly, our transition layer also includes a C-C=C trimer and SiO{sub 5} configurations, which lead tomore » the generation of interface states. The accurate positions of Kohn-Sham energy levels associated with these defects are further calculated within the hybrid functional scheme. The Kohn-Sham energy levels of the carbon trimer and SiO{sub 5} configurations are located near the conduction and valence band of bulk 4H-SiC, respectively. The result indicates that the carbon trimer occurred in the transition layer may be a possible origin of near interface traps. These findings provide novel insight into the structural and electronic properties of the realistic SiO{sub 2}/SiC interface.« less

Compact and low power operation optical switch using silicon-germanium/silicon hetero-structure waveguide.

PubMed

Sekiguchi, Shigeaki; Kurahashi, Teruo; Zhu, Lei; Kawaguchi, Kenichi; Morito, Ken

2012-04-09

We proposed a silicon-based optical switch with a carrier-plasma-induced phase shifter which employs a silicon-germanium (SiGe) / silicon (Si) hetero-structure in the waveguide core. A type-I hetero-interface formed by SiGe and Si is expected to confine carriers effectively in the SiGe waveguide core. The fabricated Mach-Zehnder optical switch shows a low switching power of only 1.53 mW with a compact phase shifter length of 250 μm. The switching time of the optical switch is less than 4.6 ns for the case of a square waveform driving condition, and 1 ns for the case of a pre-emphasis electric driving condition. These results show that our proposed SiGe/Si waveguide structure holds promise for active devices with compact size and low operation power.

The coordination chemistry of the neutral tris-2-pyridyl silicon ligand [PhSi(6-Me-2-py)3].

PubMed

Plajer, Alex J; Colebatch, Annie L; Enders, Markus; García-Romero, Álvaro; Bond, Andrew D; García-Rodríguez, Raúl; Wright, Dominic S

2018-05-22

Difficulties in the preparation of neutral ligands of the type [RSi(2-py)3] (where 2-py is an unfunctionalised 2-pyridyl ring unit) have thwarted efforts to expand the coordination chemistry of ligands of this type. However, simply switching the pyridyl substituents to 6-methyl-pyridyl groups (6-Me-2-py) in the current paper has allowed smooth, high-yielding access to the [PhSi(6-Me-2-py)3] ligand (1), and the first exploration of its coordination chemistry with transition metals. The synthesis, single-crystal X-ray structures and solution dynamics of the new complexes [{PhSi(6-Me-2-py)3}CuCH3CN][PF6], [{PhSi(6-Me-2-py)3}CuCH3CN][CuCl2], [{PhSi(6-Me-2-py)3}FeCl2], [{PhSi(6-Me-2-py)3}Mo(CO)3] and [{PhSi(6-Me-2-py)3}CoCl2] are reported. The paramagnetic Fe2+ and Co2+ complexes show strongly shifted NMR resonances for the coordinated pyridyl units due to large Fermi-contact shifts. However, magnetic anisotropy also leads to considerable pseudo-contact shifts so that both contributions have to be included in the paramagnetic NMR analysis.

Nanoscale plasmonic phenomena in CVD-grown MoS 2 monolayer revealed by ultra-broadband synchrotron radiation based nano-FTIR spectroscopy and near-field microscopy

DOE PAGES

Patoka, Piotr; Ulrich, Georg; Nguyen, Ariana E.; ...

2016-01-13

Here, nanoscale plasmonic phenomena observed in single and bi-layers of molybdenum disulfide (MoS 2) on silicon dioxide (SiO 2) are reported. A scattering type scanning near-field optical microscope (s-SNOM) with a broadband synchrotron radiation (SR) infrared source was used. We also present complementary optical mapping using tunable CO 2-laser radiation. Specifically, there is a correlation of the topography of well-defined MoS 2 islands grown by chemical vapor deposition, as determined by atomic force microscopy, with the infrared (IR) signature of MoS 2. The influence of MoS 2 islands on the SiO 2 phonon resonance is discussed. The results reveal themore » plasmonic character of the MoS 2 structures and their interaction with the SiO 2 phonons leading to an enhancement of the hybridized surface plasmon-phonon mode. A theoretical analysis shows that, in the case of monolayer islands, the coupling of the MoS 2 optical plasmon mode to the SiO 2 surface phonons does not affect the infrared spectrum significantly. For two-layer MoS 2, the coupling of the extra inter-plane acoustic plasmon mode with the SiO 2 surface transverse phonon leads to a remarkable increase of the surface phonon peak at 794 cm -1. This is in agreement with the experimental data. These results show the capability of the s-SNOM technique to study local multiple excitations in complex non-homogeneous structures.« less

Designing highly active siRNAs for therapeutic applications.

PubMed

Walton, S Patrick; Wu, Ming; Gredell, Joseph A; Chan, Christina

2010-12-01

The discovery of RNA interference (RNAi) generated considerable interest in developing short interfering RNAs (siRNAs) for understanding basic biology and as the active agents in a new variety of therapeutics. Early studies showed that selecting an active siRNA was not as straightforward as simply picking a sequence on the target mRNA and synthesizing the siRNA complementary to that sequence. As interest in applying RNAi has increased, the methods for identifying active siRNA sequences have evolved from focusing on the simplicity of synthesis and purification, to identifying preferred target sequences and secondary structures, to predicting the thermodynamic stability of the siRNA. As more specific details of the RNAi mechanism have been defined, these have been incorporated into more complex siRNA selection algorithms, increasing the reliability of selecting active siRNAs against a single target. Ultimately, design of the best siRNA therapeutics will require design of the siRNA itself, in addition to design of the vehicle and other components necessary for it to function in vivo. In this minireview, we summarize the evolution of siRNA selection techniques with a particular focus on one issue of current importance to the field, how best to identify those siRNA sequences likely to have high activity. Approaches to designing active siRNAs through chemical and structural modifications will also be highlighted. As the understanding of how to control the activity and specificity of siRNAs improves, the potential utility of siRNAs as human therapeutics will concomitantly grow. © 2010 The Authors Journal compilation © 2010 FEBS.

SiC-Based Schottky Diode Gas Sensors

NASA Technical Reports Server (NTRS)

Hunter, Gary W.; Neudeck, Philip G.; Chen, Liang-Yu; Knight, Dak; Liu, Chung-Chiun; Wu, Quing-Hai

1997-01-01

Silicon carbide based Schottky diode gas sensors are being developed for high temperature applications such as emission measurements. Two different types of gas sensitive diodes will be discussed in this paper. By varying the structure of the diode, one can affect the diode stability as well as the diode sensitivity to various gases. It is concluded that the ability of SiC to operate as a high temperature semiconductor significantly enhances the versatility of the Schottky diode gas sensing structure and will potentially allow the fabrication of a SiC-based gas sensor arrays for versatile high temperature gas sensing applications.

Lipid nanocapsule functionalization by lipopeptides derived from human papillomavirus type-16 capsid for nucleic acid delivery into cancer cells.

PubMed

Weyland, M; Griveau, A; Bejaud, J; Benoit, J-P; Coursaget, P; Garcion, E

2013-10-01

Plasmid DNA (pDNA) and small interfering RNAs (siRNAs) are very useful tools for the treatment of cancer. However, pDNA and siRNAs efficacy is restricted by their negative charge and susceptibility to degradation by endonucleases that prevent them penetrating tissue and cellular barriers such as the plasma and endolysosomal membranes. Viral vectors have some advantages but their use is largely limited by their immunogenicity. On the other hand, synthetic nanoparticles have advantage of being relatively non-immunogenic but their ability to deliver nucleic acids remains less efficient than their viral counterparts. The present study is focussed on the development and evaluation of biomimetic lipid nanocapsules (LNCs) functionalized with a L1 papillomavirus type-16 capsid-derived lipopeptide on their surface, for transfection of U87MG glioma cells and Caco-2 colorectal adenocarcinoma cells with pDNA or siRNAs. Since the L1-peptide has been described as a nuclear localization signal able to complex with nucleic acids and bind to heparan sulfate on the cell surface, the structure and function of L1-peptide bound to LNCs (L1-LNCs) were investigated. Although L1-LNCs were shown to complex with both pDNA and siRNAs, the pDNA-L1-LNC complexes showed only weak transfection efficiency. In contrast, siRNA-L1-LNC complexes appeared as effective repressors of targeted messengers. Copyright © 2013 Elsevier B.V. All rights reserved.

Structural Studies of CH_3SiF_2-X (x = Nco, Cl) by Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Guirgis, Gamil A.; Gause, Korreda K.; Seifert, Nathan A.; Zaleski, Daniel P.; Pate, Brooks H.; Palmer, Michael H.; Peebles, Rebecca A.; Peebles, Sean A.; Elmuti, Lena F.; Obenchain, Daniel A.

2012-06-01

The structures of CH_3SiF_2-NCO and CH_3SiF_2-Cl have been studied by molecular rotational spectroscopy in the 6.5-18 GHz band. The rotational spectrum was measured by cavity Fourier transform microwave (FTMW) and chirped-pulse FTMW spectroscopy. The experiment targeted the study of CH_3SiF_2-NCO, but CH_3SiF_2-Cl was also observed as an impurity. Due to the dynamic range achieved on these spectra, all isotopologs with natural abundance ≥0.2% were assigned, which includes two doubly-substituted isotopologs for the chloride (29Si/37Cl and 30Si/37Cl). Strategies for obtaining the molecular structure for these two molecules using either a Kraitchman analysis (to obtain a partial substitution structure) or r_0 analysis (with additional constraints on the structure supplied by the theoretical structure) will be discussed. Derived structural parameters for the CH_3-SiF_2-X base structure are the same for the two compounds. The hyperfine and internal rotation effects in the spectra have been analyzed for all isotopologs and the Hamiltonian parameters are in very good agreement with ab initio results. The barriers to methyl group internal rotation for the two compounds 446(50) cm-1 and 463(3) cm-1 and are independent of the isotopic structure of the heavy atom frame.

Silicon Carbide Gas Sensors for Propulsion Emissions and Safety Applications

NASA Technical Reports Server (NTRS)

Hunter, G. W.; Xu, J.; Neudeck, P. G.; Lukco, D.; Trunek, A.; Spry, D.; Lampard, P.; Androjna, D.; Makel, D.; Ward, B.

2007-01-01

Silicon carbide (SiC) based gas sensors have the ability to meet the needs of a range of aerospace propulsion applications including emissions monitoring, leak detection, and hydrazine monitoring. These applications often require sensitive gas detection in a range of environments. An effective sensing approach to meet the needs of these applications is a Schottky diode based on a SiC semiconductor. The primary advantage of using SiC as a semiconductor is its inherent stability and capability to operate at a wide range of temperatures. The complete SiC Schottky diode gas sensing structure includes both the SiC semiconductor and gas sensitive thin film metal layers; reliable operation of the SiC-based gas sensing structure requires good control of the interface between these gas sensitive layers and the SiC. This paper reports on the development of SiC gas sensors. The focus is on two efforts to better control the SiC gas sensitive Schottky diode interface. First, the use of palladium oxide (PdOx) as a barrier layer between the metal and SiC is discussed. Second, the use of atomically flat SiC to provide an improved SiC semiconductor surface for gas sensor element deposition is explored. The use of SiC gas sensors in a multi-parameter detection system is briefly discussed. It is concluded that SiC gas sensors have potential in a range of propulsion system applications, but tailoring of the sensor for each application is necessary.

Di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands: synthesis, characterization and catalytic activity towards isoprene 1,4-cis polymerization.

PubMed

Zhang, Guangchao; Deng, Baojia; Wang, Shaowu; Wei, Yun; Zhou, Shuangliu; Zhu, Xiancui; Huang, Zeming; Mu, Xiaolong

2016-10-21

Different di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands were synthesized and their catalytic activities towards isoprene polymerization were investigated. Treatment of [RE(CH 2 SiMe 3 ) 3 (thf) 2 ] with 1 equiv. of 3-(CyN[double bond, length as m-dash]CH)C 8 H 5 NH in toluene or in THF afforded dinuclear rare-earth metal alkyl complexes having indolyl ligands in different hapticities with central metals {[η 2 :η 1 -μ-η 1 -3-(CyNCH(CH 2 SiMe 3 ))Ind]RE-(thf)(CH 2 SiMe 3 )} 2 (Cy = cyclohexyl, Ind = Indolyl, RE = Yb (1), Er (2), Y (3)) or {[η 1 -μ-η 1 -3-(CyNCH(CH 2 SiMe 3 ))Ind]RE-(thf) 2 (CH 2 SiMe 3 )} 2 (RE = Yb (4), Er (5), Y (6), Gd (7)), respectively. These two series of dinuclear complexes could be transferred to each other easily by only changing the solvents in the process. Reaction of [Er(CH 2 SiMe 3 ) 3 (thf) 2 ] with 1 equiv. of 3-t-butylaminomethylindole 3-( t BuNHCH 2 )C 8 H 5 NH in THF afforded the unexpected trinuclear erbium alkyl complex [η 2 :η 1 -μ-η 1 -3-( t BuNCH 2 )Ind] 4 Er 3 (thf) 5 (CH 2 SiMe 3 ) (8), which can also be prepared by reaction of 3 equiv. of [Er(CH 2 SiMe 3 ) 3 (thf) 2 ] with 4 equiv. of 3-( t BuNHCH 2 )C 8 H 5 NH in THF. Accordingly, complexes [η 2 :η 1 -μ-η 1 -3-( t BuNCH 2 )Ind] 4 RE 3 (thf) 5 (CH 2 SiMe 3 ) (RE = Y (9), Dy (10)) were prepared by reactions of 3 equiv. of [RE(CH 2 SiMe 3 ) 3 (thf) 2 ] with 4 equiv. of 3-( t BuNHCH 2 )C 8 H 5 NH in THF. Reactions of [RE(CH 2 SiMe 3 ) 3 (thf) 2 ] with 1 equiv. of 3-t-butylaminomethylindole 3-( t BuNHCH 2 )C 8 H 5 NH in THF, followed by treatment with 1 equiv. of [(2,6- i Pr 2 C 6 H 3 )N[double bond, length as m-dash]CHNH(C 6 H 3 i Pr 2 -2,6)] afforded, after workup, the dinuclear rare-earth metal complexes [η 1 -μ-η 1 :η 1 -3-( t BuNCH 2 )Ind][η 1 -μ-η 1 :η 3 -3-( t BuNCH 2 )Ind]RE 2 (thf)[(η 3 -2,6- i Pr 2 C 6 H 3 )NCHN(C 6 H 3 i Pr 2 -2,6)] 2 (RE = Er (11), Y (12)) having the indolyl ligands bonded with the rare-earth metal in different ligations. All new complexes 1-12 were fully characterized by spectroscopic methods and elemental analyses, and their structures were determined by X-ray crystallographic analyses. It was found that, except for complexes 1, 4, 11 and 12, all complexes were highly efficient catalysts for selective isoprene polymerization (up to 99% 1,4-cis selectivity) with the cooperation of co-catalysts, and the trinuclear complexes displayed advantages over dinuclear complexes in terms of molecular weight of polymers.

Experimental and theoretical determination of σ bands on ("2 √{3 }×2 √{3 } ") silicene grown on Ag(111)

NASA Astrophysics Data System (ADS)

Wang, W.; Olovsson, W.; Uhrberg, R. I. G.

2015-11-01

Silicene, the two-dimensional (2D) allotrope of silicon, has very recently attracted a lot of attention. It has a structure that is similar to graphene and it is theoretically predicted to show the same kind of electronic properties which have put graphene into the focus of large research and development projects worldwide. In particular, a 2D structure made from Si is of high interest because of the application potential in Si-based electronic devices. However, so far there is not much known about the silicene band structure from experimental studies. A comprehensive study is here presented of the atomic and electronic structure of the silicene phase on Ag(111) denoted as (2 √ 3 ×2 √ 3 )R30° in the literature. Low energy electron diffraction (LEED) shows an unconventional rotated ("2 √ 3 ×2 √ 3 ") pattern with a complicated set of split diffraction spots. Scanning tunneling microscopy (STM) results reveal a Ag(111) surface that is homogeneously covered by the ("2 √ 3 ×2 √ 3 ") silicene which exhibits an additional quasiperiodic long-range ordered superstructure. The complex structure, revealed by STM, has been investigated in detail and we present a consistent picture of the silicene structure based on both STM and LEED. The homogeneous coverage by the ("2 √ 3 ×2 √ 3 ") silicene facilitated an angle-resolved photoelectron spectroscopy study which reveals a silicene band structure of unprecedented detail. Here we report four silicene bands which are compared to calculated dispersions based on a relaxed (2 √ 3 ×2 √ 3 ) model. We find good qualitative agreement between the experimentally observed bands and calculated silicene bands of σ character.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong Junmei; Wei Na; Chalk, Alistair

RISC (RNA-induced silencing complex) is a central protein complex in RNAi, into which a siRNA strand is assembled to become effective in gene silencing. By using an in vitro RNAi reaction based on Drosophila embryo extract, an asymmetric model was recently proposed for RISC assembly of siRNA strands, suggesting that the strand that is more loosely paired at its 5' end is selectively assembled into RISC and results in target gene silencing. However, in the present study, we were unable to establish such a correlation in cell-based RNAi assays, as well as in large-scale RNAi data analyses. This suggests thatmore » the thermodynamic stability of siRNA is not a major determinant of gene silencing in mammalian cells. Further studies on fork siRNAs showed that mismatch at the 5' end of the siRNA sense strand decreased RISC assembly of the antisense strand, but surprisingly did not increase RISC assembly of the sense strand. More interestingly, measurements of melting temperature showed that the terminal stability of fork siRNAs correlated with the positions of the mismatches, but not gene silencing efficacy. In summary, our data demonstrate that there is no definite correlation between siRNA stability and gene silencing in mammalian cells, which suggests that instead of thermodynamic stability, other features of the siRNA duplex contribute to RISC assembly in RNAi.« less

Focusing on RISC assembly in mammalian cells.

PubMed

Hong, Junmei; Wei, Na; Chalk, Alistair; Wang, Jue; Song, Yutong; Yi, Fan; Qiao, Ren-Ping; Sonnhammer, Erik L L; Wahlestedt, Claes; Liang, Zicai; Du, Quan

2008-04-11

RISC (RNA-induced silencing complex) is a central protein complex in RNAi, into which a siRNA strand is assembled to become effective in gene silencing. By using an in vitro RNAi reaction based on Drosophila embryo extract, an asymmetric model was recently proposed for RISC assembly of siRNA strands, suggesting that the strand that is more loosely paired at its 5' end is selectively assembled into RISC and results in target gene silencing. However, in the present study, we were unable to establish such a correlation in cell-based RNAi assays, as well as in large-scale RNAi data analyses. This suggests that the thermodynamic stability of siRNA is not a major determinant of gene silencing in mammalian cells. Further studies on fork siRNAs showed that mismatch at the 5' end of the siRNA sense strand decreased RISC assembly of the antisense strand, but surprisingly did not increase RISC assembly of the sense strand. More interestingly, measurements of melting temperature showed that the terminal stability of fork siRNAs correlated with the positions of the mismatches, but not gene silencing efficacy. In summary, our data demonstrate that there is no definite correlation between siRNA stability and gene silencing in mammalian cells, which suggests that instead of thermodynamic stability, other features of the siRNA duplex contribute to RISC assembly in RNAi.

High Curie temperature of Ce-Fe-Si compounds with ThMn12 structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, C; Pinkerton, FE; Herbst, JF

2015-01-15

We report the discovery of ternary CeFe(12-x)Si(x)compounds possessing the ThMn12 structure. The samples were prepared by melt spinning followed by annealing. In contrast to other known Ce Fe-based binary and ternary compounds, CeFe12-xSix compounds exhibit exceptionally high Curie temperatures whose values increase with added Si substitution. The highest T. = 583 K in CeFe10Si2 rivals that of the well-established Nd2Fe14B compound. We ascribe the T-c behavior to a combination of Si-induced 3d band structure changes and partial Ce3+ stabilization. (C) 2014 Published by Elsevier Ltd.

Possibilities of Bragg filtering structures based on subwavelength grating guiding mechanism (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kwiecien, Pavel; Litvik, Ján.; Richter, Ivan; Ctyroký, Jirí; Cheben, Pavel

2017-05-01

Silicon-on-insulator (SOI), as the most promising platform, for advanced photonic integrated structures, employs a high refractive index contrast between the silicon "core" and surrounding media. One of the recent new ideas within this field is based on the alternative formation of the subwavelength sized (quasi)periodic structures, manifesting as an effective medium with respect to propagating light. Such structures relay on Bloch wave propagation concept, in contrast to standard index guiding mechanism. Soon after the invention of such subwavelength grating (SWG) waveguides, the scientists concentrated on various functional elements such as couplers, crossings, mode transformers, convertors, MMI couplers, polarization converters, resonators, Bragg filters, and others. Our contribution is devoted to a detailed numerical analysis and design considerations of Bragg filtering structures based on SWG idea. Based on our previous studies where we have shown impossibility of application of various 2 and "2.5" dimensional methods for the proper numerical analysis, here we effectively use two independent but similar in-house approaches based on 3D Fourier modal methods, namely aperiodic rigorous coupled wave analysis (aRCWA) and bidirectional expansion and propagation method based on Fourier series (BEX) tools. As it was recently demonstrated, SWG Bragg filters are feasible. Based on this idea, we propose, simulate, and optimize spectral characteristics of such filters. In particular, we have investigated several possibilities of modifications of original SWG waveguides towards the Bragg filtering, including firstly - simple single-segment changes in position, thickness, and width, and secondly - several types of Si inclusions, in terms of perturbed width and thickness (and their combinations). The leading idea was to obtain required (e.g. sufficiently narrow) spectral characteristic while keeping the minimum size of Si features large enough. We have found that the second approach with the single element perturbations can provide promising designs. Furthermore, even more complex filtering SWG structures can be considered.

BeAtMuSiC: Prediction of changes in protein-protein binding affinity on mutations.

PubMed

Dehouck, Yves; Kwasigroch, Jean Marc; Rooman, Marianne; Gilis, Dimitri

2013-07-01

The ability of proteins to establish highly selective interactions with a variety of (macro)molecular partners is a crucial prerequisite to the realization of their biological functions. The availability of computational tools to evaluate the impact of mutations on protein-protein binding can therefore be valuable in a wide range of industrial and biomedical applications, and help rationalize the consequences of non-synonymous single-nucleotide polymorphisms. BeAtMuSiC (http://babylone.ulb.ac.be/beatmusic) is a coarse-grained predictor of the changes in binding free energy induced by point mutations. It relies on a set of statistical potentials derived from known protein structures, and combines the effect of the mutation on the strength of the interactions at the interface, and on the overall stability of the complex. The BeAtMuSiC server requires as input the structure of the protein-protein complex, and gives the possibility to assess rapidly all possible mutations in a protein chain or at the interface, with predictive performances that are in line with the best current methodologies.

A methodology of SiP testing based on boundary scan

NASA Astrophysics Data System (ADS)

Qin, He; Quan, Haiyang; Han, Yifei; Zhu, Tianrui; Zheng, Tuo

2017-10-01

System in Package (SiP) play an important role in portable, aerospace and military electronic with the microminiaturization, light weight, high density, and high reliability. At present, SiP system test has encountered the problem on system complexity and malfunction location with the system scale exponentially increase. For SiP system, this paper proposed a testing methodology and testing process based on the boundary scan technology. Combining the character of SiP system and referencing the boundary scan theory of PCB circuit and embedded core test, the specific testing methodology and process has been proposed. The hardware requirement of the under test SiP system has been provided, and the hardware platform of the testing has been constructed. The testing methodology has the character of high test efficiency and accurate malfunction location.

Selective laser melting of hypereutectic Al-Si40-powder using ultra-short laser pulses

NASA Astrophysics Data System (ADS)

Ullsperger, T.; Matthäus, G.; Kaden, L.; Engelhardt, H.; Rettenmayr, M.; Risse, S.; Tünnermann, A.; Nolte, S.

2017-12-01

We investigate the use of ultra-short laser pulses for the selective melting of Al-Si40-powder to fabricate complex light-weight structures with wall sizes below 100 μ {m} combined with higher tensile strength and lower thermal expansion coefficient in comparison to standard Al-Si alloys. During the cooling process using conventional techniques, large primary silicon particles are formed which impairs the mechanical and thermal properties. We demonstrate that these limitations can be overcome using ultra-short laser pulses enabling the rapid heating and cooling in a non-thermal equilibrium process. We analyze the morphology characteristics and micro-structures of single tracks and thin-walled structures depending on pulse energy, repetition rate and scanning velocity utilizing pulses with a duration of 500 {fs} at a wavelength of 1030 {nm}. The possibility to specifically change and optimize the microstructure is shown.

CMOS-Compatible Fabrication for Photonic Crystal-Based Nanofluidic Structure.

PubMed

Peng, Wang; Chen, Youping; Ai, Wu; Zhang, Dailin; Song, Han; Xiong, Hui; Huang, Pengcheng

2017-12-01

Photonic crystal (PC)-based devices have been widely used since 1990s, while PC has just stepped into the research area of nanofluidic. In this paper, photonic crystal had been used as a complementary metal oxide semiconductors (CMOS) compatible part to create a nanofluidic structure. A nanofluidic structure prototype had been fabricated with CMOS-compatible techniques. The nanofluidic channels were sealed by direct bonding polydimethylsiloxane (PDMS) and the periodic gratings on photonic crystal structure. The PC was fabricated on a 4-in. Si wafer with Si 3 N 4 as the guided mode layer and SiO 2 film as substrate layer. The higher order mode resonance wavelength of PC-based nanofluidic structure had been selected, which can confine the enhanced electrical field located inside the nanochannel area. A design flow chart was used to guide the fabrication process. By optimizing the fabrication device parameters, the periodic grating of PC-based nanofluidic structure had a high-fidelity profile with fill factor at 0.5. The enhanced electric field was optimized and located within the channel area, and it can be used for PC-based nanofluidic applications with high performance.

Vertical nanowire heterojunction devices based on a clean Si/Ge interface.

PubMed

Chen, Lin; Fung, Wayne Y; Lu, Wei

2013-01-01

Different vertical nanowire heterojunction devices were fabricated and tested based on vertical Ge nanowires grown epitaxially at low temperatures on (111) Si substrates with a sharp and clean Si/Ge interface. The nearly ideal Si/Ge heterojuctions with controlled and abrupt doping profiles were verified through material analysis and electrical characterizations. In the nSi/pGe heterojunction diode, an ideality factor of 1.16, subpicoampere reverse saturation current, and rectifying ratio of 10(6) were obtained, while the n+Si/p+Ge structure leads to Esaki tunnel diodes with a high peak tunneling current of 4.57 kA/cm(2) and negative differential resistance at room temperature. The large valence band discontinuity between the Ge and Si in the nanowire heterojunctions was further verified in the p+Si/pGe structure, which shows a rectifying behavior instead of an Ohmic contact and raises an important issue in making Ohmic contacts to heterogeneously integrated materials. A raised Si/Ge structure was further developed using a self-aligned etch process, allowing greater freedom in device design for applications such as the tunneling field-effect transistor (TFET). All measurement data can be well-explained and fitted with theoretical models with known bulk properties, suggesting that the Si/Ge nanowire system offers a very clean heterojunction interface with low defect density, and holds great potential as a platform for future high-density and high-performance electronics.

Temperature Dependences of the Product of the Differential Resistance by the Area in MIS-Structures Based on Cd x Hg1- x Te Grown by Molecularbeam Epitaxy on Alternative Si and GaAs Substrates

NASA Astrophysics Data System (ADS)

Voitsekhovskii, A. V.; Nesmelov, S. N.; Dzyadukh, S. M.; Varavin, V. S.; Vasil'ev, V. V.; Dvoretskii, S. A.; Mikhailov, N. N.; Yakushev, M. V.; Sidorov, G. Yu.

2017-06-01

In a temperature range of 9-200 K, temperature dependences of the differential resistance of space-charge region in the strong inversion mode are experimentally studied for MIS structures based on CdxHg1-xTe (x = 0.22-0.40) grown by molecular-beam epitaxy. The effect of various parameters of structures: the working layer composition, the type of a substrate, the type of insulator coating, and the presence of a near-surface graded-gap layer on the value of the product of differential resistance by the area is studied. It is shown that the values of the product RSCRA for MIS structures based on n-CdHgTe grown on a Si(013) substrate are smaller than those for structures based on the material grown on a GaAs(013) substrate. The values of the product RSCRA for MIS structures based on p-CdHgTe grown on a Si(013) substrate are comparable with the value of the analogous parameter for MIS structures based on p-CdHgTe grown on a GaAs(013) substrate.

Characterization of Si (sub X)Ge (sub 1-x)/Si Heterostructures for Device Applications Using Spectroscopic Ellipsometry

NASA Technical Reports Server (NTRS)

Sieg, R. M.; Alterovitz, S. A.; Croke, E. T.; Harrell, M. J.; Tanner, M.; Wang, K. L.; Mena, R. A.; Young, P. G.

1993-01-01

Spectroscopic ellipsometry (SE) characterization of several complex Si (sub X)Ge (sub 1-x)/Si heterostructures prepared for device fabrication, including structures for heterojunction bipolar transistors (HBT), p-type and n-type heterostructure modulation doped field effect transistors, has been performed. We have shown that SE can simultaneously determine all active layer thicknesses, Si (sub X)Ge (sub 1-x) compositions, and the oxide overlayer thickness, with only a general knowledge of the structure topology needed a priori. The characterization of HBT material included the SE analysis of a Si (sub X)Ge (sub 1-x) layer deeply buried (600 nanometers) under the silicon emitter and cap layers. In the SE analysis of n-type heterostructures, we examined for the first time a silicon layer under tensile strain. We found that an excellent fit can be obtained using optical constants of unstrained silicon to represent the strained silicon conduction layer. We also used SE to measure lateral sample homogeneity, providing quantitative identification of the inhomogeneous layer. Surface overlayers resulting from prior sample processing were also detected and measured quantitatively. These results should allow SE to be used extensively as a non-destructive means of characterizing Si (sub X)Ge (sub 1-x)/Si heterostructures prior to device fabrication and testing.

Lithium monosilicide (LiSi), a low-dimensional silicon-based material prepared by high pressure synthesis: NMR and vibrational spectroscopy and electrical properties characterization

NASA Astrophysics Data System (ADS)

Stearns, Linda A.; Gryko, Jan; Diefenbacher, Jason; Ramachandran, Ganesh K.; McMillan, Paul F.

2003-06-01

Lithium monosilicide (LiSi) was formed at high pressures and high temperatures (1.0-2.5 GPa and 500-700°C) in a piston-cylinder apparatus. This compound was previously shown to have an unusual structure based on 3-fold coordinated silicon atoms arranged into interpenetrating sheets. In the present investigation, lowered synthesis pressures permitted recovery of large (150-200 mg) quantities of sample for structural studies via NMR spectroscopy ( 29Si and 7Li), Raman spectroscopy and electrical conductivity measurements. The 29Si chemical shift occurs at -106.5 ppm, intermediate between SiH 4 and Si(Si(CH 3) 3) 4, but lies off the trend established by the other alkali monosilicides (NaSi, KSi, RbSi, CsSi), that contain isolated Si 44- anions. Raman spectra show a strong peak at 508 cm -1 due to symmetric Si-Si stretching vibrations, at lower frequency than for tetrahedrally coordinated Si frameworks, due to the longer Si-Si bonds in the 3-coordinated silicide. Higher frequency vibrations occur due to asymmetric stretching. Electrical conductivity measurements indicate LiSi is a narrow-gap semiconductor ( Eb˜0.057 eV). There is a rapid increase in conductivity above T=450 K, that might be due to the onset of Li + mobility.

Anneal-induced enhancement of refractive index and hardness of silicophosphate glasses containing six-fold coordinated silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Huidan, E-mail: hdzeng@ecust.edu.cn; Jiang, Qi; Li, Xiang

2015-01-12

A considerable number of optical devices have significantly benefited from the development of phosphate glasses as substrate materials. Introducing silica into sodium phosphate is an effective method to enhance its mechanical and optical properties. Through annealing treatment, the tetrahedral silicon oxide network structure (Si{sup (4)}) can be transformed into an octahedral structure (Si{sup (6)}) with more constraints. Here, we use high-temperature Raman and Nuclear Magnetic Resonance to reveal the mechanism of transformation between the Si{sup (4)} and Si{sup (6)} silicon oxide structures. The increase of the Si{sup (6)} content results in the phosphate glasses having higher refractive index and hardness.more » Based on this, the refractive index contribution of SiO{sub 6} is obtained.« less

Atomistic simulation of the thermal conductivity in amorphous SiO2 matrix/Ge nanocrystal composites

NASA Astrophysics Data System (ADS)

Kuryliuk, Vasyl V.; Korotchenkov, Oleg A.

2017-04-01

We use nonequilibrium molecular dynamics computer simulations with the Tersoff potential aiming to provide a comprehensive picture of the thermal conductivity of amorphous SiO2 (a-SiO2) matrix with embedded Ge nanocrystals (nc-Ge). The modelling predicts the a-SiO2 matrix thermal conductivity in a temperature range of 50 < T < 500 K yielding a fair agreement with experiment at around room temperature. It is worth noticing that the predicted room-temperature thermal conductivity in a-SiO2 is in very good agreement with the experimental result, which is in marked contrast with the thermal conductivity calculated employing the widely used van Beest-Kramer-van Santen (BKS) potential. We show that the thermal conductivity of composite nc-Ge/a-SiO2 systems decreases steadily with increasing the volume fraction of Ge inclusions, indicative of enhanced interface scattering of phonons imposed by embedded Ge nanocrystals. We also observe that increasing the volume fractions above a certain threshold value results in a progressively increased thermal conductivity of the nanocomposite, which can be explained by increasing volume fraction of a better thermally conducting Ge. Finally, non-equilibrium molecular dynamics simulations with the Tersoff potential are promising for computing the thermal conductivity of nanocomposites based on amorphous SiO2 and can be readily scaled to more complex composite structures with embedded nanoparticles, which thus help design nanocomposites with desired thermal properties.

HPHT synthesis, structure and electrical properties of type-I clathrates Ba{sub 8}Al{sub x}Si{sub 46−x}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Binwu; Jia, Xiaopeng; Sun, Hairui

2016-01-15

Clathrate compounds Ba{sub 8}Al{sub x}Si{sub 46−x} were successfully synthesized using the method of high-pressure and high-temperature (HPHT). In this process, we used BaSi{sub 2} as one of the starting materials in place of Ba metals, which reduces the complexity of the program caused by the extremely high chemical reactivity. By using this method, the processing time was reduced from few days to an hour. X-ray diffraction and structural refinement indicated this composition crystallized in type-I clathrate phase. Bond length analysis showed the Ba atoms in small dodecahedron had spherical thermal ellipsoids while those in large tetrakaidecahedron displayed anisotropic thermal ellipsoids.more » The negative Seebeck coefficient indicated transport processes were dominated by electrons as carriers, and increased with the increasing temperature. The electrical properties, including Seebeck coefficient and Power factor, were greatly enhanced by Al substitution. - Graphical abstract: Left: The cavity structure diagram of a China-type large volume cubic high-pressure apparatus, and the Type-I clathrate structure of sample synthesized using HPHT. Middle: X-ray Rietveld refinement profile for Ba{sub 8}Si{sub 46} and element mapping for Ba{sub 8}Al{sub 16}Si{sub 30}. Right: Temperature dependence of Seebeck coefficient for Ba{sub 8}Al{sub x}Si{sub 46−x} prepared by HPHT. - Highlights: • HPHT is a simple and rapid synthetic approach. • We use BaSi{sub 2} as one of the starting materials replacing Ba metals. • The processing time reduces from few days to an hour. • Structure determination is refined by Rietveld analysis of XRD data. • Variable temperature electrical properties are characterized.« less

Collective evolution of submicron hillocks during the early stages of anisotropic alkaline wet chemical etching of Si(1 0 0) surfaces

NASA Astrophysics Data System (ADS)

Sana, P.; Vázquez, Luis; Cuerno, Rodolfo; Sarkar, Subhendu

2017-11-01

We address experimentally the large-scale dynamics of Si(1 0 0) surfaces during the initial stages of anisotropic wet (KOH) chemical etching, which are characterized through atomic force microscopy. These systems are known to lead to the formation of characteristic pyramids, or hillocks, of typical sizes in the nanometric/micrometer scales, thus with the potential for a large number of applications that can benefit from the nanotexturing of Si surfaces. The present pattern formation process is very strongly disordered in space. We assess the space correlations in such a type of rough surface and elucidate the existence of a complex and rich morphological evolution, featuring at least three different regimes in just 10 min of etching. Such a complex time behavior cannot be consistently explained within a single formalism for dynamic scaling. The pyramidal structure reveals itself as the basic morphological motif of the surface throughout the dynamics. A detailed analysis of the surface slope distribution with etching time reveals that the texturing process induced by the KOH etching is rather gradual and progressive, which accounts for the dynamic complexity. The various stages of the morphological evolution can be accurately reproduced by computer-generated surfaces composed by uncorrelated pyramidal structures. To reach such an agreement, the key parameters are the average pyramid size, which increases with etching time, its distribution and the surface coverage by the pyramidal structures.

Oxime ether lipids containing hydroxylated head groups are more superior siRNA delivery agents than their nonhydroxylated counterparts.

PubMed

Gupta, Kshitij; Mattingly, Stephanie J; Knipp, Ralph J; Afonin, Kirill A; Viard, Mathias; Bergman, Joseph T; Stepler, Marissa; Nantz, Michael H; Puri, Anu; Shapiro, Bruce A

2015-01-01

To evaluate the structure-activity relationship of oxime ether lipids (OELs) containing modifications in the hydrophobic domains (chain length, degree of unsaturation) and hydrophilic head groups (polar domain hydroxyl groups) toward complex formation with siRNA molecules and siRNA delivery efficiency of resulting complexes to a human breast cancer cell line (MDA-MB-231). Ability of lipoplex formation between oxime ether lipids with nucleic acids were examined using biophysical techniques. The potential of OELs to deliver nucleic acids and silence green fluorescent protein (GFP) gene was analyzed using MDA-MB-231 and MDA-MB-231/GFP cells, respectively. Introduction of hydroxyl groups to the polar domain of the OELs and unsaturation into the hydrophobic domain favor higher transfection and gene silencing in a cell culture system.

Structure and Crystallization of Alkaline-Earth Aluminosilicate Glasses: Prevention of the Alumina-Avoidance Principle.

PubMed

Allu, Amarnath R; Gaddam, Anuraag; Ganisetti, Sudheer; Balaji, Sathravada; Siegel, Renée; Mather, Glenn C; Fabian, Margit; Pascual, Maria J; Ditaranto, Nicoletta; Milius, Wolfgang; Senker, Jürgen; Agarkov, Dmitrii A; Kharton, Vladislav V; Ferreira, José M F

2018-05-03

Aluminosilicate glasses are considered to follow the Al-avoidance principle, which states that Al-O-Al linkages are energetically less favorable, such that, if there is a possibility for Si-O-Al linkages to occur in a glass composition, Al-O-Al linkages are not formed. The current paper shows that breaching of the Al-avoidance principle is essential for understanding the distribution of network-forming AlO 4 and SiO 4 structural units in alkaline-earth aluminosilicate glasses. The present study proposes a new modified random network (NMRN) model, which accepts Al-O-Al linkages for aluminosilicate glasses. The NMRN model consists of two regions, a network structure region (NS-Region) composed of well-separated homonuclear and heteronuclear framework species and a channel region (C-Region) of nonbridging oxygens (NBOs) and nonframework cations. The NMRN model accounts for the structural changes and devitrification behavior of aluminosilicate glasses. A parent Ca- and Al-rich melilite-based CaO-MgO-Al 2 O 3 -SiO 2 (CMAS) glass composition was modified by substituting MgO for CaO and SiO 2 for Al 2 O 3 to understand variations in the distribution of network-forming structural units in the NS-region and devitrification behavior upon heat treating. The structural features of the glass and glass-ceramics (GCs) were meticulously assessed by advanced characterization techniques including neutron diffraction (ND), powder X-ray diffraction (XRD), 29 Si and 27 Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR), and in situ Raman spectroscopy. ND revealed the formation of SiO 4 and AlO 4 tetrahedral units in all the glass compositions. Simulations of chemical glass compositions based on deconvolution of 29 Si MAS NMR spectral analysis indicate the preferred formation of Si-O-Al over Si-O-Si and Al-O-Al linkages and the presence of a high concentration of nonbridging oxygens leading to the formation of a separate NS-region containing both SiO 4 and AlO 4 tetrahedra (Si/Al) (heteronuclear) in addition to the presence of Al [4] -O-Al [4] bonds; this region coexists with a predominantly SiO 4 -containing (homonuclear) NS-region. In GCs, obtained after heat treatment at 850 °C for 250 h, the formation of crystalline phases, as revealed from Rietveld refinement of XRD data, may be understood on the basis of the distribution of SiO 4 and AlO 4 structural units in the NS-region. The in situ Raman spectra of the GCs confirmed the formation of a Si/Al structural region, as well as indicating interaction between the Al/Si region and SiO 4 -rich region at higher temperatures, leading to the formation of additional crystalline phases.

Material parameters from frequency dispersion simulation of floating gate memory with Ge nanocrystals in HfO2

NASA Astrophysics Data System (ADS)

Palade, C.; Lepadatu, A. M.; Slav, A.; Lazanu, S.; Teodorescu, V. S.; Stoica, T.; Ciurea, M. L.

2018-01-01

Trilayer memory capacitors with Ge nanocrystals (NCs) floating gate in HfO2 were obtained by magnetron sputtering deposition on p-type Si substrate followed by rapid thermal annealing at relatively low temperature of 600 °C. The frequency dispersion of capacitance and resistance was measured in accumulation regime of Al/HfO2 gate oxide/Ge NCs in HfO2 floating gate/HfO2 tunnel oxide/SiOx/p-Si/Al memory capacitors. For simulation of the frequency dispersion a complex circuit model was used considering an equivalent parallel RC circuit for each layer of the trilayer structure. A series resistance due to metallic contacts and Si substrate was necessary to be included in the model. A very good fit to the experimental data was obtained and the parameters of each layer in the memory capacitor, i.e. capacitances and resistances were determined and in turn the intrinsic material parameters, i.e. dielectric constants and resistivities of layers were evaluated. The results are very important for the study and optimization of the hysteresis behaviour of floating gate memories based on NCs embedded in oxide.

Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation.

PubMed

Yang, Lina; Minnich, Austin J

2017-03-14

Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials.

Thermal transport in nanocrystalline Si and SiGe by ab initio based Monte Carlo simulation

PubMed Central

Yang, Lina; Minnich, Austin J.

2017-01-01

Nanocrystalline thermoelectric materials based on Si have long been of interest because Si is earth-abundant, inexpensive, and non-toxic. However, a poor understanding of phonon grain boundary scattering and its effect on thermal conductivity has impeded efforts to improve the thermoelectric figure of merit. Here, we report an ab-initio based computational study of thermal transport in nanocrystalline Si-based materials using a variance-reduced Monte Carlo method with the full phonon dispersion and intrinsic lifetimes from first-principles as input. By fitting the transmission profile of grain boundaries, we obtain excellent agreement with experimental thermal conductivity of nanocrystalline Si [Wang et al. Nano Letters 11, 2206 (2011)]. Based on these calculations, we examine phonon transport in nanocrystalline SiGe alloys with ab-initio electron-phonon scattering rates. Our calculations show that low energy phonons still transport substantial amounts of heat in these materials, despite scattering by electron-phonon interactions, due to the high transmission of phonons at grain boundaries, and thus improvements in ZT are still possible by disrupting these modes. This work demonstrates the important insights into phonon transport that can be obtained using ab-initio based Monte Carlo simulations in complex nanostructured materials. PMID:28290484

Anti-EphA10 antibody-conjugated pH-sensitive liposomes for specific intracellular delivery of siRNA.

PubMed

Zang, Xinlong; Ding, Huaiwei; Zhao, Xiufeng; Li, Xiaowei; Du, Zhouqi; Hu, Haiyang; Qiao, Mingxi; Chen, Dawei; Deng, Yuihui; Zhao, Xiuli

2016-01-01

Therapeutic delivery of small interfering RNA (siRNA) is a major challenge that limits its potential clinical application. Here, a pH-sensitive cholesterol-Schiff base-polyethylene glycol (Chol-SIB-PEG)-modified cationic liposome-siRNA complex, conjugated with the recombinant humanized anti-EphA10 antibody (Eph), was developed as an efficient nonviral siRNA delivery system. Chol-SIB-PEG was successfully synthesized and confirmed with FTIR and (1)H-NMR. An Eph-PEG-SIB-Chol-modified liposome-siRNA complex (EPSLR) was prepared and characterized by size, zeta potential, gel retardation, and encapsulation efficiency. Electrophoresis results showed that EPSLR was resistant to heparin replacement and protected siRNA from fetal bovine serum digestion. EPSLR exhibited only minor cytotoxicity in MCF-7/ADR cells. The results of flow cytometry and confocal laser scanning microscopy suggested that EPSLR enhanced siRNA transfection in MCF-7/ADR cells. Intracellular distribution experiment revealed that EPSLR could escape from the endo-lysosomal organelle and release siRNA into cytoplasm at 4 hours posttransfection. Western blot experiment demonstrated that EPSLR was able to significantly reduce the levels of MDR1 protein in MCF-7/ADR cells. The in vivo study of DIR-labeled complexes in mice bearing MCF-7/ADR tumor indicated that EPSLR could reach the tumor site rather than other organs more effectively. All these results demonstrate that EPSLR has much potential for effective siRNA delivery and may facilitate its therapeutic application.

Silica nanoparticles for micro-particle imaging velocimetry: fluorosurfactant improves nanoparticle stability and brightness of immobilized iridium(III) complexes.

PubMed

Lewis, David J; Dore, Valentina; Rogers, Nicola J; Mole, Thomas K; Nash, Gerard B; Angeli, Panagiota; Pikramenou, Zoe

2013-11-26

To establish highly luminescent nanoparticles for monitoring fluid flows, we examined the preparation of silica nanoparticles based on immobilization of a cyclometalated iridium(III) complex and an examination of the photophysical studies provided a good insight into the Ir(III) microenvironment in order to reveal the most suitable silica nanoparticles for micro particle imaging velocimetry (μ-PIV) studies. Iridium complexes covalently incorporated at the surface of preformed silica nanoparticles, [Ir-4]@Si500-Z, using a fluorinated polymer during their preparation, demonstrated better stability than those without the polymer, [Ir-4]@Si500, as well as an increase in steady state photoluminescence intensity (and therefore particle brightness) and lifetimes which are increased by 7-fold compared with nanoparticles with the same metal complex attached covalently throughout their core, [Ir-4]⊂Si500. Screening of the nanoparticles in fluid flows using epi-luminescence microscopy also confirm that the brightest, and therefore most suitable particles for microparticle imaging velocimetry (μ-PIV) measurements are those with the Ir(III) complex immobilized at the surface with fluorosurfactant, that is [Ir-4]@Si500-Z. μ-PIV studies demonstrate the suitability of these nanoparticles as nanotracers in microchannels.

The relation between residual stress, interfacial structure and the joint property in the SiO2f/SiO2-Nb joints.

PubMed

Ma, Qiang; Li, Zhuo Ran; Yang, Lai Shan; Lin, Jing Huang; Ba, Jin; Wang, Ze Yu; Qi, Jun Lei; Feng, Ji Cai

2017-06-23

In order to achieve a high-quality joint between SiO 2f /SiO 2 and metals, it is necessary to address the poor wettability of SiO 2f /SiO 2 and the high residual stress in SiO 2f /SiO 2 -Nb joint. Here, we simultaneously realize good wettability and low residual stress in SiO 2f /SiO 2 -Nb joint by combined method of HF etching treatment and Finite Element Analysis (FEA). After etching treatment, the wettability of E-SiO 2f /SiO 2 was improved, and the residual stress in the joint was decreased. In order to better control the quality of joints, efforts were made to understand the relationship between surface structure of E-SiO 2f /SiO 2 and residual stress in joint using FEA. Based on the direction of FEA results, a relationship between residual stress, surface structure and joint property in the brazed joints were investigated by experiments. As well the FEA and the brazing test results both realized the high-quality joint of E-SiO 2f /SiO 2 -Nb and the shear strength of the joint reached 61.9 MPa.

Luminescence properties of Eu2+ in M2MgSi2O7 (M=Ca, Sr, and Ba) phosphors

NASA Astrophysics Data System (ADS)

Kim, T.; Kim, Y.; Kang, S.

2012-03-01

The photoluminescence properties of alkali-earth magnesium silicates (M2MgSi2O7, M=Ca, Sr, and Ba) doped with Eu2+ were investigated. Solid solutions of Ba x Sr2- x Si2O7, Ca2MgSi2O7, and Sr2MgSi2O7 were prepared. Ba x Sr2- x Si2O7 retained a tetragonal crystal structure similar to the structure of the other compounds up to a stoichiometry of x=1.6, which enabled a systematic study of the common structure. Monoclinic Ba2MgSi2O7 was prepared, and the luminescence properties were compared with those of other samples. The emission and excitation spectra of tetragonal M2MgSi2O7 (M=Ca, Sr, and Ba) changed as a function of the covalency, site symmetry, and crystal field strength. The luminescence properties showed excellent agreement with theoretical predictions based on these factors. The Stokes shift differentiated the emission behaviors of the tetragonal and monoclinic structures.

Betavoltaic device in por-SiC/Si C-Nuclear Energy Converter

NASA Astrophysics Data System (ADS)

Akimchenko, Alina; Chepurnov, Victor; Dolgopolov, Mikhail; Gurskaya, Albina; Kuznetsov, Oleg; Mashnin, Alikhan; Radenko, Vitaliy; Radenko, Alexander; Surnin, Oleg; Zanin, George

2017-10-01

The miniature and low-power devices with long service life in hard operating conditions like the Carbon-14 beta-decay energy converters indeed as eternal resource for integrated MEMS and NEMS are considered. Authors discuss how to create the power supply for MEMS/NEMS devices, based on porous SiC/Si structure, which are tested to be used as the beta-decay energy converters of radioactive C-14 into electrical energy. This is based on the silicon carbide obtaining by self-organizing mono 3C-SiC endotaxy on the Si substrate. The new idea is the C-14 atoms including in molecules in the silicon carbide porous structure by this technology, which will increase the efficiency of the converter due to the greater intensity of electron-hole pairs generation rate in the space charge region. The synthesis of C-14 can be also performed by using the electronically controlled magneto-optic chamber.

A comparative study of n-channel low temperature poly-Si thin-film transistors with a body terminal or a lightly-doped-drain structure

NASA Astrophysics Data System (ADS)

Wu, Yanwen; Wang, Mingxiang; Wang, Huaisheng; Zhang, Dongli

2018-02-01

Hot-carrier (HC) induced degradation is a critical reliability issue of n-channel low temperature poly-Si thin-film transistors (TFTs) in TFT-based circuits. In this work, a kind of four-terminal TFT, which has an additional p+-doped lateral body terminal connecting to the floating channel, is systematically compared to conventional n-channel TFT and lightly-doped-drain (LDD) TFT. We demonstrate that the four-terminal TFT can provide similar advantages to that of the LDD TFT such as kink current suppression and DC HC degradation immunity, much superior immunity to the dynamic HC degradation, but without any tradeoffs in device performance and process complexity of the LDD TFT. It has high performance, as well as excellent reliability under both DC and AC conditions.

Stability and dynamical properties of material flow systems on random networks

NASA Astrophysics Data System (ADS)

Anand, K.; Galla, T.

2009-04-01

The theory of complex networks and of disordered systems is used to study the stability and dynamical properties of a simple model of material flow networks defined on random graphs. In particular we address instabilities that are characteristic of flow networks in economic, ecological and biological systems. Based on results from random matrix theory, we work out the phase diagram of such systems defined on extensively connected random graphs, and study in detail how the choice of control policies and the network structure affects stability. We also present results for more complex topologies of the underlying graph, focussing on finitely connected Erdös-Réyni graphs, Small-World Networks and Barabási-Albert scale-free networks. Results indicate that variability of input-output matrix elements, and random structures of the underlying graph tend to make the system less stable, while fast price dynamics or strong responsiveness to stock accumulation promote stability.

Highly uniform and reliable resistive switching characteristics of a Ni/WOx/p+-Si memory device

NASA Astrophysics Data System (ADS)

Kim, Tae-Hyeon; Kim, Sungjun; Kim, Hyungjin; Kim, Min-Hwi; Bang, Suhyun; Cho, Seongjae; Park, Byung-Gook

2018-02-01

In this paper, we investigate the resistive switching behavior of a bipolar resistive random-access memory (RRAM) in a Ni/WOx/p+-Si RRAM with CMOS compatibility. Highly unifrom and reliable bipolar resistive switching characteristics are observed by a DC voltage sweeping and its switching mechanism can be explained by SCLC model. As a result, the possibility of metal-insulator-silicon (MIS) structural WOx-based RRAM's application to Si-based 1D (diode)-1R (RRAM) or 1T (transistor)-1R (RRAM) structure is demonstrated.

siRNA delivery targeting to the lung via agglutination-induced accumulation and clearance of cationic tetraamino fullerene.

PubMed

Minami, Kosuke; Okamoto, Koji; Doi, Kent; Harano, Koji; Noiri, Eisei; Nakamura, Eiichi

2014-05-12

The efficient treatment of lung diseases requires lung-selective delivery of agents to the lung. However, lung-selective delivery is difficult because the accumulation of micrometer-sized carriers in the lung often induces inflammation and embolization-related toxicity. Here we demonstrate a lung-selective delivery system of small interfering RNA (siRNA) by controlling the size of carrier vehicle in blood vessels. The carrier is made of tetra(piperazino)fullerene epoxide (TPFE), a water-soluble cationic tetraamino fullerene. TPFE and siRNA form sub-micrometer-sized complexes in buffered solution and these complexes agglutinate further with plasma proteins in the bloodstream to form micrometer-sized particles. The agglutinate rapidly clogs the lung capillaries, releases the siRNA into lung cells to silence expression of target genes, and is then cleared rapidly from the lung after siRNA delivery. We applied our delivery system to an animal model of sepsis, indicating the potential of TPFE-based siRNA delivery for clinical applications.

siRNA delivery targeting to the lung via agglutination-induced accumulation and clearance of cationic tetraamino fullerene

NASA Astrophysics Data System (ADS)

Minami, Kosuke; Okamoto, Koji; Doi, Kent; Harano, Koji; Noiri, Eisei; Nakamura, Eiichi

2014-05-01

The efficient treatment of lung diseases requires lung-selective delivery of agents to the lung. However, lung-selective delivery is difficult because the accumulation of micrometer-sized carriers in the lung often induces inflammation and embolization-related toxicity. Here we demonstrate a lung-selective delivery system of small interfering RNA (siRNA) by controlling the size of carrier vehicle in blood vessels. The carrier is made of tetra(piperazino)fullerene epoxide (TPFE), a water-soluble cationic tetraamino fullerene. TPFE and siRNA form sub-micrometer-sized complexes in buffered solution and these complexes agglutinate further with plasma proteins in the bloodstream to form micrometer-sized particles. The agglutinate rapidly clogs the lung capillaries, releases the siRNA into lung cells to silence expression of target genes, and is then cleared rapidly from the lung after siRNA delivery. We applied our delivery system to an animal model of sepsis, indicating the potential of TPFE-based siRNA delivery for clinical applications.

siRNA delivery targeting to the lung via agglutination-induced accumulation and clearance of cationic tetraamino fullerene

PubMed Central

MINAMI, Kosuke; OKAMOTO, Koji; DOI, Kent; HARANO, Koji; NOIRI, Eisei; NAKAMURA, Eiichi

2014-01-01

The efficient treatment of lung diseases requires lung-selective delivery of agents to the lung. However, lung-selective delivery is difficult because the accumulation of micrometer-sized carriers in the lung often induces inflammation and embolization-related toxicity. Here we demonstrate a lung-selective delivery system of small interfering RNA (siRNA) by controlling the size of carrier vehicle in blood vessels. The carrier is made of tetra(piperazino)fullerene epoxide (TPFE), a water-soluble cationic tetraamino fullerene. TPFE and siRNA form sub-micrometer-sized complexes in buffered solution and these complexes agglutinate further with plasma proteins in the bloodstream to form micrometer-sized particles. The agglutinate rapidly clogs the lung capillaries, releases the siRNA into lung cells to silence expression of target genes, and is then cleared rapidly from the lung after siRNA delivery. We applied our delivery system to an animal model of sepsis, indicating the potential of TPFE-based siRNA delivery for clinical applications. PMID:24814863

Reflectance analysis of porosity gradient in nanostructured silicon layers

NASA Astrophysics Data System (ADS)

Jurečka, Stanislav; Imamura, Kentaro; Matsumoto, Taketoshi; Kobayashi, Hikaru

2017-12-01

In this work we study optical properties of nanostructured layers formed on silicon surface. Nanostructured layers on Si are formed in order to reach high suppression of the light reflectance. Low spectral reflectance is important for improvement of the conversion efficiency of solar cells and for other optoelectronic applications. Effective method of forming nanostructured layers with ultralow reflectance in a broad interval of wavelengths is in our approach based on metal assisted etching of Si. Si surface immersed in HF and H2O2 solution is etched in contact with the Pt mesh roller and the structure of the mesh is transferred on the etched surface. During this etching procedure the layer density evolves gradually and the spectral reflectance decreases exponentially with the depth in porous layer. We analyzed properties of the layer porosity by incorporating the porosity gradient into construction of the layer spectral reflectance theoretical model. Analyzed layer is splitted into 20 sublayers in our approach. Complex dielectric function in each sublayer is computed by using Bruggeman effective media theory and the theoretical spectral reflectance of modelled multilayer system is computed by using Abeles matrix formalism. Porosity gradient is extracted from the theoretical reflectance model optimized in comparison to the experimental values. Resulting values of the structure porosity development provide important information for optimization of the technological treatment operations.

Integrating aeromagnetic and Landsat™ 8 data into subsurface structural mapping of Precambrian basement complex

NASA Astrophysics Data System (ADS)

Kayode, John Stephen; Nawawi, M. N. M.; Abdullah, Khiruddin B.; Khalil, Amin E.

2017-01-01

The integration of Aeromagnetic data and remotely sensed imagery with the intents of mapping the subsurface geological structures in part of the South-western basement complex of Nigeria was developed using the PCI Geomatica Software. 2013. The data obtained from the Nigerian Geological Survey Agency; was corrected using Regional Residual Separation of the Total Magnetic field anomalies enhanced, and International Geomagnetic Reference Field removed. The principal objective of this study is, therefore, to introduce a rapid and efficient method of subsurface structural depth estimate and structural index evaluation through the incorporation of the Euler Deconvolution technique into PCI Geomatica 2013 to prospect for subsurface geological structures. The shape and depth of burial helped to define these structures from the regional aeromagnetic map. The method enabled various structural indices to be automatically delineated for an index of between 0.5 SI and 3.0 SI at a maximum depth of 1.1 km that clearly showed the best depths estimate for all the structural indices. The results delineate two major magnetic belts in the area; the first belt shows an elongated ridge-like structure trending mostly along the NorthNortheast-SouthSouthwest and the other anomalies trends primarily in the Northeast, Northwest, Northeast-Southwest parts of the study area that could be attributed to basement complex granitic intrusions from the tectonic history of the area. The majority of the second structures showed various linear structures different from the first structure. Basically, a significant offset was delineated at the core segment of the study area, suggesting a major subsurface geological feature that controls mineralisation in this area.

Design, synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes. The effect of crown ether hydrophilic substituents.

PubMed

Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin

2009-01-05

Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10(5) were reached for the devices of triple-decker compound 1 deposited on the OTS-treated SiO(2)/Si substrates, indicating the effect of substrate surface treatment on the OFET performance due to the improvement on the film quality as demonstrated by the atomic force microscope investigation results.

Effects of tripolyphosphate on cellular uptake and RNA interference efficiency of chitosan-based nanoparticles in Raw 264.7 macrophages.

PubMed

Xiao, Bo; Ma, Panpan; Ma, Lijun; Chen, Qiubing; Si, Xiaoying; Walter, Lewins; Merlin, Didier

2017-03-15

Tumor necrosis factor-α (TNF-α) is a major pro-inflammatory cytokine that is mainly secreted by macrophages during inflammation. Here, we synthesized a series of N-(2-hydroxy)propyl-3-trimethyl ammonium chitosan chlorides (HTCCs), and then used a complex coacervation technique or tripolyphosphate (TPP)-assisted ionotropic gelation strategy to complex the HTCCs with TNF-α siRNA (siTNF) to form nanoparticles (NPs). The resultant NPs had a desirable particle size (210-279nm), a slightly positive zeta potential (14-22mV), and negligible cytotoxicity against Raw 264.7 macrophages and colon-26 cells. Subsequent cellular uptake tests demonstrated that the introduction of TPP to the NPs markedly increased their cellular uptake efficiency (to nearly 100%) compared with TPP-free NPs, and yielded a correspondingly higher intracellular concentration of siRNA. Critically, in vitro gene silencing experiments revealed that all of the TPP-containing NPs showed excellent efficiency in inhibiting the mRNA expression level of TNF-α (by approximately 85-92%, which was much higher than that obtained using Oligofectamine/siTNF complexes). Collectively, these results obviously suggest that our non-toxic TPP-containing chitosan-based NPs can be exploited as efficient siTNF carriers for the treatment of inflammatory diseases. Copyright © 2016 Elsevier Inc. All rights reserved.

Titanium, zinc and alkaline-earth metal complexes supported by bulky O,N,N,O-multidentate ligands: syntheses, characterisation and activity in cyclic ester polymerisation.

PubMed

Sarazin, Yann; Howard, Ruth H; Hughes, David L; Humphrey, Simon M; Bochmann, Manfred

2006-01-14

The reactions of the bulky amino-bis(phenol) ligand Me(2)NCH(2)CH(2)N[CH(2)-3,5-Bu(t)(2)-C(6)H(2)OH-2](2)(1-H(2)) with Zn[N(SiMe(3))(2)](2)(4), [Mg[N(SiMe(3))(2)](2)](2)(5) and Ca[N(SiMe(3))(2)](2)(THF)(2)(6) yield the complexes 1-Zn, 1-Mg and 1-Ca in good yields. The X-ray structure of 1-Ca showed the complex to be dimeric, with calcium in a distorted octahedral coordination geometry. Five of the positions are occupied by an N(2)O(3) donor set, while the sixth is taken up by an intramolecular close contact to an o-Bu(t) substituent, a rare case of a Ca...H-C agostic interaction (Ca...H distances of 2.37 and 2.41 Angstroms). Another sterically hindered calcium complex, Ca[2-Bu(t)-6-(C(6)F(5)N=CH)C(6)H(3)O](2)(THF)(2).(C(7)H(8))(2/3)(7), was prepared by reaction of 6 with the iminophenol 2-Bu(t)-6-(C(6)F(5)N=CH)C(6)H(3)OH (3-H). According to the crystal structure 7 is monomeric and octahedral, with trans THF ligands. The complex Ti[N[CH(2)-3-Bu(t)-5-Me-C(6)H(2)O-2](2)[CH(2)CH(2)NMe(2)

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Optical and optomechanical ultralightweight C/SiC components

NASA Astrophysics Data System (ADS)

Papenburg, Ulrich; Pfrang, Wilhelm; Kutter, G. S.; Mueller, Claus E.; Kunkel, Bernd P.; Deyerler, Michael; Bauereisen, Stefan

1999-11-01

Optical and optomechanical structures based on silicon carbide (SiC) ceramics are becoming increasingly important for ultra- lightweight optical systems that must work in adverse environments. At IABG and Dornier Satellite Systems (DSS) in Munich, a special form of SiC ceramics carbon fiber reinforced silicon carbide (C/SiCR) has been developed partly under ESA and NASA contracts. C/SiCR is a light-weight, high- strength engineering material that features tunable mechanical and thermal properties. It offers exceptional design freedom due to its reduced brittleness and negligible volume shrinkage during processing in comparison to traditional, powder-based ceramics. Furthermore, its rapid fabrication process produces near-net-shape components using conventional NC machining/milling equipment and, thus, provides substantial schedule, cost, and risk savings. These characteristics allow C/SiCR to overcome many of the problems associated with more traditional optical materials. To date, C/SiCR has been used to produce ultra-lightweight mirrors and reflectors, antennas, optical benches, and monolithic and integrated reference structures for a variety of space and terrestrial applications. This paper describes the material properties, optical system and structural design aspects, the forming and manufacturing process including high-temperature joining technology, precision grinding and cladding techniques, and the performance results of a number of C/SiCR optical components we have built.

Dendrimers as Carriers for siRNA Delivery and Gene Silencing: A Review

PubMed Central

Huang, Weizhe; He, Ziying

2013-01-01

RNA interference (RNAi) was first literaturally reported in 1998 and has become rapidly a promising tool for therapeutic applications in gene therapy. In a typical RNAi process, small interfering RNAs (siRNA) are used to specifically downregulate the expression of the targeted gene, known as the term “gene silencing.” One key point for successful gene silencing is to employ a safe and efficient siRNA delivery system. In this context, dendrimers are emerging as potential nonviral vectors to deliver siRNA for RNAi purpose. Dendrimers have attracted intense interest since their emanating research in the 1980s and are extensively studied as efficient DNA delivery vectors in gene transfer applications, due to their unique features based on the well-defined and multivalent structures. Knowing that DNA and RNA possess a similar structure in terms of nucleic acid framework and the electronegative nature, one can also use the excellent DNA delivery properties of dendrimers to develop effective siRNA delivery systems. In this review, the development of dendrimer-based siRNA delivery vectors is summarized, focusing on the vector features (siRNA delivery efficiency, cytotoxicity, etc.) of different types of dendrimers and the related investigations on structure-activity relationship to promote safe and efficient siRNA delivery system. PMID:24288498

Terminal Duplex Stability and Nucleotide Identity Differentially Control siRNA Loading and Activity in RNA Interference

PubMed Central

Angart, Phillip A.; Carlson, Rebecca J.; Adu-Berchie, Kwasi

2016-01-01

Efficient short interfering RNA (siRNA)-mediated gene silencing requires selection of a sequence that is complementary to the intended target and possesses sequence and structural features that encourage favorable functional interactions with the RNA interference (RNAi) pathway proteins. In this study, we investigated how terminal sequence and structural characteristics of siRNAs contribute to siRNA strand loading and silencing activity and how these characteristics ultimately result in a functionally asymmetric duplex in cultured HeLa cells. Our results reiterate that the most important characteristic in determining siRNA activity is the 5′ terminal nucleotide identity. Our findings further suggest that siRNA loading is controlled principally by the hybridization stability of the 5′ terminus (Nucleotides: 1–2) of each siRNA strand, independent of the opposing terminus. Postloading, RNA-induced silencing complex (RISC)–specific activity was found to be improved by lower hybridization stability in the 5′ terminus (Nucleotides: 3–4) of the loaded siRNA strand and greater hybridization stability toward the 3′ terminus (Nucleotides: 17–18). Concomitantly, specific recognition of the 5′ terminal nucleotide sequence by human Argonaute 2 (Ago2) improves RISC half-life. These findings indicate that careful selection of siRNA sequences can maximize both the loading and the specific activity of the intended guide strand. PMID:27399870

Structure and electromagnetic properties of FeSiAl particles coated by MgO

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhou, Ting-dong

2017-03-01

FeSiAl particles with a layer of MgO surface coating have excellent soft magnetic and electromagnetic properties. In order to obtain the FeSiAl/MgO composites, Mg(OH)2 sol prepared by sol-gel process was well-mixed with FeSiAl flake particles, and then treated by calcination at 823 K in vacuum. The microstructural, morphological and electromagnetic parameters of FeSiAl/MgO particles were tested. Accordingly, the electromagnetic wave reflection loss in the frequency range of 0.5-18 GHz was calculated. The results show that the surface coating increases coercivity Hc and decreases complex permittivity, leading to a good impedance matching. When the coating amount was 7.5%, reflection loss of the composite particles can reach to -33 dB.

Si nanocrystals-based multilayers for luminescent and photovoltaic device applications

NASA Astrophysics Data System (ADS)

Lu, Peng; Li, Dongke; Cao, Yunqing; Xu, Jun; Chen, Kunji

2018-06-01

Low dimensional Si materials have attracted much attention because they can be developed in many kinds of new-generation nano-electronic and optoelectronic devices, among which Si nanocrystals-based multilayered material is one of the most promising candidates and has been extensively studied. By using multilayered structures, the size and distribution of nanocrystals as well as the barrier thickness between two adjacent Si nanocrystal layers can be well controlled, which is beneficial to the device applications. This paper presents an overview of the fabrication and device applications of Si nanocrystals, especially in luminescent and photovoltaic devices. We first introduce the fabrication methods of Si nanocrystals-based multilayers. Then, we systematically review the utilization of Si nanocrystals in luminescent and photovoltaic devices. Finally, some expectations for further development of the Si nanocrystals-based photonic and photovoltaic devices are proposed. Project supported by the National Natural Science Foundation of China (Nos. 11774155, 11274155).

Giant Phonon Anharmonicity and Anomalous Pressure Dependence of Lattice Thermal Conductivity in Y2Si2O7 silicate

PubMed Central

Luo, Yixiu; Wang, Jiemin; Li, Yiran; Wang, Jingyang

2016-01-01

Modification of lattice thermal conductivity (κL) of a solid by means of hydrostatic pressure (P) has been a crucially interesting approach that targets a broad range of advanced materials from thermoelectrics and thermal insulators to minerals in mantle. Although it is well documented knowledge that thermal conductivity of bulk materials normally increase upon hydrostatic pressure, such positive relationship is seriously challenged when it comes to ceramics with complex crystal structure and heterogeneous chemical bonds. In this paper, we predict an abnormally negative trend dκL/dP < 0 in Y2Si2O7 silicate using density functional theoretical calculations. The mechanism is disclosed as combined effects of slightly decreased group velocity and significantly augmented scattering of heat-carrying acoustic phonons in pressured lattice, which is originated from pressure-induced downward shift of low-lying optic and acoustic phonons. The structural origin of low-lying optic phonons as well as the induced phonon anharmonicity is also qualitatively elucidated with respect to intrinsic bonding heterogeneity of Y2Si2O7. The present results are expected to bring deeper insights for phonon engineering and modulation of thermal conductivity in complex solids with diverging structural flexibility, enormous bonding heterogeneity, and giant phonon anharmonicity. PMID:27430670

Interface Properties of Wide Bandgap Semiconductor Structures

DTIC Science & Technology

1994-06-01

resistive than silicides and their chemistry with 126I I Si-based materials more complex. However, in a series of studies, M. 0. Aboelfotoh et al. have...clarification of these issues. CuGe contacts on Ge:GaN and Mg:GaN. To date, the properties of Cu3Ge films have been documented by Aboelfotoh et al., but the...Martin, V. Malhotra, and J. E. Mahan, J. Vac. Sci. Technol. B 3, 836 (1985). 25. L. Krusin-Elbaum and M. 0. Aboelfotoh , Appl. Phys. Lett. 58(12), 1341

Correlations between properties and applications of the CVD amorphous silicon carbide films

NASA Astrophysics Data System (ADS)

Kleps, Irina; Angelescu, Anca

2001-12-01

The aim of this paper is to emphasise the correlation between film preparation conditions, film properties and their applications. Low pressure chemical vapour deposition amorphous silicon carbide (a-SiC) and silicon carbonitride (SiCN) films obtained from liquid precursors have different structure and composition depending on deposition conditions. Thus, the films deposited under kinetic working conditions reveal a stable structure and composition. Deposition at moderate temperature leads to stoichiometric SiC, while the films deposited at high temperatures have a composition closer to Si 1- xC x, with x=0.75. These films form a very reactive interface with metallic layers. The films realised under kinetic working regime can be used in Si membrane fabrication process or as coating films for field emission applications. SiC layers field emission properties were investigated; the field emission current density of the a-SiC/Si structures was 2.4 mA/cm 2 at 25 V/μm. An Si membrane technology based on moderate temperatures (770-850 °C) a-SiC etching mask is presented.

Light-emitting diodes based on colloidal silicon quantum dots

NASA Astrophysics Data System (ADS)

Zhao, Shuangyi; Liu, Xiangkai; Pi, Xiaodong; Yang, Deren

2018-06-01

Colloidal silicon quantum dots (Si QDs) hold great promise for the development of printed Si electronics. Given their novel electronic and optical properties, colloidal Si QDs have been intensively investigated for optoelectronic applications. Among all kinds of optoelectronic devices based on colloidal Si QDs, QD light-emitting diodes (LEDs) play an important role. It is encouraging that the performance of LEDs based on colloidal Si QDs has been significantly increasing in the past decade. In this review, we discuss the effects of the QD size, QD surface and device structure on the performance of colloidal Si-QD LEDs. The outlook on the further optimization of the device performance is presented at the end.

Development ceramic composites based on Al2O3, SiO2 and IG-017 additive

NASA Astrophysics Data System (ADS)

Kurovics, E.; Shmakova, A.; Kanev, B.; Gömze, L. A.

2017-02-01

Based on high purity alumina and quartz powders and IG-017 bio-original additives the authors have developed new ceramic composite materials for different industrial purposes. The main goal was to fine a material and morphological structures of high performance ceramic composites as frames for development complex materials for extreme consumptions in the future. For this the mixed powders of Al2O3 , SiO2 and IG-017 bio-original additive were uniaxially pressed at different compaction pressures into disc shapes and were sintered in electric kiln under air (1) and nitrogrn (2) atmosphere. The grain size distributions of the raw materials were determined by laser granulometry. There thermo-physical properties were also determined by derivatography. The prepared and sintered specimens were tested on geometrical sizes, microstructure and morphology by scanning electron microscopy, porosity and water absorption. In this work the authors present the results of their research and investigation.

A new family of multifunctional silicon clathrates: Optoelectronic and thermoelectric applications

NASA Astrophysics Data System (ADS)

Liu, Yinqiao; Jiang, Xue; Huang, Yingying; Zhou, Si; Zhao, Jijun

2017-02-01

To develop Si structures for multifunctional applications, here we proposed four new low-density silicon clathrates (Si-CL-A, Si-CL-B, Si-CL-C, and Si-CL-D) based on the same bonding topologies of clathrate hydrates. The electronic and thermal properties have been revealed by first-principles calculations. By computing their equation of states, phonon dispersion, and elastic constants, the thermodynamic, dynamic, and mechanical stabilities of Si-CL-A, Si-CL-B, Si-CL-C, and Si-CL-D allotropes are confirmed. In the low-density region of the phase diagram, Si-CL-B, Si-CL-D, and Si-CL-C would overtake diamond silicon and type II clathrate (Si-CL-II) and emerge as the most stable Si allotropes successively. Among them, the two direct semiconductors with bandgaps of 1.147 eV (Si-CL-A) and 1.086 eV (Si-CL-D) are found. The suitable bandgaps close to the optimal Shockley-Queisser limit result in better absorption efficiency in solar spectrum than conventional diamond silicon. Owing to the unique cage-based framework, the thermal conductivity of these Si allotropes at room temperature are very low (2.7-5.7 Wm-1 K-1), which are lower than that of diamond structured Si by two orders of magnitude. The suitable bandgaps, small effective masses, and low thermal conductivity of our new silicon allotropes are anticipated to find applications in photovoltaic and thermoelectric devices.

Silicon-germanium and platinum silicide nanostructures for silicon based photonics

NASA Astrophysics Data System (ADS)

Storozhevykh, M. S.; Dubkov, V. P.; Arapkina, L. V.; Chizh, K. V.; Mironov, S. A.; Chapnin, V. A.; Yuryev, V. A.

2017-05-01

This paper reports a study of two types of silicon based nanostructures prospective for applications in photonics. The first ones are Ge/Si(001) structures forming at room temperature and reconstructing after annealing at 600°C. Germanium, being deposited from a molecular beam at room temperature on the Si(001) surface, forms a thin granular film composed of Ge particles with sizes of a few nanometers. A characteristic feature of these films is that they demonstrate signs of the 2 x 1 structure in their RHEED patterns. After short-term annealing at 600°C under the closed system conditions, the granular films reconstruct to heterostructures consisting of a Ge wetting layer and oval clusters of Ge. A mixed type c(4x2) + p(2x2) reconstruction typical to the low-temperature MBE (Tgr < 600°C) forms on the wetting layer. Long-term annealing of granular films at the same conditions results in formation of c(4x2)-reconstructed wetting layer typical to high-temperature MBE (Tgr < 600°C) and huge clusters of Ge. The other type of the studied nanostructures is based on Pt silicides. This class of materials is one of the friendliest to silicon technology. But as silicide film thickness reaches a few nanometers, low resistivity becomes of primary importance. Pt3Si has the lowest sheet resistance among the Pt silicides. However, the development of a process of thin Pt3Si films formation is a challenging task. This paper describes formation of a thin Pt3Si/Pt2Si structures at room temperature on poly-Si films. Special attention is paid upon formation of poly-Si and amorphous Si films on Si3N4 substrates at low temperatures.

Si3 AlP: A New Promising Material for Solar Cell Absorber

NASA Astrophysics Data System (ADS)

Yang, Jihui; Zhai, Yingteng; Liu, Hengrui; Xiang, Hongjun; Gong, Xingao; Wei, Suhuai

2014-03-01

First-principles calculations are performed to study the structural and optoelectronic properties of the newly synthesized nonisovalent and lattice-matched (Si2)0.6(AlP)0.4 alloy [T. Watkins et al., J. Am. Chem. Soc. 2011, 133, 16212.] The most stable structure of Si3AlP is a superlattice along the <111>direction with separated AlP and Si layers, which has a similar optical absorption spectrum to silicon. The ordered C1c1-Si3AlP is found to be the most stable one among all the structures with -AlPSi3- motifs, in agreement with the experimental suggestions. We predict that C1c1-Si3AlP has good optical properties, i.e., it has a larger fundamental band gap and a smaller direct band gap than Si, thus it has much higher absorption in the visible light region, making it a promising candidate for improving the performance of the existing Si-based solar cells.

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

PubMed

Marchaj, Marzena; Freza, Sylwia; Skurski, Piotr

2012-03-01

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss). © 2012 American Chemical Society

Chemical bonding in silicon-carbene complexes.

PubMed

Liu, Z

2009-06-04

The bonding situations in the newly synthesized silicon-carbene complexes with formulas L:SiCl4, L:(Cl)Si-Si(Cl):L, and L:Si=Si:L (where L: is an N-heterocyclic carbene), are reported using density functional theory at the BP86/TZ2P level. The bonding analysis clearly shows that the bonding situation in the silicon-carbene complexes cannot be described in terms of donor-acceptor interactions depicted in the Dewar-Chatt-Duncanson model. The energy decomposition analysis (EDA) shows that the electrostatic attraction plays an important or even dominant role for the Si-C(carbene) binding interactions in the silicon-carbene complexes. That the molecular orbitals of the silicon-carbene complexes are lower in energy than the parent orbitals of carbenes indicates that these complexes are better described as stabilized carbene complexes.

siRNA carrying an (E)-vinylphosphonate moiety at the 5΄ end of the guide strand augments gene silencing by enhanced binding to human Argonaute-2

PubMed Central

Elkayam, Elad; Parmar, Rubina; Brown, Christopher R.; Willoughby, Jennifer L.; Theile, Christopher S.

2017-01-01

Abstract Efficient gene silencing by RNA interference (RNAi) in vivo requires the recognition and binding of the 5΄- phosphate of the guide strand of an siRNA by the Argonaute protein. However, for exogenous siRNAs it is limited by the rapid removal of the 5΄- phosphate of the guide strand by metabolic enzymes. Here, we have determined the crystal structure of human Argonaute-2 in complex with the metabolically stable 5΄-(E)-vinylphosphonate (5΄-E-VP) guide RNA at 2.5-Å resolution. The structure demonstrates how the 5΄ binding site in the Mid domain of human Argonaute-2 is able to adjust the key residues in the 5΄-nucleotide binding pocket to compensate for the change introduced by the modified nucleotide. This observation also explains improved binding affinity of the 5΄-E-VP -modified siRNA to human Argonaute-2 in-vitro, as well as the enhanced silencing in the context of the trivalent N-acetylgalactosamine (GalNAc)-conjugated siRNA in mice relative to the un-modified siRNA. PMID:27903888

Enhancement of Light Absorption in Silicon Nanowire Photovoltaic Devices with Dielectric and Metallic Grating Structures.

PubMed

Park, Jin-Sung; Kim, Kyoung-Ho; Hwang, Min-Soo; Zhang, Xing; Lee, Jung Min; Kim, Jungkil; Song, Kyung-Deok; No, You-Shin; Jeong, Kwang-Yong; Cahoon, James F; Kim, Sun-Kyung; Park, Hong-Gyu

2017-12-13

We report the enhancement of light absorption in Si nanowire photovoltaic devices with one-dimensional dielectric or metallic gratings that are fabricated by a damage-free, precisely aligning, polymer-assisted transfer method. Incorporation of a Si 3 N 4 grating with a Si nanowire effectively enhances the photocurrents for transverse-electric polarized light. The wavelength at which a maximum photocurrent is generated is readily tuned by adjusting the grating pitch. Moreover, the electrical properties of the nanowire devices are preserved before and after transferring the Si 3 N 4 gratings onto Si nanowires, ensuring that the quality of pristine nanowires is not degraded during the transfer. Furthermore, we demonstrate Si nanowire photovoltaic devices with Ag gratings using the same transfer method. Measurements on the fabricated devices reveal approximately 27.1% enhancement in light absorption compared to that of the same devices without the Ag gratings without any degradation of electrical properties. We believe that our polymer-assisted transfer method is not limited to the fabrication of grating-incorporated nanowire photovoltaic devices but can also be generically applied for the implementation of complex nanoscale structures toward the development of multifunctional optoelectronic devices.

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides.

PubMed

Bilyachenko, Alexey N; Yalymov, Alexey I; Shul'pina, Lidia S; Mandelli, Dalmo; Korlyukov, Alexander A; Vologzhanina, Anna V; Es'kova, Marina A; Shubina, Elena S; Levitsky, Mikhail M; Shul'pin, Georgiy B

2016-05-19

New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)₆(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)₆(NaCl)(C₄H₈O₂)13(PhCN)₂(H₂O)₂ and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

Characterization of SiO{sub 2}/SiN{sub x} gate insulators for graphene based nanoelectromechanical systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tóvári, E.; Csontos, M., E-mail: csontos@dept.phy.bme.hu; Kriváchy, T.

2014-09-22

The structural and magnetotransport characterization of graphene nanodevices exfoliated onto Si/SiO{sub 2}/SiN{sub x} heterostructures are presented. Improved visibility of the deposited flakes is achieved by optimal tuning of the dielectric film thicknesses. The conductance of single layer graphene Hall-bar nanostructures utilizing SiO{sub 2}/SiN{sub x} gate dielectrics were characterized in the quantum Hall regime. Our results highlight that, while exhibiting better mechanical and chemical stability, the effect of non-stoichiometric SiN{sub x} on the charge carrier mobility of graphene is comparable to that of SiO{sub 2}, demonstrating the merits of SiN{sub x} as an ideal material platform for graphene based nanoelectromechanical applications.

Precursor Routes to Complex Ternary Intermetallics: Single-Crystal and Microcrystalline Preparation of Clathrate-I Na8Al8Si38 from NaSi + NaAlSi.

PubMed

Dong, Yongkwan; Chai, Ping; Beekman, Matt; Zeng, Xiaoyu; Tritt, Terry M; Nolas, George S

2015-06-01

Single crystals of the ternary clathrate-I Na8Al8Si38 were synthesized by kinetically controlled thermal decomposition (KCTD), and microcrystalline Na8Al8Si38 was synthesized by spark plasma sintering (SPS) using a NaSi + NaAlSi mixture as the precursor. Na8AlxSi46-x compositions with x ≤ 8 were also synthesized by SPS from precursor mixtures of different ratios. The crystal structure of Na8Al8Si38 was investigated using both Rietveld and single-crystal refinements. Temperature-dependent transport and UV/vis measurements were employed in the characterization of Na8Al8Si38, with diffuse-reflectance measurement indicating an indirect optical gap of 0.64 eV. Our results indicate that, when more than one precursor is used, both SPS and KCTD are effective methods for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

High-Performance SiC/SiC Ceramic Composite Systems Developed for 1315 C (2400 F) Engine Components

NASA Technical Reports Server (NTRS)

DiCarlo, James A.; Yun, Hee Mann; Morscher, Gregory N.; Bhatt, Ramakrishna T.

2004-01-01

As structural materials for hot-section components in advanced aerospace and land-based gas turbine engines, silicon carbide (SiC) ceramic matrix composites reinforced by high performance SiC fibers offer a variety of performance advantages over current bill-of-materials, such as nickel-based superalloys. These advantages are based on the SiC/SiC composites displaying higher temperature capability for a given structural load, lower density (approximately 30- to 50-percent metal density), and lower thermal expansion. These properties should, in turn, result in many important engine benefits, such as reduced component cooling air requirements, simpler component design, reduced support structure weight, improved fuel efficiency, reduced emissions, higher blade frequencies, reduced blade clearances, and higher thrust. Under the NASA Ultra-Efficient Engine Technology (UEET) Project, much progress has been made at the NASA Glenn Research Center in identifying and optimizing two highperformance SiC/SiC composite systems. The table compares typical properties of oxide/oxide panels and SiC/SiC panels formed by the random stacking of balanced 0 degrees/90 degrees fabric pieces reinforced by the indicated fiber types. The Glenn SiC/SiC systems A and B (shaded area of the table) were reinforced by the Sylramic-iBN SiC fiber, which was produced at Glenn by thermal treatment of the commercial Sylramic SiC fiber (Dow Corning, Midland, MI; ref. 2). The treatment process (1) removes boron from the Sylramic fiber, thereby improving fiber creep, rupture, and oxidation resistance and (2) allows the boron to react with nitrogen to form a thin in situ grown BN coating on the fiber surface, thereby providing an oxidation-resistant buffer layer between contacting fibers in the fabric and the final composite. The fabric stacks for all SiC/SiC panels were provided to GE Power Systems Composites for chemical vapor infiltration of Glenn designed BN fiber coatings and conventional SiC matrices. Composite panels with system B were heat treated at Glenn, and the pores that remained open were filled by silicon melt infiltration (MI). Panels with system A and the other SiC/SiC systems were not heat treated, and remaining open pores in these systems were filled with SiC slurry and silicon MI.

Delivery of siRNA using ternary complexes containing branched cationic peptides: the role of peptide sequence, branching and targeting.

PubMed

Kudsiova, Laila; Welser, Katharina; Campbell, Frederick; Mohammadi, Atefeh; Dawson, Natalie; Cui, Lili; Hailes, Helen C; Lawrence, M Jayne; Tabor, Alethea B

2016-03-01

Ternary nanocomplexes, composed of bifunctional cationic peptides, lipids and siRNA, as delivery vehicles for siRNA have been investigated. The study is the first to determine the optimal sequence and architecture of the bifunctional cationic peptide used for siRNA packaging and delivery using lipopolyplexes. Specifically three series of cationic peptides of differing sequence, degrees of branching and cell-targeting sequences were co-formulated with siRNA and vesicles prepared from a 1 : 1 molar ratio of the cationic lipid DOTMA and the helper lipid, DOPE. The level of siRNA knockdown achieved in the human alveolar cell line, A549-luc cells, in both reduced serum and in serum supplemented media was evaluated, and the results correlated to the nanocomplex structure (established using a range of physico-chemical tools, namely small angle neutron scattering, transmission electron microscopy, dynamic light scattering and zeta potential measurement); the conformational properties of each component (circular dichroism); the degree of protection of the siRNA in the lipopolyplex (using gel shift assays) and to the cellular uptake, localisation and toxicity of the nanocomplexes (confocal microscopy). Although the size, charge, structure and stability of the various lipopolyplexes were broadly similar, it was clear that lipopolyplexes formulated from branched peptides containing His-Lys sequences perform best as siRNA delivery agents in serum, with protection of the siRNA in serum balanced against efficient release of the siRNA into the cytoplasm of the cell.

Deep ultraviolet photodetectors based on p-Si/ i-SiC/ n-Ga2O3 heterojunction by inserting thin SiC barrier layer

NASA Astrophysics Data System (ADS)

An, Yuehua; Zhi, Yusong; Wu, Zhenping; Cui, Wei; Zhao, Xiaolong; Guo, Daoyou; Li, Peigang; Tang, Weihua

2016-12-01

Deep ultraviolet photodetectors based on p-Si/ n-Ga2O3 and p-Si/ i-SiC/ n-Ga2O3 heterojunctions were fabricated by laser molecular beam epitaxial (L-MBE), respectively. In compare with p-Si/ n-Ga2O3 heterostructure-based photodetector, the dark current of p-Si/ i-SiC/ n-Ga2O3-based photodetector decreased by three orders of magnitude, and the rectifying behavior was tuned from reverse to forward. In order to improve the quality of the photodetector, we reduced the oxygen vacancies of p-Si/ i-SiC/ n-Ga2O3 heterostructures by changing the oxygen pressure during annealing. As a result, the rectification ratio ( I F/ I R) of the fabricated photodetectors was 36 at 4.5 V and the photosensitivity was 5.4 × 105% under the 254 nm light illumination at -4.5 V. The energy band structure of p-Si/ n-Ga2O3 and p-Si/ i-SiC/ n-Ga2O3 heterostructures was schematic drawn to explain the physic mechanism of enhancement of the performance of p-Si/ i-SiC/ n-Ga2O3 heterostructure-based deep UV photodetector by introduction of SiC layer.

Si-Mn/reduced graphene oxide nanocomposite anodes with enhanced capacity and stability for lithium-ion batteries.

PubMed

Park, A Reum; Kim, Jung Sub; Kim, Kwang Su; Zhang, Kan; Park, Juhyun; Park, Jong Hyeok; Lee, Joong Kee; Yoo, Pil J

2014-02-12

Although Si is a promising high-capacity anode material for Li-ion batteries (LIB), it suffers from capacity fading due to excessively large volumetric changes upon Li insertion. Nanocarbon materials have been used to enhance the cyclic stability of LIB anodes, but they have an inherently low specific capacity. To address these issues, we present a novel ternary nanocomposite of Si, Mn, and reduced graphene oxide (rGO) for LIB anodes, in which the Si-Mn alloy offers high capacity characteristics and embedded rGO nanosheets confer structural stability. Si-Mn/rGO ternary nanocomposites were synthesized by mechanical complexation and subsequent thermal reduction of mixtures of Si nanoparticles, MnO2 nanorods, and rGO nanosheets. Resulting ternary nanocomposite anodes displayed a specific capacity of 600 mAh/g with ∼90% capacity retention after 50 cycles at a current density of 100 mA/g. The enhanced performance is attributed to facilitated Li-ion reactions with the MnSi alloy phase and the formation of a structurally reinforced electroconductive matrix of rGO nanosheets. The ternary nanocomposite design paradigm presented in this study can be exploited for the development of high-capacity and long-life anode materials for versatile LIB applications.

Synthesis and design of silicide intermetallic materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrovic, J.J.; Castro, R.G.; Butt, D.P.

1997-04-01

The overall objective of this program is to develop structural silicide-based materials with optimum combinations of elevated temperature strength/creep resistance, low temperature fracture toughness, and high temperature oxidation and corrosion resistance for applications of importance to the U.S. processing industry. A further objective is to develop silicide-based prototype industrial components. The ultimate aim of the program is to work with industry to transfer the structural silicide materials technology to the private sector in order to promote international competitiveness in the area of advanced high temperature materials and important applications in major energy-intensive U.S. processing industries. The program presently has amore » number of developing industrial connections, including a CRADA with Schuller International Inc. targeted at the area of MoSi{sub 2}-based high temperature materials and components for fiberglass melting and processing applications. The authors are also developing an interaction with the Institute of Gas Technology (IGT) to develop silicides for high temperature radiant gas burner applications, for the glass and other industries. Current experimental emphasis is on the development and characterization of MoSi{sub 2}-Si{sub 3}N{sub 4} and MoSi{sub 2}-SiC composites, the plasma spraying of MoSi{sub 2}-based materials, and the joining of MoSi{sub 2} materials to metals.« less

Targeted therapy with MXD3 siRNA, anti-CD22 antibody and nanoparticles for precursor B-cell acute lymphoblastic leukaemia.

PubMed

Satake, Noriko; Duong, Connie; Chen, Cathy; Barisone, Gustavo A; Diaz, Elva; Tuscano, Joseph; Rocke, David M; Nolta, Jan; Nitin, Nitin

2014-11-01

Conventional chemotherapy for precursor B-cell (preB) acute lymphoblastic leukaemia (ALL) has limitations that could be overcome by targeted therapy. Previously, we discovered a potential therapeutic molecular target, MDX3 (MAX dimerization protein 3), in preB ALL. In this study, we hypothesize that an effective siRNA therapy for preB ALL can be developed using antiCD22 antibody (αCD22 Ab) and nanoparticles. We composed nanocomplexes with super paramagnetic iron oxide nanoparticles (SPIO NPs), αCD22 Abs and MXD3 siRNA molecules based on physical interactions between the molecules. We demonstrated that the MXD3 siRNA-αCD22 Ab-SPIO NP complexes entered leukaemia cells and knocked down MXD3, leading the cells to undergo apoptosis and resulting in decreased live cell counts in the cell line Reh and in primary preB ALL samples in vitro. Furthermore, the cytotoxic effects of the MXD3 siRNA-αCD22 Ab-SPIO NP complexes were significantly enhanced by addition of the chemotherapy drugs vincristine or doxorubicin. We also ruled out potential cytotoxic effects of the MXD3 siRNA-αCD22 Ab-SPIO NP complexes on normal primary haematopoietic cells. Normal B cells were affected while CD34-positive haematopoietic stem cells and non-B cells were not. These data suggest that MXD3 siRNA-αCD22 Ab-SPIO NP complexes have the potential to be a new targeted therapy for preB ALL. © 2014 John Wiley & Sons Ltd.

Comparing 2-nt 3' overhangs against blunt-ended siRNAs: a systems biology based study.

PubMed

Ghosh, Preetam; Dullea, Robert; Fischer, James E; Turi, Tom G; Sarver, Ronald W; Zhang, Chaoyang; Basu, Kalyan; Das, Sajal K; Poland, Bradley W

2009-07-07

In this study, we formulate a computational reaction model following a chemical kinetic theory approach to predict the binding rate constant for the siRNA-RISC complex formation reaction. The model allowed us to study the potency difference between 2-nt 3' overhangs against blunt-ended siRNA molecules in an RNA interference (RNAi) system. The rate constant predicted by this model was fed into a stochastic simulation of the RNAi system (using the Gillespie stochastic simulator) to study the overall potency effect. We observed that the stochasticity in the transcription/translation machinery has no observable effects in the RNAi pathway. Sustained gene silencing using siRNAs can be achieved only if there is a way to replenish the dsRNA molecules in the cell. Initial findings show about 1.5 times more blunt-ended molecules will be required to keep the mRNA at the same reduced level compared to the 2-nt overhang siRNAs. However, the mRNA levels jump back to saturation after a longer time when blunt-ended siRNAs are used. We found that the siRNA-RISC complex formation reaction rate was 2 times slower when blunt-ended molecules were used pointing to the fact that the presence of the 2-nt overhangs has a greater effect on the reaction in which the bound RISC complex cleaves the mRNA.

Comparing 2-nt 3' overhangs against blunt-ended siRNAs: a systems biology based study

PubMed Central

Ghosh, Preetam; Dullea, Robert; Fischer, James E; Turi, Tom G; Sarver, Ronald W; Zhang, Chaoyang; Basu, Kalyan; Das, Sajal K; Poland, Bradley W

2009-01-01

In this study, we formulate a computational reaction model following a chemical kinetic theory approach to predict the binding rate constant for the siRNA-RISC complex formation reaction. The model allowed us to study the potency difference between 2-nt 3' overhangs against blunt-ended siRNA molecules in an RNA interference (RNAi) system. The rate constant predicted by this model was fed into a stochastic simulation of the RNAi system (using the Gillespie stochastic simulator) to study the overall potency effect. We observed that the stochasticity in the transcription/translation machinery has no observable effects in the RNAi pathway. Sustained gene silencing using siRNAs can be achieved only if there is a way to replenish the dsRNA molecules in the cell. Initial findings show about 1.5 times more blunt-ended molecules will be required to keep the mRNA at the same reduced level compared to the 2-nt overhang siRNAs. However, the mRNA levels jump back to saturation after a longer time when blunt-ended siRNAs are used. We found that the siRNA-RISC complex formation reaction rate was 2 times slower when blunt-ended molecules were used pointing to the fact that the presence of the 2-nt overhangs has a greater effect on the reaction in which the bound RISC complex cleaves the mRNA. PMID:19594876

Light Absorption Enhancement of Silicon-Based Photovoltaic Devices with Multiple Bandgap Structures of Porous Silicon

PubMed Central

Wu, Kuen-Hsien; Li, Chong-Wei

2015-01-01

Porous-silicon (PS) multi-layered structures with three stacked PS layers of different porosity were prepared on silicon (Si) substrates by successively tuning the electrochemical-etching parameters in an anodization process. The three PS layers have different optical bandgap energy and construct a triple-layered PS (TLPS) structure with multiple bandgap energy. Photovoltaic devices were fabricated by depositing aluminum electrodes of Schottky contacts on the surfaces of the developed TLPS structures. The TLPS-based devices exhibit broadband photoresponses within the spectrum of the solar irradiation and get high photocurrent for the incident light of a tungsten lamp. The improved spectral responses of devices are owing to the multi-bandgap structures of TLPS, which are designed with a layered configuration analog to a tandem cell for absorbing a wider energy range of the incidental sun light. The large photocurrent is mainly ascribed to an enhanced light-absorption ability as a result of applying nanoporous-Si thin films as the surface layers to absorb the short-wavelength light and to improve the Schottky contacts of devices. Experimental results reveal that the multi-bandgap PS structures produced from electrochemical-etching of Si wafers are potentially promising for development of highly efficient Si-based solar cells. PMID:28793542

Ultraviolet GaN photodetectors on Si via oxide buffer heterostructures with integrated short period oxide-based distributed Bragg reflectors and leakage suppressing metal-oxide-semiconductor contacts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szyszka, A., E-mail: szyszka@ihp-microelectronics.com, E-mail: adam.szyszka@pwr.wroc.pl; Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wroclaw; Lupina, L.

2014-08-28

Based on a novel double step oxide buffer heterostructure approach for GaN integration on Si, we present an optimized Metal-Semiconductor-Metal (MSM)-based Ultraviolet (UV) GaN photodetector system with integrated short-period (oxide/Si) Distributed Bragg Reflector (DBR) and leakage suppressing Metal-Oxide-Semiconductor (MOS) electrode contacts. In terms of structural properties, it is demonstrated by in-situ reflection high energy electron diffraction and transmission electron microscopy-energy dispersive x-ray studies that the DBR heterostructure layers grow with high thickness homogeneity and sharp interface structures sufficient for UV applications; only minor Si diffusion into the Y{sub 2}O{sub 3} films is detected under the applied thermal growth budget. Asmore » revealed by comparative high resolution x-ray diffraction studies on GaN/oxide buffer/Si systems with and without DBR systems, the final GaN layer structure quality is not significantly influenced by the growth of the integrated DBR heterostructure. In terms of optoelectronic properties, it is demonstrated that—with respect to the basic GaN/oxide/Si system without DBR—the insertion of (a) the DBR heterostructures and (b) dark current suppressing MOS contacts enhances the photoresponsivity below the GaN band-gap related UV cut-off energy by almost up to two orders of magnitude. Given the in-situ oxide passivation capability of grown GaN surfaces and the one order of magnitude lower number of superlattice layers in case of higher refractive index contrast (oxide/Si) systems with respect to classical III-N DBR superlattices, virtual GaN substrates on Si via functional oxide buffer systems are thus a promising robust approach for future GaN-based UV detector technologies.« less

Positron annihilation studies of silicon-based materials

NASA Astrophysics Data System (ADS)

Petkov, Mihail Petkov

Positron Annihilation Spectroscopy (PAS) is used as a defect-profiling tool in the characterization of Si-based materials. PAS, in conjunction with variable energy positron beams, is a non-destructive depth-profiling probe, ideally suited for studying thin films, multi-layered structures, and buried interfaces. Its sensitivity to open-volume defects covers a wide range of defect sizes and concentrations, and surpasses that of most other techniques. This dissertation presents PAS investigations of electrical, chemical and mechanical properties of a number of advanced materials for future use by the semiconductor industry. Among the subjects of this work are: hydrogenated amorphous silicon (a-Si:H) for use in solar cells and flat-panel displays; low dielectric constant materials (low-k) for interlayer dielectrics; and thin-gate transistors, focusing on the defects at the Si/SiO 2 interface, which limit the device reliability. Results from extensive research on various possibilities to enhance the PAS capability by increasing its efficiency are presented in the appendices. The recognition of different dangling bond defects for low defect densities is achieved in these first PAS studies of void-free a-Si:H. Direct evidence of the existence of dopant-defect complexes is obtained for the first time. This research lays the foundation for future studies of the role of the impurities in light- and thermal degradation of a-Si:H PAS was applied to the characterization of porous low-k dielectrics. The annihilation observables are correlated with the dielectric properties of the material and their preparation conditions. PAS is the only non-destructive local k-probe, and the only tool for measuring void densities and sizes. The method is also sensitive to the chemical environment of the voids, seen during oxidation, water absorption, and forming gas anneal. Industrial research, partially based on these results, is currently in progress at IBM. A decade-old controversy, involving different models of defect states at Si/SiO2 interfaces, has been resolved. The two-defect model was confirmed and previous results were reevaluated. Research in this area will promote the use of PAS as an on-line diagnostic tool in the manufacturing of integrated circuits.

Microstructure and wear property of the Ti5Si3/TiC reinforced Co-based coatings fabricated by laser cladding on Ti-6Al-4V

NASA Astrophysics Data System (ADS)

Weng, Fei; Yu, Huijun; Liu, Jianli; Chen, Chuanzhong; Dai, Jingjie; Zhao, Zhihuan

2017-07-01

Ti5Si3/TiC reinforced Co-based composite coatings were fabricated on Ti-6Al-4V titanium alloy by laser cladding with Co42 and SiC mixture. Microstructure and wear property of the cladding coatings with different content of SiC were investigated. During the cladding process, the original SiC dissolved and reacted with Ti forming Ti5Si3 and TiC. The complex in situ formed phases were found beneficial to the improvement of the coating property. Results indicated that the microhardness of the composite coatings was enhanced to over 3 times the substrate. The wear resistance of the coatings also showed distinct improvement (18.4-57.4 times). More SiC gave rise to better wear resistance within certain limits. However, too much SiC (20 wt%) was not good for the further improvement of the wear property.

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jiangwei; Luo, Hao; Liu, Yang

2016-09-14

The electrochemically-induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can bemore » induced by increasing the thickness of SiOx on the outer surface. Moreover, both the sandwich lithiation mechanism and two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings, but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.« less

SiC Integrated Circuits for Power Device Drivers Able to Operate in Harsh Environments

NASA Astrophysics Data System (ADS)

Godignon, P.; Alexandru, M.; Banu, V.; Montserrat, J.; Jorda, X.; Vellvehi, M.; Schmidt, B.; Michel, P.; Millan, J.

2014-08-01

The currently developed SiC electronic devices are more robust to high temperature operation and radiation exposure damage than correspondingly rated Si ones. In order to integrate the existent SiC high power and high temperature electronics into more complex systems, a SiC integrated circuit (IC) technology capable of operation at temperatures substantially above the conventional ones is required. Therefore, this paper is a step towards the development of ICs-control electronics that have to attend the harsh environment power applications. Concretely, we present the development of SiC MESFET-based digital circuitry, able to integrate gate driver for SiC power devices. Furthermore, a planar lateral power MESFET is developed with the aim of its co-integration on the same chip with the previously mentioned SiC digital ICs technology. And finally, experimental results on SiC Schottky-gated devices irradiated with protons and electrons are presented. This development is based on the Tungsten-Schottky interface technology used for the fabrication of stable SiC Schottky diodes for the European Space Agency Mission BepiColombo.

Micro-structural characterization of the hydration products of bauxite-calcination-method red mud-coal gangue based cementitious materials.

PubMed

Liu, Xiaoming; Zhang, Na; Yao, Yuan; Sun, Henghu; Feng, Huan

2013-11-15

In this research, the micro-structural characterization of the hydration products of red mud-coal gangue based cementitious materials has been investigated through SEM-EDS, (27)Al MAS NMR and (29)Si MAS NMR techniques, in which the used red mud was derived from the bauxite calcination method. The results show that the red mud-coal gangue based cementitious materials mainly form fibrous C-A-S-H gel, needle-shaped/rod-like AFt in the early hydration period. With increasing of the hydration period, densification of the pastes were promoted resulting in the development of strength. EDS analysis shows that with the Ca/Si of red mud-coal gangue based cementitious materials increases, the average Ca/Si and Ca/(Si+Al) atomic ratio of C-A-S-H gel increases, while the average Al/Si atomic ratio of C-A-S-H gel decreases. MAS NMR analysis reveals that Al in the hydration products of red mud-coal gangue based cementitious materials exists in the forms of Al(IV) and Al(VI), but mainly in the form of Al(VI). Increasing the Ca/Si ratio of raw material promotes the conversion of [AlO4] to [AlO6] and inhibits the combination between [AlO4] and [SiO4] to form C-A-S-H gel. Meanwhile, the polymerization degree of [SiO4] in the hydration products declines. Published by Elsevier B.V.

Device-based local delivery of siRNA against mammalian target of rapamycin (mTOR) in a murine subcutaneous implant model to inhibit fibrous encapsulation.

PubMed

Takahashi, Hironobu; Wang, Yuwei; Grainger, David W

2010-11-01

Fibrous encapsulation of surgically implanted devices is associated with elevated proliferation and activation of fibroblasts in tissues surrounding these implants, frequently causing foreign body complications. Here we test the hypothesis that inhibition of the expression of mammalian target of rapamycin (mTOR) in fibroblasts can mitigate the soft tissue implant foreign body response by suppressing fibrotic responses around implants. In this study, mTOR was knocked down using small interfering RNA (siRNA) conjugated with branched polyethylenimine (bPEI) in fibroblastic lineage cells in serum-based cell culture as shown by both gene and protein analysis. This mTOR knock-down led to an inhibition in fibroblast proliferation by 70% and simultaneous down-regulation in the expression of type I collagen in fibroblasts in vitro. These siRNA/bPEI complexes were released from poly(ethylene glycol) (PEG)-based hydrogel coatings surrounding model polymer implants in a subcutaneous rodent model in vivo. No significant reduction in fibrous capsule thickness and mTOR expression in the foreign body capsules were observed. The siRNA inefficacy in this in vivo implant model was attributed to siRNA dosing limitations in the gel delivery system, and lack of targeting ability of the siRNA complex specifically to fibroblasts. While in vitro data supported mTOR knock-down in fibroblast cultures, in vivo siRNA delivery must be further improved to produce clinically relevant effects on fibrotic encapsulation around implants. Copyright © 2010 Elsevier B.V. All rights reserved.

Modeling of Damage Initiation and Progression in a SiC/SiC Woven Ceramic Matrix Composite

NASA Technical Reports Server (NTRS)

Mital, Subodh K.; Goldberg, Robert K.; Bonacuse, Peter J.

2012-01-01

The goal of an ongoing project at NASA Glenn is to investigate the effects of the complex microstructure of a woven ceramic matrix composite and its variability on the effective properties and the durability of the material. Detailed analysis of these complex microstructures may provide clues for the material scientists who `design the material? or to structural analysts and designers who `design with the material? regarding damage initiation and damage propagation. A model material system, specifically a five-harness satin weave architecture CVI SiC/SiC composite composed of Sylramic-iBN fibers and a SiC matrix, has been analyzed. Specimens of the material were serially sectioned and polished to capture the detailed images of fiber tows, matrix and porosity. Open source analysis tools were used to isolate various constituents and finite elements models were then generated from simplified models of those images. Detailed finite element analyses were performed that examine how the variability in the local microstructure affected the macroscopic behavior as well as the local damage initiation and progression. Results indicate that the locations where damage initiated and propagated is linked to specific microstructural features.

Using a non-spin flip model to rationalize the irregular patterns observed in the activation of the C-H and Si-H bonds of small molecules by CpMCO (M = Co, Rh) complexes.

PubMed

Castro, Guadalupe; Colmenares, Fernando

2017-09-20

The activation of the C-H and Si-H bonds of CH(CH 3 ) 3 and SiH(CH 3 ) 3 molecules by organometallic compounds CpMCO (M = Co, Rh) has been investigated through DFT and CASSCF-MRMP2 calculations. In particular, we have analyzed the pathways joining the lowest-lying triplet and singlet states of the reactants with the products arising from the insertion of the metal atom into the C-H or Si-H bonds of the organic molecules. Channels connecting the reactants with the inserted structure Cp(CO)H-M-C(CH 3 ) 3 through the oxidative addition of the C-H bond of the organic molecule to the metal fragment were found only for the reaction CpRhCO + CH(CH 3 ) 3 . However, inserted structures could also be obtained for the interactions of SiH(CH 3 ) 3 with CpCoCO and CpRhCO by two sequential reactions involving the formation and rebounding of the radical fragments Cp(CO)H-M + Si(CH 3 ) 3 . According to this two-step reaction scheme, the complex CpCoCO is unable to activate the C-H bond of the CH(CH 3 ) 3 molecule due to the high energy at which the radical fragments Cp(CO)H-M + C(CH 3 ) 3 are located. The picture attained for these interactions is consistent with the available experimental data for this kind of reaction and allows rationalization of the differences in the reactivity patterns determined for them without using spin-flip models, as has been proposed in previous studies.

Bio-inspired dewetted surfaces based on SiC/Si interlocked structures for enhanced-underwater stability and regenerative-drag reduction capability

PubMed Central

Lee, By Junghan; Zhang, Zhuo; Baek, Seunghyun; Kim, Sangkuk; Kim, Donghyung; Yong, Kijung

2016-01-01

Drag reduction has become a serious issue in recent years in terms of energy conservation and environmental protection. Among diverse approaches for drag reduction, superhydrophobic surfaces have been mainly researched due to their high drag reducing efficiency. However, due to limited lifetime of plastron (i.e., air pockets) on superhydrophobic surfaces in underwater, the instability of dewetted surfaces has been a sticking point for practical applications. This work presents a breakthrough in improving the underwater stability of superhydrophobic surfaces by optimizing nanoscale surface structures using SiC/Si interlocked structures. These structures have an unequaled stability of underwater superhydrophobicity and enhance drag reduction capabilities,with a lifetime of plastron over 18 days and maximum velocity reduction ratio of 56%. Furthermore, through photoelectrochemical water splitting on a hierarchical SiC/Si nanostructure surface, the limited lifetime problem of air pockets was overcome by refilling the escaping gas layer, which also provides continuous drag reduction effects. PMID:27095674

SiC lightweight telescopes for advanced space applications. II - Structures technology

NASA Technical Reports Server (NTRS)

Anapol, Michael I.; Hadfield, Peter; Tucker, Theodore

1992-01-01

A critical technology area for lightweight SiC-based telescope systems is the structural integrity and thermal stability over spaceborne environmental launch and thermal operating conditions. Note, it is highly desirable to have an inherently athermal design of both SiC mirrors and structure. SSG has developed an 8 inch diameter SiC telescope system for brassboard level optical and thermal testing. The brassboard telescope has demonstrated less than 0.2 waves P-V in the visible wavefront change over +50 C to -200 C temperature range. SSG has also fabricated a SiC truss structural assembly and successfully qualified this hardware at environmental levels greater than 3 times higher than normal Delta, Titan, and ARIES launch loads. SSG is currently developing two SiC telescopes; an 20 cm diameter off-axis 3 mirror re-imaging and a 60 cm aperture on-axis 3 mirror re-imager. Both hardware developments will be tested to flight level environmental, optical, and thermal specifications.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations.

PubMed

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-14

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiC x O 6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young's modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young's modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations

NASA Astrophysics Data System (ADS)

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-01

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiCxO6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young’s modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young’s modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

Structure-transfection activity relationships in a series of novel cationic lipids with heterocyclic head-groups.

PubMed

Ivanova, Ekaterina A; Maslov, Mikhail A; Kabilova, Tatyana O; Puchkov, Pavel A; Alekseeva, Anna S; Boldyrev, Ivan A; Vlassov, Valentin V; Serebrennikova, Galina A; Morozova, Nina G; Zenkova, Marina A

2013-11-07

Cationic liposomes are promising candidates for the delivery of various therapeutic nucleic acids. Here, we report a convenient synthesis of carbamate-type cationic lipids with various hydrophobic domains (tetradecanol, dialkylglycerol, cholesterol) and positively charged head-groups (pyridinium, N-methylimidazolium, N-methylmorpholinium) and data on the structure-transfection activity relationships. It was found that single-chain lipids possess high surface activity, which correlates with high cytotoxicity due to their ability to disrupt the cellular membrane by combined hydrophobic and electrostatic interactions. Liposomes containing these lipids also display high cytotoxicity with respect to all cell lines. Irrespective of chemical structures, all cationic lipids form liposomes with similar sizes and surface potentials. The characteristics of complexes composed of cationic liposomes and nucleic acids depend mostly on the type of nucleic acid and P/N ratios. In the case of oligodeoxyribonucleotide delivery, the transfection activity depends on the type of cationic head-group regardless of the type of hydrophobic domain: all types of cationic liposomes mediate efficient oligonucleotide transfer into 80-90% of the eukaryotic cells, and liposomes based on lipids with N-methylmorpholinium cationic head-group display the highest transfection activity. In the case of plasmid DNA and siRNA, the type of hydrophobic domain determines the transfection activity: liposomes composed of cholesterol-based lipids were the most efficient in DNA transfer, while liposomes containing glycerol-based lipids exhibited reasonable activity in siRNA delivery under serum-free conditions.

Microstructure and Corrosion Behavior of CrN and CrSiCN Coatings

NASA Astrophysics Data System (ADS)

Cai, Feng; Yang, Qi; Huang, Xiao; Wei, Ronghua

2010-07-01

Three CrN-based coatings were deposited on 17-4PH stainless steel substrate using plasma enhanced magnetron sputtering (PEMS) technique. The microstructure and corrosion resistance were evaluated to examine the effect of Si and C in the coatings. The three coating compositions were CrN(Cr0.69N0.31), CrSiCN-1 (Cr0.55Si0.014C0.14N0.3), and CrSiCN-2 (Cr0.43Si0.037C0.24N0.3). The testing results indicated that with the increase of Si concentration, the coating microstructure transformed from B1 structure to B1 + Si3N4 structure. All the three coating systems were subjected to electrochemical tests in 3.5% NaCl solution at room temperature. Potentiodynamic polarization results revealed that the CrSiCN-2 coating had a higher anodic current density and a lower corrosion potential when compared to the CrN and CrSiCN-1 coatings. Extended exposure in 3.5% NaCl caused several localized corrosion to the CrSiCN-2 coating due to the porous coating structure. Electrochemical impedance spectroscopic measurements demonstrated that the CrSiCN-1 has better corrosion resistance than CrN and CrSiCN-2.

Transport properties and electronic structure of Na0.28PtSi

NASA Astrophysics Data System (ADS)

Itahara, Hiroshi; Suzumura, Akitoshi; Oh, Song-Yul

2017-07-01

We have investigated the electronic structure and properties of Na0.28PtSi, which is a Pt-based intermetallic compound with no reported physical properties. Na0.28PtSi powder with an average grain size of 15 µm was demonstrated to be stable in a strongly acidic aqueous solution. The ab initio calculations revealed that there is a band crossing the Fermi level and that the density of states (DOS) under the Fermi level mainly consists of d orbitals of Pt atoms. Here, we used the model of Na0.25PtSi with an approximately ordered structure (space group I4, full Na site occupation), which was set instead of the reported statistically disordered structure of Na0.28PtSi (I4/mcm, Na site occupancy: 0.258). The calculated electronic structure corresponded to the measured metallic properties of the Na0.28PtSi sintered body: i.e., the electrical resistivity of Na0.28PtSi was increased from 1.77 × 10-8 Ω m at 30 K to 2.67 × 10-7 Ω m at 300 K and the Seebeck coefficient was 0.11 µV K-1 at 300 K.

Density-functional study of the structures and properties of holmium-doped silicon clusters HoSi n (n = 3-9) and their anions.

PubMed

Hou, Liyuan; Yang, Jucai; Liu, Yuming

2017-04-01

The structures and properties of Ho-doped Si clusters, including their adiabatic electron affinities (AEAs), simulated photoelectron spectra (PESs), stabilities, magnetic moments, and charge-transfer characteristics, were systematically investigated using four density-functional methods. The results show that the double-hybrid functional (which includes an MP2 correlation component) can accurately predict the ground-state structure and properties of Ho-doped Si clusters. The ground-state structures of HoSi n (n = 3-9) are sextuplet electronic states. The structures of these Ho-doped Si clusters (aside from HoSi 7 ) are substitutional. The ground-state structures of HoSi n - are quintuplet electronic states. Their predicted AEAs are in excellent agreement with the experimental ones. The mean absolute error in the theoretical AEAs of HoSi n (n = 4-9) is only 0.04 eV. The simulated PESs for HoSi n - (n = 5-9) are in good agreement with the experimental PESs. Based on its simulated PES and theoretical AEA, we reassigned the experimental PES of HoSi 4 - and obtained an experimental AEA of 2.2 ± 0.1 eV. The dissociation energies of Ho from HoSi n and HoSi n - (n = 3-9) were evaluated to test the relative stabilities of the clusters. HOMO-LUMO gap analysis indicated that doping the Si clusters with the rare-earth metal atom significantly increases their photochemical reactivity. Natural population analysis showed that the magnetic moments of HoSi n (n = 3-9) and their anions derive mainly from the Ho atom. It was also found that the magnetic moments of Ho in the HoSi n clusters are larger than the magnetic moment of an isolated Ho atom.

Probing the transition state for nucleic acid hybridization using phi-value analysis.

PubMed

Kim, Jandi; Shin, Jong-Shik

2010-04-27

Genetic regulation by noncoding RNA elements such as microRNA and small interfering RNA (siRNA) involves hybridization of a short single-stranded RNA with a complementary segment in a target mRNA. The physical basis of the hybridization process between the structured nucleic acids is not well understood primarily because of the lack of information about the transition-state structure. Here we use transition-state theory, inspired by phi-value analysis in protein folding studies, to provide quantitative analysis of the relationship between changes in the secondary structure stability and the activation free energy. Time course monitoring of the hybridization reaction was performed under pseudo-steady-state conditions using a single fluorophore. The phi-value analysis indicates that the native secondary structure remains intact in the transition state. The nativelike transition state was confirmed via examination of the salt dependence of the hybridization kinetics, indicating that the number of sodium ions associated with the transition state was not substantially affected by changes in the native secondary structure. These results propose that hybridization between structured nucleic acids undergoes a transition state leading to formation of a nucleation complex and then is followed by sequential displacement of preexisting base pairings involving successive small energy barriers. The proposed mechanism might provide new insight into physical processes during small RNA-mediated gene silencing, which is essential to selection of a target mRNA segment for siRNA design.

Bimetallic lanthanide amido complexes as highly active initiators for the ring-opening polymerization of lactides.

PubMed

Sun, Song; Nie, Kun; Tan, Yufang; Zhao, Bei; Zhang, Yong; Shen, Qi; Yao, Yingming

2013-02-28

A series of neutral bimetallic lanthanide amido complexes supported by rigid phenylene bridged bis(β-diketiminate) ligands were synthesized, and their catalytic behavior for the polymerization of L-lactide and rac-lactide was explored. The amine elimination reaction of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with PARA-H(2), [PARA-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(para-phenylene)] in a 2:1 molar ratio in THF at 25 °C afforded the corresponding bimetallic lanthanide amido complexes PARA-{Ln[N(SiMe(3))(2)](2)}(2) [Ln = Nd(1), Sm(2), Y(3)] in high isolated yields. Similar reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with META-H(2), [META-H(2) = 2[2,6-(i)Pr(2)C(6)H(3)NHC(Me)C(H)C(Me)N]-(meta-phenylene)] at 90 °C in toluene for about 48 h gave META-{Nd[N(SiMe(3))(2)](2)}(2) (4). Complexes 1-4 were well characterized by elemental analysis, IR spectroscopy, and their definitive structures were confirmed by an X-ray crystal structure analysis. The coordination environment and coordination geometry around the metal atoms are similar in these complexes. Each of the metal atoms is four-coordinated with two nitrogen atoms from the N,N-chelating β-diketiminate unit, and two nitrogen atoms from two (Me(3)Si)(2)N- groups to form a distorted tetrahedron. These complexes can serve as highly active initiators for L-lactide polymerization in toluene. In addition, they also showed high activity towards rac-lactide polymerization in THF at room temperature, giving heterotactic-enriched polymers (P(r) ≈ 0.70), and complex 4 displays obviously higher activity in comparison with complex 1.

Nano-Ag complexes prepared by γ-radiolysis and their structures and physical properties

NASA Astrophysics Data System (ADS)

Kim, Hwa-Jung; Choi, Seong-Ho; Park, Hae-Jun

2012-10-01

In this study, nano-silver (nano-Ag) complexes showing different properties have been synthesized as follows. Polypyrrolidone (PVP)-stabilized silver colloids (NAg), nano-Ag bound to silica (SiO2) (NSS), and nano-Ag bound to a complex of SiO2 and polyaniline (PANI) (NSSPAI) were prepared via γ-irradiation at room temperature. NAg and NSS used PVP as a colloidal stabilizer, while NSSPAI did not use PVP as a colloidal stabilizer. Interesting bonding properties occurred in the nano-Ag complex and anticipated structural changes were clearly shown through a surface analysis of x-ray photoelectron spectroscopy (XPS). The morphologies by field emission-scanning electron microscopy (FE-SEM) analysis showed that nano-Ag complexes have various particle sizes ranging from 10 to 30 nm. NSS (average, 10 nm) and NSSPAI (average, 30 nm) showed a uniformly spherical shape and size, while NAg did not. From the reflection peaks in the x-ray diffraction (XRD) patterns, surface crystallinity of the nano-Ag complexes was indicated to be in the same degree as that of NSSPAI>NSS>NAg. Also, in the contact angle (CA) determination, surface hydrophobicity of NSSPAI was stronger than those of NSS and NAg, relatively. The different nano-Ag complexes prepared by γ-irradiation can be applicable in various industry fields due to the increase in specific property.

Unexpected Magnetic Ordering on the Cr Substructure in UCr2Si2C and Structural Relationships in Quaternary U-Cr-Si-C Compounds.

PubMed

Lemoine, Pierric; Vernière, Anne; Pasturel, Mathieu; Venturini, Gérard; Malaman, Bernard

2018-03-05

Previous experimental and theoretical studies revealed that carbon insertion into the RCr 2 Si 2 compounds drastically affects the magnetic behavior, since chromium does not carry any magnetic moment in RCr 2 Si 2 C (R = Y, La-Sm, Gd-Er) compounds in contrast to RCr 2 Si 2 (R = Y, Sm, Gd-Lu, Th) compounds. In this study, we report on the unexpected magnetic ordering of chromium atoms in the isotype quaternary UCr 2 Si 2 C compound. While specific heat and magnetic measurements suggest a Pauli paramagnetic behavior, neutron powder diffraction reveals an antiferromagnetic ordering of the chromium substructure at high temperature ( T N > 300 K), while that of uranium remains nonmagnetically ordered down to 2 K. Its magnetic behavior, inverse in comparison to the RCr 2 Si 2 C carbides involving a magnetic lanthanide, is discussed in relation with the singularity of its crystal structure among the series. Moreover, the crystallographic structures and the structural stability of UCr 2 Si 2 C and of two other quaternary U-Cr-Si-C compounds (i.e., UCr 3 Si 2 C and U 2 Cr 3 Si 2 C 3 ), based on the full occupancy of interstitial sites by carbon atoms, are discussed and compared to those of the related ternary intermetallics. Finally, the low-temperature form of UCr 2 Si 2 , corresponding to a displacive transformation around 210 K of the ThCr 2 Si 2 -type structure, is reinvestigated by considering a higher symmetry monoclinic unit cell ( C2/ m) instead of the previously reported triclinic cell ( P1̅). The antiferromagnetic ordering at low temperature ( T N = 30(2) K) of the uranium substructure is confirmed, and its magnetic structure is reanalyzed and discussed considering the monoclinic crystal structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Illera, S., E-mail: sillera@el.ub.edu; Prades, J. D.; Cirera, A.

The role of different charge transport mechanisms in Si/SiO{sub 2} structures has been studied. A theoretical model based on the Transfer Hamiltonian Formalism has been developed to explain experimental current trends in terms of three different elastic tunneling processes: (1) trap assisted tunneling; (2) transport through an intermediate quantum dot; and (3) direct tunneling between leads. In general, at low fields carrier transport is dominated by the quantum dots whereas, for moderate and high fields, transport through deep traps inherent to the SiO{sub 2} is the most relevant process. Besides, current trends in Si/SiO{sub 2} superlattice structure have been properlymore » reproduced.« less

Fabrication And Evaluation Of Sic/Sic Tubes With Various Fiber Architectures

NASA Technical Reports Server (NTRS)

Yun, H. M.; DiCarlo, J. A.; Fox, D. S.

2003-01-01

SiC/SiC composites are excellent material candidates for high temperature applications where the performance requirements are high strength, high creep-rupture resistance, high environmental durability, and high thermal conductivity. In the past, the NASA UEET program has demonstrated fabrication of high-performance SiC/SiC flat panels reinforced by Sylramic-iBN SiC fibers. Currently NASA UEET is scaling up this SiC/SiC system by fabrication of more complex shaped components using the same fiber type. This paper reports the effects of various fiber architectures on the processing, mechanical, and durability behavior of small-diameter 0.5" ID SiC/SiC tubes, which are potential sub-elements for leading edges and cooling channels in turbine vanes and blades. Nine different fiber architectures were utilized for construction of seamless tube preforms, from simple 2D jelly-rolling to complex braiding, pin-weaving, filament-winding and 3D orthogonal weaving with approximately 5% fibers in the thru-thickness direction. Using the BN interphase and Sic matrix processing steps established for the flat panels, SiC/SiC tubes were fabricated with wall thicknesses of approximately 60 mils and total fiber fractions of approximately 35%. The "D" split ring tests for hoop tensile properties, micro-structural examinations for relationship between fiber architecture formation and matrix infiltration, and the low-pressure burner rig tests for the high temperature durability under thru-thickness thermal gradient were conducted. The better matrix infiltration and higher hoop strength were achieved using the tri-axial braided and the three-float pin woven SiC/SiC tubes. In general, it needs not only higher hoop direction fibers but also axial direction fibers for the higher hoop strength and the better infiltration, respectively. These results are analyzed to offer general guidelines for selecting fiber pre-form architectures and SiC/SiC processes that maximize tube hoop strength, thru-thickness thermal conductivity, and burner-rig durability under a high thermal gradient.

Raman studies of methane-ethane hydrate metastability.

PubMed

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Seok Woo; /Stanford U., Geballe Lab.; Lee, Hyun-Wook

2015-06-01

Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Herein, we demonstrate physical/mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferentialmore » lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Contract No. DE-AC02-76SF00515. SLAC-PUB-16300 2 lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high performance Li-ion batteries.« less

Device-based local delivery of siRNA against mammalian target of rapamycin (mTOR) in a murine subcutaneous implant model to inhibit fibrous encapsulation

PubMed Central

Takahashi, Hironobu; Wang, Yuwei; Grainger, David W.

2010-01-01

Fibrous encapsulation of surgically implant devices is associated with elevated proliferation and activation of fibroblasts in tissues surrounding these implants, frequently causing foreign body complications. Here we test the hypothesis that inhibition of the expression of mammalian target of rapamycin (mTOR) in fibroblasts can mitigate the soft tissue implant foreign body response by suppressing fibrotic responses around implants. In this study, mTOR was knocked down using small interfering RNA conjugated with branched cationic polyethylenimine (bPEI) in fibroblastic lineage cells in serum-based cell culture as shown by both gene and protein analysis. This mTOR knockdown led to an inhibition in fibroblast proliferation by 70% and simultaneous down-regulation in the expression of type I collagen in fibroblasts in vitro. These siRNA/bPEI complexes were released from poly(ethylene glycol) (PEG)-based hydrogel coatings surrounding model polymer implants in a subcutaneous rodent model in vivo. No significant reduction in fibrous capsule thickness and mTOR expression in the foreign body capsules was observed. Observed siRNA inefficacy in this in vivo implant model was attributed to siRNA dosing limitations in the gel delivery system, and lack of targeting ability of the siRNA complex specifically to fibroblasts. While in vitro data supported mTOR knock-down in fibroblast cultures, in vivo siRNA delivery must be further improved to produce clinically relevant effects on fibrotic encapsulation around implants. PMID:20727922

Strain-induced structural defects and their effects on the electrochemical performances of silicon core/germanium shell nanowire heterostructures

DOE PAGES

Lin, Yung-Chen; Kim, Dongheun; Li, Zhen; ...

2016-12-14

Here we report on strain-induced structural defect formation in core Si nanowire of Si/Ge core/shell nanowire heterostructure and influences of the structural defects on the electrochemical performances in lithium-ion battery anodes based on Si/Ge core/shell nanowire heterostructures. The induced structural defects consisting of stacking faults and dislocations in the core Si nanowire were observed for the first time. The generation of stacking faults in Si/Ge core/shell nanowire heterostructure is observed to prefer settling in either only Ge shell region or in both Ge shell and Si core regions and is associated with the increase of the shell volume fraction. Themore » relax of misfit strain in [112] oriented core/shell nanowire heterostructure leads to subsequent gliding of Shockley partial dislocations, preferentially forming the twins. The observation of cross-over defect formation is of great importance for the understanding of heteroepitaxy in radial heterostructures at nanoscale and building the three dimensional heterostructures for the various applications. In addition, the effect of the defect formation on nanomaterial’s functionality is investigated by electrochemical performance test. The Si/Ge core/shell nanowire heterostructures enhance the gravimetric capacity of lithium ion battery anodes under fast charging/discharging rates compared to Si nanowires. However, the induced structural defects hamper lithiation of the Si/Ge core/shell nanowire heterostructure.« less

Strain-induced structural defects and their effects on the electrochemical performances of silicon core/germanium shell nanowire heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yung-Chen; Kim, Dongheun; Li, Zhen

Here we report on strain-induced structural defect formation in core Si nanowire of Si/Ge core/shell nanowire heterostructure and influences of the structural defects on the electrochemical performances in lithium-ion battery anodes based on Si/Ge core/shell nanowire heterostructures. The induced structural defects consisting of stacking faults and dislocations in the core Si nanowire were observed for the first time. The generation of stacking faults in Si/Ge core/shell nanowire heterostructure is observed to prefer settling in either only Ge shell region or in both Ge shell and Si core regions and is associated with the increase of the shell volume fraction. Themore » relax of misfit strain in [112] oriented core/shell nanowire heterostructure leads to subsequent gliding of Shockley partial dislocations, preferentially forming the twins. The observation of cross-over defect formation is of great importance for the understanding of heteroepitaxy in radial heterostructures at nanoscale and building the three dimensional heterostructures for the various applications. In addition, the effect of the defect formation on nanomaterial’s functionality is investigated by electrochemical performance test. The Si/Ge core/shell nanowire heterostructures enhance the gravimetric capacity of lithium ion battery anodes under fast charging/discharging rates compared to Si nanowires. However, the induced structural defects hamper lithiation of the Si/Ge core/shell nanowire heterostructure.« less

An Exceptionally Narrow Band-Gap (∼4 eV) Silicate Predicted in the Cubic Perovskite Structure: BaSiO3.

PubMed

Hiramatsu, Hidenori; Yusa, Hitoshi; Igarashi, Ryo; Ohishi, Yasuo; Kamiya, Toshio; Hosono, Hideo

2017-09-05

The electronic structures of 35 A 2+ B 4+ O 3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO 3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO 2 and the calculated value of 7.3 eV for orthorhombic BaSiO 3 ) and a small electron effective mass (0.3m 0 , where m 0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO 3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO 3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.

Micromirror structure actuated by TiNi shape memory thin films

NASA Astrophysics Data System (ADS)

Fu, Y. Q.; Luo, J. K.; Hu, M.; Du, H. J.; Flewitt, A. J.; Milne, W. I.

2005-10-01

TiNi films were deposited by co-sputtering TiNi and Ti targets. Results from differential scanning calorimetry and curvature measurement revealed martensitic transformation and shape memory effect upon heating and cooling. Two types of TiNi/Si micromirror structures with a Si mirror cap (40 µm thick) and TiNi/Si actuation beams were designed and fabricated. For the first design, a V-shaped cantilever based on the TiNi/Si bimorph structure was used as the actuation mechanism for the micromirror. In the second design, three elbow-shaped Si beams with TiNi electrodes were used as the arms to actuate the mirror. The TiNi/Si microbeams were flat at room temperature and bent up by applying voltage in the TiNi electrodes (due to phase transformation and shape memory effect), thus causing changes in angles of the micromirror.

Quantum well infrared photodetectors (QWIP) with selectively regrown N-GaAs plugs

NASA Astrophysics Data System (ADS)

Matsukura, Yusuke; Nishino, Hironori; Tanaka, Hitoshi; Fujii, Toshio

2001-10-01

We fabricated the GaAs/AlGaAs Quantum Well Infrared Photo detector (QWIP) focal plane array with selectively re-grown N- GaAs interconnection plugs and demonstrated its device operation, in order to establish the technology to obtain both complex device functions and device manufacturability. MBE (Molecular Beam Epitaxy) grown QWIP MQW wafers were covered with SiON and SiNx mask films to obtain selectivity of the re-growth process. N-GaAs plugs were re-grown selectively with low-pressure MOCVD (Metal-Organic Chemical Vapor Deposition) with AsH3 and Dimethylgalliumchloride as precursors, only on the bottom surfaces of the holes for the interconnection to extract the electrodes from the underlying epilayer. Cross- sectional SEM observation revealed that the feature of the re- grown N-GaAs plugs was triangular, rather than rectangular as expected. The reason for this discrepancy is not yet clear. The electrical contact between the epilayer and re-grown N- GaAs plug was 'ohmic-like,' without any trace of interfacial barrier. The Current-Voltage characteristics of the fabricated QWIP device showed no tangible leakage current between the N- GaAs plug and device structure, indicating that electrical insulation between the N-GaAs plugs and device structure was sufficient. Fabricated devices were successfully operated as a hybrid focal plane array, indicating the selective re-growth was a promising technique to realize complex QWIP based devices.

Properties of planar structures based on Policluster films of diamond and AlN

NASA Astrophysics Data System (ADS)

Belyanin, A. F.; Luchnikov, A. P.; Nalimov, S. A.; Bagdasarian, A. S.

2018-01-01

AlN films doped with zinc were grown on Si substrates by RF magnetron reactive sputtering of a compound target. Policluster films of diamond doped with boron were formed on layered Si/AlN substrates from the gas phase hydrogen and methane, activated arc discharge. By electron microscopy, X-ray diffraction and Raman spectroscopy the composition and structure of synthetic policluster films of diamond and AlN films were studied. Photovoltaic devices based on the AlN/PFD layered structure are presented.

BiOBr@SiO2 flower-like nanospheres chemically-bonded on cement-based materials for photocatalysis

NASA Astrophysics Data System (ADS)

Wang, Dan; Hou, Pengkun; Yang, Ping; Cheng, Xin

2018-02-01

Endowment of photocatalytic property on the surface of concrete structure can contribute to the self-cleaning of the structure and purification of the polluted environment. We developed a nano-structured BiOBr@SiO2 photocatalyst and innovatively used for surface-treatment of cement-based materials with the hope of attaining the photocatalytic property in visible-light region and surface modification/densification performances. The SiO2 layer on the flower-like BiOBr@SiO2 helps to maintain a stable distribution of the photocatalyst, as well as achieving a chemical bonding between the coating and the cement matrix. Results showed that the color fading rate of during the degradation of Rhodamine B dye of the BiOBr-cem sample is 2 times higher compared with the commonly studied C, N-TiO2-cem sample. The photo-degradation rates of samples BiOBr-cem and BiOBr@SiO2-cem are 93 and 81% within 150 min, respectively, while sample BiOBr@SiO2-cem reveals a denser and smoother surface after curing for 28 days and pore-filling effect at size within 0.01-0.2 μm when compared with untreated samples. Moreover, additional C-S-H gel can be formed due to the pozzolanic reaction between BiOBr@SiO2 and the hardened cement matrix. Both advantages of the BiOBr@SiO2 favor its application for surface-treatment of hardened cement-based material to acquire an improved surface quality, as well as durable photocatalytic functionality.

Preparation and characterisation of crystalline tris(acetylacetonato)Fe(III) films grown on p-Si substrate for dielectric applications

NASA Astrophysics Data System (ADS)

Dakhel, A. A.; Ali-Mohamed, A. Y.

2007-02-01

Thin tris(acetylacetonato)iron(III) films were prepared by sublimation in vacuum on glass and p-Si substrates. Then comprehensive studies of X-ray fluorescence (XRF), X-ray diffraction (XRD), optical absorption spectroscopy, AC-conductivity, and dielectric permittivity as a function of frequency and temperature have been performed. The prepared films show a polycrystalline of orthorhombic structure. The optical absorption spectrum of the film was identical with that of the bulk powder layer. For electrical measurements of the complex as insulator, sample in form of metal insulator semiconductor (MIS) structure was prepared and characterised by the measurement of the capacitance and AC-conductance as a function of gate voltage. From those measurements, the state density Dit at insulator/semiconductor interface and the density of the fixed charges in the complex film were determined. It was found that Dit was of order 1010 eV-1/cm2 and the surface charge density in the insulator film was of order 1010 cm-2. The frequency dependence of the electrical conductivity and dielectric properties of MIS structures were studied at room temperature. It was observed that the experimental data follow the correlated barrier-hopping (CBH) model, from which the fundamental absorption edge, the cut off hopping distance, and other parameters of the model were determined. It was found that the capacitance of the complex increases as temperature increases. Generally, the present study shows that the tris(acetylacetonato)iron(III) films grown on p-Si is a promising candidate for low-k dielectric applications, it displays low-k value around 2.0.

Understanding the role played by Fe on the tuning of magnetocaloric effect in Tb5Si2Ge2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereira, Andre; Moreira Dos Santos, Antonio F; Magen Dominguez, Cesar

2011-01-01

In this work, it is shown that when replacing Ge by Fe in Tb5Si2Ge2 the structural transition still occurs and enhances the Magnetocaloric effect (up to 66%) with maximum of MCE at a critical Fe amount where the magnetic and structural transitions become fully coupled. It is observed that Fe concentration is able to mimic the e?ect of external pressure as it induces a complex microstructure, that tunes long range strain ?elds. This knowledge is crucial for the development of strategies towards materials with improved performance for e?cient magnetic refrigeration applications.

Nanoscale assembly of silicon-like [Al(As1-xNx)]ySi5-2y alloys: Fundamental theoretical and experimental studies of structural and optical properties

NASA Astrophysics Data System (ADS)

Jiang, L.; Sims, P. E.; Grzybowski, G.; Beeler, R. T.; Chizmeshya, A. V. G.; Smith, D. J.; Kouvetakis, J.; Menéndez, J.

2013-07-01

Ab initio theoretical simulations of Al(As1-xNx)Si3 alloys, a new class of optoelectronic materials, confirm that these compounds are likely to be disordered via a mechanism that preserves the integrity of the constituent III-V-Si3 tetrahedra but randomizes their orientation in the average diamond lattice of the compound. This type of disorder is consistent with experimental structural data and with the proposed growth mechanism for such alloys, according to which “III:V(SiH3)3” intermediate complexes are formed in the gas phase from reactions between group-III atomic beams and V(SiH3)3 molecules, delivering the entire III-V-Si3 tetrahedra to the growing film. Experimental optical studies of these Al(As1-xNx)Si3 alloys as well as more general [Al(As1-xNx)]ySi5-2y compounds grown on Si substrates were carried out using spectroscopic ellipsometry. The resulting dielectric functions are found to be similar to broadened versions of their counterparts in pure Si. This broadening may have important practical applications, particularly in photovoltaics, because it dramatically enhances the optical absorption of Si in the visible range of the electromagnetic spectrum. A critical point analysis reveals the existence of direct optical transitions at energies as low as 2.5 eV, well below the lowest direct absorption edge of Si at 3.3 eV. Such transitions are predicted theoretically for perfectly ordered III-V-Si3 compounds, and the experimental results suggest that they are robust against tetrahedra orientational disorder.

Solidification of Magnesium (AM50A) / vol%. SiCp composite

NASA Astrophysics Data System (ADS)

Zhang, X.; Hu, H.

2012-01-01

Magnesium matrix composite is one of the advanced lightweight materials with high potential to be used in automotive and aircraft industries due to its low density and high specific mechanical properties. The magnesium composites can be fabricated by adding the reinforcements of fibers or/and particles. In the previous literature, extensive studies have been performed on the development of matrix grain structure of aluminum-based metal matrix composites. However, there is limited information available on the development of grain structure during the solidification of particulate-reinforced magnesium. In this work, a 5 vol.% SiCp particulate-reinforced magnesium (AM50A) matrix composite (AM50A/SiCp) was prepared by stir casting. The solidification behavior of the cast AM50A/SiCp composite was investigated by computer-based thermal analysis. Optical and scanning electron microscopies (SEM) were employed to examine the occurrence of nucleation and grain refinement involved. The results indicate that the addition of SiCp particulates leads to a finer grain structure in the composite compared with the matrix alloy. The refinement of grain structure should be attributed to both the heterogeneous nucleation and the restricted primary crystal growth.

Asymmetry of intronic pre-miRNA structures in functional RISC assembly

PubMed Central

Lin, Shi-Lung; Chang, Donald; Ying, Shao-Yao

2006-01-01

The two oligonucleotide strands of a siRNA duplex are functionally asymmetric in assembling the RNAi effector, RNA-induced gene silencing complex (RISC). Based on this asymmetric RISC assembly model in vitro, formation of a microRNA (miRNA) and complementary miRNA (miRNA*) duplex was proposed to be an essential step for the assembly of miRNA-associated RISC (miRISC). We observed here that a strong structural bias exists in the selection of a mature miRNA strand for RISC assembly in zebrafish using an intronic miRNA-like vector to target EGFP mRNA for regulation. The position of the stemloop in a precursor miRNA (pre-miRNA) was involved in the determination of miRNA–miRNA* asymmetry of the pre-miRNA stemarm, leading to different miRNA maturation during miRISC assembly. These findings suggest that the miRISC assembly is likely different from the RISC assembly model of siRNA in zebrafish, providing the first in vivo evidence for asymmetric miRISC assembly. PMID:16005165

Processing-Induced Electrically Active Defects in Black Silicon Nanowire Devices.

PubMed

Carapezzi, Stefania; Castaldini, Antonio; Mancarella, Fulvio; Poggi, Antonella; Cavallini, Anna

2016-04-27

Silicon nanowires (Si NWs) are widely investigated nowadays for implementation in advanced energy conversion and storage devices, as well as many other possible applications. Black silicon (BSi)-NWs are dry etched NWs that merge the advantages related to low-dimensionality with the special industrial appeal connected to deep reactive ion etching (RIE). In fact, RIE is a well established technique in microelectronics manufacturing. However, RIE processing could affect the electrical properties of BSi-NWs by introducing deep states into their forbidden gap. This work applies deep level transient spectroscopy (DLTS) to identify electrically active deep levels and the associated defects in dry etched Si NW arrays. Besides, the successful fitting of DLTS spectra of BSi-NWs-based Schottky barrier diodes is an experimental confirmation that the same theoretical framework of dynamic electronic behavior of deep levels applies in bulk as well as in low dimensional structures like NWs, when quantum confinement conditions do not occur. This has been validated for deep levels associated with simple pointlike defects as well as for deep levels associated with defects with richer structures, whose dynamic electronic behavior implies a more complex picture.

Superconducting Open-Framework Allotrope of Silicon at Ambient Pressure

NASA Astrophysics Data System (ADS)

Sung, Ha-Jun; Han, W. H.; Lee, In-Ho; Chang, K. J.

2018-04-01

Diamond Si is a semiconductor with an indirect band gap that is the basis of modern semiconductor technology. Although many metastable forms of Si were observed using diamond anvil cells for compression and chemical precursors for synthesis, no metallic phase at ambient conditions has been reported thus far. Here we report the prediction of pure metallic Si allotropes with open channels at ambient pressure, unlike a cubic diamond structure in covalent bonding networks. The metallic phase termed P 6 /m -Si6 can be obtained by removing Na after pressure release from a novel Na-Si clathrate called P 6 /m -NaSi6 , which is predicted through first-principles study at high pressure. We identify that both P 6 /m -NaSi6 and P 6 /m -Si6 are stable and superconducting with the critical temperatures of about 13 and 12 K at ambient pressure, respectively. The prediction of new Na-Si and Si clathrate structures presents the possibility of exploring new exotic allotropes useful for Si-based devices.

Superconducting Open-Framework Allotrope of Silicon at Ambient Pressure.

PubMed

Sung, Ha-Jun; Han, W H; Lee, In-Ho; Chang, K J

2018-04-13

Diamond Si is a semiconductor with an indirect band gap that is the basis of modern semiconductor technology. Although many metastable forms of Si were observed using diamond anvil cells for compression and chemical precursors for synthesis, no metallic phase at ambient conditions has been reported thus far. Here we report the prediction of pure metallic Si allotropes with open channels at ambient pressure, unlike a cubic diamond structure in covalent bonding networks. The metallic phase termed P6/m-Si_{6} can be obtained by removing Na after pressure release from a novel Na-Si clathrate called P6/m-NaSi_{6}, which is predicted through first-principles study at high pressure. We identify that both P6/m-NaSi_{6} and P6/m-Si_{6} are stable and superconducting with the critical temperatures of about 13 and 12 K at ambient pressure, respectively. The prediction of new Na-Si and Si clathrate structures presents the possibility of exploring new exotic allotropes useful for Si-based devices.

Enhancement of electroluminescence from embedded Si quantum dots/SiO2multilayers film by localized-surface-plasmon and surface roughening.

PubMed

Li, Wei; Wang, Shaolei; Hu, Mingyue; He, Sufeng; Ge, Pengpeng; Wang, Jing; Guo, Yan Yan; Zhaowei, Liu

2015-07-03

In this paper, we prepared a novel structure to enhance the electroluminescence intensity from Si quantum dots/SiO2multilayers. An amorphous Si/SiO2 multilayer film was fabricated by plasma-enhanced chemical vapor deposition on a Pt nanoparticle (NP)-coated Si nanopillar array substrate. By thermal annealing, an embedded Si quantum dot (QDs)/SiO2 multilayer film was obtained. The result shows that electroluminescence intensity was significantly enhanced. And, the turn-on voltage of the luminescent device was reduced to 3 V. The enhancement of the light emission is due to the resonance coupling between the localized-surface-plasmon (LSP) of Pt NPs and the band-gap emission of Si QDs/SiO2 multilayers. The other factors were the improved absorption of excitation light and the increase of light extraction ratio by surface roughening structures. These excellent characteristics are promising for silicon-based light-emitting applications.

Enhancement of electroluminescence from embedded Si quantum dots/SiO2multilayers film by localized-surface-plasmon and surface roughening

PubMed Central

Li, Wei; Wang, Shaolei; Hu, Mingyue; He, Sufeng; Ge, Pengpeng; Wang, Jing; Guo, Yan Yan; Zhaowei, Liu

2015-01-01

In this paper, we prepared a novel structure to enhance the electroluminescence intensity from Si quantum dots/SiO2multilayers. An amorphous Si/SiO2 multilayer film was fabricated by plasma-enhanced chemical vapor deposition on a Pt nanoparticle (NP)-coated Si nanopillar array substrate. By thermal annealing, an embedded Si quantum dot (QDs)/SiO2 multilayer film was obtained. The result shows that electroluminescence intensity was significantly enhanced. And, the turn-on voltage of the luminescent device was reduced to 3 V. The enhancement of the light emission is due to the resonance coupling between the localized-surface-plasmon (LSP) of Pt NPs and the band-gap emission of Si QDs/SiO2 multilayers. The other factors were the improved absorption of excitation light and the increase of light extraction ratio by surface roughening structures. These excellent characteristics are promising for silicon-based light-emitting applications. PMID:26138830

Universality of the helimagnetic transition in cubic chiral magnets: Small angle neutron scattering and neutron spin echo spectroscopy studies of FeCoSi

NASA Astrophysics Data System (ADS)

Bannenberg, L. J.; Kakurai, K.; Falus, P.; Lelièvre-Berna, E.; Dalgliesh, R.; Dewhurst, C. D.; Qian, F.; Onose, Y.; Endoh, Y.; Tokura, Y.; Pappas, C.

2017-04-01

We present a comprehensive small angle neutron scattering and neutron spin echo spectroscopy study of the structural and dynamical aspects of the helimagnetic transition in Fe1 -xCoxSi with x =0.30 . In contrast to the sharp transition observed in the archetype chiral magnet MnSi, the transition in Fe1 -xCoxSi is gradual, and long-range helimagnetic ordering coexists with short-range correlations over a wide temperature range. The dynamics are more complex than in MnSi and involve long relaxation times with a stretched exponential relaxation which persists even under magnetic field. These results in conjunction with an analysis of the hierarchy of the relevant length scales show that the helimagnetic transition in Fe1 -xCoxSi differs substantially from the transition in MnSi and question the validity of a universal approach to the helimagnetic transition in chiral magnets.

Magnetic behavior of Si-Ge bond in SixGe4-x nano-clusters

NASA Astrophysics Data System (ADS)

Nahali, Masoud; Mehri, Ali

2018-06-01

The structure of SixGe4-x nano-clusters were optimized by MPW1B95 level of theory using MG3S and SDB-aug-cc-PVTZ basis set. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. Since the Si-Si bond is stronger than Si-Ge and Ge-Ge bonds, the Si-Si, Si-Ge, and Ge-Ge diagonal bonds determine the precedence of the stability in these nano-clusters. The hybrid meta density functional calculations were carried out to investigate the adsorption of CO on all possible SixGe4-x nano-clusters. It was found that the silicon atom generally makes a stronger bond with CO than germanium and thereby preferentially affects the shape of structures having higher multiplicity. In Si-Ge structures with higher spin more than 95% of spins accumulate on positions with less bonds to other atoms of the cluster. Through CO adsorption on these clusters bridge structures are made that behave as spin bridge which conduct the spin from the nano-cluster surface to the adsorbate atoms. A better understanding of bridged structures was achieved upon introducing the 'spin bridge' concept. Based on exhaustive spin density analysis, it was found that the reason for the extra negative charge on oxygen in the bridged structures is the relocation of spin from the surface through the bridge.

Theoretical prediction of a novel inorganic fullerene-like family of silicon-carbon materials

NASA Astrophysics Data System (ADS)

Wang, Ruoxi; Zhang, Dongju; Liu, Chengbu

2005-08-01

In an effort to search for new inorganic fullerene-like structures, we designed a series of novel silicon-carbon cages, (SiC) n ( n = 6-36), based on the uniformly hybrid Si-C four- and six-membered-rings, and researched their geometrical and electronic structures, as well as their relative stabilities using the density function theory. Among these cages, the structures for n = 12, 16, and 36 were found to been energetically more favorable. The calculated disproportionation energy and binding energy per SiC unit show that the (SiC) 12 cage is the most stable one among these designed structures. The present calculations not only indicate that silicon-carbon fullerenes are promised to be synthesized in future, but also provide a new way for stabilizing silicon cages by uniformly doping carbon atoms into silicon structures.

New Mononuclear Cu(II) Complexes and 1D Chains with 4-Amino-4H-1,2,4-triazole

PubMed Central

Dîrtu, Marinela M.; Boland, Yves; Gillard, Damien; Tinant, Bernard; Robeyns, Koen; Safin, Damir A.; Devlin, Eamonn; Sanakis, Yiannis; Garcia, Yann

2013-01-01

The crystal structures of two mononuclear Cu(II) NH2trz complexes [Cu(NH2trz)4(H2O)](AsF6)2 (I) and [Cu(NH2trz)4(H2O)](PF6)2 (II) as well as two coordination polymers [Cu(μ2-NH2trz)2Cl]Cl·H2O (III) and [Cu(μ2-NH2trz)2Cl] (SiF6)0.5·1.5H2O (IV) are presented. Cationic 1D chains with bridging bis-monodentate μ2-coordinated NH2trz and bridging μ2-coordinated chloride ligands are present in III and IV. In these coordination polymers, the Cu(II) ions are strongly antiferromagnetically coupled with J = −128.4 cm−1 for III and J = −143 cm−1 for IV (H = −J∑SiSi+1), due to the nature of the bridges between spin centers. Inter-chain interactions present in the crystal structures were taken into consideration, as well as g factors, which were determined experimentally, for the quantitative modeling of their magnetic properties. PMID:24300095

Super-Lensing and Sub-Wavelength Antennas in Mid-IR Using Silicon Carbide

NASA Astrophysics Data System (ADS)

Shvets, Gennady; Korobkin, Dmitriy; Urzhumov, Yaroslav A.; Zorman, Christian

2006-03-01

Extraordinary properties of SiC in mid-infrared (negative dielectric permittivity and small losses) make it an ideal building block for making negative index meta-materials in that important part of the electromagnetic spectrum. We report on a series of experiments demonstrating that thin films of SiC can be used as a ``perfect'' near-field lens. We have theoretically designed and experimentally implemented a super-lens ion mid-IR using SiC. We also report excitation of electrostatic resonances of two structures based on a sub-micron film of crystalline silicon carbide: (a) nano-holes drilled in the free-standing SiC membrane, and (b) metallic nano-posts evaporated on the SiC membrane. Applications of nano-hole resonances to excitation of magnetic moments in nano-structured SiC and development of negative index materials will be discussed, as will be the prospects of using nano-structured SiC films for laser processing of materials on a nanoscale.

Structural insights into RISC assembly facilitated by dsRNA-binding domains of human RNA helicase A (DHX9)

PubMed Central

Fu, Qinqin; Yuan, Y. Adam

2013-01-01

Intensive research interest has focused on small RNA-processing machinery and the RNA-induced silencing complex (RISC), key cellular machines in RNAi pathways. However, the structural mechanism regarding RISC assembly, the primary step linking small RNA processing and RNA-mediated gene silencing, is largely unknown. Human RNA helicase A (DHX9) was reported to function as an RISC-loading factor, and such function is mediated mainly by its dsRNA-binding domains (dsRBDs). Here, we report the crystal structures of human RNA helicase A (RHA) dsRBD1 and dsRBD2 domains in complex with dsRNAs, respectively. Structural analysis not only reveals higher siRNA duplex-binding affinity displayed by dsRBD1, but also identifies a crystallographic dsRBD1 pair of physiological significance in cooperatively recognizing dsRNAs. Structural observations are further validated by isothermal titration calorimetric (ITC) assay. Moreover, co-immunoprecipitation (co-IP) assay coupled with mutagenesis demonstrated that both dsRBDs are required for RISC association, and such association is mediated by dsRNA. Hence, our structural and functional efforts have revealed a potential working model for siRNA recognition by RHA tandem dsRBDs, and together they provide direct structural insights into RISC assembly facilitated by RHA. PMID:23361462

Structural insights into RISC assembly facilitated by dsRNA-binding domains of human RNA helicase A (DHX9).

PubMed

Fu, Qinqin; Yuan, Y Adam

2013-03-01

Intensive research interest has focused on small RNA-processing machinery and the RNA-induced silencing complex (RISC), key cellular machines in RNAi pathways. However, the structural mechanism regarding RISC assembly, the primary step linking small RNA processing and RNA-mediated gene silencing, is largely unknown. Human RNA helicase A (DHX9) was reported to function as an RISC-loading factor, and such function is mediated mainly by its dsRNA-binding domains (dsRBDs). Here, we report the crystal structures of human RNA helicase A (RHA) dsRBD1 and dsRBD2 domains in complex with dsRNAs, respectively. Structural analysis not only reveals higher siRNA duplex-binding affinity displayed by dsRBD1, but also identifies a crystallographic dsRBD1 pair of physiological significance in cooperatively recognizing dsRNAs. Structural observations are further validated by isothermal titration calorimetric (ITC) assay. Moreover, co-immunoprecipitation (co-IP) assay coupled with mutagenesis demonstrated that both dsRBDs are required for RISC association, and such association is mediated by dsRNA. Hence, our structural and functional efforts have revealed a potential working model for siRNA recognition by RHA tandem dsRBDs, and together they provide direct structural insights into RISC assembly facilitated by RHA.

New Possible Structure of Silicide Mg2Si under Pressure

NASA Astrophysics Data System (ADS)

Luniakov, Yu. V.

2018-05-01

As a result of an evolutionary search based on the density functional theory, a new low-symmetry structure of silicide Mg2Si under pressure was discovered. This structure can exist along with the known structures of the symmetry Pnma and P63/mmc and is stable at a pressure of about 20 GPa. The lattice parameters of the discovered structure are in better agreement with the experimental values than the lattice parameters of the known structures.

In-beam γ-ray Spectroscopy of {sup 30}P via the {sup 28}Si({sup 3}He,pγ){sup 30}P Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mcneice, E.; Setoodehnia, K.; Singh, B., E-mail: ndgroup@mcmaster.ca

2014-06-15

The level structure of {sup 30}P up to 8.25 MeV was investigated via in-beam γ-ray spectroscopy using the {sup 28}Si({sup 3}He,pγ){sup 30}P reaction at 9 MeV at the University of Tsukuba Tandem Accelerator Complex in Japan. An energy level scheme was deduced from γ-γ coincidence measurements. 47 new transitions have been observed from the previously known states (mostly resonances), thereby reducing the uncertainties in the excitation energies of 17 states from 3 to 10 keV to values of < 1 keV. Furthermore, spin assignments based on measurements of γ-ray angular distributions and γ-γ directional correlation of oriented nuclei (DCO ratios)more » were made for several observed levels of {sup 30}P.« less

Quaternary structure and apical membrane sorting of the mammalian NaSi-1 sulfate transporter in renal cell lines.

PubMed

Regeer, Ralf R; Nicke, Annette; Markovich, Daniel

2007-01-01

NaSi-1 encodes a Na(+)-sulfate cotransporter expressed on the apical membrane of renal proximal tubular cells, which is responsible for body sulfate homeostasis. Limited information is available on NaSi-1 protein structure and the mechanisms controlling its apical membrane sorting. The aims of this study were to biochemically determine the quaternary structure of the rat NaSi-1 protein and to characterize its expression in renal epithelial cell lines. Hexahistidyl-tagged NaSi-1 (NaSi-1-His) proteins expressed in Xenopus oocytes, appeared as two bands of about 60 and 75 kDa. PNGase F treatment shifted both bands to 57 kDa while endoglycosidase H treatment led to a downward shift of the lower molecular mass band only. Mutagenesis of a putative N-glycosylation site (N591S) produced a single band that was not shifted by endoglycosidase H or PNGase F, confirming a single glycosylation site at residue 591. Blue native-PAGE and cross-linking experiments revealed dimeric complexes, suggesting the native form of NaSi-1 to be a dimer. Transient transfection of EGFP/NaSi-1 in renal epithelial cells (OK, LLC-PK1 and MDCK) demonstrated apical membrane sorting, which was insensitive to tunicamycin. Transfection of the EGFP/NaSi-1 N591S glycosylation mutant also showed apical expression, suggesting N591 is not essential for apical sorting. Treatment with cholesterol depleting compounds did not disrupt apical sorting, but brefeldin A led to misrouting to the basolateral membrane, suggesting that NaSi-1 sorting is through the ER to Golgi pathway. Our data demonstrates that NaSi-1 forms a dimeric protein which is glycosylated at N591, whose sorting to the apical membrane in renal epithelial cells is brefeldin A-sensitive and independent of lipid rafts or glycosylation.

Reactivity of the Donor-Stabilized Silylenes [iPrNC(Ph)NiPr]2 Si and [iPrNC(NiPr2 )NiPr]2 Si: Activation of CO2 and CS2.

PubMed

Mück, Felix M; Baus, Johannes A; Nutz, Marco; Burschka, Christian; Poater, Jordi; Bickelhaupt, F Matthias; Tacke, Reinhold

2015-11-09

Activation of CO2 by the bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 leads to the structurally analogous six-coordinate silicon(IV) complexes 4 (previous work) and 8, respectively, the first silicon compounds with a chelating carbonato ligand. Likewise, CS2 activation by silylene 1 affords the analogous six-coordinate silicon(IV) complex 10, the first silicon compound with a chelating trithiocarbonato ligand. CS2 activation by silylene 2, however, yields the five-coordinate silicon(IV) complex 13 with a carbon-bound CS2 (2-) ligand, which also represents an unprecedented coordination mode in silicon coordination chemistry. Treatment of the dinuclear silicon(IV) complexes 5 and 6 with CO2 also affords the six-coordinate carbonatosilicon(IV) complexes 4 and 8, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combining experiment and optical simulation in coherent X-ray nanobeam characterization of Si/SiGe semiconductor heterostructures

DOE PAGES

Tilka, J. A.; Park, J.; Ahn, Y.; ...

2016-07-06

Here, the highly coherent and tightly focused x-ray beams produced by hard x-ray light sources enable the nanoscale characterization of the structure of electronic materials but are accompanied by significant challenges in the interpretation of diffraction and scattering patterns. X-ray nanobeams exhibit optical coherence combined with a large angular divergence introduced by the x-ray focusing optics. The scattering of nanofocused x-ray beams from intricate semiconductor heterostructures produces a complex distribution of scattered intensity. We report here an extension of coherent xray optical simulations of convergent x-ray beam diffraction patterns to arbitrary x-ray incident angles to allow the nanobeam diffraction patternsmore » of complex heterostructures to be simulated faithfully. These methods are used to extract the misorientation of lattice planes and the strain of individual layers from synchrotron x-ray nanobeam diffraction patterns of Si/SiGe heterostructures relevant to applications in quantum electronic devices. The systematic interpretation of nanobeam diffraction patterns from semiconductor heterostructures presents a new opportunity in characterizing and ultimately designing electronic materials.« less

Surface acid-base behaviors of Chinese loess.

PubMed

Chu, Zhaosheng; Liu, Wenxin; Tang, Hongxiao; Qian, Tianwei; Li, Shushen; Li, Zhentang; Wu, Guibin

2002-08-15

Acid-base titration was applied to investigate the surface acid-base properties of a Chinese loess sample at different ionic strengths. The acidimetric supernatant was regarded as the system blank of titration to correct the influence of particle dissolution on the estimation of proton consumption. The titration behavior of the system blank could be described by the hydrolysis of Al3+ and Si(OH)4 in aqueous solution as well as the production of hydroxyaluminosilicates. The formation of Al-Si species on homogeneous surface sites by hydrous aluminum and silicic acid, released from solid substrate during the acidic titration, was considered in the model description of the back-titration procedure. A surface reaction model was suggested as follows: >SOH<-->SO(-)+H+, pK(a)(int)=3.48-3.98;>SOH+Al(3+)+H4SiO4<-->SOAl(OSi(OH)3(+)+2H+, pK(SC)=3.48-4.04. Two simple surface complexation models accounted for the interfacial structure, i.e., the constant capacitance model (CCM) and the diffuse layer model (DLM), and gave a satisfactory description of the experimental data. Considering the effect of ionic strength on the electrostatic profile at the solid-aqueous interface, the DLM was appropriate at the low concentrations (0.01 and 0.005 mol/L) of background electrolyte (NaNO3 in this study), while the CCM was preferable in the case of high ionic strength (0.1 mol/L).

Structural stability and electronic behaviors of Co1-xOsxSi and macroscopic magnetic susceptibilities of CoSi and OsSi: GGA-PBEsol, GW-approximation and QTAIM investigations

NASA Astrophysics Data System (ADS)

Bouafia, H.; Sahli, B.; Timaoui, M. A.; Djebour, B.; Hiadsi, S.; Abidri, B.

2018-02-01

The present work represents a theoretical investigation based on FP-(L)APW + lo method of structural properties, mechanical stability and electronic properties of Co1-xOsxSi as well as the macroscopic magnetic susceptibilities of CoSi and OsSi. The structural properties such as cell parameter, bulk modulus, internal parameters and total energy of non-magnetic NM, ferromagnetic FM and antiferromagnetic AFM phases were predicted by GGA-PBEsol semilocal functional. The obtained results for CoSi and OsSi are in good agreement with those found previously. The spin, orbital and total macroscopic magnetic susceptibilities of CoSi and OsSi have been estimated and confirmed that these compounds are diamagnetic. The total energy of the ferromagnetic phase of Co1-xOsxSi (with x = 0.25, 0.5 and 0.75) is the lowest indicating that they are ferromagnetic materials. The generalized stability criteria indicate that Co1-xOsxSi maintain their mechanical stabilities under a hydrostatic pressure less than 10 GPa. The electronic properties calculated by GW-approximation indicate that CoSi and Co1-xOsxSi (with x = 0.25, 0.50 and 0.75) are semimetals whereas OsSi is a semiconductor with a pseudo-direct band-gap. The topological analysis by QTAIM and the charge density plots indicate that the strong covalent character is predominant for Cosbnd Si, Ossbnd Si and Cosbnd Os bonds.

Coating of 6028 Aluminum Alloy Using Aluminum Piston Alloy and Al-Si Alloy-Based Nanocomposites Produced by the Addition of Al-Ti5-B1 to the Matrix Melt

NASA Astrophysics Data System (ADS)

El-Labban, Hashem F.; Abdelaziz, M.; Mahmoud, Essam R. I.

2014-10-01

The Al-12 pctSi alloy and aluminum-based composites reinforced with TiB2 and Al3Ti intermetallics exhibit good wear resistance, strength-to-weight ratio, and strength-to-cost ratio when compared to equivalent other commercial Al alloys, which make them good candidates as coating materials. In this study, structural AA 6028 alloy is used as the base material. Four different coating materials were used. The first one is Al-Si alloy that has Si content near eutectic composition. The second, third, and fourth ones are Al-6 pctSi-based reinforced with TiB2 and Al3Ti nano-particles produced by addition of Al-Ti5-B1 master alloy with different weight percentages (1, 2, and 3 pct). The coating treatment was carried out with the aid of GTAW process. The microstructures of the base and coated materials were investigated using optical microscope and scanning electron microscope equipped with EDX analyzer. Microhardness of the base material and the coated layer were evaluated using a microhardness tester. GTAW process results in almost sound coated layer on 6028 aluminum alloy with the used four coating materials. The coating materials of Al-12 pct Si alloy resulted in very fine dendritic Al-Si eutectic structure. The interface between the coated layer and the base metal was very clean. The coated layer was almost free from porosities or other defects. The coating materials of Al-6 pct Si-based mixed with Al-Ti5-B1 master alloy with different percentages (1, 2, and 3 pct), results in coated layer consisted of matrix of fine dendrite eutectic morphology structure inside α-Al grains. Many fine in situ TiAl3 and TiB2 intermetallics were precipitated almost at the grain boundary of α-Al grains. The amounts of these precipitates are increased by increasing the addition of Al-Ti5-B1 master alloy. The surface hardness of the 6028 aluminum alloy base metal was improved with the entire four used surface coating materials. The improvement reached to about 85 pct by the first type of coating material (Al-12 pctSi alloy), while it reached to 77, 83, and 89 pct by the coating materials of Al-6 pct Si-based mixed with Al-Ti5-B1 master alloy with different percentages 1, 2, and 3 pct, respectively.

Plasmonic Structures for CMOS Photonics and Control of Spontaneous Emission

DTIC Science & Technology

2013-04-01

structures; v) developed CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vi) also engaged in a partnership with...CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vii. exploring approaches to enhance spontaneous emission in...size and bandwidth, we are exploring phase-change materials and, in particular, vanadium dioxide. VO2 undergoes an insulator-to-metal phase transition

Ternary complexes of folate-PEG-appended dendrimer (G4)/α-cyclodextrin conjugate, siRNA and low-molecular-weight polysaccharide sacran as a novel tumor-selective siRNA delivery system.

PubMed

Ohyama, Ayumu; Higashi, Taishi; Motoyama, Keiichi; Arima, Hidetoshi

2017-06-01

We previously developed a tumor-selective siRNA carrier by preparing polyamidoamine dendrimer (generation 4, G4) conjugates with α-cyclodextrin and folate-polyethylene glycol (Fol-PαC (G4)). In the present study, we developed ternary complexes of Fol-PαC (G4)/siRNA with low-molecular-weight-sacrans to achieve more effective siRNA transfer activity. Among the different molecular-weight sacrans, i.e. sacran 100, 1000 and 10,000 (MW 44,889Da, 943,692Da and 1,488,281Da, respectively), sacran 100 significantly increased the cellular uptake and the RNAi effects of Fol-PαC (G4)/siRNA binary complex with negligible cytotoxicity in KB cells (folate receptor-α positive cells). In addition, the ζ-potential and particle size of Fol-PαC (G4)/siRNA complex were decreased by the ternary complexation with sacran 100. Importantly, the in vivo RNAi effect of the ternary complex after the intravenous administration to tumor-bearing BALB/c mice was significantly higher than that of the binary complex. In conclusion, Fol-PαC (G4)/siRNA/sacran 100 ternary complex has a potential as a novel tumor-selective siRNA delivery system. Copyright © 2017 Elsevier B.V. All rights reserved.

Structural resolution of inorganic nanotubes with complex stoichiometry.

PubMed

Monet, Geoffrey; Amara, Mohamed S; Rouzière, Stéphan; Paineau, Erwan; Chai, Ziwei; Elliott, Joshua D; Poli, Emiliano; Liu, Li-Min; Teobaldi, Gilberto; Launois, Pascale

2018-05-23

Determination of the atomic structure of inorganic single-walled nanotubes with complex stoichiometry remains elusive due to the too many atomic coordinates to be fitted with respect to X-ray diffractograms inherently exhibiting rather broad features. Here we introduce a methodology to reduce the number of fitted variables and enable resolution of the atomic structure for inorganic nanotubes with complex stoichiometry. We apply it to recently synthesized methylated aluminosilicate and aluminogermanate imogolite nanotubes of nominal composition (OH) 3 Al 2 O 3 Si(Ge)CH 3 . Fitting of X-ray scattering diagrams, supported by Density Functional Theory simulations, reveals an unexpected rolling mode for these systems. The transferability of the approach opens up for improved understanding of structure-property relationships of inorganic nanotubes to the benefit of fundamental and applicative research in these systems.

Trilysinoyl oleylamide-based cationic liposomes for systemic co-delivery of siRNA and an anticancer drug.

PubMed

Shim, Gayong; Han, Su-Eun; Yu, Yong-Hee; Lee, Sangbin; Lee, Han Young; Kim, Kwangmeyung; Kwon, Ick Chan; Park, Tae Gwan; Kim, Young Bong; Choi, Yong Seok; Kim, Chan-Wha; Oh, Yu-Kyoung

2011-10-10

Oligolysine-based cationic lipid derivatives were synthesized for delivery of siRNA, and formulated into cationic liposomes. Among various oligolysine-based lipid derivatives differing in lysine residue number and lipid moiety, trilysinoyl oleylamide (TLO)-based liposomes (TLOL) showed the highest delivery efficiency combined with minimal cytotoxicity. Delivery of siRNA using TLOL silenced target genes both in vitro and in vivo. In green fluorescent protein (GFP)-expressing tumor tissue, a significant reduction of fluorescence was observed after intratumoral administration of siGFP using TLOL compared with control siGL2. Intravenous administration of siMcl1 employing pegylated TLOL (pTLOL) reduced the expression of human Mcl1 protein in KB-xenografted tumor tissue. Despite the reduction in target protein Mcl1 expression following such systemic delivery, tumor growth was only slightly reduced compared to a siGL2-treated control group. To potentiate the anticancer activity of siMcl1, the anticancer drug suberoylanilide hydroxamic acid (SAHA) was additionally encapsulated in pTLOL. After intravenous administration of siMcl1 using SAHA-loaded pTLOL (pSTLOL), a significant reduction in tumor growth was observed compared to that seen in animals treated with free SAHA or siGL2 complexed with pSTLOL. The results indicate that pTLOL could be further developed as a systemic delivery system for synergistic anticancer siRNA and a drug. Copyright © 2010 Elsevier B.V. All rights reserved.

Electrochemiluminescence detection of TNT by resonance energy transfer through the formation of a TNT-amine complex.

PubMed

Qi, Wenjing; Xu, Min; Pang, Lei; Liu, Zhongyuan; Zhang, Wei; Majeed, Saadat; Xu, Guobao

2014-04-14

2,4,6-Trinitrotoluene (TNT) is a widely used nitroaromatic explosive with significant detrimental effects on the environment and human health. Its detection is of great importance. In this study, both electrochemiluminescence (ECL)-based detection of TNT through the formation of a TNT-amine complex and the detection of TNT through electrochemiluminescence resonance energy transfer (ECRET) are developed for the first time. 3-Aminopropyltriethoxysilane (APTES)-modified [Ru(phen)3](2+) (phen=1,10-phenanthroline)-doped silica nanoparticles (RuSiNPs) with uniform sizes of (73±3) nm were synthesized. TNT can interact with APTES-modified RuSiNPs through charge transfer from electron-rich amines in the RuSiNPs to the electron-deficient aromatic ring of TNT to form a red TNT-amine complex. The absorption spectrum of this complex overlaps with the ECL spectrum of the APTES-modified RuSiNPs/triethylamine system. As a result, ECL signals of the APTES-modified RuSiNPs/triethylamine system are turned off in the presence of TNT owing to resonance energy transfer from electrochemically excited RuSiNPs to the TNT-amine complex. This ECRET method has been successfully applied for the sensitive determination of TNT with a linear range from 1×10(-9) to 1×10(-6) M with a fast response time within 1 min. The limit of detection is 0.3 nM. The method exhibits good selectivity towards 2,4-dinitrotoluene, p-nitrotoluene, nitrobenzene, phenol, p-quinone, 8-hydroxyquinoline, p-phenylenediamine, K3[Fe(CN)6], Fe(3+), NO3(-), NO2(-), Cr(3+), Fe(2+), Pb(2+), SO3(2-), formaldehyde, oxalate, proline, and glycine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron transport in all-Heusler Co2CrSi/Cu2CrAl/Co2CrSi device, based on ab-initio NEGF calculations

NASA Astrophysics Data System (ADS)

Mikaeilzadeh, L.; Pirgholi, M.; Tavana, A.

2018-05-01

Based on the ab-initio non-equilibrium Green's function (NEGF) formalism based on the density functional theory (DFT), we have studied the electron transport in the all-Heusler device Co2CrSi/Cu2CrAl/Co2CrSi. Results show that the calculated transmission spectra is very sensitive to the structural parameters and the interface. Also, we obtain a range for the thickness of the spacer layer for which the MR effect is optimum. Calculations also show a perfect GMR effect in this device.

The mixing mechanism during lithiation of Si negative electrode in Li-ion batteries: an ab initio molecular dynamics study.

PubMed

Johari, Priya; Qi, Yue; Shenoy, Vivek B

2011-12-14

In order to realize Si as a negative electrode material in commercial Li-ion batteries, it is important to understand the mixing mechanism of Li and Si, and stress evolution during lithiation in Si negative electrode of Li-ion batteries. Available experiments mainly provide the diffusivity of Li in Si as an averaged property, neglecting information regarding diffusivity of Si. However, if Si can diffuse as fast as Li, the stress generated during Li diffusion can be reduced. We, therefore, studied the diffusivity of Li as well as Si atoms in the Si-anode of Li-ion battery using an ab initio molecular dynamics-based methodology. The electrochemical insertion of Li into crystalline Si prompts a crystalline-to-amorphous phase transition. We considered this situation and thus examined the diffusion kinetics of Li and Si atoms in both crystalline and amorphous Si. We find that Li diffuses faster in amorphous Si as compared to crystalline Si, while Si remains relatively immobile in both cases and generates stresses during lithiation. To further understand the mixing mechanism and to relate the structure with electrochemical mixing, we analyzed the evolution of the structure during lithiation and studied the mechanism of breaking of Si-Si network by Li. We find that Li atoms break the Si rings and chains and create ephemeral structures such as stars and boomerangs, which eventually transform to Si-Si dumbbells and isolated Si atoms in the LiSi phase. Our results are found to be in agreement with the available experimental data and provide insights into the mixing mechanism of Li and Si in Si negative electrode of Li-ion batteries.

High Temperature and High Sensitive NOx Gas Sensor with Hetero-Junction Structure using Laser Ablation Method

NASA Astrophysics Data System (ADS)

Gao, Wei; Shi, Liqin; Hasegawa, Yuki; Katsube, Teruaki

In order to develop a high temperature (200°C˜400°C) and high sensitive NOx gas sensor, we developed a new structure of SiC-based hetero-junction device Pt/SnO2/SiC/Ni, Pt/In2O3/SiC/Ni and Pt/WO3/SiC/Ni using a laser ablation method for the preparation of both metal (Pt) electrode and metal-oxide film. It was found that Pt/In2O3/SiC/Ni sensor shows higher sensitivity to NO2 gas compared with the Pt/SnO2/SiC/Ni and Pt/WO3/SiC/Ni sensor, whereas the Pt/WO3/SiC/Ni sensor had better sensitivity to NO gas. These results suggest that selective detection of NO and NO2 gases may be obtained by choosing different metal oxide films.

Microstructure and phase analyses of melt-spun Si-Ni base anode materials for Li-ion battery

NASA Astrophysics Data System (ADS)

Jeon, Sung Min; Song, Jong Jin; Kim, Sun-I.; Kwon, Hye Jin; Sohn, Keun Yong; Park, Won-Wook

2013-01-01

Si-based anode composite materials have been studied to improve the performance and the durability of Li-ion secondary batteries in this study. Si-Ni-Al, Si-Ni-Cu and Si-Ni-Cu-Al base alloys were designed and rapidly solidified at the cooling rate of about 106 °C/sec by optimizing the melt spinning. The ribbons were characterized using FE-SEM equipped with EDS, X-ray diffractometer and HR-TEM. The thin ribbons of Si-Ni-Al alloy consisted of nano-sized Si particles and amorphous matrix, which was regarded as an ideal microstructure for the anode material. At the wheel side of the ribbon, 20-30 nm of Si particles were formed (Zone A); whereas at the air side relatively large Si particles were distributed (Zone B). The Si-Ni-Cu alloy showed coarser Si particles than the Si-Ni-Al alloy, and its matrix consisted of NiSi2, Cu3Si and amorphous structures. Finally, the microstructure of the Si-Ni-Cu-Al alloy strips was composed of coarse Si particles, CuNi, Al4Cu9, NiSi2, and unknown phases, and the size of those Si particles were too large to be used for the anode materials.

Fabrication of a high selectivity magnetic solid phase extraction adsorbent based on β-cyclodextrin and application for recognition of plant growth regulators.

PubMed

Chen, Jiuyan; Cao, Shurui; Zhu, Ming; Xi, Cunxian; Zhang, Lei; Li, Xianliang; Wang, Guomin; Zhou, Yuantao; Chen, Zhiqiong

2018-04-27

An adsorbent, consisting of silica-coated Fe 3 O 4 grafted graphene oxide and β-cyclodextrin (Fe 3 O 4 @SiO 2 /GO/β-CD), which possessed the merits of antioxidation, superparamagnetism, high surface area, high supramolecular recognition and environment friendly, was successfully fabricated. Considering the synergy between β-CD and graphene oxide in adsorption mechanism, the synthesized adsorbent could grasp compounds especially with aromatic structures through π-π interaction, hydrophobic interaction and host-guest inclusion complex forming. Based on the advantages, a magnetic solid phase extraction (MSPE) method for 9 PGRs using Fe 3 O 4 @SiO 2 /GO/β-CD as adsorbents was developed in this study. The characterizations of Fe 3 O 4 @SiO 2 /GO/β-CD were performed on Fourier transform infrared spectrometry (FT-IR), X-ray photoelectron spectroscopy (XPS), CHNS/O elemental analyzer, scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM). Under the optimal MSPE condition, the Fe 3 O 4 @SiO 2 /GO/β-CD exhibited selectivity capability toward 9 PGRs when compared with Fe 3 O 4 @SiO 2 /GO. Meanwhile, the selectivity capability of Fe 3 O 4 @SiO 2 /GO/β-CD was higher than that of Fe 3 O 4 @SiO 2 /GO/α-CD except for 4-FPA. When the developed MSPE procedure was coupled with ultra-high performance liquid chromatography-triple quadrupole linear ion trap mass spectrometry (UHPLC-QTrap-MS/MS) to quantitative analysis of 9 PGRs, linearities ranging from 2 to 50 μg/kg were achieved for 9 PGRs with the correlation coefficients (r 2 ) in the range of 0.9975-0.9999. The limits of detection (LODs) for 9 analytes varied from 0.04 to 0.29 μg/kg. Finally, the proposed technique was applied to analyze PGRs residues in mutiple vegetable samples. Copyright © 2018 Elsevier B.V. All rights reserved.

A new initiating system based on [(SiMes)Ru(PPh3)(Ind)Cl2] combined with azo-bis-isobutyronitrile in the polymerization and copolymerization of styrene and methyl methacrylate.

PubMed

Al-Majid, Abdullah M; Shamsan, Waseem Sharaf; Al-Odayn, Abdel-Basit Mohammed; Nahra, Fady; Aouak, Taieb; Nolan, Steven P

2017-01-01

The homopolymerization and copolymerization of styrene and methyl methacrylate, initiated for the first time by the combination of azo-bis-isobutyronitrile (AIBN) with [(SiMes)Ru(PPh 3 )(Ind)Cl 2 ] complex. The reactions were successfully carried out, on a large scale, in presence this complex at 80 °C. It was concluded from the data obtained that the association of AIBN with the ruthenium complex reduces considerably the transfer reactions and leads to the controlled radical polymerization and the well-defined polymers.

The fundamental problem of treating light incoherence in photovoltaics and its practical consequences

NASA Astrophysics Data System (ADS)

Herman, Aline; Sarrazin, Michaël; Deparis, Olivier

2014-01-01

The incoherence of sunlight has long been suspected to have an impact on solar cell energy conversion efficiency, although the extent of this is unclear. Existing computational methods used to optimize solar cell efficiency under incoherent light are based on multiple time-consuming runs and statistical averaging. These indirect methods show limitations related to the complexity of the solar cell structure. As a consequence, complex corrugated cells, which exploit light trapping for enhancing the efficiency, have not yet been accessible for optimization under incoherent light. To overcome this bottleneck, we developed an original direct method which has the key advantage that the treatment of incoherence can be totally decoupled from the complexity of the cell. As an illustration, surface-corrugated GaAs and c-Si thin-films are considered. The spectrally integrated absorption in these devices is found to depend strongly on the degree of light coherence and, accordingly, the maximum achievable photocurrent can be higher under incoherent light than under coherent light. These results show the importance of taking into account sunlight incoherence in solar cell optimization and point out the ability of our direct method to deal with complex solar cell structures.

Viral RNAi suppressor reversibly binds siRNA to outcompete Dicer and RISC via multiple-turnover

PubMed Central

Rawlings, Renata A.; Krishnan, Vishalakshi; Walter, Nils G.

2011-01-01

RNA interference (RNAi) is a conserved gene regulatory mechanism employed by most eukaryotes as a key component of their innate immune response against viruses and retrotransposons. During viral infection, the RNase III-type endonuclease Dicer cleaves viral double-stranded RNA into small interfering RNAs (siRNAs), 21–24 nucleotides in length, and helps load them into the RNA-induced silencing complex (RISC) to guide cleavage of complementary viral RNA. As a countermeasure, many viruses have evolved viral RNA silencing suppressor (RSS) proteins that tightly, and presumably quantitatively, bind siRNAs to thwart RNAi-mediated degradation. Viral RSS proteins also act across kingdoms as potential immunosuppressors in gene therapeutic applications. Here we report fluorescence quenching and electrophoretic mobility shift assays that probe siRNA binding by the dimeric RSS p19 from Carnation Italian Ringspot Virus (CIRV), as well as by human Dicer and RISC assembly complexes. We find that the siRNA:p19 interaction is readily reversible, characterized by rapid binding ((1.69 ± 0.07)×108 M−1s−1) and marked dissociation (koff = 0.062 ± 0.002 s−1). We also observe that p19 efficiently competes with recombinant Dicer and inhibits formation of RISC-related assembly complexes found in human cell extract. Computational modeling based on these results provides evidence for the transient formation of a ternary complex between siRNA, human Dicer, and p19. An expanded model of RNA silencing indicates that multiple-turnover by reversible binding of siRNAs potentiates the efficiency of the suppressor protein. Our predictive model is expected to be applicable to the dosing of p19 as a silencing suppressor in viral gene therapy. PMID:21354178

Viral RNAi suppressor reversibly binds siRNA to outcompete Dicer and RISC via multiple turnover.

PubMed

Rawlings, Renata A; Krishnan, Vishalakshi; Walter, Nils G

2011-04-29

RNA interference is a conserved gene regulatory mechanism employed by most eukaryotes as a key component of their innate immune response to viruses and retrotransposons. During viral infection, the RNase-III-type endonuclease Dicer cleaves viral double-stranded RNA into small interfering RNAs (siRNAs) 21-24 nucleotides in length and helps load them into the RNA-induced silencing complex (RISC) to guide the cleavage of complementary viral RNA. As a countermeasure, many viruses have evolved viral RNA silencing suppressors (RSS) that tightly, and presumably quantitatively, bind siRNAs to thwart RNA-interference-mediated degradation. Viral RSS proteins also act across kingdoms as potential immunosuppressors in gene therapeutic applications. Here we report fluorescence quenching and electrophoretic mobility shift assays that probe siRNA binding by the dimeric RSS p19 from Carnation Italian Ringspot Virus, as well as by human Dicer and RISC assembly complexes. We find that the siRNA:p19 interaction is readily reversible, characterized by rapid binding [(1.69 ± 0.07) × 10(8) M(-)(1) s(-1)] and marked dissociation (k(off)=0.062 ± 0.002 s(-1)). We also observe that p19 efficiently competes with recombinant Dicer and inhibits the formation of RISC-related assembly complexes found in human cell extract. Computational modeling based on these results provides evidence for the transient formation of a ternary complex between siRNA, human Dicer, and p19. An expanded model of RNA silencing indicates that multiple turnover by reversible binding of siRNAs potentiates the efficiency of the suppressor protein. Our predictive model is expected to be applicable to the dosing of p19 as a silencing suppressor in viral gene therapy. Copyright © 2011 Elsevier Ltd. All rights reserved.

A comparative DFT study on CO oxidation reaction over Si-doped BC2N nanosheet and nanotube

NASA Astrophysics Data System (ADS)

Nematollahi, Parisa; Neyts, Erik C.

2018-05-01

In this study, we performed density functional theory (DFT) calculations to investigate different reaction mechanisms of CO oxidation catalyzed by the Si atom embedded defective BC2N nanostructures as well as the analysis of the structural and electronic properties. The structures of all the complexes are optimized and characterized by frequency calculations at the M062X/6-31G∗ computational level. Also, The electronic structures and thermodynamic parameters of adsorbed CO and O2 molecules over Si-doped BC2N nanostructures are examined in detail. Moreover, to investigate the curvature effect on the CO oxidation reaction, all the adsorption and CO oxidation reactions on a finite-sized armchair (6,6) Si-BC2NNT are also studied. Our results indicate that there can be two possible pathways for the CO oxidation with O2 molecule: O2(g) + CO(g) → O2(ads) + CO(ads) → CO2(g) + O(ads) and O(ads) + CO(g) → CO2(g). The first reaction proceeds via the Langmuir-Hinshelwood (LH) mechanism while the second goes through the Eley-Rideal (ER) mechanism. On the other hand, by increasing the tube diameter, the energy barrier increases due to the strong adsorption energy of the O2 molecule which is related to its dissociation over the tube surface. Our calculations indicate that the two step energy barrier of the oxidation reaction over Si-BC2NNS is less than that over the Si-BC2NNT. Hence, Si-BC2NNS may serve as an efficient and highly activated substrate to CO oxidation rather than (4,4) Si-BC2NNT.

FEM Analysis of Sezawa Mode SAW Sensor for VOC Based on CMOS Compatible AlN/SiO₂/Si Multilayer Structure.

PubMed

Aslam, Muhammad Zubair; Jeoti, Varun; Karuppanan, Saravanan; Malik, Aamir Farooq; Iqbal, Asif

2018-05-24

A Finite Element Method (FEM) simulation study is conducted, aiming to scrutinize the sensitivity of Sezawa wave mode in a multilayer AlN/SiO₂/Si Surface Acoustic Wave (SAW) sensor to low concentrations of Volatile Organic Compounds (VOCs), that is, trichloromethane, trichloroethylene, carbon tetrachloride and tetrachloroethene. A Complimentary Metal-Oxide Semiconductor (CMOS) compatible AlN/SiO₂/Si based multilayer SAW resonator structure is taken into account for this purpose. In this study, first, the influence of AlN and SiO₂ layers’ thicknesses over phase velocities and electromechanical coupling coefficients ( k ²) of two SAW modes (i.e., Rayleigh and Sezawa) is analyzed and the optimal thicknesses of AlN and SiO₂ layers are opted for best propagation characteristics. Next, the study is further extended to analyze the mass loading effect on resonance frequencies of SAW modes by coating a thin Polyisobutylene (PIB) polymer film over the AlN surface. Finally, the sensitivity of the two SAW modes is examined for VOCs. This study concluded that the sensitivity of Sezawa wave mode for 1 ppm of selected volatile organic gases is twice that of the Rayleigh wave mode.

NIR-induced spatiotemporally controlled gene silencing by upconversion nanoparticle-based siRNA nanocarrier.

PubMed

Chen, Guojun; Ma, Ben; Xie, Ruosen; Wang, Yuyuan; Dou, Kefeng; Gong, Shaoqin

2017-12-27

Spatiotemporal control over the release or activation of biomacromolecules such as siRNA remains a significant challenge. Light-controlled release has gained popularity in recent years; however, a major limitation is that most photoactivable compounds/systems respond only to UV irradiation, but not near-infrared (NIR) light that offers a deeper tissue penetration depth and better biocompatibility. This paper reports a simple NIR-to-UV upconversion nanoparticle (UCNP)-based siRNA nanocarrier for NIR-controlled gene silencing. siRNA is complexed onto a NaYF 4 :Yb/Tm/Er UCNP through an azobenzene (Azo)-cyclodextrin (CD) host-guest interaction. The UV emission generated by the NIR-activated UCNP effectively triggers the trans-to-cis photoisomerization of azobenzene, thus leading to the release of siRNA due to unmatched host-guest pairs. The UCNP-siRNA complexes are also functionalized with PEG (i.e., UCNP-(CD/Azo)-siRNA/PEG NPs), targeting ligands (i.e., EGFR-specific GE11 peptide), acid-activatable cell-penetrating peptides (i.e., TH peptide), and imaging probes (i.e., Cy5 fluorophore). The UCNP-(CD/Azo)-siRNA/PEG NPs with both GE11 and TH peptides display a high level of cellular uptake and an excellent endosomal/lysosomal escape capability. More importantly, NIR-controlled spatiotemporal knockdown of GFP expression is successfully achieved in both a 2D monolayer cell model and a 3D multicellular tumor spheroid model. Thus, this simple and versatile nanoplatform has great potential for the selective activation or release of various biomacromolecules. Copyright © 2017. Published by Elsevier B.V.

Microstructural properties and evolution of nanoclusters in liquid Si during a rapid cooling process

NASA Astrophysics Data System (ADS)

Gao, T.; Hu, X.; Li, Y.; Tian, Z.; Xie, Q.; Chen, Q.; Liang, Y.; Luo, X.; Ren, L.; Luo, J.

2017-11-01

The formation of amorphous structures in Si during the rapid quenching process was studied based on molecular dynamics simulation by using the Stillinger-Weber potential. The evolution characteristics of nanoclusters during the solidification were analyzed by several structural analysis methods. The amorphous Si has been formed with many tetrahedral clusters and few nanoclusters. During the solidification, tetrahedral polyhedrons affect the local structures by their different positions and connection modes. The main kinds of polyhedrons randomly linked with one another to form an amorphous network structures in the system. The structural evolution of crystal nanocluster demonstrates that the nanocluster has difficulty to growth because of the high cooling rate of 1012 K/s.

Copper-Based OHMIC Contracts for the Si/SiGe Heterojunction Bipolar Transistor Structure

NASA Technical Reports Server (NTRS)

Das, Kalyan; Hall, Harvey

1999-01-01

Silicon based heterojunction bipolar transistors (HBT) with SiGe base are potentially important devices for high-speed and high-frequency microelectronics. These devices are particularly attractive as they can be fabricated using standard Si processing technology. However, in order to realize the full potential of devices fabricated in this material system, it is essential to be able to form low resistance ohmic contacts using low thermal budget process steps and have full compatibility with VLSI/ULSI processing. Therefore, a study was conducted in order to better understand the contact formation and to develop optimized low resistance contacts to layers with doping densities corresponding to the p-type SiGe base and n-type Si emitter regions of the HBTS. These as-grown doped layers were implanted with BF(sub 2) up to 1 X 10(exp 16)/CM(exp 2) and As up to 5 x 10(exp 15)/CM2, both at 30 keV for the p-type SiGe base and n-type Si emitter layers, respectively, in order to produce a low sheet resistance surface layer. Standard transfer length method (TLM) contact pads on both p and n type layers were deposited using an e-beam evaporated trilayer structure of Ti/CufTi/Al (25)A/1500A/250A/1000A). The TLM pads were delineated by a photoresist lift-off procedure. These contacts in the as-deposited state were ohmic, with specific contact resistances for the highest implant doses of the order of 10(exp -7) ohm-CM2 and lower.

Zwitterionic poly(carboxybetaine)-based cationic liposomes for effective delivery of small interfering RNA therapeutics without accelerated blood clearance phenomenon.

PubMed

Li, Yan; Liu, Ruiyuan; Shi, Yuanjie; Zhang, Zhenzhong; Zhang, Xin

2015-01-01

For efficient delivery of small interfering RNA (siRNA) to the target diseased site in vivo, it is important to design suitable vehicles to control the blood circulation of siRNA. It has been shown that surface modification of cationic liposome/siRNA complexes (lipoplexes) with polyethylene glycol (PEG) could enhance the circulation time of lipoplexes. However, the first injection of PEGylated lipoplexes in vivo induces accelerated blood clearance and enhances hepatic accumulation of the following injected PEGylated lipoplexes, which is known as the accelerated blood clearance (ABC) phenomenon. Herein, we developed zwitterionic poly(carboxybetaine) (PCB) modified lipoplexes for the delivery of siRNA therapeutics, which could avoid protein adsorption and enhance the stability of lipoplexes as that for PEG. Quite different from the PEGylation, the PCBylated lipoplexes could avoid ABC phenomenon, which extended the blood circulation time and enhanced the tumor accumulation of lipoplexes in vivo. After accumulation in tumor site, the PCBylation could promote the cellular uptake and endosomal/lysosomal escape of lipoplexes due to its unique chemical structure and pH-sensitive ability. With excellent tumor accumulation, cellular uptake and endosomal/lysosomal escape abilities, the PCBylated lipoplexes significantly inhibited tumor growth and induced tumor cell apoptosis.

Synthesis and structural characterisation of a novel phosphine-borane-stabilised dicarbanion and an unusual bis(phosphine-borane).

PubMed

Izod, Keith; McFarlane, William; Tyson, Brent V; Clegg, William; Harrington, Ross W

2004-03-07

The reaction between the phosphine-borane-substituted alkene [Pr(n)(2)P(BH(3))](Me(3)Si)C[double bond]CH(2) and elemental lithium in THF yields the complex [(pmdeta)Li[Pr(n)(2)P(BH(3))](Me(3)Si)CCH(2)](2)(2b) after recrystallisation; an X-ray crystallographic study of 2b reveals that the lithium is bound to the BH(3) hydrogens of the ligand, with no Li-C(carbanion) contact.

CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: A super junction SiGe low-loss fast switching power diode

NASA Astrophysics Data System (ADS)

Ma, Li; Gao, Yong

2009-01-01

This paper proposes a novel super junction (SJ) SiGe switching power diode which has a columnar structure of alternating p- and n- doped pillar substituting conventional n- base region and has far thinner strained SiGe p+ layer to overcome the drawbacks of existing Si switching power diode. The SJ SiGe diode can achieve low specific on-resistance, high breakdown voltages and fast switching speed. The results indicate that the forward voltage drop of SJ SiGe diode is much lower than that of conventional Si power diode when the operating current densities do not exceed 1000 A/cm2, which is very good for getting lower operating loss. The forward voltage drop of the Si diode is 0.66 V whereas that of the SJ SiGe diode is only 0.52 V at operating current density of 10 A/cm2. The breakdown voltages are 203 V for the former and 235 V for the latter. Compared with the conventional Si power diode, the reverse recovery time of SJ SiGe diode with 20 per cent Ge content is shortened by above a half and the peak reverse current is reduced by over 15%. The SJ SiGe diode can remarkably improve the characteristics of power diode by combining the merits of both SJ structure and SiGe material.

Neutral and cationic phosphoramide adducts of silicon tetrachloride: synthesis and characterization of their solution and solid-state structures.

PubMed

Denmark, Scott E; Eklov, Brian M

2008-01-01

The solution and solid-state structures of hexamethylphosphoramide (HMPA) adducts of tetrachlorosilane (SiCl4) are discussed. In solution, the meridional and facial isomers of the hexa-coordinate cationic complex 3 HMPASiCl3 + Cl(-) (2) predominate at all HMPA concentrations, and are in equilibrium with the hexa-coordinate neutral trans- and cis-2 HMPASiCl4 complexes (1), as well as the penta-coordinate cationic cis-2 HMPASiCl3 + Cl(-) (3). Single crystal X-ray analyses are reported for the ionized mer-3 HMPASiCl3 + HCl2 (-) and the neutral trans-2 HMPASiCl4 complexes.

Thermoelectric properties of epitaxial β-FeSi2 thin films grown on Si(111) substrates with various film qualities

NASA Astrophysics Data System (ADS)

Watanabe, Kentaro; Taniguchi, Tatsuhiko; Sakane, Shunya; Aoki, Shunsuke; Suzuki, Takeyuki; Fujita, Takeshi; Nakamura, Yoshiaki

2017-05-01

Si-based epitaxial β-FeSi2 thin films are attractive as materials for on-chip thermoelectric power generators. We investigated the structure, crystallinity, and thermoelectric properties of β-FeSi2 thin films epitaxially grown on Si(111) substrates by using three different techniques: conventional reactive deposition epitaxy followed by molecular beam epitaxy (RDE+MBE), solid phase epitaxy (SPE) based on codeposition of Fe and Si presented previously, and SPE followed by MBE (SPE+MBE) presented newly by this work. Their epitaxial growth temperatures were fixed at 530 °C for comparison. RDE+MBE thin films exhibited high crystalline quality, but rough surfaces and rugged β-FeSi2/Si(111) interfaces. On the other hand, SPE thin films showed flat surfaces and abrupt β-FeSi2/Si(111) interfaces but low crystallinity. We found that SPE+MBE thin films realized crystallinity higher than SPE thin films, and also had flatter surfaces and sharper interfaces than RDE+MBE thin films. In SPE+MBE thin film growth, due to the initial SPE process with low temperature codeposition, thermal interdiffusion of Fe and Si was suppressed, resulting in the surface flatness and abrupt interface. Second high temperature MBE process improved the crystallinity. We also investigated thermoelectric properties of these β-FeSi2 thin films. Structural factors affecting the thermoelectric properties of RDE+MBE, SPE, and SPE+MBE thin films were investigated.

a-SiNx:H-based ultra-low power resistive random access memory with tunable Si dangling bond conduction paths

PubMed Central

Jiang, Xiaofan; Ma, Zhongyuan; Xu, Jun; Chen, Kunji; Xu, Ling; Li, Wei; Huang, Xinfan; Feng, Duan

2015-01-01

The realization of ultra-low power Si-based resistive switching memory technology will be a milestone in the development of next generation non-volatile memory. Here we show that a high performance and ultra-low power resistive random access memory (RRAM) based on an Al/a-SiNx:H/p+-Si structure can be achieved by tuning the Si dangling bond conduction paths. We reveal the intrinsic relationship between the Si dangling bonds and the N/Si ratio x for the a-SiNx:H films, which ensures that the programming current can be reduced to less than 1 μA by increasing the value of x. Theoretically calculated current-voltage (I–V ) curves combined with the temperature dependence of the I–V characteristics confirm that, for the low-resistance state (LRS), the Si dangling bond conduction paths obey the trap-assisted tunneling model. In the high-resistance state (HRS), conduction is dominated by either hopping or Poole–Frenkel (P–F) processes. Our introduction of hydrogen in the a-SiNx:H layer provides a new way to control the Si dangling bond conduction paths, and thus opens up a research field for ultra-low power Si-based RRAM. PMID:26508086

a-SiNx:H-based ultra-low power resistive random access memory with tunable Si dangling bond conduction paths.

PubMed

Jiang, Xiaofan; Ma, Zhongyuan; Xu, Jun; Chen, Kunji; Xu, Ling; Li, Wei; Huang, Xinfan; Feng, Duan

2015-10-28

The realization of ultra-low power Si-based resistive switching memory technology will be a milestone in the development of next generation non-volatile memory. Here we show that a high performance and ultra-low power resistive random access memory (RRAM) based on an Al/a-SiNx:H/p(+)-Si structure can be achieved by tuning the Si dangling bond conduction paths. We reveal the intrinsic relationship between the Si dangling bonds and the N/Si ratio x for the a-SiNx:H films, which ensures that the programming current can be reduced to less than 1 μA by increasing the value of x. Theoretically calculated current-voltage (I-V) curves combined with the temperature dependence of the I-V characteristics confirm that, for the low-resistance state (LRS), the Si dangling bond conduction paths obey the trap-assisted tunneling model. In the high-resistance state (HRS), conduction is dominated by either hopping or Poole-Frenkel (P-F) processes. Our introduction of hydrogen in the a-SiNx:H layer provides a new way to control the Si dangling bond conduction paths, and thus opens up a research field for ultra-low power Si-based RRAM.

Fluorescent carbon dots as an efficient siRNA nanocarrier for its interference therapy in gastric cancer cells.

PubMed

Wang, Qing; Zhang, Chunlei; Shen, Guangxia; Liu, Huiyang; Fu, Hualin; Cui, Daxiang

2014-12-30

Fluorescent carbon dots (Cdots) have attracted increasing attention due to their potential applications in sensing, catalysis, and biomedicine. Currently, intensive research has been concentrated on the synthesis and imaging-guided therapy of these benign photoluminescent materials. Meanwhile, Cdots have been explored as nonviral vector for nucleic acid or drug delivery by chemical modification on purpose. We have developed a microwave assisted one-step synthesis of Cdots with citric acid as carbon source and tryptophan (Trp) as both nitrogen source and passivation agent. The Cdots with uniform size show superior water solubility, excellent biocompatibility, and high quantum yield. Afterwards, the PEI (polyethylenimine)-adsorbed Cdots nanoparticles (Cdots@PEI) were applied to deliver Survivin siRNA into human gastric cancer cell line MGC-803. The results have confirmed the nanocarrier exhibited excellent biocompatibility and a significant increase in cellular delivery of siRNA, inducing efficient knockdown for Survivin protein to 6.1%. In addition, PEI@Cdots complexes mediated Survivin silencing, the arrested cell cycle progression in G1 phase as well as cell apoptosis was observed. The Cdots-based and PEI-adsorbed complexes both as imaging agents and siRNA nanocarriers have been developed for Survivin siRNA delivery. And the results indicate that Cdots-based nanocarriers could be utilized in a broad range of siRNA delivery systems for cancer therapy.

Tetrel bond of pseudohalide anions with XH3F (X = C, Si, Ge, and Sn) and its role in SN2 reaction.

PubMed

Liu, Mingxiu; Li, Qingzhong; Cheng, Jianbo; Li, Wenzuo; Li, Hai-Bei

2016-12-14

The complexes of XH 3 F⋯N 3 - /OCN - /SCN - (X = C, Si, Ge, and Sn) have been investigated at the MP2/aug-cc-pVTZ(PP) level. The σ-hole of X atom in XH 3 F acts as a Lewis acid forming a tetrel bond with pseudohalide anions. Interaction energies of these complexes vary from -8 to -50 kcal/mol, mainly depending on the nature of X and pseudohalide anions. Charge transfer from N/O/S lone pair to X-F and X-H σ * orbitals results in the stabilization of these complexes, and the former orbital interaction is responsible for the large elongation of X-F bond length and the remarkable red shift of its stretch vibration. The tetrel bond in the complexes of XH 3 F (X = Si, Ge, and Sn) exhibits a significant degree of covalency with XH 3 F distorted significantly in these complexes. A breakdown of the individual forces involved attributes the stability of the interaction to mainly electrostatic energy, with a relatively large contribution from polarization. The transition state structures that connect the two minima for CH 3 Br⋯N 3 - complex have been localized and characterized. The energetic, geometrical, and topological parameters of the complexes were analyzed in the different stages of the S N 2 reaction N 3 - + CH 3 Br → Br - + CH 3 N 3 .

Thermal conductivity studies of novel nanofluids based on metallic silver decorated mesoporous silica nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tadjarodi, Azadeh, E-mail: tajarodi@iust.ac.ir; Zabihi, Fatemeh; Chemistry and Nanotechnology Laboratory, National Center for Laser Science and Technology, Tehran

2013-10-15

Graphical abstract: - Highlights: • Metallic silver was decorated in mSiO{sub 2} with grafted hemiaminal functional groups. • Synthesized nanoparticles were used for preparation of glycerol based nanofluids. • The effect of temperature, weight fraction of mSiO{sub 2} and concentration of silver nanoparticles on thermal conductivity of nanofluids was investigated. - Abstract: In the present study, the mesoporous structure of silica (mSiO{sub 2}) nanoparticles as well as hemiaminal grafted mSiO{sub 2} decorated by metallic silver (Ag/mSiO{sub 2}) has been used for the preparation of glycerol based nanofluids. Structural and morphological characterization of the synthesized products have been carried out usingmore » Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray diffraction (XRD), UV–vis spectroscopy, inductively coupled plasma (ICP) and N{sub 2} adsorption–desorption isotherms. The thermal conductivity and viscosity of the nanofluids have been measured as a function of temperature for various weight fractions and silver concentrations of mSiO{sub 2} and Ag/mSiO{sub 2} nanoparticles, respectively. The results show that the thermal conductivity of the nanofluids increase up to 9.24% as the weight fraction of mSiO{sub 2} increases up to 4 wt%. Also, increasing the percent of the silver decorated mSiO{sub 2} (Ag/mSiO{sub 2}) up to 2.98% caused an enhancement in the thermal conductivity of the base fluid up to 10.95%. Furthermore, the results show that the nanofluids have Newtonian behavior in the tested temperature range for various concentrations of nanoparticles.« less

The curious case of exploding quantum dots: anomalous migration and growth behaviors of Ge under Si oxidation

PubMed Central

2013-01-01

We have previously demonstrated the unique migration behavior of Ge quantum dots (QDs) through Si3N4 layers during high-temperature oxidation. Penetration of these QDs into the underlying Si substrate however, leads to a completely different behavior: the Ge QDs ‘explode,’ regressing back almost to their origins as individual Ge nuclei as formed during the oxidation of the original nanopatterned SiGe structures used for their generation. A kinetics-based model is proposed to explain the anomalous migration behavior and morphology changes of the Ge QDs based on the Si flux generated during the oxidation of Si-containing layers. PMID:23618165

Synthesis of silicon nanotubes with cobalt silicide ends using anodized aluminum oxide template.

PubMed

Zhang, Zhang; Liu, Lifeng; Shimizu, Tomohiro; Senz, Stephan; Gösele, Ulrich

2010-02-05

Silicon nanotubes (SiNTs) are compatible with Si-based semiconductor technology. In particular, the small diameters and controllable structure of such nanotubes are remaining challenges. Here we describe a method to fabricate SiNTs intrinsically connected with cobalt silicide ends based on highly ordered anodic aluminum oxide (AAO) templates. Size and growth direction of the SiNTs can be well controlled via the templates. The growth of SiNTs is catalyzed by the Co nanoparticles reduced on the pore walls of the AAO after annealing, with a controllable thickness at a given growth temperature and time. Simultaneously, cobalt silicide forms on the bottom side of the SiNTs.

Synthesis and Materials Design for Heteroanion Compounds

NASA Astrophysics Data System (ADS)

Machida, K.

2011-02-01

Oxynitride phosphors, SrSi2O2N2:Eu2+ were synthesized through a conventional solid state reaction between Sr2SiO4:Eu2+ precursor and Si3N4 by using NH4Cl flux, and their luminescence properties were characterized from a viewpoint of the ionic and covalent bond natures as the "heteroanion compound" containing O2- and N3- anions. The structural framework of host lattice is constructed by covalently bonded layers of SiON3 units, suggesting that the rearrangement of O2- and N3- anions effectively takes place between isolated SiO44-anions of the Sr2SiO4:Eu2+ precursor and SiN4 units of the Si3N4 raw material. Furthermore, the layered structure consisting of (Si2O2N2)n2n- polyanions as tightly connected by Si-N-Si covalent bonds depresses the lattice vibration of Sr(Eu)-O or Si-O bond, so that the temperature quenching effect is lowered to give the intense emission for LED-based illumination lamps.

Photonic-magnonic crystals: Multifunctional periodic structures for magnonic and photonic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kłos, J. W., E-mail: klos@amu.edu.pl; Krawczyk, M.; Dadoenkova, Yu. S.

2014-05-07

We investigate the properties of a photonic-magnonic crystal, a complex multifunctional one-dimensional structure with magnonic and photonic band gaps in the GHz and PHz frequency ranges for spin waves and light, respectively. The system consists of periodically distributed dielectric magnetic slabs of yttrium iron garnet and nonmagnetic spacers with an internal structure of alternating TiO{sub 2} and SiO{sub 2} layers which form finite-size dielectric photonic crystals. We show that the spin-wave coupling between the magnetic layers, and thus the formation of the magnonic band structure, necessitates a nonzero in-plane component of the spin-wave wave vector. A more complex structure perceivedmore » by light is evidenced by the photonic miniband structure and the transmission spectra in which we have observed transmission peaks related to the repetition of the magnetic slabs in the frequency ranges corresponding to the photonic band gaps of the TiO{sub 2}/SiO{sub 2} stack. Moreover, we show that these modes split to very high sharp (a few THz wide) subpeaks in the transmittance spectra. The proposed novel multifunctional artificial crystals can have interesting applications and be used for creating common resonant cavities for spin waves and light to enhance the mutual influence between them.« less

Local atomic and electronic structure of oxide/GaAs and SiO2/Si interfaces using high-resolution XPS

NASA Technical Reports Server (NTRS)

Grunthaner, F. J.; Grunthaner, P. J.; Vasquez, R. P.; Lewis, B. F.; Maserjian, J.; Madhukar, A.

1979-01-01

The chemical structures of thin SiO2 films, thin native oxides of GaAs (20-30 A), and the respective oxide-semiconductor interfaces, have been investigated using high-resolution X-ray photoelectron spectroscopy. Depth profiles of these structures have been obtained using argon ion bombardment and wet chemical etching techniques. The chemical destruction induced by the ion profiling method is shown by direct comparison of these methods for identical samples. Fourier transform data-reduction methods based on linear prediction with maximum entropy constraints are used to analyze the discrete structure in oxides and substrates. This discrete structure is interpreted by means of a structure-induced charge-transfer model.

Effects of substituents in silyl groups on the absorption, fluorescence and structural properties of 1,3,6,8-tetrasilylpyrenes.

PubMed

Maeda, Hajime; Suzuki, Tsubasa; Segi, Masahito

2018-05-09

1,3,6,8-Tetrasilylpyrenes and related germyl and stannyl derivatives were synthesized, and their absorption and fluorescence spectroscopic and structural properties were elucidated. The results show that the UV-vis absorption maxima of these substances in CH2Cl2 solutions shift to longer wavelengths as the size of the alkyl groups and numbers of phenyl groups on silicon increase. Fluorescence quantum yields of tetrasilylpyrenes in cyclohexane are larger than that of pyrene, and a pentamethyldisilyl derivative has an emission efficiency of 0.79. Except in the case of the SiMe2H derivative, excimer emission was not observed in concentrated solutions of these substances. The SiMe2H and SiMe3 derivatives were shown to form CT complexes with tetracyanoethylene in CH2Cl2 solutions. The calculated energy barriers for rotation of the silyl groups about the Si-C bond increase as the steric bulk of the silyl group increases. 29Si NMR chemical shifts were found to depend on the sizes of the alkyl groups and numbers of phenyl groups. Data arising from theoretical calculations suggest that the silyl groups act as electron-donating groups, and the donating ability of the groups decreases in the order SiR3 > GeR3 > SnR3.

Environmental Barrier Coatings for Ceramics and Ceramic Composites

NASA Technical Reports Server (NTRS)

Lee, Kang N.; Fox, Dennis; Eldridge, Jeffrey; Robinson, R. Craig; Bansal, Narottam

2004-01-01

One key factor that limits the performance of current gas turbine engines is the temperature capability of hot section structural components. Silicon-based ceramics, such as SiC/SiC composites and monolithic Si3N4, are leading candidates to replace superalloy hot section components in the next generation gas turbine engines due to their excellent high temperature properties. A major stumbling block to realizing Si-based ceramic hot section components is the recession of Si-based ceramics in combustion environments due to the volatilization of silica scale by water vapor. An external environmental barrier coating (EBC) is the most promising approach to preventing the recession. Current EBCs are based on silicon, mullite (3A12O3-2SiO2) and BSAS (barium strontium aluminum silicate with celsian structure). Volatility of BSAS, BSAS-silica chemical reaction, and low melting point of silicon limit the durability and temperature capability of current EBCs. Research is underway to develop EBCs with longer life and enhanced temperature capability. Understanding key issues affecting the performance of current EBCs is necessary for successful development of advanced EBCs. These issues include stress, chemical compatibility, adherence, and water vapor stability. Factors that affect stress are thermal expansion mismatch, phase stability, chemical stability, elastic modulus, etc. The current understanding on these issues will be discussed.

Mapping Optimal Charge Density and Length of ROMP-Based PTDMs for siRNA Internalization.

PubMed

Caffrey, Leah M; deRonde, Brittany M; Minter, Lisa M; Tew, Gregory N

2016-10-10

A fundamental understanding of how polymer structure impacts internalization and delivery of biologically relevant cargoes, particularly small interfering ribonucleic acid (siRNA), is of critical importance to the successful design of improved delivery reagents. Herein we report the use of ring-opening metathesis polymerization (ROMP) methods to synthesize two series of guanidinium-rich protein transduction domain mimics (PTDMs): one based on an imide scaffold that contains one guanidinium moiety per repeat unit, and another based on a diester scaffold that contains two guanidinium moieties per repeat unit. By varying both the degree of polymerization and, in effect, the relative number of cationic charges in each PTDM, the performances of the two ROMP backbones for siRNA internalization were evaluated and compared. Internalization of fluorescently labeled siRNA into Jurkat T cells demonstrated that fluorescein isothiocyanate (FITC)-siRNA internalization had a charge content dependence, with PTDMs containing approximately 40 to 60 cationic charges facilitating the most internalization. Despite this charge content dependence, the imide scaffold yielded much lower viabilities in Jurkat T cells than the corresponding diester PTDMs with similar numbers of cationic charges, suggesting that the diester scaffold is preferred for siRNA internalization and delivery applications. These developments will not only improve our understanding of the structural factors necessary for optimal siRNA internalization, but will also guide the future development of optimized PTDMs for siRNA internalization and delivery.

Structural and photoluminescence properties of silicon nanowires extracted by means of a centrifugation process from plasma torch synthesized silicon nanopowder.

PubMed

Le Borgne, Vincent; Agati, Marta; Boninelli, Simona; Castrucci, Paola; De Crescenzi, Maurizio; Dolbec, Richard; El Khakani, My Ali

2017-07-14

We report on a method for the extraction of silicon nanowires (SiNWs) from the by-product of a plasma torch based spheroidization process of silicon. This by-product is a nanopowder which consists of a mixture of SiNWs and silicon particles. By optimizing a centrifugation based process, we were able to extract substantial amounts of highly pure Si nanomaterials (mainly SiNWs and Si nanospheres (SiNSs)). While the purified SiNWs were found to have typical outer diameters in the 10-15 nm range and lengths of up to several μm, the SiNSs have external diameters in the 10-100 nm range. Interestingly, the SiNWs are found to have a thinner Si core (2-5 nm diam.) and an outer silicon oxide shell (with a typical thickness of ∼5-10 nm). High resolution transmission electron microscopy (HRTEM) observations revealed that many SiNWs have a continuous cylindrical core, whereas others feature a discontinuous core consisting of a chain of Si nanocrystals forming a sort of 'chaplet-like' structures. These plasma-torch-produced SiNWs are highly pure with no trace of any metal catalyst, suggesting that they mostly form through SiO-catalyzed growth scheme rather than from metal-catalyzed path. The extracted Si nanostructures are shown to exhibit a strong photoluminescence (PL) which is found to blue-shift from 950 to 680 nm as the core size of the Si nanostructures decreases from ∼5 to ∼3 nm. This near IR-visible PL is shown to originate from quantum confinement (QC) in Si nanostructures. Consistently, the sizes of the Si nanocrystals directly determined from HRTEM images corroborate well with those expected by QC theory.

Structural and photoluminescence properties of silicon nanowires extracted by means of a centrifugation process from plasma torch synthesized silicon nanopowder

NASA Astrophysics Data System (ADS)

Le Borgne, Vincent; Agati, Marta; Boninelli, Simona; Castrucci, Paola; De Crescenzi, Maurizio; Dolbec, Richard; El Khakani, My Ali

2017-07-01

We report on a method for the extraction of silicon nanowires (SiNWs) from the by-product of a plasma torch based spheroidization process of silicon. This by-product is a nanopowder which consists of a mixture of SiNWs and silicon particles. By optimizing a centrifugation based process, we were able to extract substantial amounts of highly pure Si nanomaterials (mainly SiNWs and Si nanospheres (SiNSs)). While the purified SiNWs were found to have typical outer diameters in the 10-15 nm range and lengths of up to several μm, the SiNSs have external diameters in the 10-100 nm range. Interestingly, the SiNWs are found to have a thinner Si core (2-5 nm diam.) and an outer silicon oxide shell (with a typical thickness of ˜5-10 nm). High resolution transmission electron microscopy (HRTEM) observations revealed that many SiNWs have a continuous cylindrical core, whereas others feature a discontinuous core consisting of a chain of Si nanocrystals forming a sort of ‘chaplet-like’ structures. These plasma-torch-produced SiNWs are highly pure with no trace of any metal catalyst, suggesting that they mostly form through SiO-catalyzed growth scheme rather than from metal-catalyzed path. The extracted Si nanostructures are shown to exhibit a strong photoluminescence (PL) which is found to blue-shift from 950 to 680 nm as the core size of the Si nanostructures decreases from ˜5 to ˜3 nm. This near IR-visible PL is shown to originate from quantum confinement (QC) in Si nanostructures. Consistently, the sizes of the Si nanocrystals directly determined from HRTEM images corroborate well with those expected by QC theory.

Physical and thermal behaviour of Sr-La-Al-B-Si based SOFC glass sealants as function of SrO content and B2O3/SiO2 ratio in the matrix

NASA Astrophysics Data System (ADS)

Ojha, Prasanta Kumar; Rath, S. K.; Chongdar, T. K.; Gokhale, N. M.; Kulkarni, A. R.

2011-05-01

A series of SOFC glass sealants with composition SrO (x), La2O3 (15), Al2O3 (15), B2O3 (40 - x), and SiO2 (30) [x = 10, 15, 20, 25 and 30] (wt.%) [SLABS] are investigated for their structure property correlations at different compositions. Quantitative Fourier transform infrared spectroscopy shows structural rigidity with increasing SrO content, as demonstrate by an increase in the Si-O-Si/O-Si-O bending and B-O-B stretching frequencies. The role of SrO as a modifier dominates the control of the structure and behaviour of glasses compared with the effect of network formers, i.e., the B2O3/SiO2 ratio. Consequent to the structural changes, increasing substitution of B2O3 by SrO the glasses causes increases in the density, glass transition temperature and dilatometric softening point. On the other hand, the crystallization temperatures show a decreasing trend and the coefficient of thermal expansion increases with increase in substitution.

Recent advances in mechanism-based chemotherapy drug-siRNA pairs in co-delivery systems for cancer: A review.

PubMed

Wang, Mingfang; Wang, Jinyu; Li, Bingcheng; Meng, Lingxin; Tian, Zhaoxing

2017-09-01

Co-delivery of chemotherapy drugs and siRNA for cancer therapy has achieved remarkable results according to synergistic/combined antitumor effects, and is recognized as a promising therapeutic modality. However, little attention has been paid to the extremely complex mechanisms of chemotherapy drug-siRNA pairs during co-delivery process. Proper selection of chemotherapy drug-siRNA pairs is beneficial for achieving desirable cancer therapeutic effects. Exploring the inherent principles during chemotherapy drug-siRNA pair selection for co-delivery would greatly enhanced therapeutic efficiency. To achieve ideal results, this article will systematically review current different mechanism-based chemotherapy drug-siRNA pairs for co-delivery in cancer treatment. Large-scale library screening of recent different chemotherapy drug-siRNA pairs for co-delivery would help to establish the chemotherapy drug-siRNA pair selection principle, which could pave the way for co-delivery of chemotherapy drugs and siRNA for cancer treatment in clinic. Following the inherent principle of chemotherapy drug-siRNA pair, more effective co-delivery vectors can be designed in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Creep and Environmental Durability of EBC/CMCs Under Imposed Thermal Gradient Conditions

NASA Technical Reports Server (NTRS)

Appleby, Matthew; Morscher, Gregory N.; Zhu, Dongming

2013-01-01

Interest in SiC fiber-reinforced SiC ceramic matrix composite (CMC) environmental barrier coating (EBC) systems for use in high temperature structural applications has prompted the need for characterization of material strength and creep performance under complex aerospace turbine engine environments. Stress-rupture tests have been performed on SiC/SiC composites systems, with varying fiber types and coating schemes to demonstrate material behavior under isothermal conditions. Further testing was conducted under exposure to thermal stress gradients to determine the effect on creep resistance and material durability. In order to understand the associated damage mechanisms, emphasis is placed on experimental techniques as well as implementation of non-destructive evaluation; including electrical resistivity monitoring. The influence of environmental and loading conditions on life-limiting material properties is shown.

Electrical characterizations of MIS structures based on variable-gap n(p)-HgCdTe grown by MBE on Si(0 1 3) substrates

NASA Astrophysics Data System (ADS)

Voitsekhovskii, A. V.; Nesmelov, S. N.; Dzyadukh, S. M.; Varavin, V. S.; Dvoretskii, S. A.; Mikhailov, N. N.; Yakushev, M. V.; Sidorov, G. Yu.

2017-12-01

Metal-insulator-semiconductor (MIS) structures based on n(p)-Hg1-xCdxTe (x = 0.22-0.40) with near-surface variable-gap layers were grown by the molecular-beam epitaxy (MBE) technique on the Si (0 1 3) substrates. Electrical properties of MIS structures were investigated experimentally at various temperatures (9-77 K) and directions of voltage sweep. The ;narrow swing; technique was used to determine the spectra of fast surface states with the exception of hysteresis effects. It is established that the density of fast surface states at the MCT/Al2O3 interface at a minimum does not exceed 3 × 1010 eV-1 × cm-2. For MIS structures based on n-MCT/Si(0 1 3), the differential resistance of the space-charge region in strong inversion mode in the temperature range 50-90 K is limited by the Shockley-Read-Hall generation in the space-charge region.

Fracture analysis of radial scientific instrument module registration fittings of the space telescope

NASA Technical Reports Server (NTRS)

Springfield, C. W., Jr.

1985-01-01

The space telescope contains various scientific instrument (SI) modules which are mounted to the Focal Plane Structure (FPS) in a statically determinate manner. This is accomplished by using three registration fittings per SI module, one resisting three translations, another resisting two and the third resisting only one. Due to thermal insulating requirements these fittings are complex devices composed of numerous pieces. The structural integrity of these fittings is of great importance to the safety of the orbiter transporting the telescope, so in addition to the stress analyses performed during the design of these components, fracture susceptibility also needs to be considered. The pieces of the registration fittings for the Radial SI Module containing the Wide Field Planetary Camera are examined to determine which would endanger the orbiter if they fractured and what is the likelihood of their fracture. The latter is stated in terms of maximum allowable initial flaw sizes in these pieces.

Redox-sensitive dendrimersomes assembled from amphiphilic Janus dendrimers for siRNA delivery.

PubMed

Du, Xiao-Jiao; Wang, Ze-Yu; Wang, Yu-Cai

2018-06-14

The development of delivery systems for small interfering RNA (siRNA) plays a key role in its clinical application. As the major delivery systems for siRNA, cationic polymer- or lipid-based vehicles are plagued by inherent issues. As proof of concept, a disulfide bond-containing amphiphilic Janus dendrimer (ssJD), which could be conveniently synthesized and readily scaled up with high reproducibility, was explored as a siRNA delivery system to circumvent these issues. The cationic hydrophilic head of this Janus dendrimer ensured strong and stable binding with negatively charged siRNA via electrostatic interactions, and the loaded siRNA was rapidly released from the obtained complexes under a redox environment. Therefore, after efficient internalization into tumor cells, redox-sensitive dendrimersome (RSDs)/siRNA exhibited significantly improved gene silencing efficacy.

Photoisomerization-induced manipulation of single-electron tunneling for novel Si-based optical memory.

PubMed

Hayakawa, Ryoma; Higashiguchi, Kenji; Matsuda, Kenji; Chikyow, Toyohiro; Wakayama, Yutaka

2013-11-13

We demonstrated optical manipulation of single-electron tunneling (SET) by photoisomerization of diarylethene molecules in a metal-insulator-semiconductor (MIS) structure. Stress is placed on the fact that device operation is realized in the practical device configuration of MIS structure and that it is not achieved in structures based on nanogap electrodes and scanning probe techniques. Namely, this is a basic memory device configuration that has the potential for large-scale integration. In our device, the threshold voltage of SET was clearly modulated as a reversible change in the molecular orbital induced by photoisomerization, indicating that diarylethene molecules worked as optically controllable quantum dots. These findings will allow the integration of photonic functionality into current Si-based memory devices, which is a unique feature of organic molecules that is unobtainable with inorganic materials. Our proposed device therefore has enormous potential for providing a breakthrough in Si technology.

Wafer-scale epitaxial graphene on SiC for sensing applications

NASA Astrophysics Data System (ADS)

Karlsson, Mikael; Wang, Qin; Zhao, Yichen; Zhao, Wei; Toprak, Muhammet S.; Iakimov, Tihomir; Ali, Amer; Yakimova, Rositza; Syväjärvi, Mikael; Ivanov, Ivan G.

2015-12-01

The epitaxial graphene-on-silicon carbide (SiC-G) has advantages of high quality and large area coverage owing to a natural interface between graphene and SiC substrate with dimension up to 100 mm. It enables cost effective and reliable solutions for bridging the graphene-based sensors/devices from lab to industrial applications and commercialization. In this work, the structural, optical and electrical properties of wafer-scale graphene grown on 2'' 4H semi-insulating (SI) SiC utilizing sublimation process were systemically investigated with focus on evaluation of the graphene's uniformity across the wafer. As proof of concept, two types of glucose sensors based on SiC-G/Nafion/Glucose-oxidase (GOx) and SiC-G/Nafion/Chitosan/GOx were fabricated and their electrochemical properties were characterized by cyclic voltammetry (CV) measurements. In addition, a few similar glucose sensors based on graphene by chemical synthesis using modified Hummer's method were also fabricated for comparison.

Probing lattice dynamics and electron-phonon coupling in the topological nodal-line semimetal ZrSiS

NASA Astrophysics Data System (ADS)

Singha, Ratnadwip; Samanta, Sudeshna; Chatterjee, Swastika; Pariari, Arnab; Majumdar, Dipanwita; Satpati, Biswarup; Wang, Lin; Singha, Achintya; Mandal, Prabhat

2018-03-01

Topological materials provide an exclusive platform to study the dynamics of relativistic particles in table-top experiments and offer the possibility of wide-scale technological applications. ZrSiS is a newly discovered topological nodal-line semimetal and has drawn enormous interests. In this paper, we have investigated the lattice dynamics and electron-phonon interaction in single-crystalline ZrSiS using Raman spectroscopy. Polarization and angle-resolved Raman data have been analyzed using crystal symmetries and theoretically calculated atomic vibrational patterns along with phonon dispersion spectra. Wavelength- and temperature-dependent measurements show the complex interplay of electron and phonon degrees of freedom, resulting in resonant phonon and quasielastic electron scattering through interband transition. Our high-pressure Raman studies reveal vibrational anomalies, which are the signature of structural phase transitions. Further investigations through high-pressure synchrotron x-ray diffraction clearly show pressure-induced structural transitions and coexistence of multiple phases, which also indicate possible electronic topological transitions in ZrSiS. This study not only provides the fundamental information on the phonon subsystem, but also sheds some light in understanding the topological nodal-line phase in ZrSiS and other isostructural systems.

Structure and Properties of SiO x Films Prepared by Chemical Etching of Amorphous Alloy Ribbons

NASA Astrophysics Data System (ADS)

Fedorov, V. A.; Berezner, A. D.; Beskrovnyi, A. I.; Fursova, T. N.; Pavlikov, A. V.; Bazhenov, A. V.

2018-04-01

The structure and the physical properties of amorphous SiO x films prepared by chemical etching of an iron-based amorphous ribbon alloy have been studied. The neutron diffraction and also the atomicforce and electron microscopy show that the prepared visually transparent films have amorphous structure, exhibit dielectric properties, and their morphology is similar to that of opals. The samples have been studied by differential scanning calorimetry, Raman and IR spectroscopy before and after their heat treatment. It is found that annealing of the films in air at a temperature of 1273 K leads to a change in their chemical compositions: an amorphous SiO2 compound with inclusions of SiO2 nanocrystals (crystobalite) forms.

Hole injection and dielectric breakdown in 6H-SiC and 4H-SiC metal-oxide-semiconductor structures during substrate electron injection via Fowler-Nordheim tunneling

NASA Astrophysics Data System (ADS)

Samanta, Piyas; Mandal, Krishna C.

2015-12-01

Hole injection into silicon dioxide (SiO2) films (8-40 nm thick) is investigated for the first time during substrate electron injection via Fowler-Nordheim (FN) tunneling in n-type 4H- and 6H-SiC (silicon carbide) based metal-oxide-semiconductor (MOS) structures at a wide range of temperatures (T) between 298 and 598 K and oxide electric fields Eox from 6 to 10 MV/cm. Holes are generated in heavily doped n-type polycrystalline silicon (n+ -polySi) gate serving as the anode as well as in the bulk silicon dioxide (SiO2) film via hot-electron initiated band-to-band ionization (BTBI). In absence of oxide trapped charges, it is shown that at a given temperature, the hole injection rates from either of the above two mechanisms are higher in n-4H-SiC MOS devices than those in n-6H-SiC MOS structures when compared at a given Eox and SiO2 thickness (tox). On the other hand, relative to n-4H-SiC devices, n-6H-SiC structures exhibit higher hole injection rates for a given tox during substrate electron injection at a given FN current density je,FN throughout the temperature range studied here. These two observations clearly reveal that the substrate material (n-6H-SiC and n-4H-SiC) dependencies on time-to-breakdown (tBD) or injected charge (electron) to breakdown (QBD) of the SiO2 film depend on the mode of FN injections (constant field/voltage and current) from the substrate which is further verified from the rigorous device simulation as well.

Clinical significance of enzymatic deficiencies in the gastrointestinal tract with particular reference to lactase deficiency.

PubMed

Rossi, E; Lentze, M J

1984-12-01

The study of deficiencies of small intestinal brush-border hydrolases increased our knowledge about the specific functions of hydrolases in the digestion of smaller molecules on the microvillus surface of the absorptive cells. The sucrase-isomaltase (SI) complex has been shown to be synthesized as a precursor (pro-sucrase-isomaltase) which is then incorporated into the membrane. The hydrophobic N-terminal end of the molecule is anchored in the lipid bilayer. In SI deficiency the molecular base of the disease is still not clear. Absence of SI activity could be due to complete lack of precursor synthesis or to structural changes within the N-terminal end of the SI-complex. Deficiencies of peptide hydrolases have not been reported with the exception of enteropeptidase (EP). Here a congenital deficiency of the enzyme was observed as the primary defect in enzyme synthesis within the enterocytes and as a secondary defect due to exocrine pancreatic insufficiency. In contrast to the primary EP deficiency, the activity of EP can be restored in the cases of exocrine pancreatic insufficiency by treatment with pancreatic extracts. Primary lactase deficiency exists in various forms. Besides congenital lactase deficiency, the late onset or adult type of lactase deficiency has been observed. The latter occurs in many different ethnic groups around the world. Here, using gel electrophoresis and immunoelectrophoresis, the lack of enzyme activity could be shown to be a primary defect in enzyme protein synthesis. In man and in the rat, two different lactases have been identified. In contrast to adult lactase, fetal lactase contains sialic acid at the end of carbohydrate side chains.(ABSTRACT TRUNCATED AT 250 WORDS)

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

NASA Astrophysics Data System (ADS)

Cho, Soo Haeng; Park, Sung Bin; Lee, Jong Hyeon; Hur, Jin Mok; Lee, Han Soo

2011-05-01

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li 2O molten salt at 650 °C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 °C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr 2O 3, NiCr 2O 4, Ni, NiO, and (Al,Nb,Ti)O 2; those of as cast and heat treated high Si/low Ti alloys were Cr 2O 3, NiCr 2O 4, Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

Theoretical study of the noble metals on semiconductor surfaces and Ti-base shape memory alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Yungui

1994-07-27

The electronic and structural properties of the (√3 x√3) R30° Ag/Si(111) and (√3 x √3) R30° Au/Si(111) surfaces are investigated using first principles total energy calculations. We have tested almost all experimentally proposed structural models for both surfaces and found the energetically most favorable model for each of them. The lowest energy model structure of the (√3 x √3) R30° Ag/Si(111) surface consists of a top layer of Ag atoms arranged as ``honeycomb-chained-trimers`` lying above a distorted ``missing top layer`` Si(111) substrate. The coverage of Ag is 1 monolayer (ML). We find that the honeycomb structure observed in STM imagesmore » arise from the electronic charge densities of an empty surface band near the Fermi level. The electronic density of states of this model gives a ``pseudo-gap`` around the Fermi level, which is consistent with experimental results. The lowest energy model for the (√3 x √3) R30° Au/Si(111) surface is a conjugate honeycomb-chained-trimer (CHCT-1) configuration which consists of a top layer of trimers formed by 1 ML Au atoms lying above a ``missing top layer`` Si(111) substrate with a honeycomb-chained-trimer structure for its first layer. The structures of Au and Ag are in fact quite similar and belong to the same class of structural models. However, small variation in the structural details gives rise to quite different observed STM images, as revealed in the theoretical calculations. The electronic charge density from bands around the Fermi level for the (√3 x √3) R30°, Au/Si(111) surface also gives a good description of the images observed in STM experiments. First principles calculations are performed to study the electronic and structural properties of a series of Ti-base binary alloys TiFe, TiNi, TiPd, TiMo, and TiAu in the B2 structure.« less

Atomic-scale analysis of deposition and characterization of a-Si:H thin films grown from SiH radical precursor

NASA Astrophysics Data System (ADS)

Sriraman, Saravanapriyan; Aydil, Eray S.; Maroudas, Dimitrios

2002-07-01

Growth of hydrogenated amorphous silicon films (a-Si:H) on an initial H-terminated Si(001)(2 x1) substrate at T=500 K was studied through molecular-dynamics (MD) simulations of repeated impingement of SiH radicals to elucidate the effects of reactive minority species on the structural quality of the deposited films. The important reactions contributing to film growth were identified through detailed visualization of radical-surface interaction trajectories. These reactions include (i) insertion of SiH into Si-Si bonds, (ii) adsorption onto surface dangling bonds, (iii) surface H abstraction by impinging SiH radicals through an Eley-Rideal mechanism, (iv) surface adsorption by penetration into subsurface layers or dissociation leading to interstitial atomic hydrogen, (v) desorption of interstitial hydrogen into the gas phase, (vi) formation of higher surface hydrides through the exchange of hydrogen, and (vii) dangling-bond-mediated dissociation of surface hydrides into monohydrides. The MD simulations of a-Si:H film growth predict an overall surface reaction probability of 95% for the SiH radical that is in good agreement with experimental measurements. Structural and chemical characterization of the deposited films was based on the detailed analysis of evolution of the films' structure, surface morphology and roughness, surface reactivity, and surface composition. The analysis revealed that the deposited films exhibit high dangling bond densities and rough surface morphologies. In addition, the films are abundant in voids and columnar structures that are detrimental to producing device-quality a-Si:H thin films.

Low-energy electron stimulated desorption of neutrals from multilayers of SiCl4 on Si(111).

PubMed

Lane, Christopher D; Orlando, Thomas M

2006-04-28

The interaction of low-energy electrons with multilayers of SiCl(4) adsorbed on Si(111) leads to production and desorption of Cl((2)P(32)), Cl((2)P(12)), Si, and SiCl. Resonant structure in the yield versus incident electron energy (E(i)) between 6 and 12 eV was seen in all neutral channels and assigned to dissociative electron attachment (DEA), unimolecular decay of excited products produced via autodetachment and direct dissociation. These processes yield Cl((2)P(32)) and Cl((2)P(12)) with nonthermal kinetic energies of 425 and 608 meV, respectively. The Cl((2)P(12)) is produced solely at the vacuum surface interface, whereas the formation of Cl((2)P(32)) likely involves subsurface dissociation, off-normal trajectories, and collisions with neighbors. Structure in the Cl((2)P(32)) yield near 14 and 25 eV can originate from excitation of electrons in the 2e, 7t(2) and 6t(2), 6a(1) levels, respectively. Although the 14 eV feature was not present in the Cl((2)P(12)) yield, the broad 25 eV feature, which involves complex Auger filling of holes in the 6t(2) and 6a(1) levels of SiCl(4), is observed. Direct ionization, exciton decay, and DEA from secondary electron scattering all occur at E(i)>14 eV. Si and SiCl were detected via nonresonant ionization of SiCl(x) precursors that are produced via the same states and mechanisms that yield Cl. The Si retains the kinetic energy profile of the desorbed precursors.

Lung toxicities of core–shell nanoparticles composed of carbon, cobalt, and silica

PubMed Central

Al Samri, Mohammed T; Silva, Rafael; Almarzooqi, Saeeda; Albawardi, Alia; Othman, Aws Rashad Diab; Al Hanjeri, Ruqayya SMS; Al Dawaar, Shaikha KM; Tariq, Saeed; Souid, Abdul-Kader; Asefa, Tewodros

2013-01-01

We present here comparative assessments of murine lung toxicity (biocompatibility) after in vitro and in vivo exposures to carbon (C–SiO2-etched), carbon–silica (C–SiO2), carbon–cobalt–silica (C–Co–SiO2), and carbon–cobalt oxide–silica (C–Co3O4–SiO2) nanoparticles. These nanoparticles have potential applications in clinical medicine and bioimaging, and thus their possible adverse events require thorough investigation. The primary aim of this work was to explore whether the nanoparticles are biocompatible with pneumatocyte bioenergetics (cellular respiration and adenosine triphosphate content). Other objectives included assessments of caspase activity, lung structure, and cellular organelles. Pneumatocyte bioenergetics of murine lung remained preserved after treatment with C–SiO2-etched or C–SiO2 nanoparticles. C–SiO2-etched nanoparticles, however, increased caspase activity and altered lung structure more than C–SiO2 did. Consistent with the known mitochondrial toxicity of cobalt, both C–Co–SiO2 and C–Co3O4–SiO2 impaired lung tissue bioenergetics. C–Co–SiO2, however, increased caspase activity and altered lung structure more than C–Co3O4–SiO2. The results indicate that silica shell is essential for biocompatibility. Furthermore, cobalt oxide is the preferred phase over the zerovalent Co(0) phase to impart biocompatibility to cobalt-based nanoparticles. PMID:23658487

High extraction efficiency GaN-based light-emitting diodes on embedded SiO2 nanorod array and nanoscale patterned sapphire substrate

NASA Astrophysics Data System (ADS)

Huang, Hung-Wen; Huang, Jhi-Kai; Kuo, Shou-Yi; Lee, Kang-Yuan; Kuo, Hao-Chung

2010-06-01

In this paper, GaN-based LEDs with a nanoscale patterned sapphire substrate (NPSS) and a SiO2 photonic quasicrystal (PQC) structure on an n-GaN layer using nanoimprint lithography are fabricated and investigated. The light output power of LED with a NPSS and a SiO2 PQC structure on an n-GaN layer was 48% greater than that of conventional LED. Strong enhancement in output power is attributed to better epitaxial quality and higher reflectance resulted from NPSS and PQC structures. Transmission electron microscopy images reveal that threading dislocations are blocked or bended in the vicinities of NPSS layer. These results provide promising potential to increase output power for commercial light emitting devices.

Bond-length relaxation in crystalline Si1-xGex alloys: An extended x-ray-absorption fine-structure study

NASA Astrophysics Data System (ADS)

Kajiyama, Hiroshi; Muramatsu, Shin-Ichi; Shimada, Toshikazu; Nishino, Yoichi

1992-06-01

Extended x-ray-absorption fine-structure spectra for crystalline Si1-xGex alloys, measured at the K edge of Ge at room temperature, are analyzed with a curve-fitting method based on the spherical-wave approximation. The Ge-Ge and Ge-Si bond lengths, coordination numbers of Ge and Si atoms around a Ge atom, and Debye-Waller factors of Ge and Si atoms are obtained. It is shown that Ge-Ge and Ge-Si bonds relax completely, for all Ge concentrations of their study, while the lattice constant varies monotonically, following Vegard's law. As noted by Bragg and later by Pauling and Huggins, the Ge-Ge and Ge-Si bond lengths are close to the sum of their constituent-element atomic radii: nearly 2.45 Å for Ge-Ge bonds and 2.40 Å for Ge-Si bonds. A study on the coordination around a Ge atom in the alloys revealed that Ge and Si atoms mix randomly throughout the compositional range studied.

Si-FeSi2/C nanocomposite anode materials produced by two-stage high-energy mechanical milling

NASA Astrophysics Data System (ADS)

Yang, Yun Mo; Loka, Chadrasekhar; Kim, Dong Phil; Joo, Sin Yong; Moon, Sung Whan; Choi, Yi Sik; Park, Jung Han; Lee, Kee-Sun

2017-05-01

High capacity retention Silicon-based nanocomposite anode materials have been extensively explored for use in lithium-ion rechargeable batteries. Here we report the preparation of Si-FeSi2/C nanocomposite through scalable a two-stage high-energy mechanical milling process, in which nano-scale Si-FeSi2 powders are besieged by the carbon (graphite/amorphous phase) layer; and investigation of their structure, morphology and electrochemical performance. Raman analysis revealed that the carbon layer structure comprised of graphitic and amorphous phase rather than a single amorphous phase. Anodes fabricated with the Si-FeSi2/C showed excellent electrochemical behavior such as a first discharge capacity of 1082 mAh g-1 and a high capacity retention until the 30th cycle. A remarkable coulombic efficiency of 99.5% was achieved within a few cycles. Differential capacity plots of the Si-FeSi2/C anodes revealed a stable lithium reaction with Si for lithiation/delithiation. The enhanced electrochemical properties of the Si-FeSi2/C nanocomposite are mainly attributed to the nano-size Si and stable solid electrolyte interface formation and highly conductive path driven by the carbon layer.

Study of the composition, structure, and optical properties of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket films erbium doped from the Er(pd){sub 3} complex compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kudoyarova, V. Kh., E-mail: kudoyarova@mail.ioffe.ru; Tolmachev, V. A.; Gushchina, E. V.

2013-03-15

Rutherford backscattering, IR spectroscopy, ellipsometry, and atomic-force microscopy are used to perform an integrated study of the composition, structure and optical properties of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films. The technique employed to obtain the a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films includes the high-frequency decomposition of a mixture of gases, (SiH{sub 4}){sub a} + (CH{sub 4}){sub b}, and the simultaneous thermal evaporation of a complex compound, Er(pd){sub 3}. It is demonstrated that raising the amount of CH{sub 4} in the gas mixture results in an increase in the carbon content of the films under study andmore » an increase in the optical gap E{sub g}{sup opt} from 1.75 to 2.2 eV. Changes in the composition of a-Si{sub 1-x}C{sub x}:H Left-Pointing-Angle-Bracket Er Right-Pointing-Angle-Bracket amorphous films, accompanied, in turn, by changes in the optical constants, are observed in the IR spectra. The ellipsometric spectra obtained are analyzed in terms of multiple-parameter models. The conclusion is made on the basis of this analysis that the experimental and calculated spectra coincide well when variation in the composition of the amorphous films with that of the gas mixture is taken into account. The existence of a thin (6-8 nm) silicon-oxide layer on the surface of the films under study and the validity of using the double-layer model in ellipsometric calculations is confirmed by the results of structural analyses by atomic-force microscopy.« less

Fabrication of poly-crystalline Si-based Mie resonators via amorphous Si on SiO2 dewetting.

PubMed

Naffouti, Meher; David, Thomas; Benkouider, Abdelmalek; Favre, Luc; Ronda, Antoine; Berbezier, Isabelle; Bidault, Sebastien; Bonod, Nicolas; Abbarchi, Marco

2016-02-07

We report the fabrication of Si-based dielectric Mie resonators via a low cost process based on solid-state dewetting of ultra-thin amorphous Si on SiO2. We investigate the dewetting dynamics of a few nanometer sized layers annealed at high temperature to form submicrometric Si-particles. Morphological and structural characterization reveal the polycrystalline nature of the semiconductor matrix as well as rather irregular morphologies of the dewetted islands. Optical dark field imaging and spectroscopy measurements of the single islands reveal pronounced resonant scattering at visible frequencies. The linewidth of the low-order modes can be ∼20 nm in full width at half maximum, leading to a quality factor Q exceeding 25. These values reach the state-of-the-art ones obtained for monocrystalline Mie resonators. The simplicity of the dewetting process and its cost-effectiveness opens the route to exploiting it over large scales for applications in silicon-based photonics.

Formulation of glutathione responsive anti-proliferative nanoparticles from thiolated Akt1 siRNA and disulfide-crosslinked PEI for efficient anti-cancer gene therapy.

PubMed

Muthiah, Muthunarayanan; Che, Hui-Lian; Kalash, Santhosh; Jo, Jihoon; Choi, Seok-Yong; Kim, Won Jong; Cho, Chong Su; Lee, Jae Young; Park, In-Kyu

2015-02-01

In this study, thiol-modified siRNA (SH-siRNA) was delivered by bioreducible polyethylenimine (ssPEI), to enhance physicochemical properties of polyplexes and function of siRNA through disulfide bonding between SH-siRNA and ssPEI. The ssPEI was utilized to deliver Akt1 SH-siRNA for suppression of Akt1 mRNA and blockage of Akt1 protein translation, resulting in reduced cellular proliferation and the induction of apoptosis. Disulfide bondings between the ssPEI and SH-siRNA through thiol groups in both were confirmed by DTT treatment. Complexation between ssPEI and Akt1SH-siRNA was enhanced and reduced surface charge of ssPEI/Akt1SH-siRNA complexes with smaller average particle sizes even at lower N/P ratios was obtained compared with PEI/Akt1siRNA ones. Cellular uptake of ssPEI/Akt1SH-siRNA complexes in CT-26 mouse colon cancer cells was also enhanced. The ssPEI/Akt1SH-siRNA complexes reduced proliferation and increased apoptosis of mouse colon cancer cells in vitro. In an in vivo mouse tumor model, the complexes reduced tumor proliferation and downregulation of Akt1 compared to controls. Copyright © 2014 Elsevier B.V. All rights reserved.

All-in-one assembly based on 3D-intertangled and cross-jointed architectures of Si/Cu 1D-nanowires for lithium ion batteries

PubMed Central

Hwang, Chihyun; Kim, Tae-Hee; Cho, Yoon-Gyo; Kim, Jieun; Song, Hyun-Kon

2015-01-01

All-in-one assemblies of separator, electrode and current collector (SECA) for lithium ion batteries are presented by using 1D nanowires of Si and Cu (nwSi and nwCu). Even without binders, integrity of SECA is secured via structural joints based on ductility of Cu as well as entanglement of nwSi and nwCu. By controlling the ratio of the nanowires, the number of contact points and voids accommodating volume expansion of Si active material are tunable. Zero volume expansion and high energy density are simultaneously achievable by the architecture. PMID:25720334

Development, characterization, and in vitro evaluation of phosphatidylcholine-sodium cholate-based nanoparticles for siRNA delivery to MCF-7 human breast cancer cells

NASA Astrophysics Data System (ADS)

Pérez, Sebastián Ezequiel; Gándola, Yamila; Carlucci, Adriana Mónica; González, Lorena

2015-03-01

Phosphatidylcholine-sodium cholate (SC)-based nanoparticles were designed, characterized, and evaluated as plausible oligonucleotides delivery systems. For this purpose, formulation of the systems was optimized to obtain low cytotoxic vehicles with high siRNA-loading capacity and acceptable transfection ability. Mixtures of soybean phosphatidylcholine (SPC) and SC were prepared at different molar ratios with 2 % w/v total concentration; distilled water and two different buffers were used as dispersion medium. Nanoparticles below 150 nm were observed showing spherical shape which turned smaller in diameter as the SC molar proportion increased, accounting for small unilamellar vesicles when low proportions of SC were present in the formulation, but clear mixed micellar solutions at higher SC percentages. Macroscopic characteristics along with physico-chemical parameters values supported the presence of these types of structures. SYBR green displacement assays demonstrated an important oligonucleotide binding that increased as bile salt relative content got higher. Within the same molar ratio, nanoparticles showed the following binding efficiency order: pH 7.4 > pH 5.0 > distilled water. siRNA-loading capacity assays confirmed the higher siRNA binding by the mixed micelles containing higher SC proportion; moreover, the complexes formed were smaller as the SC:SPC ratio increased. Considering cytotoxicity and siRNA-loading capacity, 1:2 and 1:4 SPC:SC formulations were selected for further biological assays. Nanoparticles prepared in any of the three media were able to induce dsRNA uptake and efficiently transfect RNA for gene silencing, for the compositions prepared in buffer pH 5.0 being the most versatile.

Selective Epitaxy of InP on Si and Rectification in Graphene/InP/Si Hybrid Structure.

PubMed

Niu, Gang; Capellini, Giovanni; Hatami, Fariba; Di Bartolomeo, Antonio; Niermann, Tore; Hussein, Emad Hameed; Schubert, Markus Andreas; Krause, Hans-Michael; Zaumseil, Peter; Skibitzki, Oliver; Lupina, Grzegorz; Masselink, William Ted; Lehmann, Michael; Xie, Ya-Hong; Schroeder, Thomas

2016-10-12

The epitaxial integration of highly heterogeneous material systems with silicon (Si) is a central topic in (opto-)electronics owing to device applications. InP could open new avenues for the realization of novel devices such as high-mobility transistors in next-generation CMOS or efficient lasers in Si photonics circuitry. However, the InP/Si heteroepitaxy is highly challenging due to the lattice (∼8%), thermal expansion mismatch (∼84%), and the different lattice symmetries. Here, we demonstrate the growth of InP nanocrystals showing high structural quality and excellent optoelectronic properties on Si. Our CMOS-compatible innovative approach exploits the selective epitaxy of InP nanocrystals on Si nanometric seeds obtained by the opening of lattice-arranged Si nanotips embedded in a SiO 2 matrix. A graphene/InP/Si-tip heterostructure was realized on obtained materials, revealing rectifying behavior and promising photodetection. This work presents a significant advance toward the monolithic integration of graphene/III-V based hybrid devices onto the mainstream Si technology platform.

Silicon Nanoparticles with Surface Nitrogen: 90% Quantum Yield with Narrow Luminescence Bandwidth and the Ligand Structure Based Energy Law.

PubMed

Li, Qi; Luo, Tian-Yi; Zhou, Meng; Abroshan, Hadi; Huang, Jingchun; Kim, Hyung J; Rosi, Nathaniel L; Shao, Zhengzhong; Jin, Rongchao

2016-09-27

Silicon nanoparticles (NPs) have been widely accepted as an alternative material for typical quantum dots and commercial organic dyes in light-emitting and bioimaging applications owing to silicon's intrinsic merits of least toxicity, low cost, and high abundance. However, to date, how to improve Si nanoparticle photoluminescence (PL) performance (such as ultrahigh quantum yield, sharp emission peak, high stability) is still a major issue. Herein, we report surface nitrogen-capped Si NPs with PL quantum yield up to 90% and narrow PL bandwidth (full width at half-maximum (fwhm) ≈ 40 nm), which can compete with commercial dyes and typical quantum dots. Comprehensive studies have been conducted to unveil the influence of particle size, structure, and amount of surface ligand on the PL of Si NPs. Especially, a general ligand-structure-based PL energy law for surface nitrogen-capped Si NPs is identified in both experimental and theoretical analyses, and the underlying PL mechanisms are further discussed.

The electroluminescence mechanism of Er³⁺ in different silicon oxide and silicon nitride environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rebohle, L., E-mail: l.rebohle@hzdr.de; Wutzler, R.; Braun, M.

Rare earth doped metal-oxide-semiconductor (MOS) structures are of great interest for Si-based light emission. However, several physical limitations make it difficult to achieve the performance of light emitters based on compound semiconductors. To address this point, in this work the electroluminescence (EL) excitation and quenching mechanism of Er-implanted MOS structures with different designs of the dielectric stack are investigated. The devices usually consist of an injection layer made of SiO₂ and an Er-implanted layer made of SiO₂, Si-rich SiO₂, silicon nitride, or Si-rich silicon nitride. All structures implanted with Er show intense EL around 1540 nm with EL power efficienciesmore » in the order of 2 × 10⁻³ (for SiO₂:Er) or 2 × 10⁻⁴(all other matrices) for lower current densities. The EL is excited by the impact of hot electrons with an excitation cross section in the range of 0.5–1.5 × 10⁻¹⁵cm⁻². Whereas the fraction of potentially excitable Er ions in SiO₂ can reach values up to 50%, five times lower values were observed for other matrices. The decrease of the EL decay time for devices with Si-rich SiO₂ or Si nitride compared to SiO₂ as host matrix implies an increase of the number of defects adding additional non-radiative de-excitation paths for Er³⁺. For all investigated devices, EL quenching cross sections in the 10⁻²⁰ cm² range and charge-to-breakdown values in the range of 1–10 C cm⁻² were measured. For the present design with a SiO₂ acceleration layer, thickness reduction and the use of different host matrices did not improve the EL power efficiency or the operation lifetime, but strongly lowered the operation voltage needed to achieve intense EL.« less

X-ray reflectometry and simulation of the parameters of SiC epitaxial films on Si(111), grown by the atomic substitution method

NASA Astrophysics Data System (ADS)

Kukushkin, S. A.; Nussupov, K. Kh.; Osipov, A. V.; Beisenkhanov, N. B.; Bakranova, D. I.

2017-05-01

The structure and composition of SiC nanolayers are comprehensively studied by X-ray reflectometry, IR-spectroscopy, and atomic-force microscopy (AFM) methods for the first time. SiC films were synthesized by the new method of topochemical substitution of substrate atoms at various temperatures and pressure of CO active gas on the surface of high-resistivity low-dislocation single-crystal n-type silicon (111). Based on an analysis and generalization of experimental data obtained using X-ray reflectometry, IR spectroscopy, and AFM methods, a structural model of SiC films on Si was proposed. According to this model, silicon carbide film consists of a number of layers parallel to the substrate, reminiscent of a layer cake. The composition and thickness of each layer entering the film structure is experimentally determined. It was found that all samples contain superstoichiometric carbon; however, its structure is significantly different for the samples synthesized at temperatures of 1250 and 1330°C, respectively. In the former case, the film surface is saturated with silicon vacancies and carbon in the structurally loose form reminiscent of HOPG carbon. In the films grown at 1330°C, carbon is in a dense structure with a close-to-diamond density.

Atomistic insights on the nanoscale single grain scratching mechanism of silicon carbide ceramic based on molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Liu, Yao; Li, Beizhi; Kong, Lingfei

2018-03-01

The precision and crack-free surface of brittle silicon carbide (SiC) ceramic was achieved in the nanoscale ductile grinding. However, the nanoscale scratching mechanism and the root causes of SiC ductile response, especially in the atomistic aspects, have not been fully understood yet. In this study, the SiC atomistic scale scratching mechanism was investigated by single diamond grain scratching simulation based on molecular dynamics. The results indicated that the ductile scratching process of SiC could be achieved in the nanoscale depth of cut through the phase transition to an amorphous structure with few hexagonal diamond structure. Furthermore, the silicon atoms in SiC could penetrate into diamond grain which may cause wear of diamond grain. It was further found out that the chip material in the front of grain flowed along the grain side surface to form the groove protrusion as the scratching speed increases. The higher scratching speed promoted more atoms to transfer into the amorphous structure and reduced the hexagonal diamond and dislocation atoms number, which resulted in higher temperature, smaller scratching force, smaller normal stress, and thinner subsurface damage thickness, due to larger speed impaction causing more bonds broken which makes the SiC more ductile.

Synthesis, characterization, and evaluation of ionizable lysine-based lipids for siRNA delivery.

PubMed

Walsh, Colin L; Nguyen, Juliane; Tiffany, Matthew R; Szoka, Francis C

2013-01-16

We report the synthesis and characterization of a series of ionizable lysine-based lipids (ILL), novel lipids containing a lysine headgroup linked to a long-chain dialkylamine through an amide linkage at the lysine α-amine. These ILLs contain two ionizable amines and a carboxylate, and exhibit pH-dependent lipid ionization that varies with lipid structure. The synthetic scheme employed allows for the simple, orthogonal manipulation of lipids. This provides a method for the development of a compositionally diverse library with varying ionizable headgroups, tail structures, and linker regions. A focused library of four ILLs was synthesized to determine the impact of hydrophobic fluidity, lipid net charge, and lipid pK(a) on the biophysical and siRNA transfection characteristics of this new class of lipids. We found that manipulation of lipid structure impacts the protonation behavior, electrostatically driven membrane disruption, and ability to promote siRNA mediated knockdown in vitro. ILL-siRNA liposomal formulations were tested in a murine Factor VII model; however, no significant siRNA-mediated knockdown was observed. These results indicate that ILL may be useful in vitro transfection reagents, but further optimization of this new class of lipids is required to develop an effective in vivo siRNA delivery system.

Si/Ge elatform for lasers, amplifiers, and nonlinear optical devices based on the Raman Effect

NASA Astrophysics Data System (ADS)

Claps, Ricardo; Dimitropoulos, Dimitrios; Raghunathan, Varun; Fathpour, Sasan; Jalali, Bahram; Jusserand, Bernard

2007-02-01

The use of a silicon-germanium platform for the development of optically active devices will be discussed in this paper, from the perspective of Raman and Brillouin scattering phenomena. Silicon-Germanium is becoming a prevalent technology for the development of high speed CMOS transistors, with advances in several key parameters as high carrier mobility, low cost, and reduced manufacturing logistics. Traditionally, Si-Ge structures have been used in the optoelectronics arena as photodetectors, due to the enhanced absorption of Ge in the telecommunications band. Recent developments in Raman-based nonlinearities for devices based on a silicon-on-insulator platform have shed light on the possibility of using these effects in Si-Ge architectures. Lasing and amplification have been demonstrated using a SiGe alloy structure, and Brillouin/Raman activity from acoustic phonon modes in SiGe superlattices has been predicted. Moreover, new Raman-active branches and inhomogeneously broadened spectra result from optical phonon modes, offering new perspectives for optical device applications. The possibilities for an electrically-pumped Raman laser will be outlined, and the potential for design and development of silicon-based, Tera-Hertz wave emitters and/or receivers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yanhong; Gao, Ping; Li, La

Pure Si{sub x}C{sub 1−x} (x > 0.5) and B-containing Si{sub x}C{sub 1−x} (x > 0.5) based resistive switching devices (RSD) with the structure of Ag/Si{sub x}C{sub 1−x}/p-Si were fabricated and their switching characteristics and mechanism were investigated systematically. Percolation mechanism through trapping/ de-trapping at defect states was suggested for the switching process. Through the introduction of B atoms into Si{sub x}C{sub 1−x}, the density of defect states was reduced, then, the SET and RESET voltages were also decreased. Based on the percolation theory, the dependence of SET/RESET voltage on the density of defect states was analyzed. These results supply a deep understanding for themore » SiC-based RSD, which have a potential application in extreme ambient conditions.« less