Photoluminescence characteristics of ZnTe bulk crystal and ZnTe epilayer grown on GaAs substrate by MOVPE

NASA Astrophysics Data System (ADS)

Lü, Hai-Yan; Mu, Qi; Zhang, Lei; Lü, Yuan-Jie; Ji, Zi-Wu; Feng, Zhi-Hong; Xu, Xian-Gang; Guo, Qi-Xin

2015-12-01

Excitation power and temperature-dependent photoluminescence (PL) spectra of the ZnTe epilayer grown on (100) GaAs substrate and ZnTe bulk crystal are investigated. The measurement results show that both the structures are of good structural quality due to their sharp bound excitonic emissions and absence of the deep level structural defect-related emissions. Furthermore, in contrast to the ZnTe bulk crystal, although excitonic emissions for the ZnTe epilayer are somewhat weak, perhaps due to As atoms diffusing from the GaAs substrate into the ZnTe epilayer and/or because of the strain-induced degradation of the crystalline quality of the ZnTe epilayer, neither the donor-acceptor pair (DAP) nor conduction band-acceptor (e-A) emissions are observed in the ZnTe epilayer. This indicates that by further optimizing the growth process it is possible to obtain a high-crystalline quality ZnTe heteroepitaxial layer that is comparable to the ZnTe bulk crystal. Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20120131110006), the Key Science and Technology Program of Shandong Province, China (Grant No. 2013GGX10221), the Key Laboratory of Functional Crystal Materials and Device (Shandong University, Ministry of Education), China (Grant No. JG1401), the National Natural Science Foundation of China (Grant No. 61306113), the Major Research Plan of the National Natural Science Foundation of China (Grant No. 91433112), and the Partnership Project for Fundamental Technology Researches of the Ministry of Education, Culture, Sports, Science and Technology, Japan.

The effect of high energy concentration source irradiation on structure and properties of Fe-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Pilarczyk, Wirginia

2016-06-01

Metallic glasses exhibit metastable structure and maintain this relatively stable amorphous state within certain temperature range. High intensity laser beam was used for the surface irradiation of Fe-Co-B-Si-Nb bulk metallic glasses. The variable parameter was laser beam pulse energy. For the analysis of structure and properties of bulk metallic glasses and their surface after laser remelting the X-ray analysis, microscopic observation and test of mechanical properties were carried out. Examination of the nanostructure of amorphous materials obtained by high pressure copper mold casting method and the irradiated with the use of TITAN 80-300 HRTEM was carried out. Nanohardness and reduced Young's modulus of particular amorphous and amorphous-crystalline material zone of the laser beam were examined with the use of Hysitron TI950 Triboindenter nanoindenter and with the use of Berkovich's indenter. The XRD and microscopic analysis showed that the test material is amorphous in its structure before irradiation. Microstructure observation with electron transmission microscopy gave information about alloy crystallization in the irradiated process. Identification of given crystal phases allows to determine the kind of crystal phases created in the first place and also further changes of phase composition of alloy. The main value of the nanohardness of the surface prepared by laser beam has the order of magnitude similar to bulk metallic glasses formed by casting process irrespective of the laser beam energy used. Research results analysis showed that the area between parent material and fusion zone is characterized by extraordinarily interesting structure which is and will be the subject of further analysis in the scope of bulk metallic glasses amorphous structure and high energy concentration source. The main goal of this work is the results' presentation of structure and chosen properties of the selected bulk metallic glasses after casting process and after irradiation process employing the high energy concentration sources.

A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission

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

Zhou, Chenkun; Lin, Haoran; Shi, Hongliang

The synthesis and characterization is reported of (C 9NH 20) 2SnBr 4, a novel organic metal halide hybrid with a zero-dimensional (0D) structure, in which individual seesaw-shaped tin (II) bromide anions (SnBr 4 2-) are co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C 9NH 20 +). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep-red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. Furthermore, the unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals tomore » exhibit the intrinsic properties of individual SnBr 4 2- species, and 2) the seesaw structure then enables a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.« less

Disentangling the surface and bulk electronic structures of LaOFeAs

DOE PAGES

Zhang, P.; Ma, J.; Qian, T.; ...

2016-09-20

We performed a comprehensive angle-resolved photoemission spectroscopy study of the electronic band structure of LaOFeAs single crystals. We found that samples cleaved at low temperature show an unstable and very complicated band structure, whereas samples cleaved at high temperature exhibit a stable and clearer electronic structure. Using in situ surface doping with K and supported by first-principles calculations, we identify both surface and bulk bands. Our assignments are confirmed by the difference in the temperature dependence of the bulk and surface states.

TaRh2B2 and NbRh2B2: Superconductors with a chiral noncentrosymmetric crystal structure.

PubMed

Carnicom, Elizabeth M; Xie, Weiwei; Klimczuk, Tomasz; Lin, Jingjing; Górnicka, Karolina; Sobczak, Zuzanna; Ong, Nai Phuan; Cava, Robert J

2018-05-01

It is a fundamental truth in solid compounds that the physical properties follow the symmetry of the crystal structure. Nowhere is the effect of symmetry more pronounced than in the electronic and magnetic properties of materials-even the projection of the bulk crystal symmetry onto different crystal faces is known to have a substantial impact on the surface electronic states. The effect of bulk crystal symmetry on the properties of superconductors is widely appreciated, although its study presents substantial challenges. The effect of a lack of a center of symmetry in a crystal structure, for example, has long been understood to necessitate that the wave function of the collective electron state that gives rise to superconductivity has to be more complex than usual. However, few nonhypothetical materials, if any, have actually been proven to display exotic superconducting properties as a result. We introduce two new superconductors that in addition to having noncentrosymmetric crystal structures also have chiral crystal structures. Because the wave function of electrons in solids is particularly sensitive to the host material's symmetry, crystal structure chirality is expected to have a substantial effect on their superconducting wave functions. Our two experimentally obtained chiral noncentrosymmetric superconducting materials have transition temperatures to superconductivity that are easily experimentally accessible, and our basic property characterization suggests that their superconducting properties may be unusual. We propose that their study may allow for a more in-depth understanding of how chirality influences the properties of superconductors and devices that incorporate them.

Observation of Dirac-like energy band and ring-torus Fermi surface associated with the nodal line in topological insulator CaAgAs

NASA Astrophysics Data System (ADS)

Takane, Daichi; Nakayama, Kosuke; Souma, Seigo; Wada, Taichi; Okamoto, Yoshihiko; Takenaka, Koshi; Yamakawa, Youichi; Yamakage, Ai; Mitsuhashi, Taichi; Horiba, Koji; Kumigashira, Hiroshi; Takahashi, Takashi; Sato, Takafumi

2018-01-01

One of key challenges in current material research is to search for new topological materials with inverted bulk-band structure. In topological insulators, the band inversion caused by strong spin-orbit coupling leads to opening of a band gap in the entire Brillouin zone, whereas an additional crystal symmetry such as point-group and nonsymmorphic symmetries sometimes prohibits the gap opening at/on specific points or line in momentum space, giving rise to topological semimetals. Despite many theoretical predictions of topological insulators/semimetals associated with such crystal symmetries, the experimental realization is still relatively scarce. Here, using angle-resolved photoemission spectroscopy with bulk-sensitive soft-x-ray photons, we experimentally demonstrate that hexagonal pnictide CaAgAs belongs to a new family of topological insulators characterized by the inverted band structure and the mirror reflection symmetry of crystal. We have established the bulk valence-band structure in three-dimensional Brillouin zone, and observed the Dirac-like energy band and ring-torus Fermi surface associated with the line node, where bulk valence and conducting bands cross on a line in the momentum space under negligible spin-orbit coupling. Intriguingly, we found that no other bands cross the Fermi level and therefore the low-energy excitations are solely characterized by the Dirac-like band. CaAgAs provides an excellent platform to study the interplay among low-energy electron dynamics, crystal symmetry, and exotic topological properties.

Magnetic properties of GdMnO3 nanoparticles embedded in mesoporous silica

NASA Astrophysics Data System (ADS)

Tajiri, Takayuki; Mito, Masaki; Deguchi, Hiroyuki; Kohno, Atsushi

2018-05-01

Perovskite manganite GdMnO3 nanoparticles were synthesized using mesoporous silica as a template, and their magnetic properties and crystal structure were investigated. Powder X-ray diffraction data indicated successful synthesis of the GdMnO3 nanoparticles, with mean particle sizes of 13.9 and 20.9 nm. The lattice constants for the nanoparticles were slightly different from those for the bulk material and varied with the particle size. The magnetic transition temperatures for the nanoparticles were higher than those of the bulk crystal. The synthesized GdMnO3 nanoparticles exhibited superparamagnetic behaviors: The blocking temperature, coercive field, and transition temperature depended on the particle size. Magnetic measurements and crystal structure analysis suggest that the changes in the magnetic properties for GdMnO3 nanoparticles can be attributed to the modulation of the crystallographic structure.

Hydrostatic Compression of 2,4,6,8,10,12 hexanitrohexaaza isowurtzitane (CL20) Co Crystals

DTIC Science & Technology

2016-12-01

crystal with analyses of the unit cell volume, band structure , elastic coefficients, and optical absorption Approved for public release...studied and for each system the high pressure (to 50 GPa) unit cell parameters, bulk modulus, and estimates of the shock, particle, and sound ...List of Figures Fig. 1 Experimental unit cell structures of ε-CL20 and co-crystals. For each structure , the CL20 molecules are red and the guest

High pressure high temperature devitrification of Fe78B13Si9 metallic glass with simultaneous x-ray structural characterization

NASA Astrophysics Data System (ADS)

Stemshorn, Andrew K.; Vohra, Yogesh K.; Smith, Spencer J.

2018-06-01

Changes in bulk crystallization behavior following devitrification at high pressure are investigated for a Fe78B13Si9 composition metallic glass using in-situ energy dispersive x-ray powder diffraction. Crystallization with time was evaluated for a series of measurements to a maximum pressure of 5.63 ± 0.15 GPa for the Fe78B13Si9 glass. Pressure was found to strongly affect onset bulk crystallization temperature Tx. Crystallization at each pressure was found to progress in two stages. In the first stage, α-Fe precipitates and in the second Fe2B forms while α-Fe continues to crystallize. Complementary high pressure room temperature studies were conducted.

X-ray structural investigation of nonsymmetrically and symmetrically alkylated [1]benzothieno[3,2-b]benzothiophene derivatives in bulk and thin films.

PubMed

Gbabode, Gabin; Dohr, Michael; Niebel, Claude; Balandier, Jean-Yves; Ruzié, Christian; Négrier, Philippe; Mondieig, Denise; Geerts, Yves H; Resel, Roland; Sferrazza, Michele

2014-08-27

A detailed structural study of the bulk and thin film phases observed for two potential high-performance organic semiconductors has been carried out. The molecules are based on [1]benzothieno[3,2-b]benzothiophene (BTBT) as conjugated core and octyl side groups, which are anchored either symmetrically at both sides of the BTBT core (C8-BTBT-C8) or nonsymmetrically at one side only (C8-BTBT). Thin films of different thickness (8-85 nm) have been prepared by spin-coating for both systems and analyzed by combining specular and grazing incidence X-ray diffraction. In the case of C8-BTBT-C8, the known crystal structure obtained from single-crystal investigations is observed within all thin films, down to a film thickness of 9 nm. In the case of C8-BTBT, the crystal structure of the bulk phase has been determined from X-ray powder diffraction data with a consistent matching of experimental and calculated X-ray diffraction patterns (Rwp = 5.8%). The packing arrangement of C8-BTBT is similar to that of C8-BTBT-C8, that is, consisting of a lamellar structure with molecules arranged in a "herringbone" fashion, yet with lamellae composed of two head-to-head (or tail-to-tail as the structure is periodic) superimposed molecules instead of only one molecule for C8-BTBT-C8. As for C8-BTBT-C8, we demonstrate that the same phase is observed in bulk and thin films for C8-BTBT whatever the film thickness investigated.

Preparation, glass forming ability, crystallization and deformation of (zirconium, hafnium)-copper-nickel-aluminum-titanium-based bulk metallic glasses

NASA Astrophysics Data System (ADS)

Gu, Xiaofeng

Multicomponent Zr-based bulk metallic glasses are the most promising metallic glass forming systems. They exhibit great glass forming ability and fascinating mechanical properties, and thus are considered as potential structural materials. One potential application is that they could be replacements of the depleted uranium for making kinetic energy armor-piercing projectiles, but the density of existing Zr-based alloys is too low for this application. Based on the chemical and crystallographic similarities between Zr and Hf, we have developed two series of bulk metallic glasses with compositions of (HfxZr1-x) 52.5Cu17.9Ni14.6Al10Ti5 and (HfxZr1-x) 57Cu20Ni8Al10Ti5 ( x = 0--1) by gradually replacing Zr by Hf. Remarkably increased density and improved mechanical properties have been achieved in these alloys. In these glasses, Hf and Zr play an interchangeable role in determining the short range order. Although the glass forming ability decreases continuously with Hf addition, most of these alloys remain bulk glass-forming. Recently, nanocomposites produced from bulk metallic glasses have attracted wide attention due to improved mechanical properties. However, their crystalline microstructure (the grain size and the crystalline volume fraction) has to be optimized. We have investigated crystallization of (Zr, Hf)-based bulk metallic glasses, including the composition dependence of crystallization paths and crystallization mechanisms. Our results indicate that the formation of high number density nanocomposites from bulk metallic glasses can be attributed to easy nucleation and slowing-down growth processes, while the multistage crystallization behavior makes it more convenient to control the microstructure evolution. Metallic glasses are known to exhibit unique plastic deformation behavior. At low temperature and high stress, plastic flow is localized in narrow shear bands. Macroscopic investigations of shear bands (e.g., chemical etching) suggest that the internal structure of shear bands is different from that of undeformed surroundings, but the direct structural characterization of shear bands down to the atomic level has been lacking. In this work, we have used transmission electron microscopy to explore the structural and chemical changes inside the shear bands. Nanometer-scale defects (void-like and high density regions) have been identified as a result of plastic deformation. It is these defects that distinguish shear bands from undeformed regions. Processes occurring in an active shear band and after stress removal are analogous to a thermally activated relaxation except that the relaxation time is much shorter in the former case.

Crystallization Behavior of A Bulk Amorphous Mg62Cu26Y12 Alloy

NASA Astrophysics Data System (ADS)

Wu, Shyue-Sheng; Chin, Tsung-Shune; Su, Kuo-Chang

1994-07-01

The crystallization temperature, the associated activation energy and the crystallized structure of a bulk amorphous Mg62Cu26Y12 alloy with a diameter of 2.5 mm were studied. It possesses a one-step crystallization behavior. The crystallization reaction was found to be represented by: AM(MG62Cu26Y12)→Mg2Cu+MgY+CuY+Mg, ( Tx=188°C, Eac=134 kJ/mol) where AM represents the amorphous state, T x the crystallization temperature at an infinitesimal heating rate, and E ac the associated activation energy. The amount of crystalline phases were found to be Mg2Cu:MgY:CuY=76:17:7. The Mg phase is identifiable only by high resolution electron microscopy, not by X-ray diffraction. The crystallization leads to a sharp rise in electrical resistivity which is reversed to those of iron-based amorphous alloys.

Protein-Precipitant-Specific Criteria for the Impact of Reduced Gravity on Crystal Perfection

NASA Technical Reports Server (NTRS)

Vekilov, Peter G.; Witherow, W. (Technical Monitor)

2003-01-01

The objective of this research is to provide quantitative criteria for the impact of reduced or enhanced convective transport on protein crystal perfection. Our earlier work strongly suggests that the magnitude of (lattice defect-inducing) fluctuations in the crystallization rate of proteins arise from the coupling of bulk transport and nonlinear interface kinetics. Hence, we surmised that, depending on the relative weight of bulk transport and interface kinetics in the control of the crystallization process on Earth, these fluctuations can either increase or decrease under reduced gravity conditions. The sign and magnitude of these changes depend on the specific protein-precipitant system. As a consequence, space environments can be either beneficial or detrimental for achieving structural perfection in protein crystals. The task objectives consist in systematic investigations of this hypothesis.

Enabling Earth-Abundant Pyrite (FeS2) Semiconductor Nanostructures for High Performance Photovoltaic Devices

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

Jin, Song

2014-11-18

This project seeks to develop nanostructures of iron pyrite, an earth-abundant semiconductor, to enable their applications in high-performance photovoltaic (PV) devices. Growth of high purity iron pyrite nanostructures (nanowires, nanorods, and nanoplates), as well as iron pyrite thin films and single crystals, has been developed and their structures characterized. These structures have been fundamentally investigated to understand the origin of the low solar energy conversion efficiency of iron pyrite and various passivation strategies and doping approaches have been explored in order to improve it. By taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we fullymore » characterized both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices and show that pyrite is n-type in the bulk and p-type near the surface due to strong inversion, which has important consequences to using nanocrystalline pyrite for efficient solar energy conversion. Furthermore, through a comprehensive investigation on n-type iron pyrite single crystals, we found the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a non-constant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explains the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings suggest new ideas on how to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films to enable them for high performance solar applications.« less

Importance of uniaxial compression for the appearance of superconductivity in NdO1-xFxBiS2

NASA Astrophysics Data System (ADS)

A, Omachi; T, Hiroi; J, Kajitani; O, Miura; Y, Mizuguchi

2014-05-01

We have investigated the crystal structure and superconducting properties of the new layered superconductor NdO1-xFxBiS2. Bulk superconductivity with a Tc above 4.5 K was observed. It was found that the Tc depended on both F concentration and crystal structure. Uniaxial compression along the c axis upon F substitution seemed to be linked with the appearance of bulk superconductivity. Furthermore, we considered that a higher Tc can be achieved when the c/a parameter was optimized in the NdO1-xFxBiS2 system.

Self-assembled ordered structures in thin films of HAT5 discotic liquid crystal.

PubMed

Morales, Piero; Lagerwall, Jan; Vacca, Paolo; Laschat, Sabine; Scalia, Giusy

2010-05-20

Thin films of the discotic liquid crystal hexapentyloxytriphenylene (HAT5), prepared from solution via casting or spin-coating, were investigated by atomic force microscopy and polarizing optical microscopy, revealing large-scale ordered structures substantially different from those typically observed in standard samples of the same material. Thin and very long fibrils of planar-aligned liquid crystal were found, possibly formed as a result of an intermediate lyotropic nematic state arising during the solvent evaporation process. Moreover, in sufficiently thin films the crystallization seems to be suppressed, extending the uniform order of the liquid crystal phase down to room temperature. This should be compared to the bulk situation, where the same material crystallizes into a polymorphic structure at 68 °C.

Crystal growth and optical properties of 4-aminobenzophenone (ABP)

NASA Astrophysics Data System (ADS)

Li, Zhengdong; Wu, Baichang; Su, Genbo; Huang, Gongfan

1997-02-01

Bulk crystals of 4-aminobenzophenone (ABP) were grown from organic solution. The crystal structure was determined by X-ray analysis. The refractive indices were determined by the method of prism minimum deviation. Some effective nonlinear-optical coefficients deff were measured. A blue second-harmonic emission with wavelengths of 433 and 460 nm were observed during laser diode pumping.

Fluid Physics and Macromolecular Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Pusey, M.; Snell, E.; Judge, R.; Chayen, N.; Boggon, T.; Helliwell, J.; Rose, M. Franklin (Technical Monitor)

2000-01-01

The molecular structure of biological macromolecules is important in understanding how these molecules work and has direct application to rational drug design for new medicines and for the improvement and development of industrial enzymes. In order to obtain the molecular structure, large, well formed, single macromolecule crystals are required. The growth of macromolecule crystals is a difficult task and is often hampered on the ground by fluid flows that result from the interaction of gravity with the crystal growth process. One such effect is the bulk movement of the crystal through the fluid due to sedimentation. A second is buoyancy driven convection close to the crystal surface. On the ground the crystallization process itself induces both of these flows.

Optical characteristics of novel bulk and nanoengineered laser host materials

NASA Astrophysics Data System (ADS)

Prasad, Narasimha S.; Sova, Stacey; Kelly, Lisa; Bevan, Talon; Arnold, Bradley; Cooper, Christopher; Choa, Fow-Sen; Singh, N. B.

2018-02-01

The hexagonal apatite single crystals have been investigated for their applications as laser host materials. Czochralksi and flux growth methods have been utilized to obtain single crystals. For low temperature processing (<100 0C), several techniques for crystal growth have been developed. The hexagonal apatite structure (space group P63/m) is characteristic of several compounds, some of which have extremely interesting and useful properties as laser hosts and bone materials. Calcium lanthanum silicate (Nd-doped) and lanthanum aluminate material systems were studied in detail. Nanoengineered calcium and lanthanum based silicates were synthesized by a solution method and their optical and morphological characteristics were compared with Czochralski grown bulk hydroxyapatite single crystals. Materials were evaluated by absorbance, fluorescence and Raman characteristics. Neodymium, iron and chromium doped crystals grown by a solution method showed weak but similar optical properties to that of Czochralski grown single crystals.

Specific features of the structural and magnetic states of a Zn1 - x Ni x Se crystal ( x = 0.0025) at low temperatures

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Teploukhov, S. G.; Gruzdev, N. B.

2008-12-01

The magnetic state and the structure of a Zn1 - x Ni x Se ( x = 0.0025) bulk crystal were studied at low temperatures. It is revealed that the magnetic and crystal structures below T ≅ 15 K are dependent on the cooling rate of this dilute semiconductor. For example, on fast cooling to 4.2 K, about 10% hexagonal ferromagnetic phase is formed in the crystal. During heating, the phase disappears at T ≅ 15 K. The results obtained are discussed with allowance for the specific features of the Jahn-Teller distortions in this compound.

Effect of solvents on the bulk growth of 4-aminobenzophenone single crystals: A potential material for blue and green lasers

NASA Astrophysics Data System (ADS)

Natarajan, V.; Usharani, S.; Arivanandhan, M.; Anandan, P.; Hayakawa, Y.

2015-06-01

Although 4-aminobenzophenone (4-ABP) is the best derivative of benzophenone with 260 times higher second harmonic generation (SHG) efficiency than potassium dihydrogen phosphate (KDP), growth of high quality bulk crystal still remains a difficult task. In the present work, the effect of solvents on solubility and growth aspects of 4-ABP was investigated to grow inclusion free 4-ABP crystals. The growth processes were discussed based on solute-solvent interaction in two different growth media of ethyl acetate and ethanol. The growth rate and thereby solvent inclusions are relatively higher in ethyl acetate grown crystal than the crystal grown from ethanol. The structural, thermal and optical properties of 4-ABP crystals were studied. The enthalpy of 4-ABP melting process was estimated from differential thermal analysis. The optical transmission study shows that 4-ABP crystals grown from ethanol has high transparency compared to ethyl acetate grown sample due to solvent inclusion in the later crystal.

Protein Crystallization: Specific Phenomena and General Insights on Crystallization Kinetics

NASA Technical Reports Server (NTRS)

Rosenberger, F.

1998-01-01

Experimental and simulation studies of the nucleation and growth kinetics of proteins have revealed phenomena that are specific for macromolecular crystallization, and others that provide a more detailed understanding of solution crystallization in general. The more specific phenomena, which include metastable liquid-liquid phase separations and gelation prior to solid nucleation, are due to the small ratio of the intermolecular interaction-range to the size of molecules involved. The apparently more generally applicable mechanisms include the cascade-like formation of macrosteps, as an intrinsic morphological instability that roots in the coupled bulk transport and nonlinear interface kinetics in systems with mixed growth rate control. Analyses of this nonlinear response provide (a) criteria for the choice of bulk transport conditions to minimize structural defect formation, and (b) indications that the "slow" protein crystallization kinetics stems from the mutual retardation of growth steps.

Hydration water and bulk water in proteins have distinct properties in radial distributions calculated from 105 atomic resolution crystal structures.

PubMed

Chen, Xianfeng; Weber, Irene; Harrison, Robert W

2008-09-25

Water plays a critical role in the structure and function of proteins, although the experimental properties of water around protein structures are not well understood. The water can be classified by the separation from the protein surface into bulk water and hydration water. Hydration water interacts closely with the protein and contributes to protein folding, stability, and dynamics, as well as interacting with the bulk water. Water potential functions are often parametrized to fit bulk water properties because of the limited experimental data for hydration water. Therefore, the structural and energetic properties of the hydration water were assessed for 105 atomic resolution (

Intrinsic Topological Insulator Bi1.5Sb0.5Te3-xSex Thin Crystals

NASA Astrophysics Data System (ADS)

Wang, Wei; Li, Li; Zou, Wenqin; He, Liang; Song, Fengqi; Zhang, Rong; Wu, Xiaoshan; Zhang, Fengming

2015-01-01

The quaternary topological insulator (Bi,Sb)2(Te,Se)3 has demonstrated topological surface states with an insulating bulk. Scientists have identified an optimized composition of Bi1.5Sb0.5Te1.7Se1.3 with the highest resistivity reported. But the physics that drive to this composition remains unclear. Here we report the crystal structure and the magneto-transport properties of Bi1.5Sb0.5Te3-xSex (BSTS) series. A correlation between the structure and the physical properties has been revealed. We found out that within the rhombohedral structure, the composition with most Te substituting Se has the highest resistivity. On the other hand, segregation of other composition phases will introduce much higher bulk concentration.

Anisotropy of atomic bonds formed by p-type dopants in bulk GaN crystals

NASA Astrophysics Data System (ADS)

Lawniczak-Jablonska, K.; Suski, T.; Gorczyca, I.; Christensen, N. E.; Libera, J.; Kachniarz, J.; Lagarde, P.; Cortes, R.; Grzegory, I.

The anisotropy of atomic bonds formed by acceptor dopants with nitrogen in bulk wurtzite GaN crystals was studied by means of linearly polarized synchrotron radiation used in measurements of X-ray-absorption spectra for the K-edgeof Mg and Zn dopants. These spectra correspond to i) a single acceptor N bond along the c-axis and ii) three bonds realized with N atoms occupying the ab-plane perpendicular to the c-axis. The Zn dopant formed resonant spectra similar to that characteristic for Ga cations. In the case of the Mg dopant, similarity to Ga cations was observed for triple bonds in the ab-plane, only. Practically no resonant structure for spectra detected along the c-axis was observed. The absorption spectra were compared with ab initio calculations using the full-potential linear muffin-tin-orbital method. These calculations were also used for determination of the bond length for Mg-N and Zn-N in wurtzite GaN crystals and show that introducing dopants causes an increase of the lengths of the bonds formed by both dopants. Extended X-ray-absorption fine-structure measurements performed for bulk GaN:Zn confirmed the prediction of the theory in the case of the Zn-N bond. Finally, it is suggested that the anisotropy in the length of the Mg-N bonds, related to their larger strength in the case of bonds in the ab-plane, can explain preferential formation of a superlattice consisting of Mg-rich layers arranged in ab-planes of several bulk GaN:Mg crystals observed by transmission electron microscopy. Within the sensitivity of the method used, no parasitic metallic clusters or oxide compounds formed by the considered acceptors in GaN crystals were found.

The influence of growth environment on the crystallization of nortriptyline hydrochloride, a tricyclic antidepressant

NASA Astrophysics Data System (ADS)

MacCalman, M. L.; Roberts, K. J.; Hendriksen, B. A.

1993-03-01

The preparation of the nortriptyline hydrochloride, an important pharmaceutical product, by crystallization from both alcohol and aqueous solutions is presented. At low temperatures this material shows a higher solubility in absolute alcohol compared to aqueous solutions in a trend which reverses at higher temperatures. Examination of crystals prepared from alcohol solutions reveal essentially a needle-like crystal habit which is in excellent agreement with morphological predictions based on the bulk crystallographic structure. In contrast crystals prepared from aqueous solution at high temperatures reveal a particulate structure dominated by heavily agglomerated crystallites with plate-like morphology. When this material is crystallized at the lower temperatures, where the solubility curve is steep, X-ray and thermal analysis appear to show that crystallization results in a new polymorphic structure associated with a less agglomerated product.

Fabrication of patterned single-crystal SrTiO3 thin films by ion slicing and anodic bonding

NASA Astrophysics Data System (ADS)

Lee, Yoo Seung; Djukic, Djordje; Roth, Ryan M.; Laibowitz, Robert; Izuhara, Tomoyuki; Osgood, Richard M.; Bakhru, Sasha; Bakhru, Hassaram; Si, Weidong; Welch, David

2006-09-01

A new technique for directly fabricating patterned thin films (<1μm thick) of fully single-crystal strontium titanate uses deep H+ implantation into the oxide sample, followed by anodic bonding of the sample to a Pyrex or Pyrex-on-Si substrate. The dielectric properties and crystal structure of such thin films are characterized and are found to be essentially those of the bulk single crystal.

Determination of bulk domain structure and magnetization processes in bcc ferromagnetic alloys: Analysis of magnetostriction in F e83G a17

NASA Astrophysics Data System (ADS)

He, Yangkun; Coey, J. M. D.; Schaefer, Rudolf; Jiang, Chengbao

2018-01-01

The ground state of macroscopic samples of magnetically ordered materials is a domain state because of magnetostatic energy or entropy, yet we have limited experimental means for imaging the bulk domain structure and the magnetization process directly. The common methods available reveal the domains at the surface or in electron- or x-ray transparent lamellae, not those in the bulk. The magnetization curve just reflects the vector sum of the moments of all the domains in the sample, but magnetostriction curves are more informative. They are strongly influenced by the domain structure in the unmagnetized state and its evolution during the magnetization process in an applied field. Here we report a method of determining the bulk domain structure in a cubic magnetostrictive material by combining magneto-optic Kerr microscopy with magnetostriction and magnetization measurements on single crystals as a function of applied field. We analyze the magnetostriction of F e83G a17 crystals in terms of a domain structure that is greatly influenced by sample shape and heat treatment. Saturation magnetostriction measurements are used to determine the fraction of domains orientated along the three 〈100 〉 axes in the initial state. Domain wall motion and rotation process have characteristic signatures in the magnetostriction curves, including those associated with the Δ E effect and domain rotation through a 〈110 〉 auxetic direction.

Development and photoelectric properties of In/p-Ag{sub 3}AsS{sub 3} surface-barrier structures

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

Rud', V. Yu., E-mail: rudvas@spbstu.ru; Rud', Yu. V.; Terukov, E. I.

2010-08-15

Homogeneous p-Ag{sub 3}AsS{sub 3} bulk single crystals with rhombic structure have been grown by planar crystallization from melts with atomic composition corresponding to this ternary compound. Photosensitive surface-barrier structures based on the interface between the surface of these crystals and thin films of pure indium are fabricated for the first time. The photosensitivity of fabricated structures is studied in natural and linearly polarized light. Photosensitivity spectra of In/p-Ag{sub 3}AsS{sub 3} structures are measured for the first time and used to determine the nature and energy of interband transitions in p-Ag{sub 3}AsS{sub 3} crystals. The phenomenon of natural photopleochroism is studiedmore » for surface-barrier structures grown on oriented p-Ag{sub 3}AsS{sub 3} single crystals. It is concluded that Ag{sub 3}AsS{sub 3} single crystals can be used in photoconverters of natural and linearly polarized light.« less

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

Todt, Michael A.; Isenberg, Allan E.; Nanayakkara, Sanjini U.

Semiconducting transition-metal dichalcogenide (TMD) nanoflake thin films are promising large-area electrodes for photo-electrochemical solar energy conversion applications. However, their energy conversion efficiencies are typically much lower than those of bulk electrodes. It is unclear to what extent this efficiency gap stems from differences among nanoflakes (e.g., area, thickness, and surface structural features). It is also unclear whether individual exfoliated nanoflakes can achieve energy conversion efficiencies similar to those of bulk crystals. Here, we use a single-nanoflake photo-electrochemical approach to show that there are both highly active and completely inactive nanoflakes within a film. For the exfoliated MoSe 2 samples studiedmore » herein, 7% of nanoflakes are highly active champions, whose photocurrent efficiency exceeds that of the bulk crystal. However, 66% of nanoflakes are inactive spectators, which are mostly responsible for the overall lower photocurrent efficiency compared to the bulk crystal. The photocurrent collection efficiency increases with nanoflake area and decreases more at perimeter edges than at interior step edges. These observations, which are hidden in ensemble-level measurements, reveal the underlying performance issues of exfoliated TMD electrodes for photo-electrochemical energy conversion applications.« less

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

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

Kumah, D. P.; Dogan, M.; Ngai, J. H.

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered Unique Elastic Modes at a BaTiO 3 / ( 2 × 1 ) - Ge ( 001 ) Interface

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

Kumah, D. P.; Dogan, M.; Ngai, J. H.

The strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO3. While the complex crystal structure is predicted using first-principles theory, it is further shown that the details of themore » structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO3 induced by the symmetry of forces exerted by the germanium substrate.« less

Engineered unique elastic modes at a BaTiO 3/2x1-Ge(001) interface

DOE PAGES

Kumah, D. P.; Dogan, M.; Ngai, J. H.; ...

2016-03-07

Here, the strong interaction at an interface between a substrate and thin film leads to epitaxy and provides a means of inducing structural changes in the epitaxial film. These induced material phases often exhibit technologically relevant electronic, magnetic, and functional properties. The 2×1 surface of a Ge(001) substrate applies a unique type of epitaxial constraint on thin films of the perovskite oxide BaTiO 3 where a change in bonding and symmetry at the interface leads to a non-bulk-like crystal structure of the BaTiO 3. While the complex crystal structure is predicted using first-principles theory, it is further shown that themore » details of the structure are a consequence of hidden phases found in the bulk elastic response of the BaTiO 3 induced by the symmetry of forces exerted by the germanium substrate.« less

Preparation and magnetic properties of nickel nanowires by reduction in ethylene glycol medium under the influence of magnetic field

NASA Astrophysics Data System (ADS)

Sun, Wanshuo; Cheng, Junsheng; Li, Lankai; Chen, Shunzhong; Chang, Kun

2017-01-01

Nickel nanowires have successfully been fabricated through a simple liquid reduction in ethylene glycol medium with a 0.3T magnetic field applied. The effect of uniform magnetic field and solvent on the morphology and the crystal structure of magnetic nickel were studied. Scanning electron microscope images and transmission electron scope images s how that the effect of the external magnetic field on the morphology of nickel nanowires. X-ray diffraction shows the crystal structure of as-prepared products. And a energy disperse spectroscopy and a vibrating sample magnetometer are used to analyze the composition and static magnetic properties. The results show that the straight wires with an average diameter of about 100 nm and a length of several microns were obtained and mainly composed by fcc structure in the solvent of ethylene glycol. Magnetic measurements show that the saturation magnetization of the as-obtained products in a 0.3 T external magnetic field is 36 emu/g, less than that of bulk nickel crystal, and the coercivity of them is 186 emu/g, larger than that of bulk crystal with the mole ratio of sodium borohydride to nickel sulfate is 1:1000. This kind of nanowires array has potential applications with the special one-dimensional structures.

Structure and transport in organic semiconductor thin films

NASA Astrophysics Data System (ADS)

Vos, Sandra Elizabeth Fritz

Organic Semiconductors represent an exciting area of research due to their potential application in cheap and flexible electronics. In spite of the abundant interest in organic electronics the electronic transport mechanism remains poorly understood. Understanding the connection between molecular structure, crystal packing, intermolecular interactions and electronic delocalization is an important aspect of improving the transport properties of organics in thin film transistors (TFTs). In an organic thin film transistor, charge carrier transport is believed to occur within the first few monolayers of the organic material adjacent to the dielectric. It is therefore critical to understand the initial stages of film growth and molecular structure in these first few layers and relate this structure to electronic transport properties. The structure of organic films at the interface with an amorphous silicon dioxide ( a-SiO2) dielectric and how structure relates to transport in a TFT is the focus of this thesis. Pentacene films on a-SiO2 were extensively characterized with specular and in-plane X-ray diffraction, and CuKalpha1, and synchrotron radiation. The first layer of pentacene molecules adjacent to the a-SiO2 crystallized in a rectangular unit cell with the long axis of the molecules perpendicular to the substrate surface. Subsequent layers of pentacene crystallized in a slightly oblique in-plane unit cell that evolved as thickness was increased. The rectangular monolayer phase of pentacene did not persist when subsequent layers were deposited. Specular diffraction with Synchrotron radiation of a 160 A pentacene film (˜ 10 layers) revealed growth initiation of a bulk-like phase and persistence of the thin-film phase. Pentacene molecules were more tilted in the bulk-like phase and the in-plane unit cell was slightly more oblique. Pentacene grains began to grow randomly oriented with respect to the substrate surface (out-of-plane) in films near 650 A in thickness. The single crystal bulk phase of pentacene was observed from specular diffraction (CuKalpha1) of a 2.5 mum film. These results suggest that the thickness of pentacene films on a-SiO2 is an important aspect in the comparison of crystal structure and electronic transport.

Effect of Polyelectrolyte and Fatty Acid Soap on the Formation of CaCO3 in the Bulk and the Deposit on Hard Surfaces.

PubMed

Wang, Hao; Alfredsson, Viveka; Tropsch, Juergen; Ettl, Roland; Nylander, Tommy

2015-09-30

The effects of sodium polyacrylate (NaPAA) as well as potassium oleate on the nucleation and calcium carbonate crystal growth on hard surfaces, i.e., stainless steel and silica, have been investigated at different temperatures. The relation between the surface deposition and the corresponding bulk processes has been revealed by combining dynamic light scattering (DLS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and ellipsometry. The aim was to further our understanding of the crystal deposition/growth mechanism and how it can be controlled by the presence of polyelectrolytes (NaPAA) or soap (potassium oleate). The addition of polyelectrolytes (NaPAA) or soap (potassium oleate) decreases the size of CaCO3 particles in bulk solution and affects both crystal structure and morphology in the bulk as well as on hard surfaces. The amount of particles on hard surfaces decreases significantly in the presence of both potassium oleate and NaPAA. This was found to be a consequence of potassium oleate or NaPAA adsorption on the hard surface as well as on the CaCO3 crystal surfaces. Here, the polymer NaPAA exhibited a stronger inhibition effect on the formation and growth of CaCO3 particles than potassium oleate.

Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

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

Bykova, E., E-mail: elena.bykova@uni-bayreuth.de; Laboratory of Crystallography, University of Bayreuth, D-95440 Bayreuth; Gou, H.

2015-10-15

We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for highmore » bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.« less

Friction stir welding of Zr-based bulk metallic glass

NASA Astrophysics Data System (ADS)

Ji, Y. S.; Fujii, H.; Maeda, M.; Nakata, K.; Kimura, H.; Inoue, A.; Nogi, K.

2009-05-01

A Zr55Cu30Al10Ni5 bulk metallic glass plate was successfully welded below its crystallization temperature by friction stir welding. The flash formation and heat concentration at the shoulder edge was minimized using a wider tool and the angle of the recessed shoulder surface was 3°. To analyze the crystallization of the base material and stir zone, the microstructure and mechanical properties were analyzed using DSC, XRD, TEM, and micro-hardness. As a result, it was found that the amorphous structure and original mechanical properties were maintained in the whole joints.

Laser generation in opal-like single-crystal and heterostructure photonic crystals

NASA Astrophysics Data System (ADS)

Kuchyanov, A. S.; Plekhanov, A. I.

2016-11-01

This study describes the laser generation of a 6Zh rhodamine in artificial opals representing single-crystal and heterostructure films. The spectral and angular properties of emission and the threshold characteristics of generation are investigated. In the case where the 6Zh rhodamine was in a bulk opal, the so-called random laser generation was observed. In contrast to this, the laser generation caused by a distributed feedback inside the structure of the photonic bandgap was observed in photonic-crystal opal films.

Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

PubMed

Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

2017-03-01

A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductivity of laser printed copper structures limited by nano-crystal grain size and amorphous metal droplet shell

NASA Astrophysics Data System (ADS)

Winter, Shoshana; Zenou, Michael; Kotler, Zvi

2016-04-01

We present a study of the morphology and electrical properties of copper structures which are printed by laser induced forward transfer from bulk copper. The percentage of voids and the oxidation levels are too low to account for the high resistivities (~4 to 14 times the resistivity of bulk monocrystalline copper) of these structures. Transmission electron microscope (TEM) images of slices cut from the printed areas using a focused ion beam (FIB) show nano-sized crystal structures with grain sizes that are smaller than the electron free path length. Scattering from such grain boundaries causes a significant increase in the resistivity and can explain the measured resistivities of the structures. The TEM images also show a nano-amorphous layer (~5 nm) at the droplet boundaries which also contributes to the overall resistivity. Such morphological characteristics are best explained by the ultrafast cooling rate of the molten copper droplets during printing.

Three-dimensional phonon population anisotropy in silicon nanomembranes

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

McElhinny, Kyle M.; Gopalakrishnan, Gokul; Holt, Martin V.

Nanoscale single crystals possess modified phonon dispersions due to the truncation of the crystal. The introduction of surfaces alters the population of phonons relative to the bulk and introduces anisotropy arising from the breaking of translational symmetry. Such modifications exist throughout the Brillouin zone, even in structures with dimensions of several nanometers, posing a challenge to the characterization of vibrational properties and leading to uncertainty in predicting the thermal, optical, and electronic properties of nanomaterials. Synchrotron x-ray thermal diffuse scattering studies find that freestanding Si nanomembranes with thicknesses as large as 21 nm exhibit a higher scattering intensity per unitmore » thickness than bulk silicon. In addition, the anisotropy arising from the finite thickness of these membranes produces particularly intense scattering along reciprocal-space directions normal to the membrane surface compared to corresponding in-plane directions. These results reveal the dimensions at which calculations of materials properties and device characteristics based on bulk phonon dispersions require consideration of the nanoscale size of the crystal.« less

Experimental Observation of Bulk Liquid Water Structure in ``No Man's Land''

NASA Astrophysics Data System (ADS)

Sellberg, Jonas; McQueen, Trevor; Huang, Congcong; Loh, Duane; Laksmono, Hartawan; Sierra, Raymond; Hampton, Christina; Starodub, Dmitri; Deponte, Daniel; Martin, Andrew; Barty, Anton; Wikfeldt, Thor; Schlesinger, Daniel; Pettersson, Lars; Beye, Martin; Nordlund, Dennis; Weiss, Thomas; Feldkamp, Jan; Caronna, Chiara; Seibert, Marvin; Messerschmidt, Marc; Williams, Garth; Boutet, Sebastien; Bogan, Michael; Nilsson, Anders

2013-03-01

Experiments on pure bulk water below about 235 K have so far been difficult: water crystallization occurs very rapidly below the homogeneous nucleation temperature of 232 K and above 160 K, leading to a ``no man's land'' devoid of experimental results regarding the structure. Here, we demonstrate a new, general experimental approach to study the structure of liquid states at supercooled conditions below their limit of homogeneous nucleation. We use femtosecond x-ray pulses generated by the LCLS x-ray laser to probe evaporatively cooled droplets of supercooled bulk water and find experimental evidence for the existence of metastable bulk liquid water down to temperatures of 223 K in the previously largely unexplored ``no man's land''. We acknoweledge NSF (CHE-0809324), Office of Basic Energy Sciences, and the Swedish Research Council for financial support.

Segregation of liquid crystal mixtures in topological defects

DOE PAGES

Rahimi, Mohammad; Ramezani-Dakhel, Hadi; Zhang, Rui; ...

2017-04-28

The structure and physical properties of liquid crystal (LC) mixtures are a function of composition, and small changes can have pronounced effects on observables, such as phase-transition temperatures. Traditionally, LC mixtures have been assumed to be compositionally homogenous. The results of chemically detailed simulations presented here show that this is not the case; pronounced deviations of the local order from that observed in the bulk at defects and interfaces lead to significant compositional segregation effects. More specifically, two disclination lines are stabilized in this work by introducing into a nematic liquid crystal mixture a cylindrical body that exhibits perpendicular anchoring.more » Here, it is found that the local composition deviates considerably from that of the bulk at the interface with the cylinder and in the defects, thereby suggesting new assembly and synthetic strategies that may capitalize on the unusual molecular environment provided by liquid crystal mixtures.« less

Sn-doped Bi 1.1Sb 0.9Te 2S bulk crystal topological insulator with excellent properties

DOE PAGES

S. K. Kushwaha; Pletikosic, I.; Liang, T.; ...

2016-04-27

A long-standing issue in topological insulator research has been to find a bulk single crystal material that provides a high quality platform for characterizing topological surface states without interference from bulk electronic states. This material would ideally be a bulk insulator, have a surface state Dirac point energy well isolated from the bulk valence and conduction bands, display quantum oscillations from the surface state electrons, and be growable as large, high quality bulk single crystals. Here we show that this materials obstacle is overcome by bulk crystals of lightly Sn-doped Bi 1.1Sb 0.9Te 2S grown by the Vertical Bridgeman method.more » We characterize Sn-BSTS via angle-resolved photoemission spectroscopy, scanning tunneling microscopy, transport studies, X-ray diffraction, and Raman scattering. We present this material as a high quality topological insulator that can be reliably grown as bulk single crystals and thus studied by many researchers interested in topological surface states.« less

Nanocrystalline high-entropy alloy (CoCrFeNiAl 0.3 ) thin-film coating by magnetron sputtering

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

Liao, Weibing; Lan, Si; Gao, Libo

High-entropy CoCrFeNiAl0.3 alloy thin films were prepared by magnetron sputtering technique. The thin film surface was very smooth and homogeneous. The synchrotron X-ray experiment confirmed that (111) type of texture existed in the thin film, and the structure was face-centered cubic nanocrystals with a minor content of ordered NiAl-type body-centered cubic structures. Interestingly, the elastic modulus of the thin film was nearly the same to the bulk single-crystal counterpart, however, the nanohardness is about four times of the bulk single-crystal counterpart. It was found that the high hardness was due to the formation of nanocrystal structure inside the thin filmsmore » and the preferred growth orientation, which could be promising for applications in micro fabrication and advanced coating technologies.« less

Anisotropic high-harmonic generation in bulk crystals

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

You, Yong Sing; Reis, David A.; Ghimire, Shambhu

2016-11-21

The microscopic valence electron density determines the optical, electronic, structural and thermal properties of materials. However, current techniques for measuring this electron charge density are limited: for example, scanning tunnelling microscopy is confined to investigations at the surface, and electron diffraction requires very thin samples to avoid multiple scattering. Therefore, an optical method is desirable for measuring the valence charge density of bulk materials. Since the discovery of high-harmonic generation (HHG) in solids, there has been growing interest in using HHG to probe the electronic structure of solids. Here, using single-crystal MgO, we demonstrate that high-harmonic generation in solids ismore » sensitive to interatomic bonding. We find that harmonic efficiency is enhanced (diminished) for semi-classical electron trajectories that connect (avoid) neighbouring atomic sites in the crystal. Finally, these results indicate the possibility of using materials’ own electrons for retrieving the interatomic potential and thus the valence electron density, and perhaps even wavefunctions, in an all-optical setting.« less

Enhancing the Thermoelectric Figure of Merit by Low-Dimensional Electrical Transport in Phonon-Glass Crystals.

PubMed

Mi, Xue-Ya; Yu, Xiaoxiang; Yao, Kai-Lun; Huang, Xiaoming; Yang, Nuo; Lü, Jing-Tao

2015-08-12

Low-dimensional electronic and glassy phononic transport are two important ingredients of highly efficient thermoelectric materials, from which two branches of thermoelectric research have emerged. One focuses on controlling electronic transport in the low dimension, while the other focuses on multiscale phonon engineering in the bulk. Recent work has benefited much from combining these two approaches, e.g., phonon engineering in low-dimensional materials. Here we propose to employ the low-dimensional electronic structure in bulk phonon-glass crystals as an alternative way to increase the thermoelectric efficiency. Through first-principles electronic structure calculations and classical molecular dynamics simulations, we show that the π-π-stacking bis(dithienothiophene) molecular crystal is a natural candidate for such an approach. This is determined by the nature of its chemical bonding. Without any optimization of the material parameters, we obtained a maximum room-temperature figure of merit, ZT, of 1.48 at optimal doping, thus validating our idea.

Single-Nanoflake Photo-Electrochemistry Reveals Champion and Spectator Flakes in Exfoliated MoSe 2 Films

DOE PAGES

Todt, Michael A.; Isenberg, Allan E.; Nanayakkara, Sanjini U.; ...

2018-03-06

Semiconducting transition-metal dichalcogenide (TMD) nanoflake thin films are promising large-area electrodes for photo-electrochemical solar energy conversion applications. However, their energy conversion efficiencies are typically much lower than those of bulk electrodes. It is unclear to what extent this efficiency gap stems from differences among nanoflakes (e.g., area, thickness, and surface structural features). It is also unclear whether individual exfoliated nanoflakes can achieve energy conversion efficiencies similar to those of bulk crystals. Here, we use a single-nanoflake photo-electrochemical approach to show that there are both highly active and completely inactive nanoflakes within a film. For the exfoliated MoSe 2 samples studiedmore » herein, 7% of nanoflakes are highly active champions, whose photocurrent efficiency exceeds that of the bulk crystal. However, 66% of nanoflakes are inactive spectators, which are mostly responsible for the overall lower photocurrent efficiency compared to the bulk crystal. The photocurrent collection efficiency increases with nanoflake area and decreases more at perimeter edges than at interior step edges. These observations, which are hidden in ensemble-level measurements, reveal the underlying performance issues of exfoliated TMD electrodes for photo-electrochemical energy conversion applications.« less

ZnO for solar cell and thermoelectric applications

NASA Astrophysics Data System (ADS)

Zhou, Chuanle; Ghods, Amirhossein; Yunghans, Kelcy L.; Saravade, Vishal G.; Patel, Paresh V.; Jiang, Xiaodong; Kucukgok, Bahadir; Lu, Na; Ferguson, Ian

2017-03-01

ZnO-based materials show promise in energy harvesting applications, such as piezoelectric, photovoltaic and thermoelectric. In this work, ZnO-based vertical Schottky barrier solar cells were fabricated by MOCVD de- position of ZnO thin films on ITO back ohmic contact, while Ag served as the top Schottky contact. Various rapid thermal annealing conditions were studied to modify the carrier density and crystal quality. Greater than 200 nm thick ZnO films formed polycrystalline crystal structure, and were used to demonstrate Schottky solar cells. I-V characterizations of the devices showed photovoltaic performance, but but need further development. This is the first demonstration of vertical Schottky barrier solar cell based on wide bandgap ZnO film. Thin film and bulk ZnO grown by MOCVD or melt growth were also investigated in regards to their room- temperature thermoelectric properties. The Seebeck coefficient of bulk ZnO was found to be much larger than that of thin film ZnO at room temperature due to the higher crystal quality in bulk materials. The Seebeck coefficients decrease while the carrier concentration increases due to the crystal defects caused by the charge carriers. The co-doped bulk Zn0:96Ga0:02Al0:02O showed enhanced power factors, lower thermal conductivities and promising ZT values in the whole temperature range (300-1300 K).

Importance of the DNA “bond” in programmable nanoparticle crystallization

PubMed Central

Macfarlane, Robert J.; Thaner, Ryan V.; Brown, Keith A.; Zhang, Jian; Lee, Byeongdu; Nguyen, SonBinh T.; Mirkin, Chad A.

2014-01-01

If a solution of DNA-coated nanoparticles is allowed to crystallize, the thermodynamic structure can be predicted by a set of structural design rules analogous to Pauling’s rules for ionic crystallization. The details of the crystallization process, however, have proved more difficult to characterize as they depend on a complex interplay of many factors. Here, we report that this crystallization process is dictated by the individual DNA bonds and that the effect of changing structural or environmental conditions can be understood by considering the effect of these parameters on free oligonucleotides. Specifically, we observed the reorganization of nanoparticle superlattices using time-resolved synchrotron small-angle X-ray scattering in systems with different DNA sequences, salt concentrations, and densities of DNA linkers on the surface of the nanoparticles. The agreement between bulk crystallization and the behavior of free oligonucleotides may bear important consequences for constructing novel classes of crystals and incorporating new interparticle bonds in a rational manner. PMID:25298535

Snapshots of crystal growth: Nanoclusters of organic conductors on Au(111) surfaces

NASA Astrophysics Data System (ADS)

Schott, J. H.; Ward, M. D.

1994-06-01

Mono- and multilayer crystalline nanoclusters of tetra-hiafulvalene-tetracyanoquinodimethane ((TTF) (TCNO)), a low-dimensional organic conductor in the bulk form, can be formed readily on Au(111) surfaces by vapor phase sublimation under ambient conditions. Scanning tunneling microscopy of monolayer (TTF)(TCNQ) films reveals a two-dimensional density of states (DOS) that is consistent with the arrangement of TTF and TCNO molecules in the ac face of bulk (TTF)(TCNO), in which the molecular planes are nearly parallel to the Au(111) substrate. In contrast, clusters with thicknesses corresponding to two or three molecular layers exhibit a transformation to a highly anisotropic DOS that can be attributed to interlayer molecular overlap in segregated TTF and TCNQ molecular chains along the c-axis, which can be described as 'molecular wires'. The orientation of the crystalline (TTF)(TCNO) clusters is preserved throughout the crystal growth sequence, leading to meso- and macroscopic (TTF)(TCNO) needles that are oriented perpendicular to the Au(111) substrate. These studies provide visualization of crystal growth from the initial stages of nucleation to macroscopic crystals, and a revealing example of the changes in electronic structure that occur during the evolution of molecular (TTF)(TCNQ) nuclei into a bulk crystalline phase.

Fast surface crystallization of amorphous griseofulvin below T g.

PubMed

Zhu, Lei; Jona, Janan; Nagapudi, Karthik; Wu, Tian

2010-08-01

To study crystal growth rates of amorphous griseofulvin (GSF) below its glass transition temperature (T (g)) and the effect of surface crystallization on the overall crystallization kinetics of amorphous GSF. Amorphous GSF was generated by melt quenching. Surface and bulk crystal growth rates were determined using polarized light microscope. X-ray powder diffraction (XRPD) and Raman microscopy were used to identify the polymorph of the crystals. Crystallization kinetics of amorphous GSF powder stored at 40 degrees C (T (g)-48 degrees C) and room temperature (T (g)-66 degrees C) was monitored using XRPD. Crystal growth at the surface of amorphous GSF is 10- to 100-fold faster than that in the bulk. The surface crystal growth can be suppressed by an ultrathin gold coating. Below T (g), the crystallization of amorphous GSF powder was biphasic with a rapid initial crystallization stage dominated by the surface crystallization and a slow or suspended late stage controlled by the bulk crystallization. GSF exhibits the fastest surface crystallization kinetics among the known amorphous pharmaceutical solids. Well below T (g), surface crystallization dominated the overall crystallization kinetics of amorphous GSF powder. Thus, surface crystallization should be distinguished from bulk crystallization in studying, modeling and controlling the crystallization of amorphous solids.

Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals

NASA Astrophysics Data System (ADS)

Wang, Chunyang; Du, Kui; Song, Kepeng; Ye, Xinglong; Qi, Lu; He, Suyun; Tang, Daiming; Lu, Ning; Jin, Haijun; Li, Feng; Ye, Hengqiang

2018-05-01

Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15 ° ) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.

Ultrasound finite element simulation sensitivity to anisotropic titanium microstructures

NASA Astrophysics Data System (ADS)

Freed, Shaun; Blackshire, James L.; Na, Jeong K.

2016-02-01

Analytical wave models are inadequate to describe complex metallic microstructure interactions especially for near field anisotropic property effects and through geometric features smaller than the wavelength. In contrast, finite element ultrasound simulations inherently capture microstructure influences due to their reliance on material definitions rather than wave descriptions. To better understand and quantify heterogeneous crystal orientation effects to ultrasonic wave propagation, a finite element modeling case study has been performed with anisotropic titanium grain structures. A parameterized model has been developed utilizing anisotropic spheres within a bulk material. The resulting wave parameters are analyzed as functions of both wavelength and sphere to bulk crystal mismatch angle.

Fluid Physics and Macromolecular Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Pusey, M.; Snell, E.; Judge, R.; Chayen, N.; Boggon, T.

2000-01-01

The molecular structure of biological macromolecules is important in understanding how these molecules work and has direct application to rational drug design for new medicines and for the improvement and development of industrial enzymes. In order to obtain the molecular structure, large, well formed, single macromolecule crystals are required. The growth of macromolecule crystals is a difficult task and is often hampered on the ground by fluid flows that result from the interaction of gravity with the crystal growth process. One such effect is the bulk movement of the crystal through the fluid due to sedimentation. A second is buoyancy driven convection close to the crystal surface. On the ground the crystallization process itself induces both of these flows. Buoyancy driven convection results from density differences between the bulk solution and fluid close to the crystal surface which has been depleted of macromolecules due to crystal growth. Schlieren photograph of a growing lysozyme crystal illustrating a 'growth plume' resulting from buoyancy driven convection. Both sedimentation and buoyancy driven convection have a negative effect on crystal growth and microgravity is seen as a way to both greatly reduce sedimentation and provide greater stability for 'depletion zones' around growing crystals. Some current crystal growth hardware however such as those based on a vapor diffusion techniques, may also be introducing unwanted Marangoni convection which becomes more pronounced in microgravity. Negative effects of g-jitter on crystal growth have also been observed. To study the magnitude of fluid flows around growing crystals we have attached a number of different fluorescent probes to lysozyme molecules. At low concentrations, less than 40% of the total protein, the probes do not appear to effect the crystal growth process. By using these probes we expect to determine not only the effect of induced flows due to crystal growth hardware design but also hope to optimize crystallization hardware so that destructive flows are minimized both on the ground and in microgravity.

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

Chuvashova, Irina, E-mail: irina.chuvashova@gmail.com; Bayerisches Geoinstitut, University of Bayreuth, D-95440 Bayreuth; Bykova, Elena

In the present study single crystals of rhombohedral α-B were investigated under pressure to 60 GPa by means of single-crystal X-ray diffraction. The bulk modulus of α-B was found to be K=224(7) GPa (K′=3.0(3)). Measurements of interatomic distances as a function of pressure revealed that the intericosahedral two-center two-electron (2c–2e) bonds are almost as stiff as some of intraicosahedral ones. The three-center two-electron (3c–2e) intericosahedral bonds show much higher compliance compared to other bonds in α-B. The vibrational properties of α-B under pressure were investigated by Raman spectroscopy at pressures up to 160 GPa and IR spectroscopy at pressures upmore » to 53 GPa. - Graphical abstract: The rhombohedral α-B is highly incompressible and extremely stable: it maintains its crystal structure up to 160 GPa and its intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones. - Highlights: • Structural stability of α-B has been investigated up to 160 GPa on single crystals. • Single-crystal x-ray diffraction reveals that α-B is highly incompressible. • Compressibility of B{sub 12} icosahedra is considerably lower than that of the bulk material. • Intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones.« less

Structure and magnetic properties of Fe-Co-B alloy thin films prepared on cubic (001) single-crystal substrates

NASA Astrophysics Data System (ADS)

Ohtake, Mitsuru; Serizawa, Kana; Futamoto, Masaaki; Kirino, Fumiyoshi; Inaba, Nobuyuki

2018-04-01

Fe70Co30 and (Fe70Co30)0.95B5 (at. %) alloy films of 5 nm thickness are prepared by sputtering on cubic (001) oxide substrates at 200 °C. The lattice mismatch between film and substrate is varied from -4.2%, 0%, to +3.5% by employing MgO, MgAl2O4, and SrTiO3 substrates, respectively. Fe70Co30 and (Fe70Co30)0.95B5 single-crystal films with bcc structure grow epitaxially on all the substrates in the orientation relationship of (001)[110]film || (001)[100]substrate. The in-plane and out-of-plane lattice constants, a and c, are in agreement within small differences ranging between +1.1% and -0.9% with the value of bulk bcc-Fe70Co30 crystal, even though there exist the lattice mismatches of -4.2% and +3.5%. The result indicates that misfit dislocations are introduced around the film/substrate interface when films are deposited on MgO and SrTiO3 substrates. The single-crystal films show in-plane magnetic anisotropies with the easy magnetization direction of bcc[100], which are reflecting the magnetocrystalline anisotropy of bulk Fe70Co30 crystal.

Microscopic Optical Characterization of Free Standing III-Nitride Substrates, ZnO Bulk Crystals, and III-V Structures for Non-Linear Optics. Part 2

DTIC Science & Technology

2010-05-18

strong radiation hardness of ZnO. Positron annihilation studies have revealed the presence of Zn vacancies under high energy electron irradiation, as...SUPPLEMENTARY NOTES 14. ABSTRACT CL study of ammonothermal GaN crystals. Preliminary results on ammonothermal AlGaN crystals show a clear...prevalence of deep level luminescence Study of the luminescence spectral characteristics. Optimization of the excitonic emission vs deep level emission

Crystallization processes in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass

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

Svoboda, Roman, E-mail: roman.svoboda@upce.cz; Bezdička, Petr; Gutwirth, Jan

2015-01-15

Highlights: • Crystallization kinetics of Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass was studied in dependence on particle size by DSC. • All studied fractions were described in terms of the SB autocatalytic model. • Relatively high amount of Te enhances manifestation of bulk crystallization mechanisms. • XRD analysis of samples crystallized under different conditions showed correlation with DSC data. • XRD analysis revealed a new crystallization mechanism indistinguishable by DSC. - Abstract: Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis were used to study crystallization in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass under non-isothermal conditions as a function of the particlemore » size. The crystallization kinetics was described in terms of the autocatalytic Šesták–Berggren model. An extensive discussion of all aspects of a full-scale kinetic study of a crystallization process was undertaken. Dominance of the crystallization process originating from mechanically induced strains and heterogeneities was confirmed. Substitution of Se by Te was found to enhance the manifestation of the bulk crystallization mechanisms (at the expense of surface crystallization). The XRD analysis showed significant dependence of the crystalline structural parameters on the crystallization conditions (initial particle size of the glassy grains and applied heating rate). Based on this information, a new microstructural crystallization mechanism, indistinguishable by DSC, was proposed.« less

Shock Induced Chemistry: Application and Development of Ultrafast Nonlinear Probes of the Energy Dynamics of Molecules in Solids

DTIC Science & Technology

1988-01-01

crystal and in a mixed crystal. The mixed crystal data was taken with resonance enhancement by the pentacene .. ... 7 Accesiw, r)re 0IE r)) NiS cR4~ IE~) D...observations as well as their implications about the nature of the coupling of a localized defect to the bulk modes of the crystal have been analyzed [7...matter systems, in addition to phonon induced fluctuations of local mechanical properties, there can be much slower timescale structural evolution

Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

1996-04-01

The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

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

Zhou, Chenkun; Worku, Michael; Neu, Jennifer

Here, we report the synthesis and characterization of (Ph 4P) 2SbCl 5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph 4P +) and antimony (Sb 3+) chloride salts, (Ph 4P) 2SbCl 5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl 5 2– with strong excited-state structuralmore » distortion. Interestingly, (Ph 4P) 2SbCl 5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.« less

Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

DOE PAGES

Zhou, Chenkun; Worku, Michael; Neu, Jennifer; ...

2018-03-12

Here, we report the synthesis and characterization of (Ph 4P) 2SbCl 5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph 4P +) and antimony (Sb 3+) chloride salts, (Ph 4P) 2SbCl 5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl 5 2– with strong excited-state structuralmore » distortion. Interestingly, (Ph 4P) 2SbCl 5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.« less

Quasi 2D electronic states with high spin-polarization in centrosymmetric MoS2 bulk crystals

NASA Astrophysics Data System (ADS)

Gehlmann, Mathias; Aguilera, Irene; Bihlmayer, Gustav; Młyńczak, Ewa; Eschbach, Markus; Döring, Sven; Gospodarič, Pika; Cramm, Stefan; Kardynał, Beata; Plucinski, Lukasz; Blügel, Stefan; Schneider, Claus M.

2016-06-01

Time reversal dictates that nonmagnetic, centrosymmetric crystals cannot be spin-polarized as a whole. However, it has been recently shown that the electronic structure in these crystals can in fact show regions of high spin-polarization, as long as it is probed locally in real and in reciprocal space. In this article we present the first observation of this type of compensated polarization in MoS2 bulk crystals. Using spin- and angle-resolved photoemission spectroscopy (ARPES), we directly observed a spin-polarization of more than 65% for distinct valleys in the electronic band structure. By additionally evaluating the probing depth of our method, we find that these valence band states at the point in the Brillouin zone are close to fully polarized for the individual atomic trilayers of MoS2, which is confirmed by our density functional theory calculations. Furthermore, we show that this spin-layer locking leads to the observation of highly spin-polarized bands in ARPES since these states are almost completely confined within two dimensions. Our findings prove that these highly desired properties of MoS2 can be accessed without thinning it down to the monolayer limit.

Novel Crystal Structure C60 Nanowire

NASA Astrophysics Data System (ADS)

Mickelson, William; Aloni, Shaul; Han, Weiqiang; Cumings, John; Zettl, Alex

2003-03-01

We have created insulated C60 nanowire by packing C60 molecules into the interior of insulating boron nitride (BN) nanotubes. For small-diameter BN tubes, the wire consists of a linear chain of C60's. With increasing BN tube inner diameter, novel C60 stacking configurations are obtained (including helical, hollow core, and incommensurate) which are unknown for bulk or thin film forms of C60. C60 in BN nanotubes presents a model system for studying the properties of new dimensionally-constrained "silo" crystal structures.

Mechanism of radiative recombination in acceptor-doped bulk GaN crystals

NASA Astrophysics Data System (ADS)

Godlewski, M.; Suski, T.; Grzegory, I.; Porowski, S.; Bergman, J. P.; Chen, W. M.; Monemar, B.

1999-12-01

Optical and electrical properties of acceptor-doped bulk GaN crystals are discussed. Though introducing Zn and Ca to bulk GaN does not significantly change electron concentration, it results in the appearance of a blue photoluminescence band accompanying the relatively strong yellow band usually present. Highly resistive GaN : Mg crystals are obtained when high amount of Mg is introduced to the Ga melt during high-pressure synthesis. Change of electrical properties of Mg-doped bulk crystals is accompanied by the appearance of a strong blue emission of GaN similar to that in Ca- and Zn-doped crystals. Optically detected magnetic resonance investigations indicate a multi-band character of this blue emission and suggest possible mechanism of compensation in acceptor-doped bulk GaN.

Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons

PubMed Central

Hahn, Christopher; Hatsukade, Toru; Kim, Youn-Geun; Vailionis, Arturas; Baricuatro, Jack H.; Higgins, Drew C.; Nitopi, Stephanie A.; Soriaga, Manuel P.; Jaramillo, Thomas F.

2017-01-01

In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C–C coupling than Cu(111), Cu(751) is the most selective for >2e− oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction. PMID:28533377

Calculated photonic structures for infrared emittance control

NASA Astrophysics Data System (ADS)

Rung, Andreas; Ribbing, Carl G.

2002-06-01

Using an available program package based on the transfer-matrix method, we calculated the photonic band structure for two different structures: a quasi-three-dimensional crystal of square air rods in a high-index matrix and an opal structure of high-index spheres in a matrix of low index, epsilon = 1.5. The high index used is representative of gallium arsenide in the thermal infrared range. The geometric parameters of the rod dimension, sphere radius, and lattice constants were chosen to give total reflectance for normal incidence, i.e., minimum thermal emittance, in either one of the two infrared atmospheric windows. For these four photonic crystals, the bulk reflectance spectra and the wavelength-averaged thermal emittance as a function of crystal thickness were calculated. The results reveal that potentially useful thermal signature suppression is obtained for crystals as thin as 20-50 mum, i.e., comparable with that of a paint layer.

Melt growth and properties of bulk BaSnO3 single crystals

NASA Astrophysics Data System (ADS)

Galazka, Z.; Uecker, R.; Irmscher, K.; Klimm, D.; Bertram, R.; Kwasniewski, A.; Naumann, M.; Schewski, R.; Pietsch, M.; Juda, U.; Fiedler, A.; Albrecht, M.; Ganschow, S.; Markurt, T.; Guguschev, C.; Bickermann, M.

2017-02-01

We present the first-time growth of bulk BaSnO3 single crystals from the melt by direct solidification, their basic electrical and optical properties as well as their structural quality. Our measurement of the melting point (MP) of BaSnO3 amounts to 1855 °C  ±  25 K. At this temperature an intensive decomposition and non-stoichiometric evaporation takes place as the partial pressure of SnO(g) is about 90 times higher than that of BaO(g). X ray powder diffraction identified only the BaSnO3 perovskite phase, while narrow rocking curves having a full width at half maximum of 26 arcsec and etch pit densities below 106 cm-2 confirm a high degree of structural perfection of the single crystals. In this respect they surpass the structural properties of those single crystals that were reported in the literature. The electrical conductivity of nominally undoped crystals depends on the growth conditions and ranges from insulating to medium n-type conductivity. After post-growth annealing in an oxidizing atmosphere undoped crystals are generally insulating. Doping the crystals with lanthanum during growth results in a high n-type conductivity. For a La doping concentration of 0.123 wt.% we measured an electron concentration of 3.3  ×  1019 cm-3 and an electron mobility of 219 cm2 V-1 s-1. Based on optical absorption measurements we determined an energy of 3.17  ±  0.04 eV at 5 K and of 2.99  ±  0.04 eV at 297 K for the indirect band gap of BaSnO3.

Colour centres and nanostructures on the surface of laser crystals

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

Kulagin, N A

2012-11-30

This paper presents a study of structural and radiationinduced colour centres in the bulk and ordered nanostructures on the surface of doped laser crystals: sapphire, yttrium aluminium garnet and strontium titanate. The influence of thermal annealing, ionising radiation and plasma exposure on the spectroscopic properties of high-purity materials and crystals containing Ti, V and Cr impurities is examined. Colour centres resulting from changes in the electronic state of impurities and plasma-induced surface modification of the crystals are studied by optical, EPR and X-ray spectroscopies, scanning electron microscopy and atomic force microscopy. X-ray line valence shift measurements are used to assessmore » changes in the electronic state of some impurity and host ions in the bulk and on the surface of oxide crystals. Conditions are examined for the formation of one- and two-level arrays of ordered crystallites 10{sup -10} to 10{sup -7} m in size on the surface of crystals doped with irongroup and lanthanoid ions. The spectroscopic properties of the crystals are analysed using ab initio self-consistent field calculations for Me{sup n+} : [O{sup 2-}]{sub k} clusters. (interaction of laser radiation with matter. laser plasma)« less

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Surface and bulk crystallization of amorphous solid water films: Confirmation of “top-down” crystallization

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

Yuan, Chunqing; Smith, R. Scott; Kay, Bruce D.

2016-01-11

Here, the crystallization kinetics of nanoscale amorphous solid water (ASW) films are investigated using temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS). TPD measurements are used to probe surface crystallization and RAIRS measurements are used to probe bulk crystallization. Isothermal TPD results show that surface crystallization is independent of the film thickness (from 100 to 1000 ML). Conversely, the RAIRS measurements show that the bulk crystallization time increases linearly with increasing film thickness. These results suggest that nucleation and crystallization begin at the ASW/vacuum interface and then the crystallization growth front propagates linearly into the bulk. This mechanism wasmore » confirmed by selective placement of an isotopic layer (5% D 2O in H 2O) at various positions in an ASW (H 2O) film. In this case, the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These experiments provide direct evidence to confirm that ASW crystallization in vacuum proceeds by a “top-down” crystallization mechanism.« less

Structure of finite sphere packings via exact enumeration: Implications for colloidal crystal nucleation

NASA Astrophysics Data System (ADS)

Hoy, Robert S.; Harwayne-Gidansky, Jared; O'Hern, Corey S.

2012-05-01

We analyze the geometric structure and mechanical stability of a complete set of isostatic and hyperstatic sphere packings obtained via exact enumeration. The number of nonisomorphic isostatic packings grows exponentially with the number of spheres N, and their diversity of structure and symmetry increases with increasing N and decreases with increasing hyperstaticity H≡Nc-NISO, where Nc is the number of pair contacts and NISO=3N-6. Maximally contacting packings are in general neither the densest nor the most symmetric. Analyses of local structure show that the fraction f of nuclei with order compatible with the bulk (rhcp) crystal decreases sharply with increasing N due to a high propensity for stacking faults, five- and near-fivefold symmetric structures, and other motifs that preclude rhcp order. While f increases with increasing H, a significant fraction of hyperstatic nuclei for N as small as 11 retain non-rhcp structure. Classical theories of nucleation that consider only spherical nuclei, or only nuclei with the same ordering as the bulk crystal, cannot capture such effects. Our results provide an explanation for the failure of classical nucleation theory for hard-sphere systems of N≲10 particles; we argue that in this size regime, it is essential to consider nuclei of unconstrained geometry. Our results are also applicable to understanding kinetic arrest and jamming in systems that interact via hard-core-like repulsive and short-ranged attractive interactions.

Structural and optical properties of indium-doped highly conductive ZnO bulk crystals grown by the hydrothermal technique

NASA Astrophysics Data System (ADS)

Wang, Buguo; Claflin, Bruce; Look, David; Jiménez, Juan

2018-02-01

Indium-doped ZnO bulk crystals grown by the hydrothermal method are highly-conductive, with resistivity at 0.01 Ωcm at room temperature as revealed by Hall-effect measurement. In this paper we report on structural and optical properties of these crystals. The grown In:ZnO crystals have been studied by high resolution X-ray diffraction, micro-Raman scattering and low-temperature photoluminescence and cathodoluminescence. It was found that the c lattice parameter of the grown In:ZnO crystal expanded 0.06% with respect to the lithium-doped ZnO crystal seed, and the In-doped ZnO overgrew the seed crystal pseudomorphically but with high quality crystallinity; the X-ray rocking curves show the FWHM of the Zn face and O faces are only 0.05° and 0.1° ; and the indium concentration in the crystal reaches the solubility limit. Raman spectra show strain relaxation gradually from the regrowth interface as well as a weak spectral feature at 723 cm-1. The peak at 312 cm-1 noticed in hydrothermally grown In:ZnO nanostructures does not appear in our In-doped crystals, indicating that this peak may be associated with specific defects (e.g. surface related) of the nanostructures. Photoluminescence measurements show that an indium donor bound exciton peak I9 (In0X) is the dominant peak in the PL spectrum, located at 3.3586 eV on the zinc face and 3.3577 eV on the oxygen face. Both of them deviated from the consensus literature value of 3.3567 eV, probably due to strain in the crystal induced by impurities.

Superheating Suppresses Structural Disorder in Layered BiI3 Semiconductors Grown by the Bridgman Method

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

Johns, Paul M.; Sulekar, Soumitra; Yeo, Shinyoung

2016-01-01

The susceptibility of layered structures to stacking faults is a problem in some of the more attractive semiconductor materials for ambient-temperature radiation detectors. In the work presented here, Bridgman-grown BiI3 layered single crystals are investigated to understand and eliminate this structural disorder, which reduces radiation detector performance. The use of superheating gradients has been shown to improve crystal quality in non-layered semiconductor crystals; thus the technique was here explored to improve the growth of BiI3. When investigating the homogeneity of non-superheated crystals, highly geometric void defects were found to populate the bulk of the crystals. Applying a superheating gradient tomore » the melt prior to crystal growth improved structural quality and decreased defect density from the order of 4600 voids per cm3 to 300 voids per cm3. Corresponding moderate improvements to electronic properties also resulted from the superheat gradient method of crystal growth. Comparative measurements through infrared microscopy, etch-pit density, x-ray rocking curves, and sheet resistivity readings show that superheat gradients in BiI3 growth led to higher quality crystals.« less

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

S. K. Kushwaha; Pletikosic, I.; Liang, T.

A long-standing issue in topological insulator research has been to find a bulk single crystal material that provides a high quality platform for characterizing topological surface states without interference from bulk electronic states. This material would ideally be a bulk insulator, have a surface state Dirac point energy well isolated from the bulk valence and conduction bands, display quantum oscillations from the surface state electrons, and be growable as large, high quality bulk single crystals. Here we show that this materials obstacle is overcome by bulk crystals of lightly Sn-doped Bi 1.1Sb 0.9Te 2S grown by the Vertical Bridgeman method.more » We characterize Sn-BSTS via angle-resolved photoemission spectroscopy, scanning tunneling microscopy, transport studies, X-ray diffraction, and Raman scattering. We present this material as a high quality topological insulator that can be reliably grown as bulk single crystals and thus studied by many researchers interested in topological surface states.« less

Silicon-based photonic crystals fabricated using proton beam writing combined with electrochemical etching method

PubMed Central

2012-01-01

A method for fabrication of three-dimensional (3D) silicon nanostructures based on selective formation of porous silicon using ion beam irradiation of bulk p-type silicon followed by electrochemical etching is shown. It opens a route towards the fabrication of two-dimensional (2D) and 3D silicon-based photonic crystals with high flexibility and industrial compatibility. In this work, we present the fabrication of 2D photonic lattice and photonic slab structures and propose a process for the fabrication of 3D woodpile photonic crystals based on this approach. Simulated results of photonic band structures for the fabricated 2D photonic crystals show the presence of TE or TM gap in mid-infrared range. PMID:22824206

Microscopic Optical Characterization of Free Standing III-Nitride Substrates, ZnO Bulk Crystals, and III-V Structures for Non-Linear Optics

DTIC Science & Technology

2013-03-01

necessary. Therefore, a study of the main defects involved in these materials is essential to the understanding of their main properties and to...working with various strains, growth conditions, temperature variation, and impurities, and studies crystal growth parameters necessary to improve the...Sirtl applied with Light), and the stress distribution around the domain walls. This study shows how to improve the crystal quality of the OP GaAs

Sintered tantalum carbide coatings on graphite substrates: Highly reliable protective coatings for bulk and epitaxial growth

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

Nakamura, Daisuke; Suzumura, Akitoshi; Shigetoh, Keisuke

2015-02-23

Highly reliable low-cost protective coatings have been sought after for use in crucibles and susceptors for bulk and epitaxial film growth processes involving wide bandgap materials. Here, we propose a production technique for ultra-thick (50–200 μmt) tantalum carbide (TaC) protective coatings on graphite substrates, which consists of TaC slurry application and subsequent sintering processes, i.e., a wet ceramic process. Structural analysis of the sintered TaC layers indicated that they have a dense granular structure containing coarse grain with sizes of 10–50 μm. Furthermore, no cracks or pinholes penetrated through the layers, i.e., the TaC layers are highly reliable protective coatings. The analysismore » also indicated that no plastic deformation occurred during the production process, and the non-textured crystalline orientation of the TaC layers is the origin of their high reliability and durability. The TaC-coated graphite crucibles were tested in an aluminum nitride (AlN) sublimation growth process, which involves extremely corrosive conditions, and demonstrated their practical reliability and durability in the AlN growth process as a TaC-coated graphite. The application of the TaC-coated graphite materials to crucibles and susceptors for use in bulk AlN single crystal growth, bulk silicon carbide (SiC) single crystal growth, chemical vapor deposition of epitaxial SiC films, and metal-organic vapor phase epitaxy of group-III nitrides will lead to further improvements in crystal quality and reduced processing costs.« less

High second-harmonic generation of antiferromagnetic/ionic-crystal composite medium with negative refraction

NASA Astrophysics Data System (ADS)

Song, Yu-Ling; Ta, Jin-Xing; Wang, Xuan-Zhang

2012-03-01

Second harmonic generation (SHG) from a short-period structure composed of alternating antiferromagnetic (AF) and ionic-crystal layers is investigated, where the generated harmonic waves are situated in the far-infrared range and attributed to the magnetically nonlinear interaction in AF layers. The presence of a kind of appropriate ionic-crystal layers in the structure can support negative refraction for the pumping wave and positive refraction for the SH wave, so the SHG is greatly amplified in the vicinity of each AF resonant frequency. For the composite structure FeF2/TlBr, we found that the SH output is about 8 times higher than that of the FeF2 bulk in the same frequency range.

Chiral Asymmetric Structures in Aspartic Acid and Valine Crystals Assessed by Atomic Force Microscopy.

PubMed

Teschke, Omar; Soares, David Mendez

2016-03-29

Structures of crystallized deposits formed by the molecular self-assembly of aspartic acid and valine on silicon substrates were imaged by atomic force microscopy. Images of d- and l-aspartic acid crystal surfaces showing extended molecularly flat sheets or regions separated by single molecule thick steps are presented. Distinct orientation surfaces were imaged, which, combined with the single molecule step size, defines the geometry of the crystal. However, single molecule step growth also reveals the crystal chirality, i.e., growth orientations. The imaged ordered lattice of aspartic acid (asp) and valine (val) mostly revealed periodicities corresponding to bulk terminations, but a previously unreported molecular hexagonal lattice configuration was observed for both l-asp and l-val but not for d-asp or d-val. Atomic force microscopy can then be used to identify the different chiral forms of aspartic acid and valine crystals.

Effect of chain topology on crystallization within nanoporous alumina

NASA Astrophysics Data System (ADS)

Yao, Yang; Suzuki, Yasuhito; Sakai, Takamasa; Seiwert, Jan; Frey, Holger; Steinhart, Martin; Butt, Hans-Juergen; Floudas, George

Polymer topology has inevitable influence on the structure, packing, and dynamic of chains. Herein, we investigate for the first time the impact of polymer architecture on crystallization under 2D confinement, the latter provided by nanoporous alumina (AAO). We employ two poly(ethylene oxide) (PEO) star polymers to study the effect of (i) end groups and (ii) molecular weight on polymer crystallization in the bulk and under confinement. Bulk end groups reduce the crystallization/melting temperatures and the corresponding equilibrium melting point. Under confinement, in the absence of catalyst, homogeneous nucleation prevails as with linear PEOs. The homogeneous nucleation temperatures for the star polymers agree with that of linear ones provided that the arm molecular weight is used instead. Long-range dynamics pertinent to star relaxation are affecting the homogeneous nucleation temperature. On the other hand, the segmental dynamics speed up on confinement. In addition to star PEO, we study the effect of another topology, i.e. hyperbranched PEO, on the nucleation mechanism.

Bulk growth of undoped and Nd3+ doped zinc thiourea chloride (ZTC) monocrystal: Exploring the remarkably enhanced structural, optical, electrical and mechanical performance of Nd3+ doped ZTC crystal for NLO device applications

NASA Astrophysics Data System (ADS)

Anis, Mohd; Muley, Gajanan. G.

2017-05-01

In current scenario good quality crystals are demanded for NLO device application hence present communication is aimed to grow bulk crystal and investigate the doping effect of rare earth element Nd3+ on structural, linear-nonlinear optical, luminescence, mechanical and dielectric properties of zinc thiourea chloride (ZTC) crystal. The ZTC crystal of dimension 21×10×8 mm3 and the Nd3+ doped ZTC crystal of dimension 27×17×5 mm3 have been grown from aqueous solution by slow evaporation technique. The elemental analysis of Nd3+ doped ZTC single crystal has been performed by means of energy dispersive spectroscopic technique. The powder X-ray diffraction technique has been employed to confirm the crystalline phase and identify the effect of Nd3+ doping on structural dimensions of ZTC crystal. The grown crystals have been characterized by UV-Vis-NIR study in the range of 190-1100 nm to ascertain the enhancement in optical transparency of ZTC crystal facilitated by dopant Nd3+. The recorded transmittance data has been utilized to investigate the vital optical constants of grown crystals. The second order nonlinear optical behavior of grown crystals has been evaluated by means of Kurtz-Perry test and the second harmonic generation efficiency of Nd3+ doped ZTC crystal is found to be 1.24 times higher than ZTC crystal. The luminescence analysis has been performed to examine the electronic purity and the color centered photoluminescence emission nature of pure and Nd3+ doped ZTC crystals. The influence of Nd3+ ion on mechanical behavior of ZTC crystal has been investigated by means of microhardness studies. The nature of dielectric constant and dielectric loss of pure and Nd3+ doped ZTC crystal has been examined in the range of 40-100 °C under dielectric study. The Z-scan technique has been employed using the He-Ne laser to investigate the third order nonlinear optical (TONLO) nature of Nd3+ doped ZTC single crystal. The magnitude of TONLO susceptibility, absorption coefficient and refraction has been determined using the Z-scan transmittance data.

Band transition and topological interface modes in 1D elastic phononic crystals.

PubMed

Yin, Jianfei; Ruzzene, Massimo; Wen, Jihong; Yu, Dianlong; Cai, Li; Yue, Linfeng

2018-05-01

In this report, we design a one-dimensional elastic phononic crystal (PC) comprised of an Aluminum beam with periodically arranged cross-sections to study the inversion of bulk bands due to the change of topological phases. As the geometric parameters of the unit cell varies, the second bulk band closes and reopens forming a topological transition point. This phenomenon is confirmed for both longitudinal waves and bending waves. By constructing a structural system formed by two PCs with different topological phases, for the first time, we experimentally demonstrate the existence of interface mode within the bulk band gap as a result of topological transition for both longitudinal and bending modes in elastic systems, although for bending modes, additional conditions have to be met in order to have the interface mode due to the dispersive nature of the bending waves in uniform media compared to the longitudinal waves.

Low-energy electron diffraction study of potassium adsorbed on single-crystal graphite and highly oriented pyrolytic graphite

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

Ferralis, N.; Diehl, R.D.; Pussi, K.

2004-12-15

Potassium adsorption on graphite has been a model system for the understanding of the interaction of alkali metals with surfaces. The geometries of the (2x2) structure of potassium on both single-crystal graphite (SCG) and highly oriented pyrolytic graphite (HOPG) were investigated for various preparation conditions for graphite temperatures between 55 and 140 K. In all cases, the geometry was found to consist of K atoms in the hollow sites on top of the surface. The K-graphite average perpendicular spacing is 2.79{+-}0.03 A , corresponding to an average C-K distance of 3.13{+-}0.03 A , and the spacing between graphite planes ismore » consistent with the bulk spacing of 3.35 A. No evidence was observed for a sublayer of potassium. The results of dynamical LEED studies for the clean SCG and HOPG surfaces indicate that the surface structures of both are consistent with the truncated bulk structure of graphite.« less

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template.

PubMed

Lee, Kihong; Choi, Bonnie; Plante, Ilan Jen-La; Paley, Maria V; Zhong, Xinjue; Crowther, Andrew C; Owen, Jonathan S; Zhu, Xiaoyang; Roy, Xavier

2018-05-22

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C 60 as a polymerizable monomer. The C 60 building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C 60 monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C 60 . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Premelting Coupled with Bulk Phase Transitions in Colloidal Crystals

NASA Astrophysics Data System (ADS)

Li, Bo; Wang, Feng; Zhou, Di; Cao, Xin; Peng, Yi; Ni, Ran; Liao, Maijia; Han, Yilong

2015-03-01

Colloids have been used as outstanding model systems for the studies of various phase transitions in bulk, but not at interface yet. Here we obtained equilibrium crystal-vapor interfaces using tunable attractive colloidal spheres and studied the surface premelting at the single-particle level by video microscopy. We found that monolayer crystals exhibit a bulk isostructural solid-solid transition which triggers the surface premelting. The premelting is incomplete due to the interruption of a mechanical-instability-induced bulk melting. By contrast, two- or multilayer crystals do not have the solid-solid transition and the mechanical instability, hence they exhibit complete premelting with divergent surface-liquid thickness. These novel interplays between bulk and surface phase transitions cast new lights for both types of transitions.

Crystalline structures, thermal properties and crystallizing mechanism of polyamide 6 nanotubes in confined space

NASA Astrophysics Data System (ADS)

Li, Xiaoru; Peng, Zhi; Yang, Chao; Han, Ping; Song, Guojun; Cong, Longliang

2016-09-01

The polyamide 6 (PA6) nanotubes were prepared by infiltrating the anodic aluminum oxide templates with polymer solution. Crystalline regions in the nanotube walls were detected by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD), Fast Fourier Transform (FFT) and differential scanning calorimetry (DSC) techniques were employed to investigate crystallization, crystal faces and thermodynamics. It was found that the crystals were transformed from α-form in bulk to γ-form in nanotubes. It was made a detailed analysis in this article. Moreover, schematic diagram for the crystallizing mechanism of PA6 nanotubes was given to explain PA6 molecules how to crystallize in the nano-pores.

Maskless nano-implant of 20 keV Ga+ in bulk Si(1 0 0) substrates

NASA Astrophysics Data System (ADS)

Milazzo, R. G.; D'Arrigo, G.; Mio, A. M.; Rimini, E.; Spinella, C.; Peto, L.; Nadzeyka, A.; Bauerdick, S.

2014-12-01

Multidirectional SPEG (Solid Phase Epitaxial Growth) of silicon has been investigated in micro and nanoamorphous structures generated on a crystalline substrate by a nano-sized ion beam, Gaussian shaped and with a standard deviation of about 5 nm. The 20 keV Ga+ ions were implanted at a fluence of 5 × 1014 ions cm-2 in a bulk Si(1 0 0) single crystal. Two structures were used for the implants: circular regions of 100 nm and 1 μm diameters respectively and straight lines 10 nm in width and few microns in length along (1 0 0) or (1 1 0) directions. The lateral spread of ions has been taken into account in the damage estimation. Transmission Electron Microscopy indicates that the structures are made of an amorphous core surrounded by a defective and filamentary shell. The recovery of the damaged outer regions promptly occurs during the early stages of the thermal treatment at 500-600 °C for all the structures. By prolonging annealing time, re-crystallization of the amorphous cores is achieved too by the movement of the underneath crystal-amorphous interface. The re-growth is almost defects free when the contribution of the crystalline seed below the structures is present, defective and twin mediated if it misses as in the thinnest regions of the specimen.

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

Zhang, Pei; Maldonis, Jason J.; Besser, M. F.

Fluctuation electron microscopy experiments combined with hybrid reverse Monte Carlo modeling show a correlation between medium-range structure at the nanometer scale and glass forming ability in two Zr–Cu–Al bulk metallic glass (BMG) alloys. Both Zr 50Cu 35Al 15 and Zr 50Cu 45Al 5 exhibit two nanoscale structure types, one icosahedral and the other more crystal-like. In Zr 50Cu 35Al 15, the poorer glass former, the crystal-like structure is more stable under annealing below the glass transition temperature, T g, than in Zr 50Cu 45Al 5. Variable resolution fluctuation microscopy of the MRO clusters show that in Zr 50Cu 35Al 15more » on sub-Tg annealing, the crystal-like clusters shrink even as they grow more ordered, while icosahedral-like clusters grow. Furthermore, the results suggest that achieving better glass forming ability in this alloy system may depend more on destabilizing crystal-like structures than enhancing non-crystalline structures.« less

Highly polarized single-c-domain single-crystal Pb(Mn,Nb)O(3)-PZT thin films.

PubMed

Wasa, Kiyotaka; Adachi, Hideaki; Nishida, Ken; Yamamoto, Takashi; Matsushima, Tomoaki; Kanno, Isaku; Kotera, Hidetoshi

2012-01-01

In-plane unstrained single-c-domain/single-crystal thin films of PZT-based ternary ferroelectric perovskite, ξPb(Mn,Nb)O3-(1 - ξ)PZT, were grown on SrRuO(3)/Pt/MgO substrates using magnetron sputtering followed by quenching. The sputtered unstrained thin films exhibit unique ferroelectric properties: high coercive field, Ec > 180 kV/cm, large remanent polarization, P(r) = 100 μC/cm(2), small relative dielectric constants, ε* = 100 to 150, high Curie temperature, Tc = ~600 °C, and bulk-like large transverse piezoelectric constants, e31,f = -12.0 C/m(2) for PZT(48/52) at ξ = 0.06. The unstrained thin films are an ideal structure to extract the bulk ferroelectric properties. Their micro-structures and ferroelectric properties are discussed in relation to the potential applications for piezoelectric MEMS. © 2012 IEEE

Defect related electrical and optical properties of AlN bulk crystals grown by physical vapor transport

NASA Astrophysics Data System (ADS)

Irmscher, Klaus

AlN crystallizes thermodynamically stable in the wurtzite structure and possesses a direct band gap of about 6 eV. It is the ideal substrate for the epitaxial growth of Al-rich AlxGa1-xN films that enable deep ultraviolet (UV) emitters. Appropriate AlN bulk crystals can be grown by physical vapor transport (PVT). Besides high structural perfection, such substrate crystals should be highly UV transparent and ideally, electrically conductive. It is well known that point defects like impurities and intrinsic defects may introduce electronic energy levels within the bandgap, which lead to additional optical absorption or electrical compensation. Among the impurities, which may be incorporated into the AlN crystals during PVT growth at well above 2000 ° C, oxygen, carbon, and silicon play the major role. Based on our own experimental data as well as on experimental and theoretical results reported in literature, we discuss energy levels, charge states and possible negative-U behavior of these impurities and of vacancy-type defects. In particular, we develop a model that explains the absorption behavior of the crystals in dependence on the Fermi level that can be controlled by the growth conditions, including intentional doping. Further, we pay attention on spectroscopic investigations giving direct evidence for the chemical nature and atomic arrangement of the involved point defects. As examples local vibrational mode (LVM) spectroscopy of carbon related defects and recent reports of electron paramagnetic resonance (EPR) spectroscopy are discussed.

Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles

NASA Astrophysics Data System (ADS)

Rulis, Paul; Yao, Hongzhi; Ouyang, Lizhi; Ching, W. Y.

2007-12-01

Fluorapatite (FAP) and hydroxyapatite (HAP) are two very important bioceramic crystals. The (001) surfaces of FAP and HAP crystals are studied by ab initio density functional calculations using a supercell slab geometry. It is shown that in both crystals, the O-terminated (001) surface is more stable with calculated surface energies of 0.865 and 0.871J/m2 for FAP and HAP, respectively. In FAP, the two surfaces are symmetric. In HAP, the orientation of the OH group along the c axis reduces the symmetry such that the top and bottom surfaces are no longer symmetric. It is revealed that the atoms near the surface and subsurface are significantly relaxed especially in the case of HAP. The largest relaxations occurred via the lateral movements of the O ions at the subsurface level. The electronic structures of the surface models in the form of layer-by-layer resolved partial density of states for all the atoms show systematic variation from the surface region toward the bulk region. The calculated Mulliken effective charge on each type of atom and the bond order values between cations (Ca, P) and anions (O, F) show different charge transfers and bond strength variations from the bulk crystal values. Electron charge density calculations show that the surfaces of both FAP and HAP crystals are mostly positively charged due to the presence of Ca ions at the surface. The positively charged surfaces have implications for the absorption on apatite surfaces of water and other organic molecules in an aqueous environment which are an important part of its bioactivity. The x-ray absorption near-edge structure (XANES) spectra ( Ca-K , O-K , F-K , P-K , and P-L3 edges) of both the surface models and the bulk crystals are calculated and compared. The calculations use a supercell approach which takes into account the electron-core-hole interaction. It is shown that the site-specific XANES spectra show significant differences between atoms near the surface and in the bulk and are very sensitive to the local atomic environment of each atom. This information will be very valuable for characterizing the apatite materials and in the interpretation of experimental data. Comparisons of several sets of experimental data with the weighted sums of the calculated spectra at different sites for the same element show very good agreement.

Structure, optical and phonon properties of bulk and nanocrystalline Al2-xScx(WO4)3 solid solutions doped with Cr3+

NASA Astrophysics Data System (ADS)

Mączka, M.; Hermanowicz, K.; Pietraszko, A.; Yordanova, A.; Koseva, I.

2014-01-01

Pure and Cr3+ doped nanosized Al2-xScx(WO4)3 solid solutions were prepared by co-precipitation method as well as Al2-xScx(WO4)3 single crystals were grown by high-temperature flux method. The obtained samples were characterized by X-ray, Raman, IR, absorption and luminescence methods. Single crystal X-ray diffraction showed that AlSc(WO4)3 is orthorhombic at room temperature with space group Pnca and trivalent cations are statistically distributed. Raman and IR studies showed that Al2-xScx(WO4)3 solid solutions show "two mode" behavior. They also showed that vibrational properties of nanosized samples have been weakly modified in comparison with the bulk materials. The luminescence and absorption spectra revealed that chromium ions occupy two sites of weak and strong crystal field strength.

Valence-band and core-level photoemission study of single-crystal Bi2CaSr2Cu2O8 superconductors

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

1988-12-01

High-quality single crystals of Bi2CaSr2Cu2O8 superconductors have been prepared and cleaved in ultrahigh vacuum. Low-energy electron diffraction measurements show that the surface structure is consistent with the bulk crystal structure. Ultraviolet photoemission and x-ray photoemission experiments were performed on these well-characterized sample surfaces. The valence-band and the core-level spectra obtained from the single-crystal surfaces are in agreement with spectra recorded from polycrystalline samples, justifying earlier results from polycrystalline samples. Cu satellites are observed both in the valence band and Cu 2p core level, signaling the strong correlation among the Cu 3d electrons. The O 1s core-level data exhibit a sharp, single peak at 529-eV binding energy without any clear satellite structures.

Synthesis, characterization and crystal structure of (2RS,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid

NASA Astrophysics Data System (ADS)

Muche, Simon; Müller, Matthias; Hołyńska, Małgorzata

2018-03-01

The condensation reaction of ortho-vanillin and L-cysteine leads to formation of a racemic mixture of (2RS,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid and not, as reported in the available literature, to a Schiff base. The racemic mixture was fully characterized by 1D and 2D NMR techniques, ESI-MS and X-ray diffraction. Addition of ZnCl2 led to formation of crystals in form of colorless needles, suitable for X-ray diffraction studies. The measured crystals were identified as the diastereomer (2R,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid 1. The bulk material is racemic. Thiazolidine exists as zwitterion in solid state, as indicated by the crystal structure.

Engineering Ferroic and Multiferroic Materials for Active Cooling Applications

DTIC Science & Technology

2014-02-11

large strain gradients (>105 m-1) – nearly 5-6 orders of magnitude larger than what can be achieved in bulk-versions of materials. These large strain...larger than what can be achieved in bulk-versions of materials. These large strain gradients gave rise to unexpected crystal and domain structure...parameters that are more favorable for generating a compressively strained variety of the Zr-rich phases. In this case, akin to what has been

2016 International Workshop on Nitride Semiconductors (IWN 2016)

DTIC Science & Technology

2017-01-01

Doping Structure & Photoluminescence Properties of Flower-Like Spiral AIN Micro-Crystal Array Thermal Conductivity of Bulk AIN Direct Determination of...5.03 Optical and Electronic Properties HVPE GaN Wafers with Improved Crystallinity 5:00pm Michael Slomski 01.5.04 Thermal Conductivity of Bulk GaN...Broad-Band Emission Effect of lnter1ayers on the Vertical Electrical Conductivity of Si-Doped AIN/GaN DBRs Grown by PA-MBE Thermal Analys is of

Structures and mechanical behaviors of Zr55Cu35Al10 bulk amorphous alloys at ambient and cryogenic temperatures

NASA Astrophysics Data System (ADS)

Fan, Cang; Liaw, P. K.; Haas, V.; Wall, J. J.; Choo, H.; Inoue, A.; Liu, C. T.

2006-07-01

Based on a systematic study of pair distribution functions, carried out at cryogenic and ambient temperatures, on as-cast and crystallized ternary Zr-based bulk amorphous alloys (BAAs), we found that the atoms in BAAs are inhomogenously distributed at a local atomic level. They exist as different clusters with significantly shorter bond lengths than their crystallized counterpart structures—intermetallic compounds, and these structures exist stably in the amorphous state. This results in additional free volume, which is about ˜7% larger than that measured by the Archimedes method. The compressive strength measured at ˜77K was found to be ˜16% larger than that measured at 298K . In this study, an amorphous structural model is proposed, in which strongly bonded clusters acting as units are randomly distributed and strongly correlated to one another, as the free volume forms between clusters. Simulations with reverse Monte Carlo were performed by combining icosehadral and cubic structures as the initial structures for the BAA. The simulations show results consistent with our model. An attempt has been made to connect the relationship between amorphous structures and their mechanical properties.

Epitaxial Ce and the magnetism of single-crystal Ce/Nd superlattices

NASA Astrophysics Data System (ADS)

Clegg, P. S.; Goff, J. P.; McIntyre, G. J.; Ward, R. C.; Wells, M. R.

2003-05-01

The chemical structure of epitaxial γ cerium and the chemical and magnetic structures of cerium/neodymium superlattices have been studied using x-ray and neutron diffraction techniques. The samples were grown using molecular-beam epitaxy, optimized to yield the desired Ce allotropes. The x-ray measurements show that, in the superlattices, both constituents adopt the dhcp structure and that the stacking sequence remains intact down to T˜2 K; these are the first measurements of magnetic ordering in single-crystal dhcp Ce. The magnetic structure of the superlattices with thicker Nd layers exhibit incommensurate order and ferromagnetism on separate sublattices in a similar manner to Nd under applied pressure. The sample with thickest Ce layers has a magnetic structure similar to bulk β Ce, which has commensurate transverse modulation with a propagation wave vector [1/2 0 0] and moments along the hexagonal a direction. These two types of magnetic order appear to be mutually exclusive. γ Ce is the high-temperature fcc phase of Ce, our single-phase epitaxial sample is observed to go through a new, but partial, structural transition not previously seen in the bulk material.

Thermal treatment induced modification of structural, surface and bulk magnetic properties of Fe61.5Co5Ni8Si13.5B9Nb3 metallic glass

NASA Astrophysics Data System (ADS)

Shah, M.; Satalkar, M.; Kane, S. N.; Ghodke, N. L.; Sinha, A. K.; Varga, L. K.; Teixeira, J. M.; Araujo, J. P.

2018-05-01

Effect of thermal annealing induced modification of structural, surface and bulk magnetic properties of Fe61.5Co5Ni8Si13.5B9Nb3 alloy is presented. The changes in properties were observed using synchrotron x-ray diffraction technique (SXRD), atomic force microscopy (AFM), magneto-optical kerr effect (MOKE) and bulk magnetic measurements. Significant variations on the both side of surface occur for the annealing temperature upto 500 °C promotes the surface crystallization. Surface roughness appears due to presence of nanocrystallization plays an important role in determining magnetic properties. Observed lower value of bulk coercivity Hc of 6.2 A/m annealed temperature at 450 °C/1 h ascribed to reduction of disorder as compared to the surface (both shiny and wheel side observed by MOKE measurement) whereas improvement of bulk saturation magnetization with annealing temperature indicates first near neighbor shell of Fe atoms are surrounded by Fe atoms. Evolution of coercivity of surface and bulk with annealing temperature has been presented in conjunction with the structural observations.

A molded surface-micromachining and bulk etching release (MOSBE) fabrication platform on (1 1 1) Si for MOEMS

NASA Astrophysics Data System (ADS)

Wu, Mingching; Fang, Weileun

2006-02-01

This work attempts to integrate poly-Si thin film and single-crystal-silicon (SCS) structures in a monolithic process. The process integrated multi-depth DRIE (deep reactive ion etching), trench-refilled molding, a two poly-Si MUMPs process and (1 1 1) Si bulk micromachining to accomplish multi-thickness and multi-depth structures for superior micro-optical devices. In application, a SCS scanning mirror driven by self-aligned vertical comb-drive actuators was demonstrated. The stiffness of the mirror was significantly increased by thick SCS structures. The thin poly-Si film served as flexible torsional springs and electrical routings. The depth difference of the vertical comb electrodes was tuned by DRIE to increase the devices' stroke. Finally, a large moving space was available after the bulk Si etching. In summary, the present fabrication process, named (1 1 1) MOSBE (molded surface-micromachining and bulk etching release on (1 1 1) Si substrate), can further integrate with the MUMPs devices to establish a more powerful platform.

Surface and electronic structure of Bi-Ca-Sr-Cu-O superconductors studied by LEED, UPS and XPS

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Wells, B. O.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Eom, C. B.; Kapitulnik, A.; Geballe, T. H.; Soukiassian, P.

1989-02-01

Single crystal and polycrystalline samples of Bi2CaSr2Cu2O8 have been studied by various surface sensitive techniques, including low energy electron diffraction (LEED), ultraviolet photoemission spectroscopy (UPS) and x-ray photoemission spectroscopy (XPS). The surface structure of the single crystals was characterized by LEED to be consistent with that of the bulk structure. Our data suggest that Bi2CaSr2Cu2O8 single crystals are very stable in the ultrahigh vacuu. No change of XPS spectra with temperature was observed. We have also studied the electronic structure of Bi2Sr2CuO6, which has a lower superconducting transition temperature Tc. Comparing the electronic structure of the two Bi-Ca-Sr-Cu-O superconductors, an important difference in the density of states near EF was observed which seems to be related to the difference in Tc.

Magnetic state of a Zn1 - x Cr x Se bulk crystal

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Korolev, A. V.; Teploukhov, S. G.; Chukalkin, Yu. G.; Parkhomenko, V. D.; Gruzdev, N. B.

2008-06-01

The spin system of a Zn1 - x Cr x Se bulk crystal ( x = 0.045) was studied using thermal-neutron diffraction and magnetic measurements. Previously, it was reported in the literature that thin films (˜200 nm thick) of this type of semiconductors exhibit a ferromagnetic order. In this study, the ferromagnetic order is found to be absent in the bulk crystal.

A spatio-spectral polarization analysis of 1 µm-pumped bulk supercontinuum in a cubic crystal (YAG)

NASA Astrophysics Data System (ADS)

Choudhuri, Aradhana; Chatterjee, Gourab; Zheng, Jiaan; Hartl, Ingmar; Ruehl, Axel; Dwayne Miller, R. J.

2018-06-01

We present the first systematic study of the spatio-spectral polarization properties of a supercontinuum generated in a cubic crystal, yttrium-aluminum garnet (YAG), including a full spectral analysis of the white light core and surrounding ring structure. We observe no depolarization of the supercontinuum, and no spatial dependence of polarization ratios for any wavelength. We discuss the discrepancy of YAG's polarization behavior in the context of well-established results in literature reporting self-induced depolarization in other cubic crystals.

Low field magnetocaloric effect in bulk and ribbon alloy La(Fe0.88Si0.12)13

NASA Astrophysics Data System (ADS)

Vuong, Van-Hiep; Do-Thi, Kim-Anh; Nguyen, Duy-Thien; Nguyen, Quang-Hoa; Hoang, Nam-Nhat

2018-03-01

Low-field magnetocaloric effect occurred in itinerant metamagnetic materials is at core for magnetic cooling application. This works reports the magnetocaloric responses obtained at 1.35 T for the silicon-doped iron-based binary alloy La(Fe0.88Si0.12)13 in the bulk and ribbon form. Both samples possess a same symmetry but with different crystallite sizes and lattice parameters. The ribbon sample shows a larger maximum entropy change (nearly 8.5 times larger) and a higher Curie temperature (5 K higher) in comparison with that of the bulk sample. The obtained relative cooling power for the ribbon is also larger and very promising for application (RCP = 153 J/kg versus 25.2 J/kg for the bulk). The origin of the effect observed is assigned to the occurrence of negative magnetovolume effect in the ribbon structure with limit crystallization, caused by rapid cooling process at the preparation, which induced smaller crystallite size and large lattice constant at the overall weaker local crystal field.

Temperature-induced band shift in bulk γ-InSe by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Huanfeng; Wang, Wei; Zhao, Yafei; Zhang, Xiaoqian; Feng, Yue; Tu, Jian; Gu, Chenyi; Sun, Yizhe; Liu, Chang; Nie, Yuefeng; Edmond Turcu, Ion C.; Xu, Yongbing; He, Liang

2018-05-01

Indium selenide (InSe) has recently become popular research topics because of its unique layered crystal structure, direct band gap and high electron mobilities. In this work, we have acquired the electronic structure of bulk γ-InSe at various temperatures using angle-resolved photoemission spectroscopy (ARPES). We have also found that as the temperature decreases, the valence bands of γ-InSe exhibit a monotonic shift to lower binding energies. This band shift is attributed to the change of lattice parameters and has been validated by variable temperature X-ray diffraction measurements and theoretical calculations.

Inhomogeneities and superconductivity in poly-phase Fe-Se-Te systems

NASA Astrophysics Data System (ADS)

Hartwig, S.; Schäfer, N.; Schulze, M.; Landsgesell, S.; Abou-Ras, D.; Blum, Ch. G. F.; Wurmehl, S.; Sokolowski, A.; Büchner, B.; Prokeš, K.

2018-02-01

The impact of synthesis conditions, post-preparation heating procedure, aging and influence of pressure on the superconducting properties of FeSe0.4Te0.6 crystals is reported. Two FeSe0.4Te0.6 single crystals were used in the study, prepared from stoichiometric melt but cooled down with very different cooling rates, and investigated using magnetic bulk and electrical-resistivity methods. The fast-cooled crystal contains large inclusions of Fe3Se2.1Te1.8 and exhibits bulk superconductivity in its as-prepared state, while the other is homogeneous and shows only traces of superconductivity. AC susceptibility measurements under hydrostatic pressure show that the superconducting transition temperature of the inhomogeneous crystal increases from 12.3 K at ambient pressure to Tsc = 17.9 K at 9 kbar. On the other hand, neither pressure nor mechanically-induced stress is sufficient to induce superconductivity in the homogeneous crystal. However, an additional heat treatment at 673 K followed by fast cooling down and/or long-term aging at ambient conditions leads to the appearance of bulk superconductivity also in the latter sample. This sample remains homogeneous on a scale down to few μm but shows an additional magnetic phase transition around 130 K suggesting that it must be inhomogeneous. For comparison also Fe3Se2.1Te1.8 polycrystals have been prepared and their magnetic properties have been studied. It appears that this phase is not superconducting by itself. It is concluded that nano-scale inhomogeneities that appear in the FeSexTe1-x system due to a spinodal decomposition in the solid state are necessary for bulk superconductivity, possibly due to minor changes in the crystal structure and microstructure. Macroscopic inclusions quenched by fast cooling from high temperatures lead obviously to strain and hence variations in the lattice constants, an effect that is further supported by application of pressure/stress.

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects.

PubMed

Titus, Michael S; Rhein, Robert K; Wells, Peter B; Dodge, Philip C; Viswanathan, Gopal Babu; Mills, Michael J; Van der Ven, Anton; Pollock, Tresa M

2016-12-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4-atomic-layer-thick phase, where segregation has occurred, compared to the approximately 35-atomic-layer-thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties.

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects

PubMed Central

Titus, Michael S.; Rhein, Robert K.; Wells, Peter B.; Dodge, Philip C.; Viswanathan, Gopal Babu; Mills, Michael J.; Van der Ven, Anton; Pollock, Tresa M.

2016-01-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4–atomic-layer–thick phase, where segregation has occurred, compared to the approximately 35–atomic-layer–thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties. PMID:28028543

Analysis of Surface and Bulk Behavior in Ni-Pd Alloys

NASA Technical Reports Server (NTRS)

Bozzolo, Guillermo; Noebe, Rondald D.

2003-01-01

The most salient features of the surface structure and bulk behavior of Ni-Pd alloys have been studied using the BFS method for alloys. Large-scale atomistic simulations were performed to investigate surface segregation profiles as a function of temperature, crystal face, and composition. Pd enrichment of the first layer was observed in (111) and (100) surfaces, and enrichment of the top two layers occurred for (110) surfaces. In all cases, the segregation profile shows alternate planes enriched and depleted in Pd. In addition, the phase structure of bulk Ni-Pd alloys as a function of temperature and composition was studied. A weak ordering tendency was observed at low temperatures, which helps explain the compositional oscillations in the segregation profiles. Finally, based on atom-by-atom static energy calculations, a comprehensive explanation for the observed surface and bulk features will be presented in terms of competing chemical and strain energy effects.

Crystal structure, thermal expansivity, and elasticity of OH-chondrodite: Trends among dense hydrous magnesium silicates

DOE PAGES

Ye, Yu; Jacobsen, Steven D.; Mao, Zhu; ...

2015-04-01

Here, we report the structure and thermoelastic properties of OH-chondrodite. The sample was synthesized at 12 GPa and 1523 K, coexisting with hydroxyl-clinohumite and hydrous olivine. The Fe content Fe/(Fe+Mg) is 1.1 mol%, and the monoclinic unit-cell parameters are: a = 4.7459(2) Å, b = 10.3480(7) Å, c = 7.9002(6) Å, α = 108.702(7)°, and V = 367.50(4) Å3. At ambient conditions the crystal structure was refined in space group P 21/b from 1915 unique reflection intensities measured by single-crystal x-ray diffraction. The volume thermal expansion coefficient was measured between 150 and 800 K, resulting in α V = 2.8(5)×10more » -9(K -2) × T + 40.9(7) × 10 -6(K -1) – 0.81(3)(K)/T 2, with an average value of 38.0(9)×10 -6 K -1. Brillouin spectroscopy was used to measure a set of acoustic velocities from which all thirteen components (C ij) of the elastic tensor were determined. The Voigt-Reuss-Hill average of the moduli yield for the adiabatic bulk modulus, K S0 = 117.9(12) GPa, and for shear modulus, G 0 = 70.1(5) GPa. The Reuss bound on the isothermal bulk modulus (K T0) is 114.2(14) GPa. From the measured thermodynamic properties, the Grüneisen parameter (γ) is calculated to be 1.66(4). Fitting previous static compression data using our independently measured bulk modulus (isothermal Reuss bound) as a fixed parameter, we refined the first pressure derivative of the bulk modulus, K T’ = 5.5(1). Systematic trends between H 2O content and physical properties are evaluated among dense hydrous magnesium silicate (DHMS) phases along the forsterite-brucite join.« less

Bulk contribution to magnetotransport properties of low-defect-density Bi2Te3 topological insulator thin films

NASA Astrophysics Data System (ADS)

Ngabonziza, P.; Wang, Y.; Brinkman, A.

2018-04-01

An important challenge in the field of topological materials is to carefully disentangle the electronic transport contribution of the topological surface states from that of the bulk. For Bi2Te3 topological insulator samples, bulk single crystals and thin films exposed to air during fabrication processes are known to be bulk conducting, with the chemical potential in the bulk conduction band. For Bi2Te3 thin films grown by molecular beam epitaxy, we combine structural characterization (transmission electron microscopy), chemical surface analysis as function of time (x-ray photoelectron spectroscopy) and magnetotransport analysis to understand the low defect density and record high bulk electron mobility once charge is doped into the bulk by surface degradation. Carrier densities and electronic mobilities extracted from the Hall effect and the quantum oscillations are consistent and reveal a large bulk carrier mobility. Because of the cylindrical shape of the bulk Fermi surface, the angle dependence of the bulk magnetoresistance oscillations is two dimensional in nature.

Crystal-to-glass-transition induced elastic anomaly of cerium-iron multilayer films and texture-related mechanical properties after hydrogenation

NASA Astrophysics Data System (ADS)

Hassdorf, R.; Arend, M.; Felsch, W.

1995-04-01

The flexural modulus EF of pure and hydrided cerium-iron multilayer films has been measured at 300 K as a function of the modulation wavelength Λ using a vibrating-reed technique. EF is strongly correlated to the structure of the layered systems. In the pure Ce/Fe multilayers, the Fe sublayers show a structural transition from an amorphous to the bcc crystalline phase for a thickness near 20 Å. At this transition, the modulus EF is reduced by ~70%. The elastic softening occurs already, as a precursor to the structural change, for the crystalline Fe sublayers somewhat above the thickness for amorphous growth. This behavior reveals close similarities to the crystal-to-glass transition in bulk metallic alloys and compounds which seems to be driven by a shear instability of the crystal lattice. Hydrogenation leads to multilayers built of CeH~2/Fe. The Fe sublayers grow in the bcc structure above 10 Å, with a pronounced (110) or (111) texture for low- or room-temperature deposition. The flexural moduli are larger as compared to the nonhydrided multilayers and distinctly different for the two Fe textures. A simple calculation shows that the texture-related differences mainly result from the bulk properties of the Fe layers, but a contribution of interfacial effects cannot be excluded.

Epitaxial BiFeO3 thin films fabricated by chemical solution deposition

NASA Astrophysics Data System (ADS)

Singh, S. K.; Kim, Y. K.; Funakubo, H.; Ishiwara, H.

2006-04-01

Epitaxial BiFeO3 (BFO) thin films were fabricated on (001)-, (110)-, and (111)-oriented single-crystal SrRuO3(SRO )/SrTiO3(STO) structures by chemical solution deposition. X-ray diffraction indicates the formation of an epitaxial single-phase perovskite structure and pole figure measurement confirms the cube-on-cube epitaxial relationship of BFO ‖SRO‖STO. Chemical-solution-deposited BFO films have a rhombohedral structure with lattice parameter of 0.395nm, which is the same structure as that of a bulk single crystal. The remanent polarization of approximately 50μC/cm2 was observed in BFO (001) thin films at 80K.

Densification behavior, nanocrystallization, and mechanical properties of spark plasma sintered Fe-based bulk amorphous alloys

NASA Astrophysics Data System (ADS)

Singh, Ashish Kumar

Fe-based amorphous alloys are gaining increasing attention due to their exceptional wear and corrosion resistance for potential structural applications. Two major challenges that are hindering the commercialization of these amorphous alloys are difficulty in processing of bulk shapes (diameter > 10 mm) and lack of ductility. Spark plasma sintering (SPS) is evolving as a promising technique for processing bulk shapes of amorphous and nanocrystalline materials. The objective of this work is to investigate densification behavior, nanocrystallization, and mechanical properties of SPS sintered Fe-based amorphous alloys of composition Fe48Cr15Mo14Y2C15B6. SPS processing was performed in three distinct temperature ranges of amorphous alloys: (a) below glass transition temperature (Tg), (b) between Tg and crystallization temperature (Tx), and (c) above Tx. Punch displacement data obtained during SPS sintering was correlated with the SPS processing parameters such as temperature, pressure, and sintering time. Powder rearrangement, plastic deformation below T g, and viscous flow of the material between Tg and Tx were observed as the main densification stages during SPS sintering. Micro-scale temperature distributions at the point of contact and macro-scale temperature distribution throughout the sample during SPS of amorphous alloys were modeled. The bulk amorphous alloys are expected to undergo structural relaxation and nanocrystallization during SPS sintering. X-ray diffraction (XRD), small angle neutron scattering (SANS), and transmission electron microscopy (TEM) was performed to investigate the evolution of nanocrystallites in SPS sintered Fe-based bulk amorphous alloys. The SANS analysis showed significant scattering for the samples sintered in the supercooled region indicating local structural and compositional changes with the profuse nucleation of nano-clusters (~4 nm). Compression tests and microhardness were performed on the samples sintered at different temperatures ranging from 570 °C to 800 °C. Maximum compression strength (1.1+/-0.2 MPa) was obtained for the samples sintered in the supercooled region. Effects of crystallization on tribological behavior of sintered samples were also investigated where crystallization resulted in increase in wear resistance. Laser surface hardening of SPS sintered amorphous samples were performed. Depending on the processing parameters, the laser surface irradiation causes structural relaxation and nanocrystallization, resulting in surface hardening.

Holographic fabrication of 3D photonic crystals through interference of multi-beams with 4 + 1, 5 + 1 and 6 + 1 configurations.

PubMed

George, D; Lutkenhaus, J; Lowell, D; Moazzezi, M; Adewole, M; Philipose, U; Zhang, H; Poole, Z L; Chen, K P; Lin, Y

2014-09-22

In this paper, we are able to fabricate 3D photonic crystals or quasi-crystals through single beam and single optical element based holographic lithography. The reflective optical elements are used to generate multiple side beams with s-polarization and one central beam with circular polarization which in turn are used for interference based holographic lithography without the need of any other bulk optics. These optical elements have been used to fabricate 3D photonic crystals with 4, 5 or 6-fold symmetry. A good agreement has been observed between fabricated holographic structures and simulated interference patterns.

Electronic and magnetic structure of ultra-thin Ni films grown on W(110)

NASA Astrophysics Data System (ADS)

Calloni, A.; Bussetti, G.; Berti, G.; Yivlialin, R.; Camera, A.; Finazzi, M.; Duò, L.; Ciccacci, F.

2016-12-01

We studied the electronic structure of thin Ni films grown on a W(110) single crystal, as a function of the Ni thickness, by means of angle-resolved photoemission and inverse photoemission spectroscopy, also with spin resolution. The results are discussed in the light of the different stages characterizing the transition from the pseudomorphic bcc to the fully relaxed fcc phase. A clear spin polarization is detected as soon as a bulk-like electronic structure is observed. In these conditions, we characterized the exchange splitting of the occupied bands at the Γbar and Mbar points of the surface Brillouin zone, providing further experimental support to previous interpretations of photoemission spectra from bulk Ni.

The structure of small, vapor-deposited particles. II - Experimental study of particles with hexagonal profile

NASA Technical Reports Server (NTRS)

Yacaman, M. J.; Heinemann, K.; Yang, C. Y.; Poppa, H.

1979-01-01

'Multiply-twinned' gold particles with hexagonal bright field TEM profile were determined to be icosahedra composed of 20 identical and twin-related tetrahedral building units that do not have an fcc structure. The crystal structure of these slightly deformed tetrahedra is rhombohedral. Experimental evidence supporting this particle model was obtained by selected-zone dark field and weak beam dark field electron microscopy. In conjunction with the results of part I, it has been concluded that multiply-twinned gold particles of pentagonal or hexagonal profile that are found during the early stages of the vapor deposition growth process on alkali halide surfaces do not have an fcc crystal structure, which is in obvious contrast to the structure of bulk gold.

Imaging of surface spin textures on bulk crystals by scanning electron microscopy

NASA Astrophysics Data System (ADS)

Akamine, Hiroshi; Okumura, So; Farjami, Sahar; Murakami, Yasukazu; Nishida, Minoru

2016-11-01

Direct observation of magnetic microstructures is vital for advancing spintronics and other technologies. Here we report a method for imaging surface domain structures on bulk samples by scanning electron microscopy (SEM). Complex magnetic domains, referred to as the maze state in CoPt/FePt alloys, were observed at a spatial resolution of less than 100 nm by using an in-lens annular detector. The method allows for imaging almost all the domain walls in the mazy structure, whereas the visualisation of the domain walls with the classical SEM method was limited. Our method provides a simple way to analyse surface domain structures in the bulk state that can be used in combination with SEM functions such as orientation or composition analysis. Thus, the method extends applications of SEM-based magnetic imaging, and is promising for resolving various problems at the forefront of fields including physics, magnetics, materials science, engineering, and chemistry.

Crystallization kinetics of Mg–Cu–Yb–Ca–Ag metallic glasses

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

Tsarkov, Andrey A., E-mail: tsarkov@misis.ru; WPI Advanced Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577; Zanaeva, Erzhena N.

The paper presents research into a Mg–Cu–Yb system based metallic glassy alloys. Metallic glasses were prepared using induction melting and further injection on a spinning copper wheel. The effect of alloying by Ag and Ca on the glass forming ability and the kinetics of crystallization of Mg–Cu–Yb system based alloys were studied. The differential scanning calorimeter and X-ray diffractometer were used to investigate the kinetics of crystallization and the phase composition of the samples. An indicator of glass forming ability, effective activation energy of crystallization, and enthalpy of mixing were calculated. An increase of the Ca and Ag content hasmore » a positive effect on the glass forming ability, the effective activation energy of crystallization, and the enthalpy of mixing. The highest indicators of the glass forming ability and the thermal stability were found for alloys that contain both alloying elements. The Ag addition suppresses precipitation of the Mg{sub 2}Cu phase during crystallization. A dual-phase glassy-nanocrystalline Mg structure was obtained in Mg{sub 65}Cu{sub 25}Yb{sub 10} and Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} alloys after annealing. Bulk samples with a composite glassy-crystalline structure were obtained in Mg{sub 59.5}Cu{sub 22.9}Yb{sub 11}Ag{sub 6.6} and Mg{sub 64}Cu{sub 21}Yb{sub 9.5}Ag{sub 5.5} alloys. A thermodynamic database for the Mg–Cu–Yb–Ca–Ag system was created to compare the process of crystallization of alloys with polythermal sections of the Mg–Cu–Yb–Ca–Ag phase diagram. - Highlights: • New alloy compositions based on Mg–Cu–Yb system were developed and investigated. • Increasing content of Ag and Ca leads to improving GFA. • Bulk samples with a composite glassy-crystalline structure were obtained. • Thermodynamic database for Mg–Cu–Yb–Ca–Ag system was created.« less

Thermal conductivity engineering of bulk and one-dimensional Si-Ge nanoarchitectures.

PubMed

Kandemir, Ali; Ozden, Ayberk; Cagin, Tahir; Sevik, Cem

2017-01-01

Various theoretical and experimental methods are utilized to investigate the thermal conductivity of nanostructured materials; this is a critical parameter to increase performance of thermoelectric devices. Among these methods, equilibrium molecular dynamics (EMD) is an accurate technique to predict lattice thermal conductivity. In this study, by means of systematic EMD simulations, thermal conductivity of bulk Si-Ge structures (pristine, alloy and superlattice) and their nanostructured one dimensional forms with square and circular cross-section geometries (asymmetric and symmetric) are calculated for different crystallographic directions. A comprehensive temperature analysis is evaluated for selected structures as well. The results show that one-dimensional structures are superior candidates in terms of their low lattice thermal conductivity and thermal conductivity tunability by nanostructuring, such as by diameter modulation, interface roughness, periodicity and number of interfaces. We find that thermal conductivity decreases with smaller diameters or cross section areas. Furthermore, interface roughness decreases thermal conductivity with a profound impact. Moreover, we predicted that there is a specific periodicity that gives minimum thermal conductivity in symmetric superlattice structures. The decreasing thermal conductivity is due to the reducing phonon movement in the system due to the effect of the number of interfaces that determine regimes of ballistic and wave transport phenomena. In some nanostructures, such as nanowire superlattices, thermal conductivity of the Si/Ge system can be reduced to nearly twice that of an amorphous silicon thermal conductivity. Additionally, it is found that one crystal orientation, [Formula: see text]100[Formula: see text], is better than the [Formula: see text]111[Formula: see text] crystal orientation in one-dimensional and bulk SiGe systems. Our results clearly point out the importance of lattice thermal conductivity engineering in bulk and nanostructures to produce high-performance thermoelectric materials.

Thermal conductivity engineering of bulk and one-dimensional Si-Ge nanoarchitectures

PubMed Central

Kandemir, Ali; Ozden, Ayberk; Cagin, Tahir; Sevik, Cem

2017-01-01

Various theoretical and experimental methods are utilized to investigate the thermal conductivity of nanostructured materials; this is a critical parameter to increase performance of thermoelectric devices. Among these methods, equilibrium molecular dynamics (EMD) is an accurate technique to predict lattice thermal conductivity. In this study, by means of systematic EMD simulations, thermal conductivity of bulk Si-Ge structures (pristine, alloy and superlattice) and their nanostructured one dimensional forms with square and circular cross-section geometries (asymmetric and symmetric) are calculated for different crystallographic directions. A comprehensive temperature analysis is evaluated for selected structures as well. The results show that one-dimensional structures are superior candidates in terms of their low lattice thermal conductivity and thermal conductivity tunability by nanostructuring, such as by diameter modulation, interface roughness, periodicity and number of interfaces. We find that thermal conductivity decreases with smaller diameters or cross section areas. Furthermore, interface roughness decreases thermal conductivity with a profound impact. Moreover, we predicted that there is a specific periodicity that gives minimum thermal conductivity in symmetric superlattice structures. The decreasing thermal conductivity is due to the reducing phonon movement in the system due to the effect of the number of interfaces that determine regimes of ballistic and wave transport phenomena. In some nanostructures, such as nanowire superlattices, thermal conductivity of the Si/Ge system can be reduced to nearly twice that of an amorphous silicon thermal conductivity. Additionally, it is found that one crystal orientation, <100>, is better than the <111> crystal orientation in one-dimensional and bulk SiGe systems. Our results clearly point out the importance of lattice thermal conductivity engineering in bulk and nanostructures to produce high-performance thermoelectric materials. PMID:28469733

Crystal Chemical Controls on Equation of State

NASA Astrophysics Data System (ADS)

Thompson, R. M.; McCarthy, A. C.; Downs, R. T.

2007-12-01

Minerals are known to compress through a number of mechanisms, ranging from polyhedral distortion to electronic transitions. Two mechanisms which can produce significant volume decreases are angle-bending and bond compression. The crystal chemical effects of these two mechanisms have been studied and documented for years. With more recent advances in theory and software enabling the accurate determination of bonding topologies, M-O bonding to bridging oxygens has been shown to modify compressibility by changing angle-bending force constants. Minerals that compress mainly through angle-bending tend be soft. Good examples are quartz and cristobalite, minerals composed solely of corner-sharing silicate tetrahedra with bulk moduli of 37 and 12 GPa, respectively. Rock salt structured oxides must compress strictly by bond compression, and are much stiffer - lime and periclase have bulk moduli of 111 and 156 GPa, respectively. Feldspars have bulk moduli intermediate to the above examples. Based solely on the presence of Al-O-Si angles, theoretically softer than Si-O-Si angles, feldspars should be softer than quartz or cristobalite, but the T-O-T angles are stiffened by bonds to interstitial cations. The number and nature of these bonds affects compressibility sufficiently to create exceptions to Bridgman's law, which correlates bulk modulus with ambient unit cell volume in isostructural materials. In this paper, we present new high-pressure refinements of the crystal structures of jadeite, aegirine, and NaGa- clinopyroxene. Bulk moduli of these pyroxenes and all other end-member clinopyroxenes we could find in the literature (19 total) are plotted vs. unit cell volumes to test Bridgman's law. The data fall along two trends, each of which is separately consistent with Bridgman's law. Pyroxenes in one trend are dramatically stiffer than those in the other trend, with bulk moduli that differ by approximately 40 GPa. The only difference between the topologies of the structures in the two trends is in the bonding around M2. Structures in the less compressible trend have M2-O3 bonds that oppose Si-O-Si angle-bending in the tetrahedral chains. This angle-bending is an important compression mechanism in pyroxenes. McCarthy et al. (in press) term these bonds "antipathetic". Pyroxenes in the more compressible trend lack these bonds. There are other M2-O3 bonds that visual inspection suggests might tend to encourage angle-bending, but do not appear to have an effect. McCarthy et al. term these bonds "apathetic," and suggest the term "sympathetic" for M-O bonds that actually soften angles. Other examples from the literature will be presented including one from the feldspars that may be a truly sympathetic bond. McCarthy, A.C., Downs, R.T., and Thompson, R.M. (in press) Compressibility trends of the clinopyroxenes, and in- situ high-pressure single-crystal X-ray diffraction study of jadeite. American Mineralogist.

High-quality single-crystal thulium iron garnet films with perpendicular magnetic anisotropy by off-axis sputtering

NASA Astrophysics Data System (ADS)

Wu, C. N.; Tseng, C. C.; Lin, K. Y.; Cheng, C. K.; Yeh, S. L.; Fanchiang, Y. T.; Hong, M.; Kwo, J.

2018-05-01

High-quality single-crystal thulium iron garnet (TmIG) films of 10-30 nm thick were grown by off-axis sputtering at room temperature (RT) followed by post-annealing. X-ray photoelectron spectroscopy (XPS) was employed to determine the TmIG film composition to optimize the growth conditions, along with the aid of x-ray diffraction (XRD) structural analysis and atomic force microscope (AFM) for surface morphology. The optimized films exhibited perpendicular magnetic anisotropy (PMA) and the saturation magnetization at RT was ˜99 emu/cm3, close to the RT bulk value ˜110 emu/cm3 with a very low coercive field of ˜2.4 Oe. We extracted the H⊥ of 1734 Oe and the peak-to-peak linewidth ΔH of ferromagnetic resonance are only about 99 Oe, significantly lower than that of PLD grown TmIG film and bulk single crystals. The high-quality sputtered single-crystal TmIG films show great potential to be integrated with topological insulators or heavy metals with strong spin-orbit coupling for spintronic applications.

Coexistence of twisted and untwisted crystals: An impurity/structural order model with implications for agate patterns

USGS Publications Warehouse

Comer, J.; Ortoleva, P.

2007-01-01

Coexistence of twisted and untwisted crystals is explained via a model that accounts for the coupling of the entropic and energetic effects of impurities and a supra-lattice-scale structural order parameter. It is shown that twisted impure crystals can be in equilibrium with untwisted purer ones. The model explains how coexistence can occur in agates and other systems under hydrostatic stress. The model implies that untwisted crystals grown under one set of conditions could undergo a phase separation that, when accompanied by an imposed compositional gradient, leads to commonly observed, alternating bands of twisted and untwisted crystals and, when occurring in the absence of an external gradient, mossy patterns of crystal texture can emerge. This phenomenon is not related to anisotropic applied stress. Rather coexistence is a consequence of a compositional segregation/twist phase transition. Since twist coexistence is a compositional equilibrium, it arises from the exchange between bulk phases; hence, the detailed nature of the atomic structure within an interface between twisted and untwisted zones is not relevant. The approach places crystal-twist phenomena within the theory of order/disorder phase transitions.

Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl 3 crystals

DOE PAGES

McGuire, Michael A.; Clark, Genevieve; KC, Santosh; ...

2017-06-19

CrCl 3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl 3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stagesmore » on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl 3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.« less

Magnetic behavior and spin-lattice coupling in cleavable van der Waals layered CrCl 3 crystals

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

McGuire, Michael A.; Clark, Genevieve; KC, Santosh

CrCl 3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl 3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stagesmore » on cooling, with ferromagnetic correlations forming before long-range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First-principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Lastly, we demonstrate that monolayer and few-layer CrCl 3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.« less

Prediction study of structural, elastic and electronic properties of FeMP (M = Ti, Zr, Hf) compounds

NASA Astrophysics Data System (ADS)

Tanto, A.; Chihi, T.; Ghebouli, M. A.; Reffas, M.; Fatmi, M.; Ghebouli, B.

2018-06-01

First principles calculations are applied in the study of FeMP (M = Ti, Zr, Hf) compounds. We investigate the structural, elastic, mechanical and electronic properties by combining first-principles calculations with the CASTEP approach. For ideal polycrystalline FeMP (M = Ti, Zr, Hf) the shear modulus, Young's modulus, Poisson's ratio, elastic anisotropy indexes, Pugh's criterion, elastic wave velocities and Debye temperature are also calculated from the single crystal elastic constants. The shear anisotropic factors and anisotropy are obtained from the single crystal elastic constants. The Debye temperature is calculated from the average elastic wave velocity obtained from shear and bulk modulus as well as the integration of elastic wave velocities in different directions of the single crystal.

Molecular engineering of colloidal liquid crystals using DNA origami

NASA Astrophysics Data System (ADS)

Siavashpouri, Mahsa; Wachauf, Christian; Zakhary, Mark; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

Understanding the microscopic origin of cholesteric phase remains a foundational, yet unresolved problem in the field of liquid crystals. Lack of experimental model system that allows for the systematic control of the microscopic chiral structure makes it difficult to investigate this problem for several years. Here, using DNA origami technology, we systematically vary the chirality of the colloidal particles with molecular precision and establish a quantitative relationship between the microscopic structure of particles and the macroscopic cholesteric pitch. Our study presents a new methodology for predicting bulk behavior of diverse phases based on the microscopic architectures of the constituent molecules.

Surface modes and reconstruction of diamond structure crystals

NASA Astrophysics Data System (ADS)

Goldammer, W.; Ludwig, W.; Zierau, W.

1986-08-01

Applying our recently proposed Green function method we calculate the surface phonon spectra for the (111) surfaces of the diamond structure crystals C, Si, Ge and α-Sn on the basis of a phenomenological force constant model. Allowing for changes in the surface force constants we investigate the possibility of a surface phonon softening. Relating these soft modes to surface reconstructions we find evidence for a Si (7 × 7), Ge (8 × 8) and α-Sn (3 × 3) reconstruction, while diamond does not exhibit a soft mode behavior at all. We can thus explain the occurrence of different surface structures in these geometrically identical crystals as being determined to a great extent already by bulk properties. Finally, we derive models of the reconstructed surfaces and discuss our model for the Si (7 × 7) surface with respect to experimental TED patterns.

Low-temperature crystal and magnetic structure of α – RuCl 3

DOE PAGES

Cao, Huibo B.; Yan, Jiaqiang; Bridges, Craig A.; ...

2016-04-19

Here, single crystals of the Kitaev spin-liquid candidate α – RuCl 3 have been studied to determine the low-temperature bulk properties, the structure, and the magnetic ground state. Refinements of x-ray diffraction data show that the low-temperature crystal structure is described by space group C2/m with a nearly perfect honeycomb lattice exhibiting less than 0.2% in-plane distortion. The as-grown single crystals exhibit only one sharp magnetic transition at T N = 7 K. The magnetic order below this temperature exhibits a propagation vector of k=(0,1,1/3), which coincides with a three-layer stacking of the C2/m unit cells. Magnetic transitions at highermore » temperatures up to 14 K can be introduced by deformations of the crystal that result in regions in the crystal with a two-layer stacking sequence. The best-fit symmetry-allowed magnetic structure of the as-grown crystals shows that the spins lie in the ac plane, with a zigzag configuration in each honeycomb layer. The three-layer repeat out-of-plane structure can be refined as a 120° spiral order or a collinear structure with a spin direction of 35° away from the a axis. The collinear spin configuration yields a slightly better fit and also is physically preferred. The average ordered moment in either structure is less than 0.45(5) μB per Ru 3+ ion.« less

Structure and optical properties of evaporated films of the Cr- and V-group metals

NASA Technical Reports Server (NTRS)

Nestell, J. E., Jr.; Christy, R. W.; Cohen, M. H.; Ruben, G. C.

1980-01-01

Thin films of Cr, Mo, and W rapidly evaporated in high vacuum (5 x 10 to the -7th torr) onto room-temperature substrates show anomalously low reflectance (compared to bulk samples). From electron and X-ray diffraction and electron microscopy, the normal bcc crystal structure is found, but with very fine grains. Columnar grains about 100 A in diameter were separated by a less dense grain-boundary network about 10-A wide. The measured optical conductivity agrees with an inhomogeneous-medium model that assumes the normal crystalline conductivity for the grain interiors, with model parameters that correlate to the observed columnar grain size. In contrast, V and Nb films rapidly evaporated onto room-temperature substrates have the reflectance of bulk crystalline material. On liquid-nitrogen temperature substrates, however, V and Nb have normal bcc crystal structure but with small flat-plate grains, and the same model, with appropriate parameters, accounts for the optical conductivity. The difference between these two groups apparently depends on residual gases segregated at the grain boundaries in the Cr-group films.

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

Yuan, Chunqing; Smith, R. Scott; Kay, Bruce D.

The crystallization kinetics of nanoscale amorphous solid water (ASW) films are investigated using temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS). TPD measurements are used to probe surface crystallization and RAIRS measurements are used to probe bulk crystallization. Isothermal TPD results show that surface crystallization is independent of the film thickness (from 100 to 1000 ML). Conversely, the RAIRS measurements show that the bulk crystallization time increases linearly with increasing film thickness. These results suggest that nucleation and crystallization begin at the ASW/vacuum interface and then the crystallization growth front propagates linearly into the bulk. This mechanism was confirmedmore » by selective placement of an isotopic layer (5% D2O in H2O) at various positions in an ASW (H2O) film. In this case, the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These experiments provide direct evidence to confirm that ASW crystallization in vacuum proceeds by a “top-down” crystallization mechanism.« less

Temperature-programed time-of-flight secondary ion mass spectrometry study of 1-butyl-3-methylimidazolium trifluoromethanesulfonate during glass-liquid transition, crystallization, melting, and solvation

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

Souda, Ryutaro; Guenster, Jens; CiC Ceramic Institute Clausthal GmbH, D-38678 Clausthal-Zellerfeld

2008-09-07

For this study, time-of-flight secondary ion mass spectrometry was used to analyze the molecular orientation of 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim][OTf]) and its interaction with the adsorbed Na and LiI species at temperatures of 150-300 K. A glassy [bmim][OTf] film crystallizes at around 230 K, as observed from the increase in the [bmim]{sup +} yield. LiI and Na adsorbed on the glassy film are solvated, whereas they tend to form islands on a crystalline film. The crystalline surface inertness is ascribable to the termination with the CF{sub 3} and C{sub 4}H{sub 9} groups, whereas the exposure of polar SO{sub 3} and imidazolemore » groups at the glassy film results in the solvation. Surface layering occurs during solvation of LiI on the glassy film in such a way that the [bmim]{sup +} ([OTf]{sup -}) moiety is exposed to the vacuum (oriented to the bulk). The LiI adsorbed on the glassy film is incorporated into the bulk at temperatures higher than 200 K because of the glass-liquid transition. No further uptake of LiI is observed during crystallization, providing a contrast to the results of normal molecular solids such as water and ethanol. The surface layers of the crystal melt at temperatures below the bulk melting point, as confirmed from the dissolution of adsorbed LiI, but the melting layer retains a short-range order similar to the crystal. The [bmim][OTf] can be regarded as a strongly correlated liquid with the combined liquid property and crystal-type local structure. The origin of this behavior is discussed.« less

Direct measurement of the thickness-dependent electronic band structure of MoS2 using angle-resolved photoemission spectroscopy.

PubMed

Jin, Wencan; Yeh, Po-Chun; Zaki, Nader; Zhang, Datong; Sadowski, Jerzy T; Al-Mahboob, Abdullah; van der Zande, Arend M; Chenet, Daniel A; Dadap, Jerry I; Herman, Irving P; Sutter, Peter; Hone, James; Osgood, Richard M

2013-09-06

We report on the evolution of the thickness-dependent electronic band structure of the two-dimensional layered-dichalcogenide molybdenum disulfide (MoS2). Micrometer-scale angle-resolved photoemission spectroscopy of mechanically exfoliated and chemical-vapor-deposition-grown crystals provides direct evidence for the shifting of the valence band maximum from Γ to K, for the case of MoS2 having more than one layer, to the case of single-layer MoS2, as predicted by density functional theory. This evolution of the electronic structure from bulk to few-layer to monolayer MoS2 had earlier been predicted to arise from quantum confinement. Furthermore, one of the consequences of this progression in the electronic structure is the dramatic increase in the hole effective mass, in going from bulk to monolayer MoS2 at its Brillouin zone center, which is known as the cause for the decreased carrier mobility of the monolayer form compared to that of bulk MoS2.

Extreme low thermal conductivity in nanoscale 3D Si phononic crystal with spherical pores.

PubMed

Yang, Lina; Yang, Nuo; Li, Baowen

2014-01-01

In this work, we propose a nanoscale three-dimensional (3D) Si phononic crystal (PnC) with spherical pores, which can reduce the thermal conductivity of bulk Si by a factor up to 10,000 times at room temperature. Thermal conductivity of Si PnCs depends on the porosity, for example, the thermal conductivity of Si PnCs with porosity 50% is 300 times smaller than that of bulk Si. The phonon participation ratio spectra demonstrate that more phonons are localized as the porosity increases. The thermal conductivity is insensitive to the temperature changes from room temperature to 1100 K. The extreme-low thermal conductivity could lead to a larger value of ZT than unity as the periodic structure affects very little the electric conductivity.

Mosaic anisotropy model for magnetic interactions in mesostructured crystals

NASA Astrophysics Data System (ADS)

Goldman, Abby R.; Asenath-Smith, Emily; Estroff, Lara A.

2017-10-01

We propose a new model for interpreting the magnetic interactions in crystals with mosaic texture called the mosaic anisotropy (MA) model. We test the MA model using hematite as a model system, comparing mosaic crystals to polycrystals, single crystal nanoparticles, and bulk single crystals. Vibrating sample magnetometry confirms the hypothesis of the MA model that mosaic crystals have larger remanence (Mr/Ms) and coercivity (Hc) compared to polycrystalline or bulk single crystals. By exploring the magnetic properties of mesostructured crystalline materials, we may be able to develop new routes to engineering harder magnets.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit.

PubMed

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-08

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3  nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit

NASA Astrophysics Data System (ADS)

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-01

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ˜3 nm . Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

Polymorphic polytypic transition induced in crystals by interaction of spirals and 2D growth mechanisms

NASA Astrophysics Data System (ADS)

Aquilano, Dino; Veesler, Stéphane; Astier, Jean Pierre; Pastero, Linda

2003-01-01

The relationship between crystal polymorphism and polytypism can be revealed by surface patterns through the interlacing of the growth spirals. Simple high-symmetry structures as SiC, ZnS, CdI2 and more complex low-symmetry layered structures as n-paraffins, n-alcohols and micas are concerned with polymorphic-polytypic transition. In this paper, we will show for the first time, through in situ AFM observations and X-ray diffractometry, that a protein polymorph (P2 12 12 1α-amylase) locally changes, during growth, to a monoclinic P2 1 polytype, thanks to the screw dislocation activity. The interplay between spiral steps and 2D nuclei of the polytypes coexisting in the same crystalline individual allows to foresee the consequences on the crystal quality. The discussion is extended to other mineral and biological molecules and a new general rule is proposed to explain the interactions between surface patterns and the bulk crystal structure.

Defect topologies in chiral liquid crystals confined to mesoscopic channels

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

Schlotthauer, Sergej, E-mail: s.schlotthauer@mailbox.tu-berlin.de; Skutnik, Robert A.; Stieger, Tillmann

2015-05-21

We present Monte Carlo simulations in the grand canonical and canonical ensembles of a chiral liquid crystal confined to mesochannels of variable sizes and geometries. The mesochannels are taken to be quasi-infinite in one dimension but finite in the two other directions. Under thermodynamic conditions chosen and for a selected value of the chirality coupling constant, the bulk liquid crystal exhibits structural characteristics of a blue phase II. This is established through the tetrahedral symmetry of disclination lines and the characteristic simple-cubic arrangement of double-twist helices formed by the liquid-crystal molecules along all three axes of a Cartesian coordinate system.more » If the blue phase II is then exposed to confinement, the interplay between its helical structure, various anchoring conditions at the walls of the mesochannels, and the shape of the mesochannels gives rise to a broad variety of novel, qualitative disclination-line structures that are reported here for the first time.« less

Crystal structure and thermal expansion of a CsCe 2Cl 7 scintillator

DOE PAGES

Zhuravleva, M.; Lindsey, A.; Chakoumakos, B. C.; ...

2015-04-06

Here we used single-crystal X-ray diffraction data to determine crystal structure of CsCe 2Cl 7. It crystallizes in a P112 1/b space group with a = 19.352(1) Å, b = 19.352(1) Å, c = 14.838(1) Å, γ = 119.87(2) ° , and V = 4818.6(5) Å 3. Differential scanning calorimetry measurements combined with the structural evolution of CsCe 2Cl 7 via X-ray diffractometry over a temperature range from room temperature to the melting point indicates no obvious intermediate solid-solid phase transitions. The anisotropy in the average linear coefficient of thermal expansion of the a axis (21.3 10 -6/ °C) withmore » respect to the b and c axes (27.0 10 -6/ °C) was determined through lattice parameter refinement of the temperature dependent diffraction patterns. Lastly, these findings suggest that the reported cracking behavior during melt growth of CsCe 2Cl 7 bulk crystals using conventional Bridgman and Czochralski techniques may be largely attributed to the anisotropy in thermal expansion.« less

History of the "Detector Materials Engineering" Crystal Growth Process for Bulk Hg1- x Cd x Te

NASA Astrophysics Data System (ADS)

Higgins, W. M.; Nelson, D. A.; Roy, R. G.; Murosako, R. P.; Lancaster, R. A.; Tower, J.; Norton, P.

2013-11-01

This paper reviews the history and technology of a bulk Hg1- x Cd x Te crystal growth process that was developed in the early 1980s at Honeywell Electro-Optics Division (presently BAE Systems, Electronic Solutions). The crystal growth process name, DME, was an acronym for the department name: Detector Materials Engineering. This was an accelerated crucible rotation technique (ACRT) vertical traveling heater method growth process. Crystal growth occurred in the pseudobinary Hg1- x Cd x Te system. ACRT mixing allowed the lower-density, higher- x-value Hg1- x Cd x Te growth nutrient in the upper region of the ampoule to replenish the depleted melt and allowed the growth of constant- x-value, higher-density Hg1- x Cd x Te. The material grown by this research and production growth process yielded single crystals that had improved purity, compositional uniformity, precipitate density, and reproducibility in comparison with solid-state recrystallization and other bulk Hg1- x Cd x Te growth techniques. Radial and longitudinal nonuniformities in x-value for Hg1- x Cd x Te were reduced to <0.0008/cm. The net electrically active background impurities did not exceed 1 × 1014 cm-3. Electron mobilities in excess of 1.5 × 106 cm2/V-s were observed at 77 K. Structural defects of less than 104 cm-2 were measured. Te precipitates were not observed. As a result of these material improvements, long-wavelength infrared (LWIR) photoconductive devices fabricated from DME material had highly desired performance characteristics.

Fine Structure in the Secondary Electron Emission Peak for Diamond Crystal with (100) Negative Electron Affinity Surface

NASA Technical Reports Server (NTRS)

Asnin, V. M.; Krainsky, I. L.

1998-01-01

A fine structure was discovered in the low-energy peak of the secondary electron emission spectra of the diamond surface with negative electron affinity. We studied this structure for the (100) surface of the natural type-IIb diamond crystal. We have found that the low-energy peak consists of a total of four maxima. The relative energy positions of three of them could be related to the electron energy minima near the bottom of the conduction band. The fourth peak, having the lowest energy, was attributed to the breakup of the bulk exciton at the surface during the process of secondary electron emission.

Tailoring single-cycle electromagnetic pulses in the 2-9 THz frequency range using DAST/SiO₂ multilayer structures pumped at Ti:sapphire wavelength.

PubMed

Stepanov, Andrei G; Rogov, Andrii; Bonacina, Luigi; Wolf, Jean-Pierre; Hauri, Christoph P

2014-09-08

We present a numerical parametric study of single-cycle electromagnetic pulse generation in a DAST/SiO₂multilayer structure via collinear optical rectification of 800 nm femtosecond laser pulses. It is shown that modifications of the thicknesses of the DAST and SiO₂layers allow tuning of the average frequency of the generated THz pulses in the frequency range from 3 to 6 THz. The laser-to-THz energy conversion efficiency in the proposed structures is compared with that in a bulk DAST crystal and a quasi-phase-matching periodically poled DAST crystal and shows significant enhancement.

Nonlinear optical and microscopic analysis of Cu2+ doped zinc thiourea chloride (ZTC) monocrystal

NASA Astrophysics Data System (ADS)

Ramteke, S. P.; Anis, Mohd; Pandian, M. S.; Kalainathan, S.; Baig, M. I.; Ramasamy, P.; Muley, G. G.

2018-02-01

Organometallic crystals offer considerable nonlinear response therefore, present article focuses on bulk growth and investigation of Cu2+ ion doped zinc thiourea chloride (ZTC) crystal to explore its technological impetus for laser assisted nonlinear optical (NLO) device applications. The Cu2+ ion doped ZTC bulk single crystal of dimension 03 × 2.4 × 0.4 cm3 has been grown from pH controlled aqueous solution by employing slow solvent evaporation technique. The structural analysis has been performed by means of single crystal X-ray diffraction technique. The doping of Cu2+ ion in ZTC crystal matrix has been confirmed by means of energy dispersive spectroscopic (EDS) technique. The origin of nonlinear optical properties in Cu2+ ion doped ZTC crystal has been studied by employing the Kurtz-Perry test and Z-scan analysis. The remarkable enhancement in second harmonic generation (SHG) efficiency of Cu2+ ion doped ZTC crystal with reference to ZTC crystal has been determined. The He-Ne laser assisted Z-scan analysis has been performed to determine the third order nonlinear optical (TONLO) nature of grown crystal. The TONLO parameters such as susceptibility, absorption coefficient, refractive index and figure of merit of Cu-ZTC crystal have been evaluated using the Z-scan transmittance data. The laser damage threshold of grown crystal to high intensity of Nd:YAG laser is found to be 706.2 MW/cm2. The hardness number, work hardening index, yield strength and elastic stiffness coefficient of grown crystal has been investigated under microhardness study. The etching study has been carried out to determine the growth likelihood, nature of etch pits and surface quality of grown crystal.

Pressure-induced amorphization in orthorhombic Ta{sub 2}O{sub 5}: An intrinsic character of crystal

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

Li, Quanjun; Zhang, Huafang; Cheng, Benyuan

2014-05-21

The phase transition of orthorhombic Ta{sub 2}O{sub 5} was investigated by in situ synchrotron X-ray diffraction and Raman spectroscopy. The orthorhombic phase transforms into an amorphous form completely at 24.7 GPa. A bulk modulus B{sub 0} = 139 (9) GPa for the orthorhombic Ta{sub 2}O{sub 5} is derived from the P-V data. We suggest that the pressure-induced amorphization (PIA) in Ta{sub 2}O{sub 5} can be attributed to the unstability of the a axis under high pressure leads to the connections of polyhedral breaking down and even triggers disorder of the whole crystal frame. These results demonstrate that the PIA is an intrinsic charactermore » of Ta{sub 2}O{sub 5} which depends on its orthorhombic crystal structure rather than nanosize effects. This study provides a new kind of bulk material for investigating PIA in metal oxides.« less

Identifying barriers to charge-carriers in the bulk and surface regions of Cu2ZnSnS4 nanocrystal films by x-ray absorption fine structures (XAFSs)

NASA Astrophysics Data System (ADS)

Turnbull, Matthew J.; Vaccarello, Daniel; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

2016-11-01

Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it. To examine these relationships, the measured photoresponse from the photo-generation of charge-carrier electron-hole pairs was compared against the crystal structure, as short-range and long-range crystal orders for the films. The photoresponse simplifies the electronic properties into three basic steps that can be associated with changes in energy levels within the band structure. These changes result in the formation of barriers to charge-carrier flow. The extent of these barriers was determined using synchrotron-based X-ray absorbance fine structure to probe the individual metal centers in the film, and comparing these to molecular simulations of the ideal extended x-ray absorbance fine structure scattering. This allowed for the quantification of bond lengths, and thus an interpretation of the distortions in the crystal lattice. The various characteristics of the photoresponse were then correlated to the crystallographic order and used to gain physical insight into barriers to charge-carriers in the bulk and surface regions of CZTS films.

New Form Discovery for the Analgesics Flurbiprofen and Sulindac Facilitated by Polymer-Induced Heteronucleation

PubMed Central

GRZESIAK, ADAM L.; MATZGER, ADAM J.

2008-01-01

The selection and discovery of new crystalline forms is a longstanding issue in solid-state chemistry of critical importance because of the effect molecular packing arrangement exerts on materials properties. Polymer-induced heteronucleation has recently been developed as a powerful approach to discover and control the production of crystal modifications based on the insoluble polymer heteronucleant added to the crystallization solution. The selective nucleation and discovery of new crystal forms of the well-studied pharmaceuticals flurbiprofen (FBP) and sulindac (SUL) has been achieved utilizing this approach. For the first time, FBP form III was produced in bulk quantities and its crystal structure was also determined. Furthermore, a novel 3:2 FBP:H2O phase was discovered that nucleates selectively from only a few polymers. Crystallization of SUL in the presence of insoluble polymers facilitated the growth of form I single crystals suitable for structure determination. Additionally, a new SUL polymorph (form IV) was discovered by this method. The crystal forms of FBP and SUL are characterized by Raman and FTIR spectroscopies, X-ray diffraction, and differential scanning calorimetry. PMID:17567888

Growth and structural characterization of single crystals of the magnetic superconductor Ru1-xSr2-yGd1+yCu2+xO8-δ (RuGd-1212) obtained by the partial melting technique

NASA Astrophysics Data System (ADS)

Yamaki, K.; Bamba, Y.; Mochiku, T.; Funahashi, S.; Matsushita, Y.; Irie, A.

2018-05-01

In this study, cubic single crystals of the magnetic superconductor Ru1-xSr2-yGd1+yCu2+xO8-δ (RuGd-1212) with typical dimensions of 100-150 μm in length were grown by the partial melting technique. Multiple 00l reflections were first observed by XRD measurements of the bulk RuGd-1212 single crystals. The resistivity of the obtained crystals was roughly estimated to be ∼24-80 mΩ cm and no superconducting transition was observed down to 4.2 K. From the XRD measurements and refinement of the crystal structure, it was apparent that the Ru and Sr sites of the single-crystal RuGd-1212 were partially substituted by Cu and Gd, respectively. Oxygen defects were found to be minor (δ ≈ 0.1). The lattice parameters a and c of the single crystals were found to be larger and smaller, respectively, than those of a polycrystalline sample.

The aggregation and characteristics of radiation-induced defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Korzhik, M. V.; Martynovich, E. F.; Runets, L. P.; Stupak, A. P.

2013-02-01

It has been established that diffusion activation energies for anion vacancies and centres ? in lithium fluoride nanocrystals are higher than those in bulk crystals. In nanocrystals, ? centres migrating in the range of the temperature close to room temperature is not observed and these centres remain stable. The ratio of centres ? and F 2 concentrations in nanocrystals is higher than in bulk crystals. A new type of colour centres, which is absent in bulk crystals, is discovered in nanocrystals.

Electronic structure of Fe1.08Te bulk crystals and epitaxial FeTe thin films on Bi2Te3

NASA Astrophysics Data System (ADS)

Arnold, Fabian; Warmuth, Jonas; Michiardi, Matteo; Fikáček, Jan; Bianchi, Marco; Hu, Jin; Mao, Zhiqiang; Miwa, Jill; Singh, Udai Raj; Bremholm, Martin; Wiesendanger, Roland; Honolka, Jan; Wehling, Tim; Wiebe, Jens; Hofmann, Philip

2018-02-01

The electronic structure of thin films of FeTe grown on Bi2Te3 is investigated using angle-resolved photoemission spectroscopy, scanning tunneling microscopy and first principles calculations. As a comparison, data from cleaved bulk Fe1.08Te taken under the same experimental conditions is also presented. Due to the substrate and thin film symmetry, FeTe thin films grow on Bi2Te3 in three domains, rotated by 0°, 120°, and 240°. This results in a superposition of photoemission intensity from the domains, complicating the analysis. However, by combining bulk and thin film data, it is possible to partly disentangle the contributions from three domains. We find a close similarity between thin film and bulk electronic structure and an overall good agreement with first principles calculations, assuming a p-doping shift of 65 meV for the bulk and a renormalization factor of around two. By tracking the change of substrate electronic structure upon film growth, we find indications of an electron transfer from the FeTe film to the substrate. No significant change of the film’s electronic structure or doping is observed when alkali atoms are dosed onto the surface. This is ascribed to the film’s high density of states at the Fermi energy. This behavior is also supported by the ab initio calculations.

Bulk growth of <001> organic nonlinear optical (NLO) L-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) single crystals by SR method

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

Pandian, Muthu Senthil, E-mail: senthilpandianm@ssn.edu.in; Sivasubramani, V.; Ramasamy, P.

2015-06-24

A transparent uniaxial L-arginine 4-nitrophenolate 4-nitrophenol dehydrate (LAPP) single crystal having dimension of 20 mm diameter and 45 mm length was grown by Sankaranarayanan-Ramasamy (SR) method with a growth rate of 1 mm per day. Using an identical solution the conventional crystal grown to a dimension of 8×5×5 mm{sup 3} was obtained over a period of 30 days. The crystal structure has been confirmed by single crystal X-ray diffraction measurement. The crystalline perfection of LAPP crystals grown by slow evaporation solution technique (SEST) and SR method were characterized using Vickers microhardness, UV-Vis NIR, chemical etching, dark and photo current measurements. The above study indicatesmore » that the crystal quality of the Sankaranarayanan-Ramasamy (SR) method grown LAPP is good compared to the conventional method grown crystal.« less

Microtube-Czochralski technique (μT-CZ):. a novel way of seeding the melt to grow bulk single crystal

NASA Astrophysics Data System (ADS)

Sankaranarayanan, K.; Ramasamy, P.

1998-09-01

A novel microtube seeding has been proposed in the conventional Czochralski pulling technique to grow a bulk single crystal. The versatility of the technique has been shown by adopting this method for the growth of benzil. Benzil single crystals having hexagonal facets are grown by this technique called the microtube-Czochralski technique (μT-CZ). Due to capillary rise, a fine column of melt was crystallized inside the microtube, which leads to the formation of the single crystal nucleation and ends up with hexagonal morphology. The reproducibility for getting single crystal is about 80%. It is evident that this technique is more viable to grow a bulk single crystal from the melt without a pregrown-seed. Further, the proposed μT-CZ technique can also be extended to other newer materials with the proper choice of the microtube.

Substrate-induced phase of a [1]benzothieno[3,2-b]benzothiophene derivative and phase evolution by aging and solvent vapor annealing.

PubMed

Jones, Andrew O F; Geerts, Yves H; Karpinska, Jolanta; Kennedy, Alan R; Resel, Roland; Röthel, Christian; Ruzié, Christian; Werzer, Oliver; Sferrazza, Michele

2015-01-28

Substrate-induced phases (SIPs) are polymorphic phases that are found in thin films of a material and are different from the single crystal or "bulk" structure of a material. In this work, we investigate the presence of a SIP in the family of [1]benzothieno[3,2-b]benzothiophene (BTBT) organic semiconductors and the effect of aging and solvent vapor annealing on the film structure. Through extensive X-ray structural investigations of spin coated films, we find a SIP with a significantly different structure to that found in single crystals of the same material forms; the SIP has a herringbone motif while single crystals display layered π-π stacking. Over time, the structure of the film is found to slowly convert to the single crystal structure. Solvent vapor annealing initiates the same structural evolution process but at a greatly increased rate, and near complete conversion can be achieved in a short period of time. As properties such as charge transport capability are determined by the molecular structure, this work highlights the importance of understanding and controlling the structure of organic semiconductor films and presents a simple method to control the film structure by solvent vapor annealing.

The densification, crystallization and mechanical properties of allylhydridopolycarbosilane-derived silicon carbide

NASA Astrophysics Data System (ADS)

Moraes, Kevin V.

Allylhydridopolycarbosilane is a precursor of growing importance in the fabrication of silicon carbide ceramics. However, prior to this study few details were available about the processing-structure-property relationships for this material. In Part 1 of this study the processes of densification and microstructural transformation of the partially pyrolysed amorphous AHPCS-SiC was investigated in the temperature region of 800°C to 1600°C. In Part 2 of this study, mechanical properties, specifically fracture toughness (K1c) and Vickers hardness, were measured on bulk specimens in the temperature range of 1000°C to 1600°C. A combination of X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM), 29Si Nuclear Magnetic Resonance (NMR) and micro Raman spectroscopy, along with simultaneous Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) were used to follow the structural transformation of the partially pyrolysed AHPCS-SiC on several length scales between the temperature of 800 to 1600°C. It was determined that the rate of densification of amorphous AHPCS-SiC, partially pyrolysed to 600°C, depends on the surface to volume ratio. Calculations were preformed that suggested that nucleation of the SiC crystals should occur preferentially on the surface of the powder particles rather than in the bulk. However, TEM on samples heat-treated to 1600°C did not show a preponderance of crystals on the surface of the particles compared to their bulk. Crystallization of beta-SiC occurs at ca. 1250°C, as determined by DSC and supported by NMR and electron diffraction. The average size of the beta-SiC crystallites, as determined by XRD, was ca. 5 nm at 1600°C. Prior to the crystallization of beta-SiC, Raman spectroscopy indicates the presence of carbon clusters in the otherwise amorphous matrix. These carbon clusters have predominantly sp3 bonding at 1100°C that gradually converts to predominantly sp 2 bonded carbon at higher temperatures, with average basal plane sizes of 20--25 A between 1100 in addition to 1600°C. The amorphous structure formed at temperatures below the crystallization temperature is unstable. It is seen from DSC that amorphous AHPCS-SiC undergoes two distinct exothermic events: a broad, irreversible, exotherm that corresponds to structural relaxation and chemical condensation and a second, much sharper, exotherm that corresponds to crystallization. Fracture toughness values measured on cold-pressed and infiltrated AHPCS-SiC samples were in the range of 1.4 to 1.67 MPam1/2. It appears that toughness increases with increasing heat treatment temperature. The Vickers hardness at 10 N was ca. 8.7 to 12.6 MPa. The Vickers hardness does not appear to vary significantly with the heat-treatment temperature.

Effect of Sintering Temperature to Physical, Magnetic Properties and Crystal Structure on Permanent Magnet BaFe12O19 Prepared From Mill Scale

NASA Astrophysics Data System (ADS)

Ramlan; Muljadi; Sardjono, Priyo; Gulo, Fakhili; Setiabudidaya, Dedi

2017-07-01

Permanent magnet of Barium hexa Ferrite with formula BaFe12O19 has been made by metallurgy powder method from raw materials : Barium carbonate (BaCO3 E-merck) and Iron Oxide (Fe2O3 from mill scale). Both of raw materials have been mixed with stoichiometry composition by using a ball mill for 24 hours. The fine powder obtained from milling process was formed by using a hydraulic press at pressure 50 MPa and continued with sintering process. The sintering temperature was varied : 1150°C, 1200°C, 1250°C and 1300°C with holding time for 1 hour. The sintered samples were characterized such as : physical properties (bulk density, porosity and shrinkage), magnetic properties (flux density, remanence, coercivity and magnetic saturation) by using VSM and crystal structure by using XRD. According characterization results show that the crystal structure of BaFe12O19 does not change after sintering process, but the grain size tends to increase. The optimum condition is achieved at temperature 1250°C, and at this condition, the sample has characterization such as : bulk density = 4.35 g/cm3, porosity = 1.03% and firing shrinkage = 11.63%, flux density = 681.1 Gauss, remanence (σr) = 20.78 emu/g, coercivity (Hc) = 2058 Oe and magnetic saturation (σs) 45.16 emu/g.

Increase of bulk optical damage threshold fluences of KDP crystals by laser irradiation and heat treatment

DOEpatents

Swain, J.E.; Stokowski, S.E.; Milam, D.; Kennedy, G.C.; Rainer, F.

1982-07-07

The bulk optical damage threshold fluence of potassium dihydrogen phosphate (KDP) crystals is increased by irradiating the crystals with laser pulses of duration 1 to 20 nanoseconds of increasing fluence, below the optical damage threshold fluence for untreated crystals, or by baking the crystals for times of the order of 24 hours at temperatures of 110 to 165/sup 0/C, or by a combination of laser irradiation and baking.

The growth and perfection of β-cyclotetramethylene-tetranitramine (HMX) studied by laboratory and synchrotron X-ray topography

NASA Astrophysics Data System (ADS)

Gallagher, H. G.; Sherwood, J. N.; Vrcelj, R. M.

2017-10-01

An examination has been made of the defect structure of crystals of the energetic material β-cyclotetramethylene-tetranitramine (HMX) using both Laboratory (Lang method) and Synchrotron (Bragg Reflection and Laue method) techniques. The results of the three methods are compared with particular attention to the influence of potential radiation damage caused to the samples by the latter, more energetic, technique. The comparison shows that both techniques can be confidently used to evaluate the defect structures yielding closely similar results. The results show that, even under the relatively casual preparative methods used (slow evaporation of unstirred solutions at constant temperature), HMX crystals of high perfection can be produced. The crystals show well defined bulk defect structures characteristic of organic materials in general: growth dislocations, twins, growth sector boundaries, growth banding and solvent inclusions. The distribution of the defects in specific samples is correlated with the morphological variation of the grown crystals. The results show promise for the further evaluation and characterisation of the structure and properties of dislocations and other defects and their involvement in mechanical and energetic processes in this material.

Single Crystal Synthesis and STM Studies of High Temperature Superconductors

NASA Technical Reports Server (NTRS)

Barrientos, Alfonso

1997-01-01

This is a final report for the work initiated in September of 1994 under the grant NAG8-1085 - NASA/OMU, on the fabrication of bulk and single crystal synthesis, specific heat measuring and STM studies of high temperature superconductors. Efforts were made to fabricate bulk and single crystals of mercury based superconducting material. A systematic thermal analysis on the precursors for the corresponding oxides and carbonates were carried out to synthesized bulk samples. Bulk material was used as seed in an attempt to grow single crystals by a two-step self flux process. On the other hand bulk samples were characterized by x-ray diffraction, electrical resistivity and magnetic susceptibility, We studied the specific heat behavior in the range from 80 to 300 K. Some preliminary attempts were made to study the atomic morphology of our samples. As part of our efforts we built an ac susceptibility apparatus for measuring the transition temperature of our sintered samples.

Emergent Low-Symmetry Phases and Large Property Enhancements in Ferroelectric KNbO 3 Bulk Crystals [Emergent Low-Symmetry Phases with Large Property Enhancement in Ferroelectric KNbO 3 Bulk Crystals

DOE PAGES

Lummen, Tom T. A.; Leung, J.; Kumar, Amit; ...

2017-06-19

The design of new or enhanced functionality in materials is traditionally viewed as requiring the discovery of new chemical compositions through synthesis. Large property enhancements may however also be hidden within already well-known materials, when their structural symmetry is deviated from equilibrium through a small local strain or field. Here, the discovery of enhanced material properties associated with a new metastable phase of monoclinic symmetry within bulk KNbO 3 is reported. This phase is found to coexist with the nominal orthorhombic phase at room temperature, and is both induced by and stabilized with local strains generated by a network ofmore » ferroelectric domain walls. While the local microstructural shear strain involved is only ≈0.017%, the concurrent symmetry reduction results in an optical second harmonic generation response that is over 550% higher at room temperature. Moreover, the meandering walls of the low-symmetry domains also exhibit enhanced electrical conductivity on the order of 1 S m -1. In conclusion, this discovery reveals a potential new route to local engineering of significant property enhancements and conductivity through symmetry lowering in ferroelectric crystals.« less

Surface and interior views on origins of two types of banded spherulites in poly(nonamethylene terephthalate).

PubMed

Woo, Eamor M; Nurkhamidah, Siti; Chen, Yu-Fan

2011-10-21

Top-surface and three-dimensional views of Type-1 and Type-2 of ring-banded spherulites in poly(nonamethylene terephthalate) (PNT) in thicker bulk crystallized on a nucleating potassium bromide (KBr) substrate were examined using various microscopy techniques: scanning electron microscopy (SEM), polarized-optical microscopy (POM), and atomic-force microscopy (AFM). In PNT crystallized at higher crystallization temperature (T(c)) with heterogeneous nucleating substrate, typically two types of ring-banded spherulites are present that differ significantly in patterns and ring spacings: Type-1 Type-2 (single- and double-ring-banded spherulites). Three-dimensional view on fractured spherulites in bulk PNT samples reveals that the single-ring-banded spherulite (Type-1) tends to be well-rounded spheres as they are nucleated homogeneously from bulk; the double-ring-banded spherulite (Type-2) is concentric hemisphere or truncated sphere shells owing to be nucleated from bottom. With confined thickness of films, the 3-D hemispheres in PNT may become truncated into multi-shell annular cones or arcs when thickness or growth is restricted. Based on the top-surface vs. interior views of banded lamellar assembly, origins and inner structures of dual types of ring bands in PNT were examined in greater details. This journal is © the Owner Societies 2011

Photonic and phononic surface and edge modes in three-dimensional phoxonic crystals

NASA Astrophysics Data System (ADS)

Ma, Tian-Xue; Wang, Yue-Sheng; Zhang, Chuanzeng

2018-04-01

We investigate the photonic and phononic surface and edge modes in finite-size three-dimensional phoxonic crystals. By appropriately terminating the phoxonic crystals, the photons and phonons can be simultaneously guided at the two-dimensional surface and/or the one-dimensional edge of the terminated crystals. The Bloch surface and edge modes show that the electromagnetic and acoustic waves are highly localized near the surface and edge, respectively. The surface and edge geometries play important roles in tailoring the dispersion relations of the surface and edge modes, and dual band gaps for the surface or edge modes can be simultaneously achieved by changing the geometrical configurations. Furthermore, as the band gaps for the bulk modes are the essential prerequisites for the realization of dual surface and edge modes, the photonic and phononic bulk-mode band gap properties of three different types of phoxonic crystals with six-connected networks are revealed. It is found that the geometrical characteristic of the crystals with six-connected networks leads to dual large bulk-mode band gaps. Compared with the conventional bulk modes, the surface and edge modes provide a new approach for the photon and phonon manipulation and show great potential for phoxonic crystal devices and optomechanics.

Experimental Observation of Three-Component New Fermions in Topological Semimetal MoP

NASA Astrophysics Data System (ADS)

Lv, B. Q.; Feng, Z.-L.; Xu, Q.-N.; Ma, J.-Z.; Kong, L.-Y.; Richard, Pierre; Huang, Y.-B.; Strocov, V. N.; Fang, C.; Weng, H.-M.; Shi, Y.-G.; Qian, Tian; Ding, Hong; Paul Scherrer Institute, Swiss Light Source, CH-5232 Villigen PSI, Switzerland Team; Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics Team; University of Chinese Academy of Sciences, Beijing 100190, China Team; Collaborative Innovation Center of Quantum Matter, Beijing, China Collaboration; Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China Team

Condensed matter systems can host quasiparticle excitations that are analogues to elementary particles such as Majorana, Weyl, and Dirac fermions. Recent advances in band theory have expanded the classification of fermions in crystals, and revealed crystal symmetry-protected electron excitations that have no high-energy counterparts. Here, using angle-resolved photoemission spectroscopy, we demonstrate the existence of a triply degenerate point in the electronic structure of MoP crystal, where the quasiparticle excitations are beyond the Majorana-Weyl-Dirac classification. Furthermore, we observe pairs of Weyl points in the bulk electronic structure coexisting with the new fermions, thus introducing a platform for studying the interplay between different types of fermions. We thank Binbin Fu, Nan Xu, and Xin Gao for the assistance in the ARPES experiments.

Theoretical studies on leaky-SAW properties influenced by layers on anisotropic piezoelectric crystals.

PubMed

Wallner, P; Ruile, W; Weigel, R

2000-01-01

Theoretical studies on the behavior of leaky-SAW (LSAW) properties in layered structures were performed. For these calculations rotYX LiTaO (3) and rotYX LiNbO(3) LSAW crystal cuts were used, assuming different layer materials. For LSAWs both the velocity and the inherent loss due to bulk wave emission into the substrate are strongly influenced by distinct layer parameters. As a result, these layer properties like elastic constants or thickness have shown a strong influence on the crystal cut angle of minimum LSAW loss. Moreover, for soft and stiff layer materials, a different shift of the LSAW loss minimum can occur. Therefore, using double-layer structures, the shift of the LSAW loss minimum can be influenced by appropriate chosen layers and ratios.

Evidence for graphite-like hexagonal AlN nanosheets epitaxially grown on single crystal Ag(111)

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

Tsipas, P.; Kassavetis, S.; Tsoutsou, D.

Ultrathin (sub-monolayer to 12 monolayers) AlN nanosheets are grown epitaxially by plasma assisted molecular beam epitaxy on Ag(111) single crystals. Electron diffraction and scanning tunneling microscopy provide evidence that AlN on Ag adopts a graphite-like hexagonal structure with a larger lattice constant compared to bulk-like wurtzite AlN. This claim is further supported by ultraviolet photoelectron spectroscopy indicating a reduced energy bandgap as expected for hexagonal AlN.

Silicon nanostructure arrays prepared by single step metal assisted chemical etching from single crystal wafer

NASA Astrophysics Data System (ADS)

Sarkar, Kalyan; Das, Debajyoti

2018-04-01

Arrays of silicon nanostructures have been produced by single step Metal Assisted Chemical Etching (MACE) of single crystal Si-wafers at room temp and normal atmospheric condition. By studying optical and structural properties of the silicon nanowire like structures synthesized by Ag catalyst assisted chemical etching, a significant change in the reflectance spectra has been obtained leading to a gross reduction in reflectance from ˜31% to less than 1%. In comparison with bulk c-Si, the surface areas of the nanostructured samples have been increased significantly with the etching time, leading to an efficient absorption of light, favorable for photovoltaic applications.

Growth of high quality bulk size single crystals of inverted solubility lithium sulphate monohydrate

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

Silambarasan, A.; Rajesh, P., E-mail: rajeshp@ssn.edu.in; Ramasamy, P.

2015-06-24

The paper summarizes the processes of growing large lithium sulfate monohydrate (LSMH) single crystals. We have established a procedure to grow high quality bulk size single crystals of inverted solubility LSMH by a newly developed unidirectional crystallization technique called the Sankeranarayenan - Ramasamy (SR) method. The convective flow of crystal growth processes from solution and the conditions of growing crystals of various aspects were discussed. Good quality LSMH single crystal is grown of the size 20 mmX80 mm without cracks, localized-defects and inclusions. The as-grown crystals are suitable for piezoelectric and nonlinear optical applications.

Two-step crystal growth mechanism during crystallization of an undercooled Ni50Al50 alloy

NASA Astrophysics Data System (ADS)

An, Simin; Li, Jiahao; Li, Yang; Li, Shunning; Wang, Qi; Liu, Baixin

2016-08-01

Crystallization processes are always accompanied by the emergence of multiple intermediate states, of which the structures and transition dynamics are far from clarity, since it is difficult to experimentally observe the microscopic pathway. To insight the structural evolution and the crystallization dynamics, we perform large-scale molecular dynamics simulations to investigate the time-dependent crystallization behavior of the NiAl intermetallic upon rapid solidification. The simulation results reveal that the crystallization process occurs via a two-step growth mechanism, involving the formation of initial non-equilibrium long range order (NLRO) regions and of the subsequent equilibrium long range order (ELRO) regions. The formation of the NLRO regions makes the grains rather inhomogeneous, while the rearrangement of the NLRO regions into the ELRO regions makes the grains more ordered and compact. This two-step growth mechanism is actually controlled by the evolution of the coordination polyhedra, which are characterized predominantly by the transformation from five-fold symmetry to four-fold and six-fold symmetry. From liquids to NLRO and further to ELRO, the five-fold symmetry of these polyhedra gradually fades, and finally vanishes when B2 structure is distributed throughout the grain bulk. The energy decrease along the pathway further implies the reliability of the proposed crystallization processes.

Structural characterization of bulk GaN crystals grown under high hydrostatic pressure

NASA Astrophysics Data System (ADS)

Liliental-Weber, Zuzanna; Kisielowski, C.; Ruvimov, S.; Chen, Y.; Washburn, J.; Grzegory, I.; Bockowski, M.; Jun, J.; Porowski, S.

1996-09-01

This paper describes TEM characterization of bulk GaN crystals grown at 1500-1800Kin the form of plates from a solution of atomic nitrogen in liquid gallium under high nitrogen pressure (up to 20 kbars). The x-ray rocking curves for these crystals were in the range of 20-30 arc-sec. The plate thickness along the c axis was about 100 times smaller than the nonpolar growth directions. A substantial difference in material quality was observed on the opposite sides of the plates normal to the c direction. On one side the surface was atomically flat, while on the other side the surface was rough, with pyramidal features up to 100 nm high. The polarity of the crystals was determined using convergent-beam electron diffraction. The results showed that, regarding the long bond between Ga and N along the c-axis, Ga atoms were found to be closer to the flat side of the crystal, while N atoms were found to be closer to the rough side. Near the rough side, within 1/10 to 1/4 of the plate thickness, there was a high density of planar defects (stacking faults and dislocation loops decorated by Ga/void precipitates). A model explaining the defect formation is proposed.

Experimental and quantum chemical studies on Nsbnd Hsbnd sbnd sbnd O hydrogen bonded helical chain type Morpholinium 2-chloro-4-nitrobenzoate: A phasematchable organic nonlinear optical material

NASA Astrophysics Data System (ADS)

Karthick, S.; Thirupugalmani, K.; Shanmugam, G.; Kannan, V.; Brahadeeswaran, S.

2018-03-01

We report on the studies performed on Morpholinium 2-chloro-4-nitrobenzoate (M2C4N), a second order nonlinear optical (NLO) material, which has been proved to crystallize with chiral structure as compared to its other two variants. The synthesized powder was studied for its composition, crystalline phase and NLO efficiency and phasematchability. The solubility and the metastable zone width (MSZW) of the title compound were measured for the growth of bulk crystals of M2C4N. A smoky pattern observed in the middle region of the crystals that could prevent it from optical applications was greatly reduced, through suitable modifications in the growth process. The optical properties such as luminescence and laser damage threshold resistance were studied for the bulk crystals whereas the molecular vibrations of M2C4N were studied through Fourier transform infrared (FTIR) and FT-Raman spectral analysis using the polycrystalline powders derived from the single crystals. In addition, quantum chemical studies on M2C4N molecule were performed by using density functional theory (DFT) at the B3LYP/6-311++G (d, p) basis set. These studies showed that the M2C4N is a phasematchable NLO crystal and could be used for device fabrication.

Electronic structure of ytterbium-implanted GaN at ambient and high pressure: experimental and crystal field studies.

PubMed

Kaminska, A; Ma, C-G; Brik, M G; Kozanecki, A; Boćkowski, M; Alves, E; Suchocki, A

2012-03-07

The results of high-pressure low-temperature optical measurements in a diamond-anvil cell of bulk gallium nitride crystals implanted with ytterbium are reported in combination with crystal field calculations of the Yb(3+) energy levels. Crystal field analysis of splitting of the (2)F(7/2) and (2)F(5/2) states has been performed, with the aim of assigning all features of the experimental luminescence spectra. A thorough analysis of the pressure behavior of the Yb(3+) luminescence lines in GaN allowed the determination of the ambient-pressure positions and pressure dependence of the Yb(3+) energy levels in the trigonal crystal field as well as the pressure-induced changes of the spin-orbit coupling coefficient.

Models of Mass Transport During Microgravity Crystal Growth of Alloyed Semiconductors in a Magnetic Field

NASA Technical Reports Server (NTRS)

Ma, Nancy

2003-01-01

Alloyed semiconductor crystals, such as germanium-silicon (GeSi) and various II-VI alloyed crystals, are extremely important for optoelectronic devices. Currently, high-quality crystals of GeSi and of II-VI alloys can be grown by epitaxial processes, but the time required to grow a certain amount of single crystal is roughly 1,000 times longer than the time required for Bridgman growth from a melt. Recent rapid advances in optoelectronics have led to a great demand for more and larger crystals with fewer dislocations and other microdefects and with more uniform and controllable compositions. Currently, alloyed crystals grown by bulk methods have unacceptable levels of segregation in the composition of the crystal. Alloyed crystals are being grown by the Bridgman process in space in order to develop successful bulk-growth methods, with the hope that the technology will be equally successful on earth. Unfortunately some crystals grown in space still have unacceptable segregation, for example, due to residual accelerations. The application of a weak magnetic field during crystal growth in space may eliminate the undesirable segregation. Understanding and improving the bulk growth of alloyed semiconductors in microgravity is critically important. The purpose of this grant to to develop models of the unsteady species transport during the bulk growth of alloyed semiconductor crystals in the presence of a magnetic field in microgravity. The research supports experiments being conducted in the High Magnetic Field Solidification Facility at Marshall Space Flight Center (MSFC) and future experiments on the International Space Station.

Bulk single crystal ternary substrates for a thermophotovoltaic energy conversion system

DOEpatents

Charache, Greg W.; Baldasaro, Paul F.; Nichols, Greg J.

1998-01-01

A thermophotovoltaic energy conversion device and a method for making the device. The device includes a substrate formed from a bulk single crystal material having a bandgap (E.sub.g) of 0.4 eV

Bulk single crystal ternary substrates for a thermophotovoltaic energy conversion system

DOEpatents

Charache, G.W.; Baldasaro, P.F.; Nichols, G.J.

1998-06-23

A thermophotovoltaic energy conversion device and a method for making the device are disclosed. The device includes a substrate formed from a bulk single crystal material having a bandgap (E{sub g}) of 0.4 eV < E{sub g} < 0.7 eV and an emitter fabricated on the substrate formed from one of a p-type or an n-type material. Another thermophotovoltaic energy conversion device includes a host substrate formed from a bulk single crystal material and lattice-matched ternary or quaternary III-V semiconductor active layers. 12 figs.

Selective heteroepitaxy on deeply grooved substrate: A route to low cost semipolar GaN platforms of bulk quality

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

Tendille, Florian, E-mail: florian.tendille@crhea.cnrs.fr; Vennéguès, Philippe; De Mierry, Philippe

2016-08-22

Semipolar GaN crystal stripes larger than 100 μm with dislocation densities below 5 × 10{sup 6} cm{sup −2} are achieved using a low cost fabrication process. An original sapphire patterning procedure is proposed, enabling selective growth of semipolar oriented GaN stripes while confining the defects to specific areas. Radiative and non-radiative crystalline defects are investigated by cathodoluminescence and can be correlated to the development of crystal microstructure during the growth process. A dislocation reduction mechanism, supported by transmission electron microscopy, is proposed. This method represents a step forward toward low-cost quasi-bulk semipolar GaN epitaxial platforms with an excellent structural quality which will allowmore » for even more efficient III-nitride based devices.« less

Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

PubMed Central

Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

2016-01-01

Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

HREM study of irradiation damage in human dental enamel crystals.

PubMed

Brès, E F; Hutchison, J L; Senger, B; Voegel, J C; Frank, R M

1991-06-01

Several phenomena have been observed during the examination of human dental enamel crystals (mainly constituted by hydroxyapatite (OHAP] by high-resolution electron microscopy (HREM) at 300 and 400 keV: orientation-dependent damage in the form of mass loss from voids or uniform destruction of crystal structure, beam-induced diffusion creating outgrowths at the crystal surfaces, recrystallization of the bulk crystal and crystallization of the inorganic components of the matrix surrounding the crystals. These beam-induced crystals have the CaO structure. The phenomena observed are most likely due to various electron-crystal interaction mechanisms (ballistic knock-on damage, electronic excitations, temperature rise, etc.). In this paper, the contribution of the ballistic process to the phenomena observed is discussed. The quantitative description of the knock-on collisions rests on the McKinley-Feshbach cross-section formula. The minimum ion displacement energies which appear in this expression have been estimated on the basis of the electrostatic ion binding energies, and the covalent bond energies if required. It is shown that hydroxyl, calcium and oxygen ions can effectively be displaced by the incident 300 and 400 keV electrons. Thus, the formation of CaO crystals by the combination of calcium and oxygen ions diffusing from their initial sites inside the OHAP lattice can tentatively be explained.

Self-alignment of plasmonic gold nanorods in reconfigurable anisotropic fluids for tunable bulk metamaterial applications.

PubMed

Liu, Qingkun; Cui, Yanxia; Gardner, Dennis; Li, Xin; He, Sailing; Smalyukh, Ivan I

2010-04-14

We demonstrate the bulk self-alignment of dispersed gold nanorods imposed by the intrinsic cylindrical micelle self-assembly in nematic and hexagonal liquid crystalline phases of anisotropic fluids. External magnetic field and shearing allow for alignment and realignment of the liquid crystal matrix with the ensuing long-range orientational order of well-dispersed plasmonic nanorods. This results in a switchable polarization-sensitive plasmon resonance exhibiting stark differences from that of the same nanorods in isotropic fluids. The device-scale bulk nanoparticle alignment may enable optical metamaterial mass production and control of properties arising from combining the switchable nanoscale structure of anisotropic fluids with the surface plasmon resonance properties of the plasmonic nanorods.

Solution electrostatic levitator for measuring surface properties and bulk structures of an extremely supersaturated solution drop above metastable zone width limit.

PubMed

Lee, Sooheyong; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Lee, Geun Woo

2017-05-01

We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH 2 PO 4 ) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.

Variation of relative intensities between surface and bulk plasmon losses due to crystal orientations for aluminium in low energy electron reflection loss spectroscopy

NASA Astrophysics Data System (ADS)

Ichinokawa, T.; Le Gressus, C.; Mogami, A.; Pellerin, F.; Massignon, D.

The contrast change of secondary electron images due to the crystal orientations is observed by the ultra high vacuum scanning electron microscope (UHV-SEM) for crystal grains of clean surface of polycrystalline Al in the primary energy Ep of 200 eV to 5 KeV. The low energy electron loss spectra are measured by the cylindrical mirror analyzer. The relative intensity ratio between surface and bulk plasmon loss spectra was dependent on the crystal orientations. The SEM images taken by the surface and bulk plasmon signals at Ep = 230 eV show the inverse contrast depending on the grains. The inversion of the relative intensities between the surface and bulk plasmon losses is explained qualitatively by taking into account of variation of the penetration depth of the incident beam caused by the electron channeling.

Variation of relative intensities between surface and bulk plasmon losses due to crystal orientations for aluminium in low energy electron reflection loss spectroscopy

NASA Astrophysics Data System (ADS)

Ichinokawa, T.; Le Gressus, C.; Mogami, A.; Pellerin, F.; Massignon, D.

1981-10-01

The contrast change of secondary electron images due to the crystal orientations is observed by the ultra high vacuum scanning electron microscope (UHV-SEM) for crystal grains of clean surface of polycrystalline Al in the primary energy Ep of 200 eV to 5 keV. The low energy electron loss spectra are measured by the cylindrical mirror analyzer. The relative intensity ratio between surface and bulk plasmon loss spectra was dependent on the crystal orientations. The SEM images taken by the surface and bulk plasmon signals at Ep = 230 eV show the inverse contrast depending on the grains. The inversion of the relative intensities between the surface and bulk plasmon losses is explained qualitatively by taking into account of variation of the penetration depth of the incident beam caused by the electron channeling.

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

Heffernan, Karina M.; Ross, Nancy L., E-mail: nross@vt.edu; Spencer, Elinor C.

Accurate elastic constants for gadolinium phosphate (GdPO{sub 4}) have been measured by single-crystal high-pressure diffraction methods. The bulk modulus of GdPO{sub 4} determined under hydrostatic conditions, 128.1(8) GPa (K′=5.8(2)), is markedly different from that obtained with GdPO{sub 4} under non-hydrostatic conditions (160(2) GPa), which indicates the importance of shear stresses on the elastic response of this phosphate. High pressure Raman and diffraction analysis indicate that the PO{sub 4} tetrahedra behave as rigid units in response to pressure and that contraction of the GdPO{sub 4} structure is facilitated by bending/twisting of the Gd–O–P links that result in increased distortion in themore » GdO{sub 9} polyhedra. - Graphical abstract: A high-pressure single crystal diffraction study of GdPO{sub 4} with the monazite structure is presented. The elastic behaviour of rare-earth phosphates are believed to be sensitive to shear forces. The bulk modulus of GdPO{sub 4} measured under hydrostatic conditions is 128.1(8) GPa. Compression of the structure is facilitated by bending/twisting of the Gd−O−P links that result in increased distortion in the GdO{sub 9} polyhedra. Display Omitted - Highlights: • The elastic responses of rare-earth phosphates are sensitive to shear forces. • The bulk modulus of GdPO{sub 4} measured under hydrostatic conditions is 128.1(8) GPa. • Twisting of the inter-polyhedral links allows compression of the GdPO{sub 4} structure. • Changes to the GdO{sub 9} polyhedra occur in response to pressure (<7.0 GPa).« less

Solvent additive effects on small molecule crystallization in bulk heterojunction solar cells probed during spin casting.

PubMed

Perez, Louis A; Chou, Kang Wei; Love, John A; van der Poll, Thomas S; Smilgies, Detlef-M; Nguyen, Thuc-Quyen; Kramer, Edward J; Amassian, Aram; Bazan, Guillermo C

2013-11-26

Solvent additive processing can lead to drastic improvements in the power conversion efficiency (PCE) in solution processable small molecule (SPSM) bulk heterojunction solar cells. In situ grazing incidence wide-angle X-ray scattering is used to investigate the kinetics of crystallite formation during and shortly after spin casting. The additive is shown to have a complex effect on structural evolution invoking polymorphism and enhanced crystalline quality of the donor SPSM. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subsurface bending and reorientation of tilted vortex lattices in bulk isotropic superconductors due to Coulomb-like repulsion at the surface

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

Herrera, E.; Guillamón, I.; Galvis, J. A.

Here, we study vortex lattices (VLs) in superconducting weak-pinning platelet-like single crystals of β–Bi 2Pd in tilted magnetic fields with a scanning tunneling microscope. We show that vortices exit the sample perpendicular to the surface and are thus bent beneath the surface. The structure and orientation of the tilted VLs in the bulk are, for large tilt angles, strongly affected by Coulomb-type intervortex repulsion at the surface due to stray magnetic fields.

Ti, Ni and TiNi nanoparticles physically synthesized by Ar+ beam milling.

PubMed

Torres Castro, A; López Cuéllar, E; José Yacamán, M; Ortiz Méndez, U

2008-12-01

When the size of a particle decreases around 100 nm or less, there is a change in properties from those shown in the bulk material. In this work approximately 3 nm nanoparticles of Ni, Ti and TiNi bimetallic are produced using physical vapor deposition (PVD). Nanoparticles are characterized by High Resolution Transmission Electron Microscopy (HRTEM), High Angle Annular Dark Field (HAADF), Electron Diffraction (ED). The results show that all nanoparticles maintain the same crystal structure of bulk material but a change in their lattice parameter is produced.

Subsurface bending and reorientation of tilted vortex lattices in bulk isotropic superconductors due to Coulomb-like repulsion at the surface

DOE PAGES

Herrera, E.; Guillamón, I.; Galvis, J. A.; ...

2017-11-03

Here, we study vortex lattices (VLs) in superconducting weak-pinning platelet-like single crystals of β–Bi 2Pd in tilted magnetic fields with a scanning tunneling microscope. We show that vortices exit the sample perpendicular to the surface and are thus bent beneath the surface. The structure and orientation of the tilted VLs in the bulk are, for large tilt angles, strongly affected by Coulomb-type intervortex repulsion at the surface due to stray magnetic fields.

Dehydration process in NaCl solutions under various external electric fields

NASA Astrophysics Data System (ADS)

Kadota, Kazunori; Shimosaka, Atsuko; Shirakawa, Yoshiyuki; Hidaka, Jusuke

2007-06-01

Ionic motions at solid-liquid interface in supersaturated NaCl solutions have been investigated by molecular dynamics (MD) simulation for understanding crystal growth processes. The density profile in the vicinity of the interfaces between NaCl(100) and the supersaturated NaCl solution was calculated. Diffusion coefficients of water molecules in the solution were estimated as a function of distance from the crystal interface. It turned out that the structure and dynamics of the solution in the interfaces was different from those of bulk solution owing to electric fields depending on the surface charge. Therefore, the electric field was applied to the supersaturated solutions and dehydration phenomenon occurring in the process of the crystal growth was discussed. As the electric field increased, it was observed that the Na+ keeping strongly hydration structure broke out by the electric force. In supersaturated concentration, the solution structure is significantly different from that of dilution and has a complicated structure with hydration ions and clusters of NaCl. If the electric fields were applied to the solutions, the breakout of hydration structure was not affected with increasing the supersaturated ratio. This reason is that the cluster structures are destroyed by the electric force. The situation depends on the electric field or crystal surface structure.

Single crystal growth, crystalline structure investigation and high-pressure behavior of impurity-free siderite (FeCO3)

NASA Astrophysics Data System (ADS)

Liang, Wen; Yin, Yuan; Li, Zeming; Li, Rui; Li, Lin; He, Yu; Dong, Haini; Li, Zengsheng; Yan, Shuai; Zhai, Shuangmeng; Li, Heping

2018-03-01

Single crystals of impurity-free siderite were grown successfully using high-temperature-pressure annealing. The size of crystals ranged up to 100 µm, and they exhibited a rhomboid shape upon cleavage along the (101) plane. The composition of Fe0.9988±0.0011CO3 was quantified using electron probe analysis. Accurate crystalline structural data were investigated by means of single crystal X-ray diffraction (XRD) and the unit cell dimensions obtained in the rhombohedral symmetry of the R\\bar {3}c space group were a = 4.6861(3) and c = 15.362(2), and the final R = 0.0499. Using in situ synchrotron XRD, the high-pressure behavior of impurity-free siderite was investigated up to 20 GPa at ambient temperature. The pressure-volume (P-V) EoS was fitted by a third-order Birch-Murnaghan equation, and the isothermal bulk modulus was K 0 = 97.5(11) GPa for K 0' = 4. High-pressure Raman spectroscopy was performed at up to 30 GPa at ambient temperature, and the Raman bands shifted as the increase of pressure ({{d/ν _i}}{{{d}P}} ) was determined. In combination with the high-pressure Raman results and the bulk modulus K 0, the mode Grüneisen parameters of each vibration were calculated. Meanwhile, high-temperature Raman spectroscopy was carried out at up to 300 °C and the Raman band shift ({{d/ν _i}}{{{d}t}} ) was also quantified.

First principles study of structural stability, electronic structure and mechanical properties of ReN and TcN

NASA Astrophysics Data System (ADS)

Rajeswarapalanichamy, R.; Kavitha, M.; Sudha Priyanga, G.; Iyakutti, K.

2015-03-01

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.

Raman Spectrum of Er-Y-codoped ZrO2 and Fluorescence Properties of Er3+

NASA Astrophysics Data System (ADS)

He, Jun; Luo, Meng-fei; Jin, Ling-yun; He, Mai; Fang, Ping; Xie, Yun-long

2007-02-01

Er-Y-codoped ZrO2 mixed oxides with monoclinic, tetragonal and cubic structures were prepared by a sol-gel method. The crystal structure of ZrO2 matrix and the effect of the ZrO2 phases on the fluorescence properties of Er3+ were studied using Raman spectroscopy. The results indicated that the fluorescence properties of Er3+ depend on its local ZrO2 crystal structures. As ZrO2 matrix transferred from monoclinic to tetragonal and cubic phase, the Raman and fluorescence bands of Er3+ decreased in intensities and tended to form a single peak. With 632.8 nm excitation, the bands between 640 and 680 nm were attributed to the fluorescence of Er3+ in the ZrO2 environment. However, only the fluorescence was observed and no Raman spectra were seen under 514.5 nm excitation, while only Raman spectra were observed under 325 nm excitation. UV Raman spectroscopy was found to be more sensitive in the surface region while the information provided by XRD mainly came from the bulk. The phase with lower symmetry forms more easily on the surface than in the bulk.

Magnetocrystalline anisotropy of ɛ-Fe2O3

NASA Astrophysics Data System (ADS)

Ahamed, Imran; Pathak, Rohit; Skomski, Ralph; Kashyap, Arti

2018-05-01

The epsilon Fe2O3 phase of iron oxide has been studied to understand the spin structure and the magnetocrystalline anisotropy in the bulk and in thin films of ɛ-Fe2O3 and Co-doped ɛ-Fe2O3. The preferential magnetization direction in the nanoparticles of ɛ-Fe2O3 is along the a-axis [M. Gich et al., Chem. Mater. 18, 3889 (2006)]. Compared to the bulk band gap of 1.9 eV, the thin-film band gap is reduced to 1.3 eV in the Co-free films and to 0.7 eV in the film with partial Co substitution. The easy magnetization direction of the bulk and Co-free ɛ-Fe2O3 is along the c-axis, but it switches to the a-axis on Co substitution. All three systems exhibit in-plane anisotropies associated with the orthorhombic crystal structure of the oxide.

Large moments in bcc FexCoyMnz ternary alloy thin films

NASA Astrophysics Data System (ADS)

Snow, R. J.; Bhatkar, H.; N'Diaye, A. T.; Arenholz, E.; Idzerda, Y. U.

2018-02-01

The elemental magnetic moments and the average atomic moment of 10-20 nm thick single crystal bcc (bct) FexCoyMnz films deposited on MgO(001) have been determined as a function of a broad range of compositions. Thin film epitaxy stabilized the bcc structure for 80% of the available ternary compositional space compared to only a 23% stability region for the bulk. The films that display ferromagnetism represent 60% of the available compositional possibilities compared to 25% for the bulk. A maximum average atomic moment of 3.25 ± 0.3 μB/atom was observed for a bcc Fe9Co62Mn29 film (well above the limit of the Slater-Pauling binary alloy curve of 2.45 μB/atom). The FexCoyMnz ternary alloys that exhibit high moments can only be synthesized as ultrathin films since the bcc structure is not stable in the bulk for those compositions.

Studies on the growth, structural, spectral and third-order nonlinear optical properties of ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate single crystal.

PubMed

Silambarasan, A; Krishna Kumar, M; Thirunavukkarasu, A; Mohan Kumar, R; Umarani, P R

2015-01-25

An organic nonlinear optical bulk single crystal, Ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate (ACHBS) was successfully grown by solution growth technique. Single crystal X-ray diffraction study confirms that, the grown crystal belongs to P21/c space group. Powder X-ray diffraction and high resolution X-ray diffraction analyses revealed the crystallinity of the grown crystal. Infrared spectral analysis showed the vibrational behavior of chemical bonds and its functional groups. The thermal stability and decomposition stages of the grown crystal were studied by TG-DTA analysis. UV-Visible transmittance studies showed the transparency region and cut-off wavelength of the grown crystal. The third-order nonlinear optical susceptibility of the grown crystal was estimated by Z-scan technique using He-Ne laser source. The mechanical property of the grown crystal was studied by using Vicker's microhardness test. Copyright © 2014 Elsevier B.V. All rights reserved.

Growth and dielectric, mechanical, thermal and etching studies of an organic nonlinear optical L-arginine trifluoroacetate (LATF) single crystal

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

Arjunan, S.; Department of Physics, Presidency College, Chennai 600005; Mohan Kumar, R.

2008-08-04

L-arginine trifluoroacetate, an organic nonlinear optical material, has been synthesized from aqueous solution. Bulk single crystal of dimension 57 mm x 5 mm x 3 mm has been grown by temperature lowering technique. Powder X-ray diffraction studies confirmed the monoclinic structure of the grown L-arginine trifluoroacetate crystal. Linear optical property of the grown crystal has been studied by UV-vis spectrum. Dielectric response of the L-arginine trifluoroacetate crystal was analysed for different frequencies and temperatures in detail. Microhardness study on the sample reveals that the crystal possesses relatively higher hardness compared to many organic crystals. Thermal analyses confirmed that the L-argininemore » trifluoroacetate material is thermally stable upto 212 deg. C. The etching studies have been performed to assess the perfection of the L-arginine trifluoroacetate crystal. Kurtz powder second harmonic generation test confirms the nonlinear optical properties of the as-grown L-arginine trifluoroacetate crystal.« less

Real-time molecular scale observation of crystal formation.

PubMed

Schreiber, Roy E; Houben, Lothar; Wolf, Sharon G; Leitus, Gregory; Lang, Zhong-Ling; Carbó, Jorge J; Poblet, Josep M; Neumann, Ronny

2017-04-01

How molecules in solution form crystal nuclei, which then grow into large crystals, is a poorly understood phenomenon. The classical mechanism of homogeneous crystal nucleation proceeds via the spontaneous random aggregation of species from liquid or solution. However, a non-classical mechanism suggests the formation of an amorphous dense phase that reorders to form stable crystal nuclei. So far it has remained an experimental challenge to observe the formation of crystal nuclei from five to thirty molecules. Here, using polyoxometallates, we show that the formation of small crystal nuclei is observable by cryogenic transmission electron microscopy. We observe both classical and non-classical nucleation processes, depending on the identity of the cation present. The experiments verify theoretical studies that suggest non-classical nucleation is the lower of the two energy pathways. The arrangement in just a seven-molecule proto-crystal matches the order found by X-ray diffraction of a single bulk crystal, which demonstrates that the same structure was formed in each case.

Characterization of 4H <000-1> Silicon Carbide Films Grown by Solvent-Laser Heated Floating Zone

NASA Technical Reports Server (NTRS)

Woodworth, Andrew, A; Sayir, Ali; Neudeck, Philip, G; Raghothamachar, Balaji; Dudley, Michael

2012-01-01

Commercially available bulk silicon carbide (SiC) has a high number (>2000/sq cm) of screw dislocations (SD) that have been linked to degradation of high-field power device electrical performance properties. Researchers at the NASA Glenn Research Center have proposed a method to mass-produce significantly higher quality bulk SiC. In order for this bulk growth method to become reality, growth of long single crystal SiC fibers must first be achieved. Therefore, a new growth method, Solvent-Laser Heated Floating Zone (Solvent-LHFZ), has been implemented. While some of the initial Solvent-LHFZ results have recently been reported, this paper focuses on further characterization of grown crystals and their growth fronts. To this end, secondary ion mass spectroscopy (SIMS) depth profiles, cross section analysis by focused ion beam (FIB) milling and mechanical polishing, and orientation and structural characterization by x-ray transmission Laue diffraction patterns and x-ray topography were used. Results paint a picture of a chaotic growth front, with Fe incorporation dependant on C concentration.

Positrons as interface-sensitive probes of polar semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Makkonen, I.; Snicker, A.; Puska, M. J.; Mäki, J.-M.; Tuomisto, F.

2010-07-01

Group-III nitrides in their wurtzite crystal structure are characterized by large spontaneous polarization and significant piezoelectric contributions in heterostructures formed of these materials. Polarization discontinuities in polar heterostructures grown along the (0001) direction result in huge built-in electric fields on the order of megavolt per centimeter. We choose the III-nitride heterostructures as archetypal representatives of polar heterostructures formed of semiconducting or insulating materials and study the behavior of positrons in these structures using first-principles electronic-structure theory supported by positron annihilation experiments for bulk systems. The strong electric fields drive positrons close to interfaces, which is clearly seen in the predicted momentum distributions of annihilating electron-positron pairs as changes relative to the constituent bulk materials. Implications of the effect to positron defect studies of polar heterostructures are addressed.

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

DOE PAGES

Gammer, C.; Escher, B.; Ebner, C.; ...

2017-03-21

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. Furthermore, by analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result thus demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clustersmore » is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.« less

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

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

Gammer, C.; Escher, B.; Ebner, C.

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. Furthermore, by analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result thus demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clustersmore » is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.« less

Transfiguring structural, optical and dielectric properties of cadmium thiourea acetate crystal by the addition of L-threonine for laser assisted device applications

NASA Astrophysics Data System (ADS)

Kulkarni, Rupali B.; Anis, Mohd; Hussaini, S. S.; Shirsat, Mahendra D.

2018-03-01

Present investigation reports the growth of pure and L-threonine (LT) doped cadmium thiourea acetate (CTA) crystals by slow solution evaporation technique followed by structural, optical and dielectric characterization studies. A bulk single crystal of LT-CTA has been grown at temperature 38 °C. The single crystal x-ray diffraction technique has been employed to confirm the structural parameters of pure and LT doped CTA crystals. The increase in optical transparency of LT-CTA crystal was ascertained in the range of 200 to 900 nm using UV-visible spectral analysis. The widened optical band gap of the LT-CTA crystal is found to be 4.7 eV. Pure and doped crystals are subjected to FT-IR analysis to indicate the presence of functional groups quantitatively. Appreciable enhancement in second harmonic generation (SHG) efficiency of LT-CTA crystal with reference to parent CTA was confirmed from Kurtz-Perry SHG test (1.31 times of CTA crystal). The assertive influence of LT on electrical properties of grown crystals has been investigated in the temperature range 35 °C-120 °C. Electronic purity and the color centered photoluminescence emission nature of pure and IA-CTA crystals were justified by luminescence analysis. With the aid of single beam Z-scan analysis, the Kerr lensing nonlinearity was identified and the magnitude of TONLO parameters has been determined. The cubic susceptibility (χ3) and figure of merit (FOM) was found to be 4.81 × 10-4esu and 978.35. Results vitalize LT-CTA for laser stabilization systems.

Diamond Lattice Colloidal Crystals from Binary DNA-grafted Microspheres

NASA Astrophysics Data System (ADS)

Crocker, John; Wang, Yifan; Jenkins, Ian; McGinley, James; Sinno, Talid

Future optical materials promise to do for photonics what semiconductors did for electronics, but the challenge has long been in creating the structure they require regular, three-dimensional array of transparent microspheres arranged like the atoms in a diamond crystal. Here we demonstrate a simple approach for spontaneously growing double-diamond (or B32) crystals from a binary suspension of sub-micron polymer microspheres with synthetic DNA grafted to their surfaces. While diamond symmetry crystals have previously been grown from much smaller nanoparticles, none of those methods appear workable for the larger particles needed for photonic applications, whose size must be comparable to the wavelength of visible light. Intriguingly, matched simulations fail to nucleate or grow B32 crystals from suspension; nor have they been predicted on the basis of theoretical arguments. We conjecture that the B32 crystals may form via transformation from a precursor with a different lattice structure in the bulk or on its surface. The feasibility of converting our self-assembled crystals into diamond-symmetry photonic templates will be discussed. This finding suggests that still other unexpected microstructures may be accessible using this approach. US National Science Foundation, CBET- 1403237.

Light-Activated Gigahertz Ferroelectric Domain Dynamics

NASA Astrophysics Data System (ADS)

Akamatsu, Hirofumi; Yuan, Yakun; Stoica, Vladimir A.; Stone, Greg; Yang, Tiannan; Hong, Zijian; Lei, Shiming; Zhu, Yi; Haislmaier, Ryan C.; Freeland, John W.; Chen, Long-Qing; Wen, Haidan; Gopalan, Venkatraman

2018-03-01

Using time- and spatially resolved hard x-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO3 are simultaneously captured on subnanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photoinduced electric field of up to 20 ×106 V /m is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling method is developed that reveals the microscopic origin of these dynamics, leading to gigahertz polarization and elastic waves traveling in the crystal with sonic speeds and spatially varying frequencies. The advances in spatiotemporal imaging and dynamical modeling tools open up opportunities for disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains.

Structural and magnetic investigations of single-crystalline neodymium zirconate pyrochlore Nd2Zr2O7

NASA Astrophysics Data System (ADS)

Hatnean, M. Ciomaga; Lees, M. R.; Petrenko, O. A.; Keeble, D. S.; Balakrishnan, G.; Gutmann, M. J.; Klekovkina, V. V.; Malkin, B. Z.

2015-05-01

We report structural and magnetic properties studies of large high-quality single crystals of the frustrated magnet Nd2Zr2O7 . Powder x-ray diffraction analysis confirms that Nd2Zr2O7 adopts the pyrochlore structure. Room-temperature x-ray diffraction and time-of-flight neutron-scattering experiments show that the crystals are stoichiometric in composition with no measurable site disorder. The temperature dependence of the magnetic susceptibility shows no magnetic ordering at temperatures down to 0.5 K. Fits to the magnetic susceptibility data using a Curie-Weiss law reveal a ferromagnetic coupling between the Nd moments. Magnetization versus field measurements show a local Ising anisotropy along the <111 > axes of the Nd3 + ions in the ground state. Specific heat versus temperature measurements in zero applied magnetic field indicate the presence of a thermal anomaly below T ˜7 K, but no evidence of magnetic ordering is observed down to 0.5 K. The experimental temperature dependence of the single-crystal bulk dc susceptibility and isothermal magnetization are analyzed using crystal field theory and the crystal field parameters and exchange coupling constants determined.

Study of the specific features of single-crystal boron microstructure

NASA Astrophysics Data System (ADS)

Blagov, A. E.; Vasil'ev, A. L.; Dmitriev, V. P.; Ivanova, A. G.; Kulikov, A. G.; Marchenkov, N. V.; Popov, P. A.; Presnyakov, M. Yu.; Prosekov, P. A.; Pisarevskii, Yu. V.; Targonskii, A. V.; Chernaya, T. S.; Chernyshov, D. Yu.

2017-09-01

A complex study of the structure of β-boron single crystal grown by the floating-zone method, with sizes significantly exceeding the analogs known in the literature, has been performed. The study includes X-ray diffraction analysis and X-ray diffractometry (measurement of pole figures and rocking curves), performed on both laboratory and synchrotron sources; atomic-resolution scanning transmission electron microscopy with spherical aberration correction; and energy-dispersive microanalysis. X-ray diffraction analysis using synchrotron radiation has been used to refine the β-boron structure and find impurity Si atoms. The relative variations in the unit-cell parameters a and c for the crystal bulk are found to be δ a/ a ≈ 0.4 and δ c/ c ≈ 0.1%. X-ray diffractometry has revealed that the single-crystal growth axis coincides with the [2\\bar 2013] crystallographic axis and makes an angle of 21.12° with the [0001] threefold axis. Electron microscopy data have confirmed that the sample under study is a β-boron crystal, which may contain 0.3-0.4 at % Si as an impurity. Planar defects (stacking faults and dislocations) are found. The results of additional measurements of the temperature dependence of the thermal conductivity of the crystal in the range of 50-300 K are indicative of its high structural quality.

Solid-state diffusion-controlled growth of the phases in the Au-Sn system

NASA Astrophysics Data System (ADS)

Baheti, Varun A.; Kashyap, Sanjay; Kumar, Praveen; Chattopadhyay, Kamanio; Paul, Aloke

2018-01-01

The solid state diffusion-controlled growth of the phases is studied for the Au-Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn4 phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn4 phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.

Bulk Crystal Growth of Nonlinear Optical Organic Materials Using Inverted Vertical Gradient Freeze Method

NASA Technical Reports Server (NTRS)

Choi, J.; Cruz, Magda; Metzl, R.; Wang, W. S.; Aggarwal, M. D.; Penn, Benjamin G.; Frazier, Donald O.

1998-01-01

A new process for producing large bulk single crystals of benzil (C6H5COCOC6H5) is reported in this paper. Good quality crystals have been successfully grown using this approach to crystal growth. This method seems to be very promising for other thermally stable NLO organic materials also. The entire contents vycor crucible 1.5 inch in diameter and 2 inch deep was converted to single crystal. Purity of the starting growth material is also an important factor in the final quality of the grown crystals. The entire crystal can be very easily taken out of the crucible by simple maneuvering. Initial characterization of the grown crystals indicated that the crystals are as good as other crystals grown by conventional Bridgman Stockbarger technique.

Bulk crystal growth of Ga2O3

NASA Astrophysics Data System (ADS)

Kuramata, Akito; Koshi, Kimiyoshi; Watanabe, Shinya; Yamaoka, Yu; Masui, Takekazu; Yamakoshi, Shigenobu

2018-02-01

This paper describes the bulk crystal growth of β-Ga2O3 using edge-defined film-fed growth (EFG) process. We first describe the method of the crystal growth and show that large-size crystal with width of up to 6 inch can be grown. Then, we discuss the way to control electrical properties. In the discussion, we give some experimental results of residual impurity measurement, intentional doping using Si and Sn for n-type doping and Fe for insulating doping.

Solid-state microrefrigerator

DOEpatents

Ullom, Joel N.

2003-06-24

A normal-insulator-superconductor (NIS) microrefrigerator in which a superconducting single crystal is both the substrate and the superconducting electrode of the NIS junction. The refrigerator consists of a large ultra-pure superconducting single crystal and a normal metal layer on top of the superconducting crystal, separated by a thin insulating layer. The superconducting crystal can be either cut from bulk material or grown as a thick epitaxial film. The large single superconducting crystal allows quasiparticles created in the superconducting crystal to easily diffuse away from the NIS junction through the lattice structure of the crystal to normal metal traps to prevent the quasiparticles from returning across the NIS junction. In comparison to thin film NIS refrigerators, the invention provides orders of magnitude larger cooling power than thin film microrefrigerators. The superconducting crystal can serve as the superconducting electrode for multiple NIS junctions to provide an array of microrefrigerators. The normal electrode can be extended and supported by microsupports to provide support and cooling of sensors or arrays of sensors.

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar

2002-01-01

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Growth and characterization of new nonlinear optical 1-phenyl-3-(4-dimethylamino phenyl) prop-2-en-1-one (PDAC) single crystals

NASA Astrophysics Data System (ADS)

Ravindraswami, K.; Janardhana, K.; Gowda, Jayaprakash; Moolya, B. Narayana

2018-04-01

Non linear optical 1-phenyl-3-(4-dimethylamino phenyl) prop-2-en-1-one (PDAC) was synthesized using Claisen - Schmidt condensation method and studied for optical nonlinearity with an emphasis on structure-property relationship. The structural confirmation studies were carried out using 1H-NMR, FT-IR and single crystal XRD techniques. The nonlinear absorption and nonlinear refraction parameters in z-scan with nano second laser pulses were obtained by measuring the profile of propagated beam through the samples. The real and imaginary parts of third-order bulk susceptibility χ(3) were evaluated. Thermo gravimetric analysis is carried out to investigate the thermal stability.

Fabrication and characterization of dichroic fine crystals by the reprecipitation method

NASA Astrophysics Data System (ADS)

Iino, Tatsuya; Mori, Shunsuke; Shito, Keiji; Kimura, Ayaka; Morishita, Yoshii; Chiba, Takayuki; Katagiri, Hiroshi; Okada, Shuji; Masuhara, Akito

2018-06-01

Suspended particle devices can rapidly switch from a dark blue state to a clear state by applying AC voltage, but their maximum transmittance has to be improved. In this work, we have targeted dichroic dyes and applied the reprecipitation method to KPD-503, a trisazo dye showing little dichroism in bulk crystals despite the dye molecules having large dichroism. As a result, microcrystals showing large dichroism were obtained. These microcrystals were considered to have a kinetically stable structure and oriented by voltage in a dispersing medium.

Dielectric relaxation of guest molecules in a clathrate structure of syndiotactic polystyrene.

PubMed

Urakawa, Osamu; Kaneko, Fumitoshi; Kobayashi, Hideo

2012-12-13

Structure and dynamics of semicrystalline polymer films composed of syndiotactic polystyrene (sPS) and 2-butanone were examined through X-ray diffraction, polarized FTIR, and dielectric relaxation measurements. The X-ray and FTIR measurements revealed its crystal structure to be δ-clathrate containing 2-butanone molecules inside. The carbonyl group of 2-butanone in the crystal was found to orient preferentially parallel to the ac plane of the crystal through the polarized ATR FTIR measurements. Dielectric measurements were also conducted on these film samples to see only the relaxation dynamics of 2-butanone thanks to the high dielectric intensity of 2-butanone compared to sPS. Two relaxation modes denoted by slow and fast modes appeared. The former was assigned to the motion of 2-butanone molecules entrapped in the cavities of the crystalline (δ-form) and the latter to those in the amorphous region. We focused on the slow mode in order to elucidate the specific dynamics of the guest molecule confined in the crystalline region. The relaxation time of the slow mode was about 4 orders of magnitude longer than that of liquid 2-butanone. This suggests that the dynamics of guest molecules is highly restricted due to the high barrier to conformational and/or orientational change of the guest molecule in the cavity of δ-crystal. Furthermore, the dielectric intensity Δε of the slow mode was much smaller than the one calculated from that of bulk liquid 2-butanone and the guest concentration in the crystalline region (the intensity was only 10% of the estimated value from the bulk liquid data). This result also indicates that the free rotational motion of 2-butanone molecules is restricted inside the crystal. This will be consistently related to the weak uniplanar orientation of the carbonyl group of 2-butanone parallel to the ac plane revealed by the X-ray and polarized ATR FTIR measurements.

Crystal growth, structural, thermal and mechanical behavior of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) single crystals.

PubMed

Mahadevan, M; Ramachandran, K; Anandan, P; Arivanandhan, M; Bhagavannarayana, G; Hayakawa, Y

2014-12-10

Single crystals of l-arginine 4-nitrophenolate 4-nitrophenol dihydrate (LAPP) have been grown successfully from the solution of l-arginine and 4-nitrophenol. Slow evaporation of solvent technique was adopted to grow the bulk single crystals. Single crystal X-ray diffraction analysis confirms the grown crystal has monoclinic crystal system with space group of P21. Powder X-ray diffraction analysis shows the good crystalline nature. The crystalline perfection of the grown single crystals was analyzed by HRXRD by employing a multicrystal X-ray diffractometer. The functional groups were identified from proton NMR spectroscopic analysis. Linear and nonlinear optical properties were determined by UV-Vis spectrophotometer and Kurtz powder technique respectively. It is found that the grown crystal has no absorption in the green wavelength region and the SHG efficiency was found to be 2.66 times that of the standard KDP. The Thermal stability of the crystal was found by obtaining TG/DTA curve. The mechanical behavior of the grown crystal has been studied by Vicker's microhardness method. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface crystallographic structures of cellulose nanofiber films and overlayers of pentacene

NASA Astrophysics Data System (ADS)

Nakayama, Yasuo; Mori, Toshiaki; Tsuruta, Ryohei; Yamanaka, Soichiro; Yoshida, Koki; Imai, Kento; Koganezawa, Tomoyuki; Hosokai, Takuya

2018-03-01

Cellulose nanofibers or nanocellulose is a promising recently developed biomass and biodegradable material used for various applications. In order to utilize this material as a substrate in organic electronic devices, thorough understanding of the crystallographic structures of the surfaces of the nanocellulose composites and of their interfaces with organic semiconductor molecules is essential. In this work, surface crystallographic structures of nanocellulose films (NCFs) and overlayers of pentacene were investigated by two-dimensional grazing-incidence X-ray diffraction. The NCFs are found to crystallize on solid surfaces with the crystal lattice preserving the same structure of the known bulk phase, whereas distortion of interchain packing toward the surface normal direction is suggested. The pentacene overlayers on the NCFs are found to form the thin-film phase with an in-plane mean crystallite size of over 10 nm.

Onset of bulk pinning in BSCCO single crystals

NASA Astrophysics Data System (ADS)

van der Beek, C. J.; Indenbom, M. V.; Berseth, V.; Li, T. W.; Benoit, W.

1996-11-01

The long growth defects often found in Bi2Sr2CaCu2O8, “single” crystals effectively weaken the geometrical barrier and lower the field of first flux penetration. This means that the intrinsic (bulk) magnetic properties can be more easily accessed using magnetic measurements. Thus, the onset of strong bulk flux pinning in the sample bulk is determined to lie at T ≈ 40 K, indepedent of whether the field strength is above or below the field of the second peak in the magnetisation.

A Differential Scanning Calorimetry Method for Construction of Continuous Cooling Transformation Diagram of Blast Furnace Slag

NASA Astrophysics Data System (ADS)

Gan, Lei; Zhang, Chunxia; Shangguan, Fangqin; Li, Xiuping

2012-06-01

The continuous cooling crystallization of a blast furnace slag was studied by the application of the differential scanning calorimetry (DSC) method. A kinetic model describing the correlation between the evolution of the degree of crystallization with time was obtained. Bulk cooling experiments of the molten slag coupled with numerical simulation of heat transfer were conducted to validate the results of the DSC methods. The degrees of crystallization of the samples from the bulk cooling experiments were estimated by means of the X-ray diffraction (XRD) and the DSC method. It was found that the results from the DSC cooling and bulk cooling experiments are in good agreement. The continuous cooling transformation (CCT) diagram of the blast furnace slag was constructed according to crystallization kinetic model and experimental data. The obtained CCT diagram characterizes with two crystallization noses at different temperature ranges.

Monitoring the recrystallisation of amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering.

PubMed

Palomäki, Emmi; Ahvenainen, Patrik; Ehlers, Henrik; Svedström, Kirsi; Huotari, Simo; Yliruusi, Jouko

2016-07-11

In this paper we present a fast model system for monitoring the recrystallization of quench-cooled amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering. The use of these two methods enables comparison between surface and bulk crystallization. Non-ordered mesoporous silica micro-particles were added to the system in order to alter the rate of crystallization of the amorphous xylitol. Raman measurements showed that adding silica to the system increased the rate of surface crystallization, while X-ray measurements showed that the rate of bulk crystallization decreased. Using this model system it is possible to measure fast changes, which occur in minutes or within a few hours. Raman-spectroscopy and wide-angle X-ray scattering were found to be complementary techniques when assessing surface and bulk crystallization of amorphous xylitol. Copyright © 2016 Elsevier B.V. All rights reserved.

Growth and structural characterization of large superconducting crystals of La 2 - x Ca 1 + x Cu 2 O 6

DOE PAGES

Schneeloch, J. A.; Guguchia, Z.; Stone, M. B.; ...

2017-12-01

Lmore » arge crystals of a 2 - x Ca 1 + x Cu 2 O 6 (a-Ca-2126) with x = 0:10 and 0.15 have been grown and converted to bulk superconductors by high-pressure oxygen annealing. The superconducting transition temperature, T c, is as high as 55 K; this can be raised to 60 K by post-annealing in air. Here we present structural and magnetic characterizations of these crystals using neutron scattering and muon spin rotation techniques. While the as-grown, non-superconducting crystals are single phase, we nd that the superconducting crystals contain 3 phases forming coherent domains stacked along the c axis: the dominant a-Ca-2126 phase, very thin (1.5 unit-cell) intergrowths of a 2CuO 4, and an antiferromagnetic a 8Cu 8O 20 phase. We propose that the formation and segregation of the latter phases increases the Ca concentration of the a-Ca-2126, thus providing the hole-doping that supports superconductivity.« less

Growth and structural characterization of large superconducting crystals of La 2 - x Ca 1 + x Cu 2 O 6

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

Schneeloch, J. A.; Guguchia, Z.; Stone, M. B.

Lmore » arge crystals of a 2 - x Ca 1 + x Cu 2 O 6 (a-Ca-2126) with x = 0:10 and 0.15 have been grown and converted to bulk superconductors by high-pressure oxygen annealing. The superconducting transition temperature, T c, is as high as 55 K; this can be raised to 60 K by post-annealing in air. Here we present structural and magnetic characterizations of these crystals using neutron scattering and muon spin rotation techniques. While the as-grown, non-superconducting crystals are single phase, we nd that the superconducting crystals contain 3 phases forming coherent domains stacked along the c axis: the dominant a-Ca-2126 phase, very thin (1.5 unit-cell) intergrowths of a 2CuO 4, and an antiferromagnetic a 8Cu 8O 20 phase. We propose that the formation and segregation of the latter phases increases the Ca concentration of the a-Ca-2126, thus providing the hole-doping that supports superconductivity.« less

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

NASA Technical Reports Server (NTRS)

Manthiram, Arumugam (Inventor); Wu, Yan (Inventor)

2010-01-01

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

DOEpatents

Manthiram, Arumugam; Wu, Yan

2010-03-16

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

Structural and vibrational properties of solid nitromethane under high pressure by density functional theory.

PubMed

Liu, Hong; Zhao, Jijun; Wei, Dongqing; Gong, Zizheng

2006-03-28

The structural, vibrational, and electronic properties of solid nitromethane under hydrostatic pressure of up to 20 GPa have been studied using density functional theory. The changes of cell volume, the lattice constants, and the molecular geometry of solid nitromethane under hydrostatic loading are examined, and the bulk modulus B0 and its pressure derivative B0' are fitted from the volume-pressure relation. Our theoretical results are compared with available experiments. The change of electron band gap of nitromethane under high pressure is also discussed. Based on the optimized crystal structures, the vibrational frequencies for the internal and lattice modes of the nitromethane crystal at ambient and high pressures are computed, and the pressure-induced frequency shifts of these modes are discussed.

Structural investigation of the (010) surface of the Al13 Fe4 catalyst.

PubMed

Ledieu, J; Gaudry, É; Loli, L N Serkovic; Villaseca, S Alarcón; de Weerd, M-C; Hahne, M; Gille, P; Grin, Y; Dubois, J-M; Fournée, V

2013-02-15

We have investigated the structure of the Al(13)Fe(4)(010) surface using both experimental and ab initio computational methods. The results indicate that the topmost surface layers correspond to incomplete puckered (P) planes present in the bulk crystal structure. The main building block of the corrugated termination consists of two adjacent pentagons of Al atoms, each centered by a protruding Fe atom. These motifs are interconnected via additional Al atoms referred to as "glue" atoms which partially desorb above 873 K. The surface structure of lower atomic density compared to the bulk P plane is explained by a strong Fe-Al-Fe covalent polar interaction that preserves intact clusters at the surface. The proposed surface model with identified Fe-containing atomic ensembles could explain the Al(13)Fe(4) catalytic properties recently reported in line with the site-isolation concept [M. Armbrüster et al., Nat. Mater. 11, 690 (2012)].

DAST single-nanometer crystal preparation using a substrate-supported rapid evaporation crystallization method.

PubMed

Tian, Tian; Cai, Bin; Sugihara, Okihiro

2016-12-07

A substrate-supported rapid evaporation crystallization (SSREC) method was used to develop a highly nonlinear optical material, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), which satisfies the Rayleigh scattering requirement for the fabrication of highly transparent composites. DAST nanocrystals have a second harmonic generation active crystal structure and a high signal-to-noise ratio second harmonic generation signal when excited by using a 1064 nm cw laser. The nanocrystals also possess size-dependent UV-vis absorption and fluorescence behavior which is not seen in the bulk state. SSREC offers a very convenient means of nanocrystal size control for fabricating nonlinear optical nanomaterials, and the unique properties of these DAST NCs provide potential applications in the fields of lasing, fluorescence probes, and other nonlinear optical photonics.

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan

1996-01-01

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

Surface Crystallization of a MgO/Y2O3/SiO2/Al2O3/ZrO2 Glass: Growth of an Oriented β-Y2Si2O7 Layer and Epitaxial ZrO2

PubMed Central

Wisniewski, Wolfgang; Seidel, Sabrina; Patzig, Christian; Rüssel, Christian

2017-01-01

The crystallization behavior of a glass with the composition 54.7 SiO2·10.9 Al2O3·15.0 MgO·3.4 ZrO2·16.0 Y2O3 is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD) and (scanning) transmission electron microscopy [(S)TEM] including energy-dispersive X-ray spectrometry (EDXS). This glass shows the sole surface crystallization of four different yttrium silicates of the composition Y2Si2O7 (YS). The almost simultaneous but independent nucleation of α-, β-, δ-, and ε-YS at the surface is followed by growth into the bulk, where ε-YS quickly dominates a first crystallized layer. An accumulation of Mg at the growth front probably triggers a secondary nucleation of β-YS, which forms a thin compact layer before fragmenting into a highly oriented layer of fine grained crystals occupying the remaining bulk. The residual glass between the YS growth structures allows the crystallization of indialite, yttrium stabilized ZrO2 (Y-ZrO2) and very probably μ-cordierite during cooling. Hence, this glass basically shows the inverted order of crystallization observed in other magnesium yttrium alumosilicate glasses containing less Y2O3. An epitaxial relationship between Y-ZrO2 and ε-YS is proven and multiple twinning relationships occur in the YS phases. PMID:28281661

Sequential structural and optical evolution of MoS2 by chemical synthesis and exfoliation

NASA Astrophysics Data System (ADS)

Kim, Ju Hwan; Kim, Jungkil; Oh, Si Duck; Kim, Sung; Choi, Suk-Ho

2015-06-01

Various types of MoS2 structures are successfully obtained by using economical and facile sequential synthesis and exfoliation methods. Spherically-shaped lumps of multilayer (ML) MoS2 are prepared by using a conventional hydrothermal method and were subsequently 1st-exfoliated in hydrazine while being kept in autoclave to be unrolled and separated into five-to-six-layer MoS2 pieces of several-hundred nm in size. The MoS2 MLs are 2nd-exfoliated in sodium naphthalenide under an Ar ambient to finally produce bilayer MoS2 crystals of ~100 nm. The sequential exfoliation processes downsize MoS2 laterally and reduce its number of layers. The three types of MoS2 allotropes exhibit particular optical properties corresponding to their structural differences. These results suggest that two-dimensional MoS2 crystals can be prepared by employing only chemical techniques without starting from high-pressure-synthesized bulk MoS2 crystals.

Semiconducting molecular crystals: Bulk in-gap states modified by structural and chemical defects

NASA Astrophysics Data System (ADS)

Haas, S.; Krellner, C.; Goldmann, C.; Pernstich, K. P.; Gundlach, D. J.; Batlogg, B.

2007-03-01

Charge transport in organic molecular crystals is strongly influenced by the density of localized in-gap states (traps). Thus, a profound knowledge of the defect states' origin is essential. Temperature-dependent space-charge limited current (TD-SCLC) spectroscopy was used as a powerful tool to quantitatively study the density of states (DOS) in high-quality rubrene and pentacene single crystals. In particular, changes of the DOS due to intentionally induced chemical and structural defects were monitored. For instance, the controlled exposure of pentacene and rubrene to x-ray radiation results in a broad over-all increase of the DOS. Namely, the ionizing radiation induces a variety of both chemical and structural defects. On the other hand, exposure of rubrene to UV-excited oxygen is reflected in a sharp peak in the DOS, whereas in a similar experiment with pentacene oxygen acts as a dopant, and possible defects are metastable on the time-scale of the measurement, thus leaving the extracted DOS virtually unchanged.

Pressure evolution of electrical transport in the 3D topological insulator (Bi,Sb) 2 (Se,Te) 3

DOE PAGES

Jeffries, J. R.; Butch, N. P.; Vohra, Y. K.; ...

2015-03-18

The group V-VI compounds|like Bi 2Se 3, Sb 2Te 3, or Bi 2Te 3|have been widely studied in recent years for their bulk topological properties. The high-Z members of this series form with the same crystal structure, and are therefore amenable to isostructural substitution studies. It is possible to tune the Bi-Sb and Te-Se ratios such that the material exhibits insulating behavior, thus providing an excellent platform for understanding how a topological insulator evolves with applied pressure. We report our observations of the pressure-dependent electrical transport and crystal structure of a pseudobinary (Bi,Sb) 2(Te,Se) 3 compound. Similar to some ofmore » its sister compounds, the (Bi,Sb) 2(Te,Se) 3 pseudobinary compound undergoes multiple, pressure-induced phase transformations that result in metallization, the onset of a close-packed crystal structure, and the development of distinct superconducting phases.« less

Photonic guiding structures in lithium niobate crystals produced by energetic ion beams

NASA Astrophysics Data System (ADS)

Chen, Feng

2009-10-01

A range of ion beam techniques have been used to fabricate a variety of photonic guiding structures in the well-known lithium niobate (LiNbO3 or LN) crystals that are of great importance in integrated photonics/optics. This paper reviews the up-to-date research progress of ion-beam-processed LiNbO3 photonic structures and reports on their fabrication, characterization, and applications. Ion beams are being used with this material in a wide range of techniques, as exemplified by the following examples. Ion beam milling/etching can remove the selected surface regions of LiNbO3 crystals via the sputtering effects. Ion implantation and swift ion irradiation can form optical waveguide structures by modifying the surface refractive indices of the LiNbO3 wafers. Crystal ion slicing has been used to obtain bulk-quality LiNbO3 single-crystalline thin films or membranes by exfoliating the implanted layer from the original substrate. Focused ion beams can either generate small structures of micron or submicron dimensions, to realize photonic bandgap crystals in LiNbO3, or directly write surface waveguides or other guiding devices in the crystal. Ion beam-enhanced etching has been extensively applied for micro- or nanostructuring of LiNbO3 surfaces. Methods developed to fabricate a range of photonic guiding structures in LiNbO3 are introduced. Modifications of LiNbO3 through the use of various energetic ion beams, including changes in refractive index and properties related to the photonic guiding structures as well as to the materials (i.e., electro-optic, nonlinear optic, luminescent, and photorefractive features), are overviewed in detail. The application of these LiNbO3 photonic guiding structures in both micro- and nanophotonics are briefly summarized.

Young-Laplace equation for liquid crystal interfaces

NASA Astrophysics Data System (ADS)

Rey, Alejandro D.

2000-12-01

This letter uses the classical theories of liquid crystal physics to derive the Young-Laplace equation of capillary hydrostatics for interfaces between viscous isotropic (I) fluids and nematic liquid crystals (NLC's), and establishes the existence of four energy contributions to pressure jumps across these unusual anisotropic interfaces. It is shown that in addition to the usual curvature contribution, bulk and surface gradient elasticity, elastic stress, and anchoring energy contribute to pressure differentials across the interface. The magnitude of the effect is proportional to the elastic moduli of the NLC, and to the bulk and surface orientation gradients that may be present in the nematic phase. In contrast to the planar interface between isotropic fluids, flat liquid crystal interfaces support pressure jumps if elastic stresses, bulk and surface gradient energy, and/or anchoring energies are finite.

In-line bulk supersaturation measurement by electrical conductometry in KDP crystal growth from aqueous solution

NASA Astrophysics Data System (ADS)

Bordui, P. F.; Loiacono, G. M.

1984-07-01

A method is presented for in-line bulk supersaturation measurement in crystal growth from aqueous solution. The method is based on a computer-controlled concentration measurement exploiting an experimentally predetermined cross-correlation between the concentration, electrical conductivity, and temperature of the growth solution. The method was applied to Holden crystallization of potassium dihydrogen phosphate (KDP). An extensive conductivity-temperature-concentration data base was generated for this system over a temperature range of 31 to 41°C. The method yielded continous, automated bulk supersaturation output accurate to within ±0.05 g KDP100 g water (±0.15% relative supersaturation).

Prediction of weak topological insulators in layered semiconductors.

PubMed

Yan, Binghai; Müchler, Lukas; Felser, Claudia

2012-09-14

We report the discovery of weak topological insulators by ab initio calculations in a honeycomb lattice. We propose a structure with an odd number of layers in the primitive unit cell as a prerequisite for forming weak topological insulators. Here, the single-layered KHgSb is the most suitable candidate for its large bulk energy gap of 0.24 eV. Its side surface hosts metallic surface states, forming two anisotropic Dirac cones. Although the stacking of even-layered structures leads to trivial insulators, the structures can host a quantum spin Hall layer with a large bulk gap, if an additional single layer exists as a stacking fault in the crystal. The reported honeycomb compounds can serve as prototypes to aid in the finding of new weak topological insulators in layered small-gap semiconductors.

Structural origins of broadband emission from layered Pb-Br hybrid perovskites.

PubMed

Smith, Matthew D; Jaffe, Adam; Dohner, Emma R; Lindenberg, Aaron M; Karunadasa, Hemamala I

2017-06-01

Through structural and optical studies of a series of two-dimensional hybrid perovskites, we show that broadband emission upon near-ultraviolet excitation is common to (001) lead-bromide perovskites. Importantly, we find that the relative intensity of the broad emission correlates with increasing out-of-plane distortion of the Pb-(μ-Br)-Pb angle in the inorganic sheets. Temperature- and power-dependent photoluminescence data obtained on a representative (001) perovskite support an intrinsic origin to the broad emission from the bulk material, where photogenerated carriers cause excited-state lattice distortions mediated through electron-lattice coupling. In contrast, most inorganic phosphors contain extrinsic emissive dopants or emissive surface sites. The design rules established here could allow us to systematically optimize white-light emission from layered hybrid perovskites by fine-tuning the bulk crystal structure.

Super heavy element Copernicium: Cohesive and electronic properties revisited

NASA Astrophysics Data System (ADS)

Gyanchandani, Jyoti; Mishra, Vinayak; Dey, G. K.; Sikka, S. K.

2018-01-01

First principles scalar relativistic (SR) calculations with and without including the spin orbit (SO) interactions have been performed for solid Copernicium (Cn) to determine its ground state equilibrium structure, volume, bulk modulus, pressure derivative of the bulk modulus, density of states and band structure. Both SR and SR+SO calculations have been performed with 6p levels treated as part of core electrons and also as part of valence electrons. These calculations have been performed for the rhombohedral, BCT, FCC, HCP, BCC and SC structures. Results have been compared with the results for Hg which is lighter homologue of Cn in the periodic table. We find hcp to be the stable crystal structure at SR level of theory and also at SR+SO level of theory when the 6p electrons are treated as part of core electrons. With 6p as part of valence electrons, SR+SO level of computations, however, yield bcc structure to be the most stable structure. Equilibrium volume (V0) of the most stable crystal structure at SR level of theory viz. hcp structure is 188.66 a.u.3whereas its value for the bcc structure, the equilibrium ground state structure at SR+SO level of theory is 165.71 a.u.3 i.e a large change due to relativistic effects is seen. The density of states at Fermi level is much smaller in Cn than in Hg, making it a poorer metal than mercury. In addition the cohesive energy of Cn is computed to be almost two times that of Hg for SR+SO case.

Study of linear optical parameters of sodium sulphide nano-particles added ADP crystals

NASA Astrophysics Data System (ADS)

Kochuparampil, A. P.; Joshi, J. H.; Dixit, K. P.; Jethva, H. O.; Joshi, M. J.

2017-05-01

Ammonium Dihydrogen Phosphate (ADP) is one of the nonlinear optical crystals. It is having various applications like optical mixing, electro-optical modulator, harmonic generators, etc. Chalcogenide compounds are poorly soluble in water and difficult to add in the water soluble ADP crystals. The solubility of Chalcogenide compounds can be increased by synthesizing the nano-structured samples with suitable capping agent. In the present study sodium sulphide was added in to ADP to modify its linear optical parameters. Sodium sulphide nano particles were synthesized by co-precipitation technique using Ethylene diamine as capping agent followed by microwave irradiation. The powder XRD confirmed the nano-structured nature of sodium sulphide nano particles. The solubility of nanoparticles of sodium sulphide increased significantly in water compared to the bulk. Pure and Na2S added ADP crystals were grown by slow solvent evaporation method at room temperature. The presence of sodium in ADP was confirmed by AAS. The UV-Vis spectra were recorded for all crystals. Various optical parameters like, transmittance, energy band gap, extinction coefficient, refractive index, optical conductivity, etc. were evaluated. The electronic polarizibility of pure and doped crystals calculated from energy band gap. The effect of doping concentration was found on various parameters.

Probing periodic potential of crystals via strong-field re-scattering

NASA Astrophysics Data System (ADS)

You, Yong Sing; Cunningham, Eric; Reis, David A.; Ghimire, Shambhu

2018-06-01

Strong-field ionization and re-scattering phenomena have been used to image angstrom-scale structures of isolated molecules in the gas phase. These methods typically make use of the anisotropic response of the participating molecular orbital. Recently, an anisotropic strong-field response has also been observed in high-order harmonic generation (HHG) from bulk crystals (2016 Nat. Phys. 13 345). In a (100) cut magnesium oxide crystal, extreme ultraviolet high-harmonics are found to depend strongly on the crystal structure and inter-atomic bonding. Here, we extend these measurements to other two important crystal orientations: (111) and (110). We find that HHG from these orientations is also strongly anisotropic. The underlying dynamics is understood using a real-space picture, where high-harmonics are produced via coherent collision of strong-field driven electrons from the atomic sites, including from the nearest neighbor atoms. We find that harmonic efficiency is enhanced when semi-classical electron trajectories connect to the concentrated valence charge distribution regions around the atomic cores. Similarly, the efficiency is suppressed when the trajectories miss the atomic cores. These results further support the real-space picture of HHG with implications for retrieving the periodic potential of the crystal, if not the wavefunctions in three-dimensions.

Localization of the interband transitions in the bulk of the Brillouin zone of III–V compound crystals

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

Sobolev, V. V., E-mail: sobolev@uni.udm.ru; Perevoshchikov, D. A.

2016-05-15

The localization of the transitions in the bulk of the Brillouin zone that form the main structures in the spectra of the imaginary part of the permittivity in the range up to ~7 eV for III–V semiconductors (AlSb, GaSb, InSb, and InAs) is determined using electron density functional theory. It is established that intense transitions occur not only in the vicinity of the high-symmetry axes of the Brillouin zone, but also in some specific large volumes of the irreducible part of the Brillouin zone.

Crystallization, melting, and structure of water nanoparticles at atmospherically relevant temperatures.

PubMed

Johnston, Jessica C; Molinero, Valeria

2012-04-18

Water nanoparticles play an important role in atmospheric processes, yet their equilibrium and nonequilibrium liquid-ice phase transitions and the structures they form on freezing are not yet fully elucidated. Here we use molecular dynamics simulations with the mW water model to investigate the nonequilibrium freezing and equilibrium melting of water nanoparticles with radii R between 1 and 4.7 nm and the structure of the ice formed by crystallization at temperatures between 150 and 200 K. The ice crystallized in the particles is a hybrid form of ice I with stacked layers of the cubic and hexagonal ice polymorphs in a ratio approximately 2:1. The ratio of cubic ice to hexagonal ice is insensitive to the radius of the water particle and is comparable to that found in simulations of bulk water around the same temperature. Heating frozen particles that contain multiple crystallites leads to Ostwald ripening and annealing of the ice structures, accompanied by an increase in the amount of ice at the expense of the liquid water, before the particles finally melt from the hybrid ice I to liquid, without a transition to hexagonal ice. The melting temperatures T(m) of the nanoparticles are not affected by the ratio of cubic to hexagonal layers in the crystal. T(m) of the ice particles decreases from 255 to 170 K with the particle size and is well described by the Gibbs-Thomson equation, T(m)(R) = T(m)(bulk) - K(GT)/(R - d), with constant K(GT) = 82 ± 5 K·nm and a premelted liquid of width d = 0.26 ± 0.05 nm, about one monolayer. The freezing temperatures also decrease with the particles' radii. These results are important for understanding the composition, freezing, and melting properties of ice and liquid water particles under atmospheric conditions. © 2012 American Chemical Society

Direct optical transitions at K- and H-point of Brillouin zone in bulk MoS2, MoSe2, WS2, and WSe2

NASA Astrophysics Data System (ADS)

Kopaczek, J.; Polak, M. P.; Scharoch, P.; Wu, K.; Chen, B.; Tongay, S.; Kudrawiec, R.

2016-06-01

Modulated reflectance (contactless electroreflectance (CER), photoreflectance (PR), and piezoreflectance (PzR)) has been applied to study direct optical transitions in bulk MoS2, MoSe2, WS2, and WSe2. In order to interpret optical transitions observed in CER, PR, and PzR spectra, the electronic band structure for the four crystals has been calculated from the first principles within the density functional theory for various points of Brillouin zone including K and H points. It is clearly shown that the electronic band structure at H point of Brillouin zone is very symmetric and similar to the electronic band structure at K point, and therefore, direct optical transitions at H point should be expected in modulated reflectance spectra besides the direct optical transitions at the K point of Brillouin zone. This prediction is confirmed by experimental studies of the electronic band structure of MoS2, MoSe2, WS2, and WSe2 crystals by CER, PR, and PzR spectroscopy, i.e., techniques which are very sensitive to critical points of Brillouin zone. For the four crystals besides the A transition at K point, an AH transition at H point has been observed in CER, PR, and PzR spectra a few tens of meV above the A transition. The spectral difference between A and AH transition has been found to be in a very good agreement with theoretical predictions. The second transition at the H point of Brillouin zone (BH transition) overlaps spectrally with the B transition at K point because of small energy differences in the valence (conduction) band positions at H and K points. Therefore, an extra resonance which could be related to the BH transition is not resolved in modulated reflectance spectra at room temperature for the four crystals.

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

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

Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T.

1994-12-31

The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relationmore » between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.« less

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

NASA Technical Reports Server (NTRS)

Tatarenko, Valentine A.; Tsysman, Constantin L.; Oltarzhevskaya, Yelena T.

1995-01-01

The calculations in a majority of previous works for the fulleride (AqC-60) crystals were performed within the framework of the rigid-lattice model, neglecting the distortion relaxation of the host fullerene (C-60) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distortion field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. The given paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of static concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method(*). In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the static inherent reorientation and/or displacements of the solvent molecules from the 'average-lattice' sites' as well as on the lattice parameter a of a elastically-anysotropic 'cubic' C-60 crystal are taken into account.

Synthesis and morphology of Ba1-xRE2x/3Nb2O6 nanocrystals with tungsten bronze structure in RE2O3-BaO-Nb2O5-B2O3 glasses (RE: Sm, Eu, Gd, Dy, Er)

NASA Astrophysics Data System (ADS)

Ida, H.; Shinozaki, K.; Honma, T.; Oh-ishi, K.; Komatsu, T.

2012-12-01

Ba1-xRE2x/3Nb2O6 nanocrystals with a tetragonal tungsten bronze (TTB) structure are synthesized using a conventional glass crystallization technique in 2.3RE2O3-27.4BaO-34.3Nb2O5-36B2O3 (mol%) (RE=Sm, Eu, Gd, Dy, and Er) glasses. One sharp crystallization peak is observed at ∼670 °C in both powdered and bulk glasses, and the formation of Ba1-xRE2x/3Nb2O6 nanocrystals with unit cell parameters of a∼1.24 nm and c∼0.39 nm was confirmed. It is found from high resolution transmission electron microscope observations that the morphology of Ba1-xRE2x/3Nb2O6 nanocrystals is ellipsoidal. Their average particle size is in the range of 15-60 nm and decreases with decreasing ionic radius of RE3+ being present in the precursor glasses. The optical transparent crystallized glass (bulk) shows the total photoluminescence (PL) quantum yield of 53% in the visible region of Eu3+ ions, suggesting a high potential of Ba1-xRE2x/3Nb2O6 nanocrystals as PL materials.

Light-activated Gigahertz Ferroelectric Domain Dynamics

DOE PAGES

Akamatsu, Hirofumii; Yuan, Yakun; Stoica, Vladimir A.; ...

2018-02-26

Using time- and spatially-resolved hard X-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO 3 are simultaneously captured on sub-nanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photo-induced electric field of up to 20 million volts per meter is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling (DPFM) method is developed that reveals the microscopic origin of these dynamics, leading to GHz polarization andmore » elastic waves travelling in the crystal with sonic speeds and spatially varying frequencies. The advance of spatiotemporal imaging and dynamical modeling tools open opportunities of disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains« less

Investigation on the growth and characterization of 4-aminobenzophenone single crystal by the vertical dynamic gradient freeze technique

NASA Astrophysics Data System (ADS)

Prabhakaran, SP.; Ramesh Babu, R.; Sukumar, M.; Bhagavannarayana, G.; Ramamurthi, K.

2014-03-01

Growth of bulk single crystal of 4-Aminobenzophenone (4-ABP) from the vertical dynamic gradient freeze (VDGF) setup designed with eight zone furnace was investigated. The experimental parameters for the growth of 4-ABP single crystal with respect to the design of VDGF setup are discussed. The eight zones were used to generate multiple temperature gradients over the furnace, and video imaging system helped to capture the real time growth and solid-liquid interface. 4-ABP single crystal with the size of 18 mm diameter and 40 mm length was grown from this investigation. Structural and optical quality of grown crystal was examined by high resolution X-ray diffraction and UV-visible spectral analysis, respectively and the blue emission was also confirmed from the photoluminescence spectrum. Microhardness number of the crystal was estimated at different loads using Vicker's microhardness tester. The size and quality of single crystal grown from the present investigation are compared with the vertical Bridgman grown 4-ABP.

Point defects at the ice (0001) surface

PubMed Central

Watkins, Matthew; VandeVondele, Joost; Slater, Ben

2010-01-01

Using density functional theory we investigate whether intrinsic defects in ice surface segregate. We predict that hydronium, hydroxide, and the Bjerrum L- and D-defects are all more stable at the surface. However, the energetic cost to create a D-defect at the surface and migrate it into the bulk crystal is smaller than its bulk formation energy. Absolute and relative segregation energies are sensitive to the surface structure of ice, especially the spatial distribution of protons associated with dangling hydrogen bonds. It is found that the basal plane surface of hexagonal ice increases the bulk concentration of Bjerrum defects, strongly favoring D-defects over L-defects. Dangling protons associated with undercoordinated water molecules are preferentially injected into the crystal bulk as Bjerrum D-defects, leading to a surface dipole that attracts hydronium ions. Aside from the disparity in segregation energies for the Bjerrum defects, we find the interactions between defect species to be very finely balanced; surface segregation energies for hydronium and hydroxide species and trapping energies of these ionic species with Bjerrum defects are equal within the accuracy of our calculations. The mobility of the ionic hydronium and hydroxide species is greatly reduced at the surface in comparison to the bulk due to surface sites with high trapping affinities. We suggest that, in pure ice samples, the surface of ice will have an acidic character due to the presence of hydronium ions. This may be important in understanding the reactivity of ice particulates in the upper atmosphere and at the boundary layer. PMID:20615938

Bulk Crystal Growth of Piezoelectric PMN-PT Crystals Using Gradient Freeze Technique for Improved SHM Sensors

NASA Technical Reports Server (NTRS)

Aggarwal, Mohan D.; Kochary, F.; Penn, Benjamin G.; Miller, Jim

2007-01-01

There has been a growing interest in recent years in lead based perovskite ferroelectric and relaxor ferroelectric solid solutions because of their excellent dielectric, piezoelectric and electrostrictive properties that make them very attractive for various sensing, actuating and structural health monitoring (SHM) applications. We are interested in the development of highly sensitive and efficient PMN-PT sensors based on large single crystals for the structural health monitoring of composite materials that may be used in future spacecrafts. Highly sensitive sensors are needed for detection of defects in these materials because they often tend to fail by distributed and interacting damage modes and much of the damage occurs beneath the top surface of the laminate and not detectable by visual inspection. Research is being carried out for various combinations of solid solutions for PMN-PT piezoelectric materials and bigger size crystals are being sought for improved sensor applications. Single crystals of this material are of interest for sensor applications because of their high piezoelectric coefficient (d33 greater than 1700 pC/N) and electromechanical coefficients (k33 greater than 0.90). For comparison, the commonly used piezoelectric ceramic lead zirconate titanate (PZT) has a d33 of about 600 pC/N and electromechanical coefficients k33 of about 0.75. At the present time, these piezoelectric relaxor crystals are grown by high temperature flux growth method and the size of these crystals are rather small (3x4x5 mm(exp 3). In the present paper, we have attempted to grow bulk single crystals of PMN-PT in a 2 inch diameter platinum crucible and successfully grown a large size crystal of 67%PMN-33%PT using the vertical gradient freeze technique with no flux. Piezoelectric properties of the grown crystals are investigated. PMN-PT plates show excellent piezoelectric properties. Samples were poled under an applied electric field of 5 kV/cm. Dielectric properties at a frequency of 1 kHz are examined. The grown PMN-PT crystals show typical relaxor dielectric properties. Additionally, the thermal properties of the sample are tested. The results are in good agreement with those found in the literature and some are reported for the first time.

Crystal Growth of II-VI Semiconducting Alloys by Directional Solidification

NASA Technical Reports Server (NTRS)

Lehoczky, Sandor L.; Szofran, Frank R.; Su, Ching-Hua; Cobb, Sharon D.; Scripa, Rosalia A.; Sha, Yi-Gao

1999-01-01

This research study is investigating the effects of a microgravity environment during the crystal growth of selected II-VI semiconducting alloys on their compositional, metallurgical, electrical and optical properties. The on-going work includes both Bridgman-Stockbarger and solvent growth methods, as well as growth in a magnetic field. The materials investigated are II-VI, Hg(1-x)Zn(x)Te, and Hg(1-x)Zn(x)Se, where x is between 0 and 1 inclusive, with particular emphasis on x-values appropriate for infrared detection and imaging in the 5 to 30 micron wavelength region. Wide separation between the liquidus and solidus of the phase diagrams with consequent segregation during solidification and problems associated with the high volatility of one of the components (Hg), make the preparation of homogeneous, high-quality, bulk crystals of the alloys an extremely difficult nearly an impossible task in a gravitational environment. The three-fold objectives of the on-going investigation are as follows: (1) To determine the relative contributions of gravitationally-driven fluid flows to the compositional redistribution observed during the unidirectional crystal growth of selected semiconducting solid solution alloys having large separation between the liquidus and solidus of the constitutional phase diagram; (2) To ascertain the potential role of irregular fluid flows and hydrostatic pressure effects in generation of extended crystal defects and second-phase inclusions in the crystals; and, (3) To obtain a limited amount of "high quality" materials needed for bulk crystal property characterizations and for the fabrication of various device structures needed to establish ultimate material performance limits. The flight portion of the study was to be accomplished by performing growth experiments using the Crystal Growth Furnace (CGF) manifested to fly on various Spacelab missions.

Growth, structural, optical, thermal and mechanical properties of cytosinium hydrogen selenite: A novel nonlinear optical single crystal

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

Jaikumar, P.; Sathiskumar, S.; Balakrishnan, T., E-mail: balacrystalgrowth@gmail.com

Highlights: • Growth of bulk single crystals of cytosinium hydrogen selenite (CHS) is reported. • Dielectric constant of CHS is measured as a function of Frequency and temperature. • Lower cut off value of UV–vis-NIR spectrum of CHS crystal is observed at 210 nm. • Meyer’s index value of CHS crystal calculated identifies it as a soft material. • Powder SHG efficiency of CHS is about 1.5 times that of KDP crystal. - Abstract: A novel nonlinear optical single crystal of cytosinium hydrogen selenite was grown from aqueous solution of cytosinium hydrogen selenite by slow solvent evaporation method at roommore » temperature. The structural properties of grown crystal have been studied by single crystal and powder X-ray diffraction analysis. Presence of various functional groups was identified from Fourier transform infrared spectroscopy. The optical transmittance and absorbance spectra were recorded by UV–vis-NIR spectrometer and the grown crystal possesses good transparency in the entire visible region. The dielectric constant and dielectric loss of the crystal were calculated as a function of frequency at different temperatures. The mechanical strength of the cytosinium hydrogen selenite crystal was estimated using Vicker’s microhardness tester. Etch patterns of the cytosinium hydrogen selenite crystal were obtained using distilled water as etchant for different etching time. Second harmonic generation efficiency tested using Nd:YAG laser is about 1.5 times that of KDP.« less

Congruent melting of gallium nitride at 6 GPa and its application to single-crystal growth.

PubMed

Utsumi, Wataru; Saitoh, Hiroyuki; Kaneko, Hiroshi; Watanuki, Tetsu; Aoki, Katsutoshi; Shimomura, Osamu

2003-11-01

The synthesis of large single crystals of GaN (gallium nitride) is a matter of great importance in optoelectronic devices for blue-light-emitting diodes and lasers. Although high-quality bulk single crystals of GaN suitable for substrates are desired, the standard method of cooling its stoichiometric melt has been unsuccessful for GaN because it decomposes into Ga and N(2) at high temperatures before its melting point. Here we report that applying high pressure completely prevents the decomposition and allows the stoichiometric melting of GaN. At pressures above 6.0 GPa, congruent melting of GaN occurred at about 2,220 degrees C, and decreasing the temperature allowed the GaN melt to crystallize to the original structure, which was confirmed by in situ X-ray diffraction. Single crystals of GaN were formed by cooling the melt slowly under high pressures and were recovered at ambient conditions.

Structural properties of ultrafine Ba-hexaferrite nanoparticles

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

Makovec, Darko, E-mail: Darko.Makovec@ijs.si; Primc, Darinka; Sturm, Saso

2012-12-15

Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was studied using X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDXS), X-ray absorption fine structure (XAFS), and Moessbauer spectroscopy (MS), to be compared to the structure of larger nanoparticles and the bulk. The nanoparticles were synthesized with hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH{sup -}. The ultrafine nanoparticles were formed in a discoid shape, {approx}10 nm wide and only {approx}3 nm thick, comparable to the size of the hexagonal unit cell in the c-direction.more » The HRTEM image analysis confirmed the hexaferrite structure, whereas EDXS showed the composition matching the BaFe{sub 12}O{sub 19} formula. XAFS and MS analyses showed considerable disorder of the structure, most probably responsible for the low magnetization. - Graphical abstract: Left: HREM image of an ultrafine Ba-hexaferrite nanoparticle (inset: TEM image of the nanoparticles); Right: the experimental HRTEM image is compared with calculated image and corresponding atomic model. Highlights: Black-Right-Pointing-Pointer Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was compared to the structure of the bulk. Black-Right-Pointing-Pointer Thickness the discoid nanoparticles was comparable to the size of the hexagonal unit cell in the c-direction. Black-Right-Pointing-Pointer Considerable disorder of the nanoparticles' structure is most probably responsible for their low magnetization.« less

Crystal Growth and Characterization of THO2 and UxTh1-xO2

DTIC Science & Technology

2013-03-01

bulk actinide crystals would open up new possibilities for the detection of weapons of mass destruction, the study of the effect of aging on...way of growing bulk actinide materials of optical quality. These refractory oxide single crystals offer potential applications in thorium nuclear...fuel technology, wide-band-gap uranium-based direct-conversion solid state neutron detectors, and understanding how actinide fuels age with time. ThO2

Average and local crystal structures of (Ga 1–xZn x)(N 1–xO x) solid solution nanoparticles

DOE PAGES

Feygenson, Mikhail; Neuefeind, Joerg C.; Tyson, Trevor A.; ...

2015-11-06

We report the comprehensive study of the crystal structure of (Ga 1–xZn x)(N 1–xO x) solid solution nanoparticles by means of neutron and synchrotron x-ray scattering. In our study we used four different types of (Ga 1–xZn x)(N 1–xO x) nanoparticles, with diameters of 10–27 nm and x = 0.075–0.51, which show the narrow energy-band gaps from 2.21 to 2.61 eV. The Rietveld analysis of the neutron diffraction data revealed that the average crystal structure is the hexagonal wurtzite (space group P6 3mc), in agreement with previous reports on similar bulk materials. The pair-distribution function (PDF) analysis of the samemore » data found that the local structure is more disordered than the average one. It is best described by the model with a lower symmetry space group P1, where atoms are quasirandomly distorted from their nominal positions in the hexagonal wurtzite lattice.« less

Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides

DOE PAGES

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin; ...

2015-10-29

Although Li- and Mn-rich transition metal oxides have been extensively studied as high-capacity cathode materials for Li-ion batteries, the crystal structure of these materials in their pristine state is not yet fully understood. Here we apply complementary electron microscopy and spectroscopy techniques at multi-length scale on well-formed Li1.2(Ni0.13Mn0.54Co0.13)O2 crystals with two different morphologies as well as two commercially available materials with similar compositions, and unambiguously describe the structural make-up of these samples. Systematically observing the entire primary particles along multiple zone axes reveals that they are consistently made up of a single phase, save for rare localized defects and amore » thin surface layer on certain crystallographic facets. Finally and more specifically, we show the bulk of the oxides can be described as an aperiodic crystal consisting of randomly stacked domains that correspond to three variants of monoclinic structure, while the surface is composed of a Co- and/or Ni-rich spinel with antisite defects.« less

Atomic structure and dynamics properties of Cu50Zr50 films

NASA Astrophysics Data System (ADS)

Chen, Heng; Qu, Bingyan; Li, Dongdong; Zhou, Rulong; Zhang, Bo

2018-01-01

In this paper, the structural and dynamic properties of Cu50Zr50 films are investigated by molecular dynamics simulations. Our results show that the dynamics of the surface atoms are much faster than those of the bulk. Especially, the diffusion coefficient of the surface atoms is about forty times larger than that of the bulk at 600 K, which qualitatively agrees with the experimental results. Meanwhile, we find that the population of the icosahedral (-like) clusters in the surface region is obviously higher than that of the bulk, which prevents the surface from crystallization. A new method to determine the string-like collective atomic motion is introduced in the paper, and it suggests a possible connection between the glass formation ability and collective atomic motion. By using the method, the effects of surface on collective motion are illustrated. Our results show that the string-like collective atomic motion of surface atoms is weakened while that of the interior atoms is strengthened. The studies clearly explain the effects of surface on the structural and dynamic properties of Cu50Zr50 films from the atomic scale.

Influence of non-covalent modification of multiwalled carbon nanotubes on the crystallization behaviour of binary blends of polypropylene and polyamide 6.

PubMed

Mukhopadhyay, Nabaneeta; Panwar, Ajay S; Kumar, Gulshan; Samajdar, I; Bhattacharyya, Arup R

2015-02-14

Blends of polypropylene (PP) and polyamide 6 (PA6) with multiwalled carbon nanotubes (MWNTs) were prepared using different processing strategies in a twin-screw micro-compounder. The effect of MWNTs on the crystallization behaviour of the PP phase and the PA6 phase of the blend has been investigated through non-isothermal crystallization studies by differential scanning calorimetric analysis. Furthermore, the effect of the addition of the compatibilizer (PP-g-MA) and the modification of MWNTs (m-MWNTs) with a non-covalent organic modifier (Li-salt of 6 amino hexanoic acid, Li-AHA) has also been studied in context to the crystallization behaviour of the PP and PA6 phase in the blend. The crystallization studies have indicated a significant increase in bulk crystallization temperature of the PP phase in the blend in the presence of MWNTs. Moreover, the formation of 'trans-lamellar crystalline' structure consisting of PA6 'trans-crystalline lamellae' on MWNTs surface was facilitated in the case of blends prepared via 'protocol 2' as compared to the corresponding blends prepared via 'protocol 1'. Wide angle X-ray diffraction analysis has showed the existence of a β-polymorph of the PP phase due to incorporation of the PA6 phase in the blend. Addition of MWNTs in the blends has facilitated further β-crystalline structure formation of the PP phase. In the presence of m-MWNTs, a higher β-fraction was observed in the PP phase as compared to the blend with pristine MWNTs. Addition of PP-g-MA has suppressed the β-phase formation in the PP phase in the blend. X-ray bulk texture analysis revealed that incorporation of PA6 as well as pristine/modified MWNTs has influenced the extent of orientation of the PP chains towards specific crystalline planes in various blend compositions of PP and PA6.

Ground Based Experiments in Support of Microgravity Research Results-Vapor Growth of Organic Nonlinear Optical Thin Film

NASA Technical Reports Server (NTRS)

Zugrav, M. Ittu; Carswell, William E.; Haulenbeek, Glen B.; Wessling, Francis C.

2001-01-01

This work is specifically focused on explaining previous results obtained for the crystal growth of an organic material in a reduced gravity environment. On STS-59, in April 1994, two experiments were conducted with N,N-dimethyl-p-(2,2-dicyanovinyl) aniline (DCVA), a promising nonlinear optical (NLO) material. The space experiments were set to reproduce laboratory experiments that yielded small, bulk crystals of DCVA. The results of the flight experiment, however, were surprising. Rather than producing a bulk single crystal, the result was the production of two high quality, single crystalline thin films. This result was even more intriguing when it is considered that thin films are more desirable for NLO applications than are bulk single crystals. Repeated attempts on the ground to reproduce these results were fruitless. A second set of flight experiments was conducted on STS-69 in September 1995. This time eight DCVA experiments were flown, with each of seven experiments containing a slight change from the first reference experiment. The reference experiment was programmed with growth conditions identical to those of the STS-59 mission. The slight variations in each of the other seven were an attempt to understand what particular parameter was responsible for the preference of thin film growth over bulk crystal growth in microgravity. Once again the results were surprising. In all eight cases thin films were grown again, albeit with varying quality. So now we were faced with a phenomenon that not only takes place in microgravity, but also is very robust, resisting all attempts to force the growth of bulk single crystals.

Quasi-Phase Diagrams at Air/Oil Interfaces and Bulk Oil Phases for Crystallization of Small-Molecular Semiconductors by Adjusting Gibbs Adsorption.

PubMed

Watanabe, Satoshi; Ohta, Takahisa; Urata, Ryota; Sato, Tetsuya; Takaishi, Kazuto; Uchiyama, Masanobu; Aoyama, Tetsuya; Kunitake, Masashi

2017-09-12

The temperature and concentration dependencies of the crystallization of two small-molecular semiconductors were clarified by constructing quasi-phase diagrams at air/oil interfaces and in bulk oil phases. A quinoidal quaterthiophene derivative with four alkyl chains (QQT(CN)4) in 1,1,2,2-tetrachroloethane (TCE) and a thienoacene derivative with two alkyl chains (C8-BTBT) in o-dichlorobenzene were used. The apparent crystal nucleation temperature (T n ) and dissolution temperature (T d ) of the molecules were determined based on optical microscopy examination in closed glass capillaries and open dishes during slow cooling and heating processes, respectively. T n and T d were considered estimates of the critical temperatures for nuclear formation and crystal growth, respectively. The T n values of QQT(CN)4 and C8-BTBT at the air/oil interfaces were higher than those in the bulk oil phases, whereas the T d values at the air/oil interfaces were almost the same as those in the bulk oil phases. These Gibbs adsorption phenomena were attributed to the solvophobic effect of the alkyl chain moieties. The temperature range between T n and T d corresponds to suitable supercooling conditions for ideal crystal growth based on the suppression of nucleation. The T n values at the water/oil and oil/glass interfaces did not shift compared with those of the bulk phases, indicating that adsorption did not occur at the hydrophilic interfaces. Promotion and inhibition of nuclear formation for crystal growth of the semiconductors were achieved at the air/oil and hydrophilic interfaces, respectively.

Synthesis, crystal structure, characterizations and magnetic study of a novel two-dimensional iron fluoride

NASA Astrophysics Data System (ADS)

Bouketaya, Sabrine; Smida, Mouna; Abdelbaky, Mohammed S. M.; Dammak, Mohamed; García-Granda, Santiago

2018-06-01

A new hybrid compound formulated as [Fe3F8(H2O)2](Am2TAZ)2 (Am2TAZ= 3,5-diamino-1,2,4-triazole) was prepared under hydrothermal conditions. The crystal structure was solved by single-crystal X-ray diffraction and the bulk was characterized by thermal analyses (TG-MS), vibrational spectroscopy (FTIR, Raman), Ultraviolet-visible spectroscopy (UV-Vis), and scanning electron microscopy (SEM-EDX). It crystallizes in the triclinic system space group P 1 ̅ with unit cell parameters a= 7.100(2) Å, b= 7.658(2) Å, c= 8.321(2) Å, α = 107.330(20)°, β = 111.842(18)°, γ = 93.049(17)°, Z = 1 and V= 394.01(17) Å3. The studied X-ray crystal structure shows the two oxidation states for iron atoms (Fe2+, Fe3+) and generates a 2D inorganic network, built up of inorganic layers constructed from infinite inorganic chains running along a axis. In fact, these chains are connected via (Fe3+(3)F6) octahedral. OW-H…F and N-H…F hydrogen bonds, making up the whole 3D network, are strongly linked in the layers. Magnetization measurements were performed, exhibiting the paramagnetic feature of the studied compound above 150 K.

The Vitrification and Determination of the Crystallization Time Scales of a Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Bulk Metallic Glass Forming Liquid

NASA Technical Reports Server (NTRS)

Hays, C. C.; Schroers, J.; Johnson, W. L.; Rathz, T. J.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Zr58.5Nb2.8Cul5.6Nil2.8All0.3 is the first bulk glass forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the containerless electrostatic levitation process. The measured critical cooling rate is 1.75 K/s. The sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. At the nose of the TTT diagram, the shortest time to reach crystallization in an isothermal experiment is 32 seconds. In contrast to other bulk metallic glasses the scatter in the crystallization onset times are small at both high and low temperatures.

Relationship between crystal structure and thermo-mechanical properties of kaolinite clay: Beyond standard density functional theory

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Jove-Colon, Carlos F.

2015-03-04

In this study, the structural, mechanical and thermodynamic properties of 1 : 1 layered dioctahedral kaolinite clay, with ideal Al 2Si 2O 5(OH) 4 stoichiometry, were investigated using density functional theory corrected for dispersion interactions (DFT-D2). The bulk moduli of 56.2 and 56.0 GPa predicted at 298 K using the Vinet and Birch–Murnaghan equations of state, respectively, are in good agreement with the recent experimental value of 59.7 GPa reported for well-crystallized samples. The isobaric heat capacity computed for uniaxial deformation of kaolinite along the stacking direction reproduces calorimetric data within 0.7–3.0% from room temperature up to its thermal stabilitymore » limit.« less

Atomically thin two-dimensional organic-inorganic hybrid perovskites

NASA Astrophysics Data System (ADS)

Dou, Letian; Wong, Andrew B.; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W.; Fu, Anthony; Bischak, Connor G.; Ma, Jie; Ding, Tina; Ginsberg, Naomi S.; Wang, Lin-Wang; Alivisatos, A. Paul; Yang, Peidong

2015-09-01

Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

Structural, magnetic and magnetocaloric properties of sputtered Gd films

NASA Astrophysics Data System (ADS)

Kumar, N. Pavan; Shaleni, V.; Satyanarayana, L.; Manorama, S. V.; Raja, M. Manivel

2018-05-01

Gd films with different thicknesses varying from 100 nm to 750 nm have been deposited on single crystal Si (100) substrate by ultra high vacuum magnetron sputtering system. X-ray diffraction analysis reveals the crystalline nature and hcp crystal structure of the films. Microstructure investigations have been carried to study the surface morphology of the films. Thermo magnetic studies confirm the magnetic transition of the films and are ˜275 K, close to bulk. Magnetocaloric effect (MCE) has been studied from magnetic isotherms measured around magnetic transition and the maximum isothermal entropy change of 2.0 J/kg-K is achieved for a magnetic field change of 2 T for the 750 nm film. The sputtered Gd films are useful for micro cooling device applications.

Polymer Deposition from a Quasi-Vapor Phase as a New Route to Access a Wide Temperature Range for Crystallization

NASA Astrophysics Data System (ADS)

Jeong, Hyuncheol; Arnold, Craig; Priestley, Rodney

Polymer crystallization is strongly governed by kinetics where crystallization temperature (Tc) plays an important role in determining materials properties. Due to the high entropic barrier required for reorganization, the long-chain molecules typically form folded-chain crystals, whose thickness and thermal stability decrease as Tc is lowered. Interesting questions remain regarding crystallization in the deeply supercooled regime. This is partially due to the difficulty in accessing the low Tc range without nucleation. For a strong crystal-former like polyethylene (PE), cooling from a melt or solution always confronts the onset of nucleation at a high Tc followed by rapid crystal growth. Here, we introduce an alternative approach to grow polymer crystals via Matrix Assisted Pulsed Laser Evaporation (MAPLE). This methodology achieves the crystallization of polymers from a quasi-vapor phase at a controlled temperature, allowing for the study of the empirical relationship between Tc and crystal structure over a wide range of Tc. With PE as a model polymer, we investigated the morphological and thermal properties of crystals grown over a wide temperature range down to 120 °C below bulk crystallization point.

Modes of surface premelting in colloidal crystals composed of attractive particles

NASA Astrophysics Data System (ADS)

Li, Bo; Wang, Feng; Zhou, Di; Peng, Yi; Ni, Ran; Han, Yilong

2016-03-01

Crystal surfaces typically melt into a thin liquid layer at temperatures slightly below the melting point of the crystal. Such surface premelting is prevalent in all classes of solids and is important in a variety of metallurgical, geological and meteorological phenomena. Premelting has been studied using X-ray diffraction and differential scanning calorimetry, but the lack of single-particle resolution makes it hard to elucidate the underlying mechanisms. Colloids are good model systems for studying phase transitions because the thermal motions of individual micrometre-sized particles can be tracked directly using optical microscopy. Here we use colloidal spheres with tunable attractions to form equilibrium crystal-vapour interfaces, and study their surface premelting behaviour at the single-particle level. We find that monolayer colloidal crystals exhibit incomplete premelting at their perimeter, with a constant liquid-layer thickness. In contrast, two- and three-layer crystals exhibit conventional complete melting, with the thickness of the surface liquid diverging as the melting point is approached. The microstructures of the surface liquids differ in certain aspects from what would be predicted by conventional premelting theories. Incomplete premelting in the monolayer crystals is triggered by a bulk isostructural solid-solid transition and truncated by a mechanical instability that separately induces homogeneous melting within the bulk. This finding is in contrast to the conventional assumption that two-dimensional crystals melt heterogeneously from their free surfaces (that is, at the solid-vapour interface). The unexpected bulk melting that we observe for the monolayer crystals is accompanied by the formation of grain boundaries, which supports a previously proposed grain-boundary-mediated two-dimensional melting theory. The observed interplay between surface premelting, bulk melting and solid-solid transitions challenges existing theories of surface premelting and two-dimensional melting.

Structural Analysis of MoS2 and other 2D layered materials using LEEM/LEED-I(V) and STM

NASA Astrophysics Data System (ADS)

Grady, Maxwell; Dai, Zhongwei; Jin, Wencan; Dadap, Jerry; Osgood, Richard; Sadowski, Jerzy; Pohl, Karsten

Layered two-dimensional materials, such as molybdenum disulfide, MoS2, are of interest for the development of many types of novel electronic devices. To fully understand the interfaces between these new materials, the atomic reconstructions at their surfaces must be understood. Low Energy Electron Microscopy and Diffraction, LEEM/ μLEED, present a unique method for rapid material characterization in real space and reciprocal space with high resolution. Here we present a study of the surface structure of 2H-MoS2 using μLEED intensity-voltage analysis. To aid this analysis, software is under development to automate the procedure of extracting I(V) curves from LEEM and LEED data. When matched with computational modeling, this data provides information with angstrom level resolution concerning the three dimensional atomic positions. We demonstrate that the surface structure of bulk MoS2 is distinct from the bulk crystal structure and exhibits a smaller surface relaxation at 320K compared to previous results at 95K. Furthermore, suspended monolayer samples exhibit large interlayer relaxations compared to the bulk surface termination. Further techniques for refining layer thickness determination are under development.

One-way propagation of bulk states and robust edge states in photonic crystals with broken inversion and time-reversal symmetries

NASA Astrophysics Data System (ADS)

Lu, Jin-Cheng; Chen, Xiao-Dong; Deng, Wei-Min; Chen, Min; Dong, Jian-Wen

2018-07-01

The valley is a flexible degree of freedom for light manipulation in photonic systems. In this work, we introduce the valley concept in magnetic photonic crystals with broken inversion symmetry. One-way propagation of bulk states is demonstrated by exploiting the pseudo-gap where bulk states only exist at one single valley. In addition, the transition between Hall and valley-Hall nontrivial topological phases is also studied in terms of the competition between the broken inversion and time-reversal symmetries. At the photonic boundary between two topologically distinct photonic crystals, we illustrate the one-way propagation of edge states and demonstrate their robustness against defects.

Naphtho[2,1-b:3,4-b']dithiophene-based bulk heterojunction solar cells: how molecular structure influences nanoscale morphology and photovoltaic properties.

PubMed

Kim, Yu Jin; Cheon, Ye Rim; Back, Jang Yeol; Kim, Yun-Hi; Chung, Dae Sung; Park, Chan Eon

2014-11-10

Organic bulk heterojunction photovoltaic devices based on a series of three naphtho[2,1-b:3,4-b']dithiophene (NDT) derivatives blended with phenyl-C71-butyric acid methyl ester were studied. These three derivatives, which have NDT units with various thiophene-chain lengths, were employed as the donor polymers. The influence of their molecular structures on the correlation between their solar-cell performances and their degree of crystallization was assessed. The grazing-incidence angle X-ray diffraction and atomic force microscopy results showed that the three derivatives exhibit three distinct nanoscale morphologies. We correlated these morphologies with the device physics by determining the J-V characteristics and the hole and electron mobilities of the devices. On the basis of our results, we propose new rules for the design of future generations of NDT-based polymers for use in bulk heterojunction solar cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-Principles Calculations of Structural, Electronic and Optical Properties of Ternary Semiconductor Alloys ZAs x Sb1- x ( Z = B, Al, Ga, In)

NASA Astrophysics Data System (ADS)

Bounab, S.; Bentabet, A.; Bouhadda, Y.; Belgoumri, Gh.; Fenineche, N.

2017-08-01

We have investigated the structural and electronic properties of the BAs x Sb 1- x , AlAs x Sb 1- x , GaAs x Sb 1- x and InAs x Sb 1- x semiconductor alloys using first-principles calculations under the virtual crystal approximation within both the density functional perturbation theory and the pseudopotential approach. In addition the optical properties have been calculated by using empirical methods. The ground state properties such as lattice constants, both bulk modulus and derivative of bulk modulus, energy gap, refractive index and optical dielectric constant have been calculated and discussed. The obtained results are in reasonable agreement with numerous experimental and theoretical data. The compositional dependence of the lattice constant, bulk modulus, energy gap and effective mass of electrons for ternary alloys show deviations from Vegard's law where our results are in agreement with the available data in the literature.

Surface Composition of NiPd Alloys

NASA Technical Reports Server (NTRS)

Noebe, Ronald D.; Khalil, Joe; Bozzolo, Guillermo; Gray, Hugh R. (Technical Monitor)

2002-01-01

Surface segregation in Ni-Pd alloys has been studied using the BFS method for alloys. Not only does the method predict an oscillatory segregation profile but it also indicates that the number of Pd-enriched surface planes can vary as a function of orientation. The segregation profiles were computed as a function of temperature, crystal face, and composition. Pd enrichment of the first layer is observed in (111) and (100) surfaces, and enrichment of the top two layers occurs for (110) surfaces. In all cases, the segregation profile shows oscillations that are actually related to weak ordering tendencies in the bulk. An atom-by-atom analysis was performed to identify the competing mechanisms leading to the observed surface behaviors. Large-scale atomistic simulations were also performed to investigate the temperature dependence of the segregation profiles as well as for analysis of the bulk structures. Finally, the observed surface behaviors are discussed in relation to the bulk phase structure of Ni-Pd alloys, which exhibit a tendency to weakly order.

Surface and Bulk Carbide Transformations in High-Speed Steel

PubMed Central

Godec, M.; Večko Pirtovšek, T.; Šetina Batič, B.; McGuiness, P.; Burja, J.; Podgornik, B.

2015-01-01

We have studied the transformation of carbides in AISI M42 high-speed steels in the temperature window used for forging. The annealing was found to result in the partial transformation of the large, metastable M2C carbides into small, more stable grains of M6C, with an associated change in the crystal orientation. In addition, MC carbides form during the transformation of M2C to M6C. From the high-speed-steel production point of view, it is beneficial to have large, metastable carbides in the cast structure, which later during annealing, before the forging, transform into a structure of polycrystalline carbides. Such carbides can be easily decomposed into several small carbides, which are then randomly distributed in the microstructure. The results also show an interesting difference in the carbide-transformation reactions on the surface versus the bulk of the alloy, which has implications for in-situ studies of bulk phenomena that are based on surface observations. PMID:26537780

Growth of bulk ZnO crystals by self-selecting CVT method

NASA Astrophysics Data System (ADS)

Fan, Long; Jiang, Tao; Xiao, TingTing; Chen, Jie; Peng, Liping; Wang, Xuemin; Yan, Dawei; Wu, Weidong

2018-05-01

Bulk ZnO crystals were grown by self-selecting CVT method using carbon as the transport agent. The crystal growth process took place on the top of the polycrystalline source material, and deep-red colored ZnO crystals of several millimeters were obtained. The as-grown crystals were characterized by X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS), Raman scattering (RS) spectroscopy, visible-near infrared (VIS-NIR) spectrophotometer and room temperature photoluminescence (PL) spectroscopy. XRD results indicate good crystallinity of the ZnO crystal. The EDS analysis shows that the crystal has a stoichiometry ratio Zn: O = 52: 48. The results suggest the existence of native defects of oxygen vacancies (OV) in the as-grown ZnO samples, which is caused by the stoichiometry shift to Zn-rich.

Zak phase induced multiband waveguide by two-dimensional photonic crystals.

PubMed

Yang, Yuting; Xu, Tao; Xu, Yun Fei; Hang, Zhi Hong

2017-08-15

Interface states in photonic crystals provide efficient approaches to control the flow of light. Photonic Zak phase determines the bulk band properties of photonic crystals, and, by assembling two photonic crystals with different bulk band properties together, deterministic interface states can be realized. By translating each unit cell of a photonic crystal by half the lattice constant, another photonic crystal with identical common gaps but a different Zak phase at each photonic band can be created. By assembling these two photonic crystals together, multiband waveguide can thus be easily created and then experimentally characterized. Our experimental results have good agreement with numerical simulations, and the propagation properties of these measured interface states indicate that this new type of interface state will be a good candidate for future applications of optical communications.

Insights into radiation damage from atomic resolution scanning transmission electron microscopy imaging of mono-layer CuPcCl16 films on graphene.

PubMed

Mittelberger, Andreas; Kramberger, Christian; Meyer, Jannik C

2018-03-19

Atomically resolved images of monolayer organic crystals have only been obtained with scanning probe methods so far. On the one hand, they are usually prepared on surfaces of bulk materials, which are not accessible by (scanning) transmission electron microscopy. On the other hand, the critical electron dose of a monolayer organic crystal is orders of magnitudes lower than the one for bulk crystals, making (scanning) transmission electron microscopy characterization very challenging. In this work we present an atomically resolved study on the dynamics of a monolayer CuPcCl 16 crystal under the electron beam as well as an image of the undamaged molecules obtained by low-dose electron microscopy. The results show the dynamics and the radiation damage mechanisms in the 2D layer of this material, complementing what has been found for bulk crystals in earlier studies. Furthermore, being able to image the undamaged molecular crystal allows the characterization of new composites consisting of 2D materials and organic molecules.

Supercritical carbon dioxide treatment as a method for polymorph preparation of deoxycholic acid.

PubMed

Tozuka, Yuichi; Kawada, Dai; Oguchi, Toshio; Yamamoto, Keiji

2003-09-16

A new polymorph of deoxycholic acid (DCA) was formed by using a supercritical carbon dioxide treatment. Deoxycholic acid crystals were stored in a pressure vessel purged with carbon dioxide at 12MPa, 60 degrees C for definite intervals. After storage for 1h in supercritical carbon dioxide (SC-CO2), new X-ray diffraction (XRD) peaks, not found in the bulk DCA crystal, were observed at 2theta = 7.4 degrees, 9.7 degrees and 14.0 degrees. The intensities of the new diffraction peaks increased with an increase in storage time, whereas the intensities of the diffraction peaks due to bulk DCA crystal decreased. On the DSC curves, the crystals obtained showed an exothermic peak at around 155 degrees C followed by the melting peak of bulk DCA crystal at 175 degrees C. By the temperature-controlled powder XRD measurement, the crystals obtained were found to be a metastable form of DCA. The polymorphs of DCA have not been reported; therefore, the SC-CO2 treatment would be a peculiar method to obtain a DCA polymorph.

Structure and high-pressure behavior of 2,5-di-(4-aminophenyl)-1,3,4-oxadiazole

NASA Astrophysics Data System (ADS)

Franco, Olga; Orgzall, Ingo; Reck, Günter; Stockhause, Sabine; Schulz, Burkhard

2005-06-01

The crystalline structures of two modifications of a compound containing the oxadiazole ring, 2,5-di-(4-aminophenyl)-1,3,4-oxadiazole (DAPO) were determined. One of these modifications contains water molecules in the crystal structure, which is observed for the first time for an oxadiazole crystal. Both crystals show an orthorhombic structure. The water free modification, DAPO I, belongs to the space group Pbca (61) and has the lattice parameters: a=13.461(5), b=7.937(3) and c=22.816(8) Å (CCDC 246608). The water containing pseudo-polymorph, DAPO II, has the space group Cmcm (63) and the lattice parameters: a=16.330(5), b=12.307(2) and c=6.9978(14) Å (CCDC 246609). To gain information on the inter molecular interactions within the crystals, X-ray experiments under compression at ambient temperature and under heating at vacuum conditions were performed. Neither DAPO I nor DAPO II undergo phase transitions in the ressure range up to 5 GPa, as could be concluded from X-ray and Raman experiments. X-ray and calorimetric studies indicate that DAPO II dehydrates into DAPO I under increasing temperature. Structural considerations suggest a two-stage process. The compression behavior of both substances is well described by the Murnaghan equation of state (MEOS) and the values of the bulk modulus and its pressure derivative are determined for these crystals. Additionally, in the case of DAPO I, also the thermal expansion coefficient α0 was measured.

Growth and characterization of Yb:Ho:YAG single crystal fiber

NASA Astrophysics Data System (ADS)

Yang, Yilun; Ye, Linhua; Bao, Renjie; Li, Shanming; Zhang, Peixiong; Xu, Min; Hang, Yin

2018-06-01

High quality Yb and Ho co-doped Y3Al5O12 single crystal fibers have been successfully grown by the laser heated pedestal growth method of up to 124 mm in length and 450 μm in diameter for the first time. The results of inductively coupled plasma-atomic emission spectrometry analysis, X-ray diffraction and Raman spectroscopy reveal that the lattice structure and doping concentrations of the SCF are the same as that of the bulk. Scanning electron microscopy microphotographs shows that the fibers only have minor diameter fluctuations within 0.5%.

High-pressure structural, elastic, and thermodynamic properties of zircon-type HoPO 4 and TmPO 4

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

Gomis, O.; Lavina, B.; Rodríguez-Hernández, P.

2017-01-20

Zircon-type holmium phosphate (HoPO 4) and thulium phosphate (TmPO 4) have been studied by single-crystal x-ray diffraction and ab initio calculations. We report on the influence of pressure on the crystal structure, and on the elastic and thermodynamic properties. The equation of state for both compounds is accurately determined. We have also obtained information on the polyhedral compressibility which is used to explain the anisotropic axial compressibility and the bulk compressibility. Both compounds are ductile and more resistive to volume compression than to shear deformation at all pressures. Furthermore, the elastic anisotropy is enhanced upon compression. Finally, the calculations indicatemore » that the possible causes that make the zircon structure unstable are mechanical instabilities and the softening of a silent B 1u mode.« less

Variability of the resulting microdeformation field in the Zn1 - x V x Se crystals (0.01 ≤ x ≤ 0.10)

NASA Astrophysics Data System (ADS)

Maksimov, V. I.; Maksimova, E. N.; Surkova, T. P.

2018-01-01

A detailed neutronographic study of the bulk ZnSe crystals doped with vanadium up to the content commensurate with the solubility limit in a semiconductor matrix has been carried out for the first time at room temperature. The data that characterize nonuniformly-deformed states based on the cubic structural modification of the II-VI compounds are obtained. A simplified analysis of the broadening patterns of the diffraction profiles of main Bragg reflexes of the studied crystals shows that the resulting deformation covers macroscopic volumes, and the distribution of vanadium ions in the given cases may significantly deviate from the uniform distribution over volume. Relative to the initial cubic lattice, dominating trends towards symmetry changes preceding the phase stratification in the ZnSe crystals heavily doped with vanadium are revealed.

Room temperature ferromagnetism in BiFe1-xMnxO3 thin film induced by spin-structure manipulation

NASA Astrophysics Data System (ADS)

Shigematsu, Kei; Asakura, Takeshi; Yamamoto, Hajime; Shimizu, Keisuke; Katsumata, Marin; Shimizu, Haruki; Sakai, Yuki; Hojo, Hajime; Mibu, Ko; Azuma, Masaki

2018-05-01

The evolution of crystal structure, spin structure, and macroscopic magnetization of manganese-substituted BiFeO3 (BiFe1-xMnxO3), a candidate for multiferroic materials, were investigated on bulk and epitaxial thin-film. Mn substitution for Fe induced collinear antiferromagnetic spin structure around room temperature by destabilizing the cycloidal spin modulation which prohibited the appearance of net magnetization generated by Dzyaloshinskii-Moriya interaction. For the bulk samples, however, no significant signal of ferromagnetism was observed because the direction of the ordered spins was close to parallel to the electric polarization so that spin-canting did not occur. On the contrary, BiFe1-xMnxO3 thin film on SrTiO3 (001) had a collinear spin structure with the spin direction perpendicular to the electric polarization at room temperature, where the appearance of spontaneous magnetization was expected. Indeed, ferromagnetic hysteresis behavior was observed for BiFe0.9Mn0.1O3 thin film.

Crystallization kinetics and Avrami index of Sb-doped Se-Te-Sn chalcogenide glasses

NASA Astrophysics Data System (ADS)

Dwivedi, D. K.; Rao, Vandita; Mehta, N.; Chandel, N.

2018-05-01

Bulk amorphous samples of Sb-substituted Se78-xTe20Sn2Sbx (0 < x < 6) have been prepared using melt quench technique. The structure of Se78-xTe20Sn2Sbx (x = 0, 2, 4, 6) glassy alloys has been investigated using X-ray diffraction technique. Calorimetric studies of the prepared samples have been performed under non-isothermal conditions using differential scanning calorimetry (DSC) and glass transition temperature as well as crystallization temperature has been evaluated using DSC scans. The activation energy of crystallization kinetics (Ec) has been determined using model-free approaches such as Kissinger, Ozawa, Tang and Starink methods. The Avrami index (n) and frequency factor (Ko) have been calculated by Matusita and Augis-Benett method.

Re-solution of xenon clusters in plutonium dioxide under the collision cascade impact: A molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Seitov, D. D.; Nekrasov, K. A.; Kupryazhkin, A. Ya.; Gupta, S. K.; Akilbekov, A. T.

2017-09-01

The interaction of xenon clusters with the collision cascades in the PuO2 crystals is investigated using the molecular dynamics simulation and the approximation of the pair interaction potentials. The potentials of interaction of Xe atoms with the surrounding particles in the crystal lattice are suggested, that are valid in the range of high collision energies. The cascades created by the recoil 235U ions formed as the plutonium α-decay product are considered, and the influence of such cascades on the structure of the xenon clusters is analyzed. It is shown, that the cascade-cluster interaction leads to release of the xenon atoms from the clusters and their subsequent re-solution in the crystal bulk.

GEODE 2: Manufacturing large area format cadmium-mercury-telluride crystals in a microgravity environment. Pressure sensor proof of concept

NASA Astrophysics Data System (ADS)

Gale, M. R.; Beattie, D. A.

In the GEODE 1 experiment, a semiconductor Cd-Hg telluride crystal was grown in the MASER1 sounding rocket. It was shown that bulk-quench Cd-Hg telluride crystallization in a microgravity environment results in a more homogeneous crystal structure than can be achieved terrestrially. In the GEODE 2 program, the wall thickness of the quartz ampoule containing the crystal will be reduced to improve the heat transfer characteristics during crystallization. Ampoule explosion must be prevented by active control of the pressure surrounding the weaker, thin-walled ampoule to match that inside the furnace. A prototype pressure sensor that uses the absorption of ultraviolet light by Hg vapor has been built and tested. Pressures from 4 to 40 atmospheres have been measured with a resolution better than 0.35 atmospheres over the entire range. The feasibility of the pressure measurement technique has been demonstrated, although some design improvements are required in order to make measurements more repeatable.

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

NASA Astrophysics Data System (ADS)

Walton, E. L.; Jugo, P. J.; Herd, C. D. K.; Wilke, M.

2010-08-01

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S 2- versus S 6+). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En 72-75Fs 20-21Wo 5-7) and olivine (Fo 75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite. Our results show that EETA79001 shock veins and melt pockets represent local mineral melts formed by shock impedance contrasts, which can account for the observed compositional anomalies compared to the whole rock sample. The observation that melts produced during shock commonly deviate from the bulk composition of the host rock has been well documented from chondrites, rocks from terrestrial impact structures and other Martian meteorites. The bulk composition of shock melts reflects the proportions of minerals melted; large melt pockets encompass more minerals and approach the whole rock whereas small melt pockets and thin veins reflect local mineralogy. In the latter, the modal abundance of sulfide globules may reach up to 15 vol%. We conclude the shock melt pockets in EETA79001 lithology A contain no significant proportion of Martian regolith.

A Rationale for System-Dependent Advantages and Disadvantages of Solution Crystal Growth at Low Gravity

NASA Technical Reports Server (NTRS)

Rosenberger, Franz; Vekilov, Peter G.; Lin, Hong; Alexander, J. Iwan D.

1997-01-01

Protein crystallization experiments at reduced gravity have yielded crystals that, depending on the specific material, are either superior or inferior in their structural perfection compared to counterparts grown at normal gravity. A reduction of the crystals' quality due to their growth at low gravity cannot be understood from existing models. Our experimental investigations of the ground-based crystallization of the protein lysozyme have revealed pronounced unsteady growth layer dynamics and associated defect formation under steady external conditions. Through scaling analysis and numerical simulations we show that the observed fluctuations originate from the coupling of bulk transport with non-linear interface kinetics under mixed kinetics-transport control of the growth rate. The amplitude of the fluctuations is smallest when either transport or interfacial kinetics dominate the control of the crystallization process. Thus, depending on the specific system, crystal quality may be improved by either enhancing or suppressing the transport in the solution. These considerations provide, for the first time, a material-dependent rationale for the advantages, as well as the disadvantages, of reduced gravity for (protein) crystallization.

Single crystalline thin films as a novel class of electrocatalysts

DOE PAGES

Snyder, Joshua; Markovic, Nenad; Stamenkovic, Vojislav

2013-01-01

The ubiquitous use of single crystal metal electrodes has garnered invaluable insight into the relationship between surface atomic structure and functional electrochemical properties. But, the sensitivity of their electrochemical response to surface orientation and the amount of precious metal required can limit their use. We present here a generally applicable procedure for producing thin metal films with a large proportion of atomically flat (111) terraces without the use of an epitaxial template. Thermal annealing in a controlled atmosphere induces long-range ordering of magnetron sputtered thin metal films deposited on an amorphous substrate. The ordering transition in these thin metal filmsmore » yields characteristic (111) electrochemical signatures with minimal amount of material and provides an adequate replacement for oriented bulk single crystals. Our procedure can be generalized towards a novel class of practical multimetallic thin film based electrocatalysts with tunable near-surface compositional profile and morphology. Annealing of atomically corrugated sputtered thin film Pt-alloy catalysts yields an atomically smooth structure with highly crystalline, (111)-like ordered and Pt segregated surface that displays superior functional properties, bridging the gap between extended/bulk surfaces and nanoscale systems.« less

Effects of Alternating Hydrogenated and Protonated Segments in polymers on their Wettability.

NASA Astrophysics Data System (ADS)

Smith, Dennis; Traiphol, Rakchart; Cheng, Gang; Perahia, Dvora

2003-03-01

Polymers consisting of alternating hydrogenated and fluorinated segments exhibit unique interfacial characteristics governed by the components that dominate the interface. Presence of fluorine reduces the interfacial energy and is expected to decrease the adhesion to the polymer surface. Thin liquid crystalline (LC) layers of 4,4?-octyl-cyanobiphenyl, cast on top of a polymeric layer consisting of alternating methylstylbine protonated segments bridged by a fluorinated group was used as a mechanistic tool to study of interfacial effects on three parameters: wetting, interfacial alignment and surface induces structures. The liquid crystal cast on a low interfacial energy fluorinated polymeric film exhibits bulk homeotropic alignment as expected. However it fully wetted the polymer surface despite the incompatibility of the protonated LC and mainly fluorinated polymer interface. Further more, it was found to stabilize the interfacial Semitic layers to a higher temperature and induce different surface ordering that was not observed at the same temperature neither in the bulk nor at the interfaces with silicon or glass surface. These results indicate that the interfacial interactions of polymers with liquid crystals are a complex function of both surface energies and the interfacial structure of the polymer.

Lack of quantum confinement in Ga2O3 nanolayers

NASA Astrophysics Data System (ADS)

Peelaers, Hartwin; Van de Walle, Chris G.

2017-08-01

β -Ga2Ox3 is a wide-band-gap semiconductor with promising applications in transparent electronics and in power devices. β -Ga2O3 has monoclinic crystal symmetry and does not display a layered structured characteristic of 2D materials in the bulk; nevertheless, monolayer-thin Ga2O3 layers can be created. We used first-principles techniques to investigate the structural and electronic properties of these nanolayers. Surprisingly, freestanding films do not exhibit any signs of quantum confinement and exhibit the same electronic structure as bulk material. A detailed examination reveals that this can be attributed to the presence of states that are strongly confined near the surface. When the Ga2O3 layers are embedded in a wider band-gap material such as Al2O3 , the expected effects of quantum confinement can be observed. The effective mass of electrons in all the nanolayers is small, indicating promising device applications.

The (111) Surface of NaAu 2. Structure, Composition, and Stability

DOE PAGES

Kwolek, Emma J.; Widmer, Roland; Gröning, Oliver; ...

2014-12-17

The (111) surface of single-crystal NaAu 2 is a model for catalytically active, powdered NaAu 2. We prepare and characterize this surface with a broad suite of techniques. Preparation in ultrahigh vacuum consists of the traditional approach of ion bombardment (to remove impurities) and thermal annealing (to restore surface order). Both of these steps cause loss of sodium (Na), and repeated treatments eventually trigger conversion of the surface and near-surface regions to crystalline gold. The bulk has a limited ability to repopulate the surface Na. Under conditions where Na depletion is minimized, electron diffraction patterns are consistent with the bulk-terminatedmore » structure, and scanning tunneling microscopy reveals mesa-like features with lateral dimensions of a few tens of nanometers. The tops of the mesas do not possess fine structure characteristic of a periodic lattice, suggesting that the surface layer is disordered under the conditions of these experiments.« less

Electronic structure of β-Ga2O3 single crystals investigated by hard X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Li, Guo-Ling; Zhang, Fabi; Cui, Yi-Tao; Oji, Hiroshi; Son, Jin-Young; Guo, Qixin

2015-07-01

By combination of hard X-ray photoelectron spectroscopy (HAXPES) and first-principles band structure calculations, the electronic states of β-Ga2O3 were investigated to deepen the understanding of bulk information for this compound. The valence band spectra of HAXPES presented the main contribution from Ga 4sp, which are well represented by photoionization cross section weighted partial density of states. The experimental data complemented with the theoretical study yield a realistic picture of the electronic structure for β-Ga2O3.

Structural defects in GaN revealed by Transmission Electron Microscopy

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

Liliental-Weber, Zuzanna

This paper reviews the various types of structural defects observed by Transmission Electron Microscopy in GaN heteroepitaxial layers grown on foreign substrates and homoepitaxial layers grown on bulk GaN substrates. The structural perfection of these layers is compared to the platelet self-standing crystals grown by High Nitrogen Pressure Solution. Defects in undoped and Mg doped GaN are discussed. Lastly, some models explaining the formation of inversion domains in heavily Mg doped layers that are possible defects responsible for the difficulties of p-doping in GaN are also reviewed.

Structural defects in GaN revealed by Transmission Electron Microscopy

DOE PAGES

Liliental-Weber, Zuzanna

2014-09-08

This paper reviews the various types of structural defects observed by Transmission Electron Microscopy in GaN heteroepitaxial layers grown on foreign substrates and homoepitaxial layers grown on bulk GaN substrates. The structural perfection of these layers is compared to the platelet self-standing crystals grown by High Nitrogen Pressure Solution. Defects in undoped and Mg doped GaN are discussed. Lastly, some models explaining the formation of inversion domains in heavily Mg doped layers that are possible defects responsible for the difficulties of p-doping in GaN are also reviewed.

Vacancy-induced initial decomposition of condensed phase NTO via bimolecular hydrogen transfer mechanisms at high pressure: a DFT-D study.

PubMed

Liu, Zhichao; Wu, Qiong; Zhu, Weihua; Xiao, Heming

2015-04-28

Density functional theory with dispersion-correction (DFT-D) was employed to study the effects of vacancy and pressure on the structure and initial decomposition of crystalline 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (β-NTO), a high-energy insensitive explosive. A comparative analysis of the chemical behaviors of NTO in the ideal bulk crystal and vacancy-containing crystals under applied hydrostatic compression was considered. Our calculated formation energy, vacancy interaction energy, electron density difference, and frontier orbitals reveal that the stability of NTO can be effectively manipulated by changing the molecular environment. Bimolecular hydrogen transfer is suggested to be a potential initial chemical reaction in the vacancy-containing NTO solid at 50 GPa, which is prior to the C-NO2 bond dissociation as its initiation decomposition in the gas phase. The vacancy defects introduced into the ideal bulk NTO crystal can produce a localized site, where the initiation decomposition is preferentially accelerated and then promotes further decompositions. Our results may shed some light on the influence of the molecular environments on the initial pathways in molecular explosives.

The trap DOS in small molecule organic semiconductors: A quantitative comparison of thin-film transistors with single crystals

NASA Astrophysics Data System (ADS)

Kalb, Wolfgang; Haas, Simon; Pernstich, Kurt; Mathis, Thomas; Batlogg, Bertram

2010-03-01

Our study shows that it is possible to reach one of the ultimate goals of organic electronics: organic field-effect transistors can be produced with trap densities as low as in the bulk of single crystals. Several analytical methods to calculate the spectral density of localized states in the band gap (trap DOS) from measured data were used to clarify, if the different methods lead to similar results. We then compared quantitatively trap DOS information from the literature, correcting for differences due to different calculation methods. In the bulk of single crystals the trap DOS is lower by several orders of magnitude than in thin films. The compilation of all data strongly suggests that structural defects at grain boundaries are the main cause of ``fast'' traps in TFT's made with vacuum-evaporated pentacene. For high-performance transistors made with small molecule semiconductors such as rubrene it is essential to reduce the dipolar disorder caused by water adsorbed on the gate dielectric. We will discuss to what degree band broadening due to the thermal fluctuations of the intermolecular transfer integral is reflected in the trap DOS very close (<0.15 eV) to the mobility edge.

Bulk Group-III Nitride Crystal Growth in Supercritical Ammonia-Sodium Solutions

NASA Astrophysics Data System (ADS)

Griffiths, Steven Herbert

Gallium nitride (GaN) and its alloys with indium nitride (InGaN) and aluminum nitride (AlGaN), collectively referred to as Group-III Nitride semiconductors, have enabled white solid-state lighting (SSL) sources and power electronic devices. While these technologies have already made a lasting, positive impact on society, improvements in design and efficiency are anticipated by shifting from heteroepitaxial growth on foreign substrates (such as sapphire, Si, SiC, etc.) to homoepitaxial growth on native, bulk GaN substrates. Bulk GaN has not supplanted foreign substrate materials due to the extreme conditions required to achieve a stoichiometric GaN melt (temperatures and pressures in excess of 2200°C and 6 GPa, respectively). The only method used to produce bulk GaN on an industrial scale is hydride vapor phase epitaxy (HVPE), but the high cost of gaseous precursors and relatively poor crystal quality have limited the adoption of this technology. A solution growth technique known as the ammonothermal method has attracted interest from academia and industry alike for its ability to produce bulk GaN boules of exceedingly high crystal quality. The ammonothermal method employs supercritical ammonia (NH3) solutions to dissolve, transport, and crystallize GaN. However, ammonothermal growth pressures are still relatively high (˜200 MPa), which has thus far prevented the acquisition of fundamental crystal growth knowledge needed to efficiently (i.e. through data-driven approaches) advance the field. This dissertation focused on addressing the gaps in the literature through two studies employing in situ fluid temperature analysis. The first study focused on identifying the solubility of GaN in supercritical NH3-Na solutions. The design and utilization of in situ and ex situ monitoring equipment enabled the first reports of the two-phase nature of supercritical NH3-Na solutions, and of Ga-alloying of Ni-containing autoclave components. The effects of these error sources on the gravimetric determination of GaN solubility were explored in detail. The second study was aimed at correlating autoclave dissolution and growth zone fluid temperatures with bulk GaN crystal growth kinetics, crystal quality, and impurity incorporation. The insights resulting from this analysis include the identification of the barrier between mass transport and surface integration-limited GaN growth regimes, GaN crystal shape evolution with fluid temperature, the sensitivity of (0001)-orientation crystal quality with fluid temperature, and impurity-specific incorporation activated from the dissolution and growth zones of the autoclave. The results of the aforementioned studies motivated a paradigm-shift in ammonothermal growth. To address this need, a fundamentally different crystal growth approach involving isothermal solutions and tailor-made Group-III alloy source materials was developed/demonstrated. This growth method enabled impurity incorporation reduction compared to traditional ammonothermal GaN growth, and the realization of bulk, ternary Group-III Nitride crystals.

Coupling of Crystal Structure and Magnetism in the Layered, Ferromagnetic Insulator CrI 3

DOE PAGES

McGuire, Michael A.; Dixit, Hemant; Cooper, Valentino R.; ...

2014-12-23

Here, we examine the crystallographic and magnetic properties of single crystals of CrI 3, an easily cleavable, layered and insulating ferromagnet with a Curie temperature of 61 K. Our X-ray diffraction studies reveal a first-order crystallographic phase transition occurring near 210–220 K upon warming, with significant thermal hysteresis. The low-temperature structure is rhombohedral (Rmore » $$\\bar{3}$$, BiI 3-type) and the high-temperature structure is monoclinic (C2/m, AlCl 3-type). Evidence for coupling between the crystallographic and magnetic degrees of freedom in CrI 3 was found; we observed an anomaly in the interlayer spacing at the Curie temperature and an anomaly in the magnetic susceptibility at the structural transition. First-principles calculations reveal the importance of proper treatment of the long-ranged interlayer forces, and van der Waals density functional theory does an excellent job of predicting the crystal structures and their relative stability. Our calculations suggest that the ferromagnetic order found in the bulk material may persist into monolayer form, suggesting that CrI 3 and other chromium trihalides may be promising materials for spintronic and magnetoelectronic research.« less

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

An Alternative Hypothesis for How Microgravity Improves Macromolecular Crystal Quality

NASA Technical Reports Server (NTRS)

Pusey, Marc

2003-01-01

There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests that for many proteins crystal nucleation and growth is by addition of associated species that are preformed by reversible concentration-driven self association processes in the bulk solution. We have developed a self-association model for the crystal nucleation and growth of the protein chicken egg lysozyme. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small an octamer in the 43 helix configuration (the proposed average sized growth unit) would have a M.W. approx. 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm (a 24-mer) commonly attach to the crystal. AFM results from Weichmann et al. (Ultramicroscopy 86, 159-166, 2001) suggest that associated species of up to 40-mers in size add to the (101) faces. These measurements reflect the sizes of units that both added and desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. On Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species is more likely to be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Crystal surface integrity and diffusion measurements on Earth and planetary materials

NASA Astrophysics Data System (ADS)

Watson, E. B.; Cherniak, D. J.; Thomas, J. B.; Hanchar, J. M.; Wirth, R.

2016-09-01

Characterization of diffusion behavior in minerals is key to providing quantitative constraints on the ages and thermal histories of Earth and planetary materials. Laboratory experiments are a vital source of the needed diffusion measurements, but these can pose challenges because the length scales of diffusion achievable in a laboratory time are commonly less than 1 μm. An effective strategy for dealing with this challenge is to conduct experiments involving inward diffusion of the element of interest from a surface source, followed by quantification of the resulting diffusive-uptake profile using a high-resolution depth-profiling technique such as Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), or ion microprobe (SIMS). The value of data from such experiments is crucially dependent on the assumption that diffusion in the near-surface of the sample is representative of diffusion in the bulk material. Historical arguments suggest that the very process of preparing a polished surface for diffusion studies introduces defects-in the form of dislocations and cracks-in the outermost micrometer of the sample that make this region fundamentally different from the bulk crystal in terms of its diffusion properties. Extensive indirect evidence suggests that, in fact, the near-surface region of carefully prepared samples is no different from the bulk crystal in terms of its diffusion properties. A direct confirmation of this conclusion is nevertheless clearly important. Here we use transmission electron microscopy to confirm that the near-surface regions of olivine, quartz and feldspar crystals prepared using careful polishing protocols contain no features that could plausibly affect diffusion. This finding does not preclude damage to the mineral structure from other techniques used in diffusion studies (e.g., ion implantation), but even in this case the role of possible structural damage can be objectively assessed and controlled. While all evidence points to the reliability of diffusivities obtained from in-diffusion experiments, we do not recommend experiments of this type using a powder source as a means of obtaining diffusant solubility or partitioning information for the mineral of interest.

Sub-second thermoplastic forming of bulk metallic glasses by ultrasonic beating

PubMed Central

Ma, Jiang; Liang, Xiong; Wu, Xiaoyu; Liu, Zhiyuan; Gong, Feng

2015-01-01

The work proposed a novel thermoplastic forming approach–the ultrasonic beating forming (UBF) method for bulk metallic glasses (BMGs) in present work. The rapid forming approach can finish the thermoplastic forming of BMGs in less than one second, avoiding the time-dependent crystallization and oxidation to the most extent. Besides, the UBF is also proved to be competent in the fabrication of structures with the length scale ranging from macro scale to nano scale. Our results propose a novel route for the thermoplastic forming of BMGs and have promising applications in the rapid fabrication of macro to nano scale products and devices. PMID:26644149

Effects of molecular geometry on the properties of compressed diamondoid crystals

DOE PAGES

Yang, Fan; Lin, Yu; Baldini, Maria; ...

2016-11-01

Diamondoids are an intriguing group of carbon-based nanomaterials, which combine desired properties of inorganic nanomaterials and small hydrocarbon molecules with atomic-level uniformity. In this Letter, we report the first comparative study on the effect of pressure on a series of diamondoid crystals with systematically varying molecular geometries and shapes, including zero-dimensional (0D) adamantane; one-dimensional (1D) diamantane, [121]tetramantane, [123]tetramantane, and [1212]pentamantane; two-dimensional (2D) [12312]hexamantane; and three-dimensional (3D) triamantane and [1(2,3)4]pentamantane. We find the bulk moduli of these diamondoid crystals are strongly dependent on the diamondoids’ molecular geometry with 3D [1(2,3)4]pentamantane being the least compressible and 0D adamantane being the most compressible.more » These diamondoid crystals possess excellent structural rigidity and are able to sustain large volume deformation without structural failure even after repetitive pressure loading cycles. These properties are desirable for constructing cushioning devices. Furthermore, we also demonstrate that lower diamondoids outperform the conventional cushioning materials in both the working pressure range and energy absorption density.« less

Growth, structural, thermal, linear and nonlinear optical and laser damage threshold studies of picolinium tartrate monohydrate single crystals.

PubMed

Peramaiyan, G; Pandi, P; Sornamurthy, B M; Bhagavannarayana, G; Mohan Kumar, R

2012-09-01

Picolinium tartrate monohydrate (PTM), a novel organic nonlinear optical material was synthesized and bulk crystals were grown from aqueous solution by slow cooling technique. The cell parameters of the grown crystal were found by single and powder X-ray diffraction analyses. The crystalline perfection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. The presence of functional groups in the grown crystal was identified by FTIR and FT-Raman spectral analyses. UV-Vis spectral studies reveal PTM crystals are transparent in the wavelength region of 295-1100 nm. The thermal characteristics of PTM were analyzed by TGA/DTA studies. The dielectric and mechanical behaviours of PTM crystals were investigated. Dislocation density was estimated to be 2.89 × 10(3) cm(-2) on the flat-surface of PTM crystals from the etching studies. The laser induced surface damage threshold for the grown crystal was measured using Nd:YAG laser. Its second harmonic generation relative efficiency was measured by Kurtz and Perry powder technique and was observed to be comparable with KDP crystal. Copyright © 2012 Elsevier B.V. All rights reserved.

Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

NASA Astrophysics Data System (ADS)

Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

2014-09-01

We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

Effects of fabrication methods on spin relaxation and crystallite quality in Tm-doped ? powders studied using spectral hole burning

NASA Astrophysics Data System (ADS)

Lutz, Thomas; Veissier, Lucile; Thiel, Charles W.; Woodburn, Philip J. T.; Cone, Rufus L.; Barclay, Paul E.; Tittel, Wolfgang

2016-01-01

High-quality rare-earth-ion (REI) doped materials are a prerequisite for many applications such as quantum memories, ultra-high-resolution optical spectrum analyzers and information processing. Compared to bulk materials, REI doped powders offer low-cost fabrication and a greater range of accessible material systems. Here we show that crystal properties, such as nuclear spin lifetime, are strongly affected by mechanical treatment, and that spectral hole burning can serve as a sensitive method to characterize the quality of REI doped powders. We focus on the specific case of thulium doped ? (Tm:YAG). Different methods for obtaining the powders are compared and the influence of annealing on the spectroscopic quality of powders is investigated on a few examples. We conclude that annealing can reverse some detrimental effects of powder fabrication and, in certain cases, the properties of the bulk material can be reached. Our results may be applicable to other impurities and other crystals, including color centers in nano-structured diamond.

Cumulant Green's function calculations of plasmon satellites in bulk sodium: Influence of screening and the crystal environment

NASA Astrophysics Data System (ADS)

Zhou, Jianqiang Sky; Gatti, Matteo; Kas, J. J.; Rehr, J. J.; Reining, Lucia

2018-01-01

We present ab initio calculations of the photoemission spectra of bulk sodium using different flavors of the cumulant expansion approximation for the Green's function. In particular, we study the dispersion and intensity of the plasmon satellites. We show that the satellite spectrum is much more sensitive to many details than the quasiparticle spectrum, which suggests that the experimental investigation of satellites could yield additional information beyond the usual studies of the band structure. In particular, a comparison to the homogeneous electron gas shows that the satellites are influenced by the crystal environment, although the crystal potential in sodium is weak. Moreover, the temperature dependence of the lattice constant is reflected in the position of the satellites. Details of the screening also play an important role; in particular, the contribution of transitions from 2 s and 2 p semicore levels influences the satellites, but not the quasiparticle. Moreover, inclusion of contributions to the screening beyond the random-phase approximation has an effect on the satellites. Finally, we elucidate the importance of the coupling of electrons and holes by comparing the results of the time-ordered and the retarded cumulant expansion approximations. Again, we find small but noticeable differences. Since all the small effects add up, our most advanced calculation yields a satellite position which is improved with respect to previous calculations by almost 1 eV. This stresses the fact that the calculation of satellites is much more delicate than the calculation of a quasiparticle band structure.

High-pressure behavior of intermediate scapolite: compressibility, structure deformation and phase transition

NASA Astrophysics Data System (ADS)

Lotti, Paolo; Comboni, Davide; Merlini, Marco; Hanfland, Michael

2018-05-01

Scapolites are common volatile-bearing minerals in metamorphic rocks. In this study, the high-pressure behavior of an intermediate member of the scapolite solid solution series (Me47), chemical formula (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01], has been investigated up to 17.79 GPa, by means of in situ single-crystal synchrotron X-ray diffraction. The isothermal elastic behavior of the studied scapolite has been described by a III-order Birch-Murnaghan equation of state, which provided the following refined parameters: V 0 = 1110.6(7) Å3, {K_{{V_0}}} = 70(2) GPa ({β _{{V_0}}} = 0.0143(4) GPa-1) and {K_{{V}}^' = 4.8(7). The refined bulk modulus is intermediate between those previously reported for Me17 and Me68 scapolite samples, confirming that the bulk compressibility among the solid solution increases with the Na content. A discussion on the P-induced structure deformation mechanisms of tetragonal scapolite at the atomic scale is provided, along with the implications of the reported results for the modeling of scapolite stability. In addition, a single-crystal to single-crystal phase transition, which is displacive in character, has been observed toward a triclinic polymorph at 9.87 GPa. The high-pressure triclinic polymorph was found to be stable up to the highest pressure investigated.

Nucleation and Crystallization of Globular Proteins: What we Know and What is Missing

NASA Technical Reports Server (NTRS)

Rosenberger, F.; Vekilov, P. G.; Muschol, M.; Thomas, B. R.

1996-01-01

Recently. much progress has been made in understanding the nucleation and crystallization of globular proteins, including the formation of compositional and structural crystal defects, Insight into the interactions of (screened) protein macro-ions in solution, obtained from light scattering, small angle X-ray scattering and osmotic pressure studies. can guide the search for crystallization conditions. These studies show that the nucleation of globular proteins is governed by the same principles as that of small molecules. However, failure to account for direct and indirect (hydrodynamic) protein interactions in the solutions results in unrealistic aggregation scenarios. Microscopic studies of numerous proteins reveal that crystals grow by the attachment of growth units through the same layer-spreading mechanisms as inorganic crystals. Investigations of the growth kinetics of hen-egg-white lysozyme (HEWL) reveal non-steady behavior under steady external conditions. Long-term variations in growth rates are due to changes in step-originating dislocation groups. Fluctuations on a shorter timescale reflect the non-linear dynamics of layer growth that results from the interplay between interfacial kinetics and bulk transport. Systematic gel electrophoretic analyses suggest that most HEWL crystallization studies have been performed with material containing other proteins at percent levels. Yet, sub-percent levels of protein impurities impede growth step propagation and play a role in the formation of structural/compositional inhomogeneities. In crystal growth from highly purified HEWL solutions, however, such inhomogeneities are much weaker and form only in response to unusually large changes in growth conditions. Equally important for connecting growth conditions to crystal perfection and diffraction resolution are recent advances in structural characterization through high-resolution Bragg reflection profiling and X-ray topography.

Influence of the liquid crystal behaviour on the Langmuir and Langmuir-Blodgett film supramolecular architecture of an ionic liquid crystal.

PubMed

Pérez-Gregorio, Víctor; Giner, Ignacio; López, M Carmen; Gascón, Ignacio; Cavero, Emma; Giménez, Raquel

2012-06-01

A new luminescent ionic liquid crystal, called Ipz-2, has been synthesised and its mesophase behaviour and also at the air-liquid interface has been studied and compared with Ipz, another ionic pyrazole derivative, with a similar molecular structure, previously studied. The X-ray diffraction pattern shows that Ipz-2 exhibits hexagonal columnar mesomorphism, while Ipz adopts lamellar mesophases. Langmuir films of both compounds are flat and homogeneous at large areas per molecule, but create different supramolecular structures under further compression. Ipz-2 Langmuir films have been transferred onto solid substrates, and Atomic Force Microscopy (AFM) images of the Langmuir-Blodgett films have shown that large columnar structures hundreds of nm in diameter are formed on top of the initial monolayer, in contrast with well-defined trilayer LB films obtained for Ipz. Our results show that Ipz-2 has a tendency to stack in columnar arrangements both in liquid crystalline bulk and in Langmuir and Langmuir-Blodgett films. Copyright © 2012 Elsevier Inc. All rights reserved.

Ultra-thin ZnSe: Anisotropic and flexible crystal structure

NASA Astrophysics Data System (ADS)

Bacaksiz, C.; Senger, R. T.; Sahin, H.

2017-07-01

By performing density functional theory-based calculations, we investigate the structural, electronic, and mechanical properties of the thinnest ever ZnSe crystal [11]. The vibrational spectrum analysis reveals that the monolayer ZnSe is dynamically stable and has flexible nature with its soft phonon modes. In addition, a direct electronic band gap is found at the gamma point for the monolayer structure of ZnSe. We also elucidate that the monolayer ZnSe has angle dependent in-plane elastic parameters. In particular, the in-plane stiffness values are found to be 2.07 and 6.89 N/m for the arm-chair and zig-zag directions, respectively. The angle dependency is also valid for the Poisson ratio of the monolayer ZnSe. More significantly, the in-plane stiffness of the monolayer ZnSe is the one-tenth of Young modulus of bulk zb-ZnSe which indicates that the monolayer ZnSe is a quite flexible single layer crystal. With its flexible nature and in-plane anisotropic mechanical properties, the monolayer ZnSe is a good candidate for nanoscale mechanical applications.

Study of Etching Pits in a Large-grain Single Cell Bulk Niobium Cavity

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

Zhao, Xin; Ciovati, Gianluigi; Reece, Charles E.

2009-11-01

Performance of SRF cavities are limited by non-linear localized effects. The variation of local material characters between "hot" and "cold" spots is thus of intense interest. Such locations were identified in a BCP-etched large-grain single-cell cavity and removed for examination by high resolution electron microscopy (SEM), electron-back scattering diffraction microscopy (EBSD), optical microscopy, and 3D profilometry. Pits with clearly discernable crystal facets were observed in both "hotspot" and "coldspot" specimens. The pits were found in-grain, at bi-crystal boundaries, and on tri-crystal junctions. They are interpreted as etch pits induced by surface crystal defects (e.g. dislocations). All "coldspots" examined had qualitativelymore » low density of etching pits or very shallow tri-crystal boundary junction. EBSD revealed crystal structure surrounding the pits via crystal phase orientation mapping, while 3D profilometry gave information on the depth and size of the pits. In addition, a survey of the samples by energy dispersive X-ray analysis (EDX) did not show any significant contamination of the samples surface.« less

Structural Investigation of the (010) Surface of the Al13Fe4 Catalyst

NASA Astrophysics Data System (ADS)

Ledieu, J.; Gaudry, É.; Loli, L. N. Serkovic; Villaseca, S. Alarcón; de Weerd, M.-C.; Hahne, M.; Gille, P.; Grin, Y.; Dubois, J.-M.; Fournée, V.

2013-02-01

We have investigated the structure of the Al13Fe4(010) surface using both experimental and ab initio computational methods. The results indicate that the topmost surface layers correspond to incomplete puckered (P) planes present in the bulk crystal structure. The main building block of the corrugated termination consists of two adjacent pentagons of Al atoms, each centered by a protruding Fe atom. These motifs are interconnected via additional Al atoms referred to as “glue” atoms which partially desorb above 873 K. The surface structure of lower atomic density compared to the bulk P plane is explained by a strong Fe-Al-Fe covalent polar interaction that preserves intact clusters at the surface. The proposed surface model with identified Fe-containing atomic ensembles could explain the Al13Fe4 catalytic properties recently reported in line with the site-isolation concept [M. Armbrüster , Nat. Mater. 11, 690 (2012)NMAACR1476-1122].

Raman vibrational spectra of bulk to monolayer Re S 2 with lower symmetry

DOE PAGES

Feng, Yanqing; Zhou, Wei; Wang, Yaojia; ...

2015-08-26

Lattice structure and symmetry of two-dimensional (2D) layered materials are of key importance to their fundamental mechanical, thermal, electronic and optical properties. Raman spectroscopy, as a convenient and nondestructive tool, however has its limitations on identifying all symmetry allowing Raman modes and determining the corresponding crystal structure of 2D layered materials with high symmetry like graphene and MoS 2. Due to lower structural symmetry and extraordinary weak interlayer coupling of ReS 2, we successfully identified all 18 first-order Raman active modes for bulk and monolayer ReS 2. Without van der Waals (vdW) correction, our local density approximation (LDA) calculations successfullymore » reproduce all the Raman modes. Our calculations also suggest no surface reconstruction effect and the absence of low frequency rigid-layer Raman modes below 100 cm -1. As a result, combining with Raman and LDA thus provides a general approach for studying the vibrational and structural properties of 2D layered materials with lower symmetry.« less

Probing Single Pt Atoms in Complex Intermetallic Al13Fe4.

PubMed

Yamada, Tsunetomo; Kojima, Takayuki; Abe, Eiji; Kameoka, Satoshi; Murakami, Yumi; Gille, Peter; Tsai, An Pang

2018-03-21

The atomic structure of a 0.2 atom % Pt-doped complex metallic alloy, monoclinic Al 13 Fe 4 , was investigated using a single crystal prepared by the Czochralski method. High-angle annular dark-field scanning transmission electron microscopy showed that the Pt atoms were dispersed as single atoms and substituted at Fe sites in Al 13 Fe 4 . Single-crystal X-ray structural analysis revealed that the Pt atoms preferentially substitute at Fe(1). Unlike those that have been reported, Pt single atoms in the surface layers showed lower activity and selectivity than those of Al 2 Pt and bulk Pt for propyne hydrogenation, indicating that the active state of a given single-atom Pt site is strongly dominated by the bonding to surrounding Al atoms.

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

Fe/Rh (100) multilayer magnetism probed by x-ray magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Tomaz, M. A.; Ingram, D. C.; Harp, G. R.; Lederman, D.; Mayo, E.; O'brien, W. L.

1997-09-01

We report the layer-averaged magnetic moments of both Fe and Rh in sputtered Fe/Rh (100) multilayer thin films as measured by x-ray magnetic circular dichroism. We observe two distinct regimes in these films. The first is characterized by Rh moments of at least 1μB, Fe moments enhanced as much as 30% above bulk, and a bct crystal structure. The second regime is distinguished by sharp declines of both Fe and Rh moments accompanied by a transition to an fct crystal lattice. The demarcation between the two regions is identified as the layer thickness for which both bct and fct phases first coexist, which we term the critical thickness tcrit. We attribute the change in magnetic behavior to the structural transformation.

Atomically thin two-dimensional organic-inorganic hybrid perovskites.

PubMed

Dou, Letian; Wong, Andrew B; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W; Fu, Anthony; Bischak, Connor G; Ma, Jie; Ding, Tina; Ginsberg, Naomi S; Wang, Lin-Wang; Alivisatos, A Paul; Yang, Peidong

2015-09-25

Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials. Copyright © 2015, American Association for the Advancement of Science.

The low temperature synthesis, characterization and properties of ferroelectrics

NASA Astrophysics Data System (ADS)

Xu, Jie

2000-10-01

PZT 50:50 xerogels prepared by two different sol-gel routes crystallized in a similar fashion to give a mixture of tetragonal and rhombohedral at high temperature (1000°C). Both the diffraction and EXAFS data suggest that the compositional inhomogeneity of the samples prepared by the two routes is similar. The crystallization of CZT gels is complicated. Crystalline CaCO 3 was always detected in the dry gels regardless of the sample composition and preparation methods. At intermediate temperatures a fluorite related phase was always formed and it transformed to perovskite at higher temperatures. The EXAFS data suggest that perovskite CZT samples prepared using alkoxide sol-gel chemistry may not be random solid solutions. All the solution processed ZrTiO4 materials crystallized in the range 600--700°C. The KTN samples prepared using a conventional alkoxide sol-gel route crystallized completely to perovskite at lower temperatures than those prepared using prehydrolyzed precursors. The EXAFS data for the KTN samples prepared using a conventional alkoxide sol-gel route are consistent with a random distribution of tantalum and niobium in the solid solution. However, materials prepared using the inhomogeneous sol-gel route and by the direct reaction of mixed oxides were shown to be compositionally inhomogeneous. The heterogeneity could not be removed by regrinding and heating the mixed oxide samples several times. K2Ta4-xNbxO11 (x = 0, 2, 4) samples were prepared using alkoxide sol-gel chemistry and their crystallization was examined by powder X-ray diffraction. A Rietveld structure analysis of the pyrochlore formed from a gel with bulk composition K2Ta 2Nb2O11 indicated that it was rich in potassium relative to the bulk sample. On heating to high temperatures tetragonal tungsten bronzes were formed. A Rietveld analysis was also performed for K2Ta 2Nb2O11 with tetragonal tungsten bronze structure. The defect pyrochlores "AgTaO3" and GaTaO 3 were synthesized by ion-exchange using pyrochlore KTaO3 as a starting material. The structures of the pyrochlores were examined using the Rietveld method. The pyrochlore-to-perovskite transformations were also explored.

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

Ben Smida, Youssef; Marzouki, Riadh; Georges, Samuel

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, andmore » its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Static magnetic susceptibility, crystal field and exchange interactions in rare earth titanate pyrochlores.

PubMed

Malkin, B Z; Lummen, T T A; van Loosdrecht, P H M; Dhalenne, G; Zakirov, A R

2010-07-14

The experimental temperature dependence (T = 2-300 K) of single crystal bulk and site susceptibilities of rare earth titanate pyrochlores R(2)Ti(2)O(7) (R = Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) is analyzed in the framework of crystal field theory and a mean field approximation. Analytical expressions for the site and bulk susceptibilities of the pyrochlore lattice are derived taking into account long range dipole-dipole interactions and anisotropic exchange interactions between the nearest neighbor rare earth ions. The sets of crystal field parameters and anisotropic exchange coupling constants have been determined and their variations along the lanthanide series are discussed.

The relationship between elastic constants and structure of shock waves in a zinc single crystal

NASA Astrophysics Data System (ADS)

Krivosheina, M. N.; Kobenko, S. V.; Tuch, E. V.

2017-12-01

The paper provides a 3D finite element simulation of shock-loaded anisotropic single crystals on the example of a Zn plate under impact using a mathematical model, which allows for anisotropy in hydrostatic stress and wave velocities in elastic and plastic ranges. The simulation results agree with experimental data, showing the absence of shock wave splitting into an elastic precursor and a plastic wave in Zn single crystals impacted in the [0001] direction. It is assumed that the absence of an elastic precursor under impact loading of a zinc single crystal along the [0001] direction is determined by the anomalously large ratio of the c/a-axes and close values of the propagation velocities of longitudinal and bulk elastic waves. It is shown that an increase in only one elastic constant along the [0001] direction results in shock wave splitting into an elastic precursor and a shock wave of "plastic" compression.

Engineering thermal conductance using a two-dimensional phononic crystal.

PubMed

Zen, Nobuyuki; Puurtinen, Tuomas A; Isotalo, Tero J; Chaudhuri, Saumyadip; Maasilta, Ilari J

2014-03-19

Controlling thermal transport has become relevant in recent years. Traditionally, this control has been achieved by tuning the scattering of phonons by including various types of scattering centres in the material (nanoparticles, impurities, etc). Here we take another approach and demonstrate that one can also use coherent band structure effects to control phonon thermal conductance, with the help of periodically nanostructured phononic crystals. We perform the experiments at low temperatures below 1 K, which not only leads to negligible bulk phonon scattering, but also increases the wavelength of the dominant thermal phonons by more than two orders of magnitude compared to room temperature. Thus, phononic crystals with lattice constants ≥1 μm are shown to strongly reduce the thermal conduction. The observed effect is in quantitative agreement with the theoretical calculation presented, which accurately determined the ballistic thermal conductance in a phononic crystal device.

Crystal-Phase Quantum Wires: One-Dimensional Heterostructures with Atomically Flat Interfaces.

PubMed

Corfdir, Pierre; Li, Hong; Marquardt, Oliver; Gao, Guanhui; Molas, Maciej R; Zettler, Johannes K; van Treeck, David; Flissikowski, Timur; Potemski, Marek; Draxl, Claudia; Trampert, Achim; Fernández-Garrido, Sergio; Grahn, Holger T; Brandt, Oliver

2018-01-10

In semiconductor quantum-wire heterostructures, interface roughness leads to exciton localization and to a radiative decay rate much smaller than that expected for structures with flat interfaces. Here, we uncover the electronic and optical properties of the one-dimensional extended defects that form at the intersection between stacking faults and inversion domain boundaries in GaN nanowires. We show that they act as crystal-phase quantum wires, a novel one-dimensional quantum system with atomically flat interfaces. These quantum wires efficiently capture excitons whose radiative decay gives rise to an optical doublet at 3.36 eV at 4.2 K. The binding energy of excitons confined in crystal-phase quantum wires is measured to be more than twice larger than that of the bulk. As a result of their unprecedented interface quality, these crystal-phase quantum wires constitute a model system for the study of one-dimensional excitons.

The undercooling of liquids

NASA Technical Reports Server (NTRS)

Turnbull, D.

1984-01-01

The formation by melt quenching of such metastable structures as glassy or microcrystalline solids and highly supersaturated solutions is made possible by the extreme resistance of most melts to homophase crystal nucleation at deep undercooling. This nucleation resistance contrasts sharply with the very low kinetic resistance to the movement of crystal-melt interfaces, once formed, in metals and other fluid systems at even minute undercooling. The methods of nucleation study which have proven especially effective in bypassing nucleation by heterophase impurities thereby exposing the high resistance of melts to homophase nucleation may be summarized as follows: observation of the crystallization behavior of dispersed small droplets; drop tube experiments in which liquid drops solidify, under containerless conditions, during their fall in the tube; and observation of the crystallization of bulk specimens immersed in fluxes chosen to dissolve or otherwise deactivate (e.g., by wetting) heterophase nucleants. This method has proven to be remarkably effective in deactivating such nucleants in certain pure metals.

Crystal growth of device quality GaAs in space

NASA Technical Reports Server (NTRS)

Gatos, H. C.; Lagowski, J.

1985-01-01

The present program has been aimed at solving the fundamental and technological problems associated with Crystal Growth of Device Quality in Space. The initial stage of the program was devoted strictly to ground-based research. The unsolved problems associated with the growth of bulk GaAs in the presence of gravitational forces were explored. Reliable chemical, structural and electronic characterization methods were developed which would permit the direct relation of the salient materials parameters (particularly those affected by zero gravity conditions) to the electronic characteristics of single crystal GaAs, in turn to device performance. These relationships are essential for the development of optimum approaches and techniques. It was concluded that the findings on elemental semiconductors Ge and Si regarding crystal growth, segregation, chemical composition, defect interactions, and materials properties-electronic properties relationships are not necessarily applicable to GaAs (and to other semiconductor compounds). In many instances totally unexpected relationships were found to prevail.

Atomistic Structure, Strength, and Kinetic Properties of Intergranular Films in Ceramics

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

Garofalini, Stephen H

2015-01-08

Intergranular films (IGFs) present in polycrystalline oxide and nitride ceramics provide an excellent example of nanoconfined glasses that occupy only a small volume percentage of the bulk ceramic, but can significantly influence various mechanical, thermal, chemical, and optical properties. By employing molecular dynamics computer simulations, we have been able to predict structures and the locations of atoms at the crystal/IGF interface that were subsequently verified with the newest electron microscopies. Modification of the chemistry of the crystal surface in the simulations provided the necessary mechanism for adsorption of specific rare earth ions from the IGF in the liquid state tomore » the crystal surface. Such results had eluded other computational approaches such as ab-initio calculations because of the need to include not only the modified chemistry of the crystal surfaces but also an accurate description of the adjoining glassy IGF. This segregation of certain ions from the IGF to the crystal caused changes in the local chemistry of the IGF that affected fracture behavior in the simulations. Additional work with the rare earth ions La and Lu in the silicon oxynitride IGFs showed the mechanisms for their different affects on crystal growth, even though both types of ions are seen adhering to a bounding crystal surface that would normally imply equivalent affects on grain growth.« less

Magnetic field controlled floating-zone single crystal growth of intermetallic compounds

NASA Astrophysics Data System (ADS)

Hermann, R.; Gerbeth, G.; Priede, J.

2013-03-01

Radio-frequency (RF) floating zone single crystal growth is an important technique for the preparation of single bulk crystals. The advantage of the floating-zone method is the crucible-free growth of single crystals of reactive materials with high melting points. The strong heat diffusion on the surface, as well as the melt convection in the molten zone due to induction heating, often leads to an undesired solid-liquid interface geometry with a concave (towards the solid phase) outer rim. These concave parts aggravate the single crystal growth over the full cross-section. A two-phase stirrer was developed at IFW Dresden in order to avoid the problems connected with these concave parts. It acts as a magnetic field pump and changes the typical double vortex structure to a single roll structure, thus pushing hot melt into the regions where the concave parts may arise. The current in the secondary coil is induced by the primary coil, and the capacitor and the resistance of the secondary circuit are adjusted to get a stable 90 degree phase-shift between the coil currents. Single crystal growth of industrial relevant RuAl and TiAl intermetallic compounds was performed based on the material parameters and using the adjusted two-phase stirrer. Very recently, the magnetic system was applied to the crystal growth of biocompatible TiNb alloys and antiferromagnetic Heusler MnSi compounds.

Microscopic Optical Characterization of ZnO Bulk Crystals, Free Standing III-Nitride Substrates and III-V Structures for Non-Linear Optics

DTIC Science & Technology

2008-10-01

concentration (M.R. Phillips, M.Wagner, O.Gelhausen, V.Coleman, J.B. Brady, C. Jagadish, E. Malguth, A. Hoffmann, E.M. Goldys , J.J. Rusell; E.MRS...Malguth, A. Hoffmann, E.M. Goldys , J.J. Rusell; E.MRS Fall meeting, Symp. F, (Warsaw, Poland, 2004)); it suggests that the shift towards the red of

Simulation studies for surfaces and materials strength

NASA Technical Reports Server (NTRS)

Halicioglu, T.

1985-01-01

From intermolecular force studies, it is now known that the overall non-additive contribution to the lattice enegy is positive so that analysis based on only pairwise additivity suggests a shallower intermolecular potential than the true value. Two body contributions alone are also known to be categorically unable to even qualitatively describe some configurations of molecular clusters in the gas phase or the general relaxation and reconstruction of fcc crystal surfaces. In addition, the many-body contribution was shown to play a key role in the stability of certain crystal structures. In these recent analyses, a relatively simple potential energy function (PEF), comprising only a two-body Mie-type potential plus a three-body Axilrod-Teller-type potential, was found to be extremely effective. This same parametric PEF is applied to describe the bulk stability and surface energy for the diamond cubic structure. To test the stability condition, the FCC, BCC, diamond cubic, graphite and beta-tin structures were considered.

Molecular engineering of chiral colloidal liquid crystals using DNA origami

NASA Astrophysics Data System (ADS)

Siavashpouri, Mahsa; Wachauf, Christian H.; Zakhary, Mark J.; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Molecular engineering of chiral colloidal liquid crystals using DNA origami.

PubMed

Siavashpouri, Mahsa; Wachauf, Christian H; Zakhary, Mark J; Praetorius, Florian; Dietz, Hendrik; Dogic, Zvonimir

2017-08-01

Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials.

Exfoliation of graphene sheets via high energy wet milling of graphite in 2-ethylhexanol and kerosene.

PubMed

Al-Sherbini, Al-Sayed; Bakr, Mona; Ghoneim, Iman; Saad, Mohamed

2017-05-01

Graphene sheets have been exfoliated from bulk graphite using high energy wet milling in two different solvents that were 2-ethylhexanol and kerosene. The milling process was performed for 60 h using a planetary ball mill. Morphological characteristics were investigated using scanning electron microscope (SEM) and transmission electron microscope (TEM). On the other hand, the structural characterization was performed using X-ray diffraction technique (XRD) and Raman spectrometry. The exfoliated graphene sheets have represented good morphological and structural characteristics with a valuable amount of defects and a good graphitic structure. The graphene sheets exfoliated in the presence of 2-ethylhexanol have represented many layers, large crystal size and low level of defects, while the graphene sheets exfoliated in the presence of kerosene have represented fewer number of layers, smaller crystal size and higher level of defects.

A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals.

PubMed

Wilson, S R; Mendelev, M I

2016-04-14

We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, we found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).

A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals

NASA Astrophysics Data System (ADS)

Wilson, S. R.; Mendelev, M. I.

2016-04-01

We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, we found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).

Effect of Ultrasonic Surface Treatment on the Transparency and Orientation of Fresnoite Surface Crystallization

NASA Astrophysics Data System (ADS)

Endo, A.; Sakida, S.; Benino, Y.; Nanba, T.

2011-10-01

Surface crystallized glass ceramics with fresnoite (Ba2TiSi2O8) phase were prepared by conventional heat treatment of 30BaO-20TiO2-50SiO2 glass together with ultrasonic surface treatment (UST) technique. The precursor glass was fully crystallized in a bulk form without any cracks, and the optical transparency and crystallographic orientation of the crystalline layers were evaluated by UV-Vis spectroscopy and XRD diffraction analyses, respectively. These properties were both enhanced significantly by applying UST using fresnoite/water suspension before the crystallization process, which is advantage for nonlinear optical applications of bulk glass ceramics. The effects of UST on the crystallization behavior were investigated by applying UST with various conditions.

Pressure-volume relations and bulk modulus under pressure of tetrahedral compounds

NASA Astrophysics Data System (ADS)

Soma, T.; Takahashi, Y.; Kagaya, H.-M.

1985-03-01

The pressure-volume relation and the compression effect on the bulk modulus of tetrahedral compounds such as GaP, InP, ZnS, ZnSe, ZnTe and CdTe are investigated from the electronic theory of solids by using a recently presented binding force, which includes mainly covalent interactions in the pseudopotential formalism and partially ionic interactions. The calculated results of the pressure-volume relations involving the pressure-induced phase transition are useful when comparing with the experimental data under high pressure. The calculated bulk modulus of these compounds increases as the crystal volume decreases. Further, the pressure derivative of bulk modulus is not constant and decreases with the reduction of the crystal volume.

Magneto-phonon polaritons of antiferromagnetic/ion-crystal superlattices

NASA Astrophysics Data System (ADS)

Ta, Jin-Xing; Song, Yu-Ling; Wang, Xuan-Zhang

2010-07-01

Magnetophonon polaritons in the superlattices composed of alternating antiferromagnetic and ion-crystal components are investigated with the transfer matrix method. Numerical simulations based on FeF2/TlBr superlattices show that there are four different bulk polariton bands, with negative refraction and positive refraction. Many surface polariton modes with various features arise around the bulk bands with negative refraction.

Relationship of Open-Circuit Voltage to CdTe Hole Concentration and Lifetime

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

Duenow, Joel N.; Burst, James M.; Albin, David S.

We investigate the correlation of bulk CdTe and CdZnTe material properties with experimental open-circuit voltage (Voc) through fabrication and characterization of diverse single-crystal solar cells with different dopants. Several distinct crystal types reach Voc >900 mV. Correlations are in general agreement with Voc limits modeled from bulk minority-carrier lifetime and hole concentration.

Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

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

Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.

Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

Antiferromagnetic defect structure in LaNi O3 -δ single crystals

NASA Astrophysics Data System (ADS)

Wang, Bi-Xia; Rosenkranz, S.; Rui, X.; Zhang, Junjie; Ye, F.; Zheng, H.; Klie, R. F.; Mitchell, J. F.; Phelan, D.

2018-06-01

The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNi O3 -δ crystals, we show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ˜152 K and a Curie temperature of ˜225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNi O3 -δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO3 are discussed.

Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

DOE PAGES

Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.; ...

2018-06-12

Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

Optical and Electrical Properties of Sn-Doped Zinc Oxide Single Crystals

DOE PAGES

Haseman, M. S.; Saadatkia, Pooneh; Warfield, J. T.; ...

2017-11-28

Here, Sn dopant in ZnO may significantly improve the n-type conductivity of ZnO through a characteristic double effect. However, studies on bulk Sn-doped ZnO are rare, and the effect of Sn doping on the optoelectronic properties of bulk ZnO is not well understood. In this work, the effect of Sn doping on the optical and electrical properties of ZnO bulk single crystals was investigated through optical absorption spectroscopy, Hall-effect measurements, and thermoluminescence (TL) spectroscopy. Undoped and Sn-doped ZnO single crystals were grown by chemical vapor transport method and characterized by x-ray diffraction analysis. The Sn doping level in the crystalsmore » was evaluated by inductively coupled plasma mass spectroscopy measurements. Hall-effect measurements revealed an increase in conductivity and carrier concentration with increasing Sn doping, while TL measurements identified a few donor species in the crystals with donor ionization energy ranging from 35 meV to 118 meV. Increasing Sn doping was also associated with a color change of single crystals from colorless to dark blue.« less

Pretreatment of Hanford medium-curie wastes by fractional crystallization.

PubMed

Nassif, Laurent; Dumont, George; Alysouri, Hatem; Rousseau, Ronald W

2008-07-01

Acceleration of the schedule for decontamination of the Hanford site using bulk vitrification requires implementation of a pretreatment operation. Medium-curie waste must be separated into two fractions: one is to go to a waste treatment and immobilization plant and a second, which is low-activity waste, is to be processed by bulk vitrification. The work described here reports research on using fractional crystallization for that pretreatment. Sodium salts are crystallized by evaporation of water from solutions simulating those removed from single-shell tanks, while leaving cesium in solution. The crystalline products are then recovered and qualified as low-activity waste, which is suitable upon redissolution for processing by bulk vitrification. The experimental program used semibatch operation in which a feed solution was continuously added to maintain a constant level in the crystallizer while evaporating water. The slurry recovered at the end of a run was filtered to recover product crystals, which were then analyzed to determine their composition. The results demonstrated that targets on cesium separation from the solids, fractional recovery of sodium salts, and sulfate content of the recovered salts can be achieved by the process tested.

Electrooptic crystal growth and properties

NASA Astrophysics Data System (ADS)

1994-02-01

A new member in the tungsten-bronze family of ferroelectric lead potassium niobate (PKN), with general formula Pb(1-x)K(2x)Nb2O6, has been grown as bulk single crystal. Growth of PKN with charge composition x = 0.23 has been achieved using the Czochralski technique of crystal pulling. Large diameter boules were grown in platinum crucibles at temperatures between 1280 and 1300 C. Crystallographic studies were conducted using x ray diffraction techniques. The samples were characterized for ferroelectric properties between 25 and 600 C and for optical absorption. This paper presents the crystal synthesis and the results of ferroelectric and optical characterization. Bulk single crystals of potassium tantalate niobate, KTa(1-x)Nb(x)O3, ferroelectric with different values of Ta/Nb ratios have been grown by temperature gradient transport technique (TGTT). A second attached paper presents the results of the crystal growth experiments, ferroelectric characterization techniques, and properties of potassium tantalate niobate crystals.

Superconductivity in CaBi 2

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

Winiarski, M. J.; Wiendlocha, B.; Golba, S.

We observed superconductivity with critical temperature T c = 2.0 K in self-flux-grown single crystals of CaBi 2. This material adopts the ZrSi 2 structure type with lattice parameters a = 4.696(1) Å, b = 17.081(2) Å and c = 4.611(1) Å. The crystals of CaBi 2 were studied by means of magnetic susceptibility, specific heat and electrical resistivity measurements. The heat capacity jump at T c is ΔC/γT c = 1.41, confirming bulk superconductivity; the Sommerfeld coefficient γ = 4.1 mJ mol -1 K -2 and the Debye temperature Θ D = 157 K. The electron–phonon coupling strength ismore » λ el–ph = 0.59, and the thermodynamic critical field H c is low, between 111 and 124 Oe CaBi 2 is a moderate coupling type-I superconductor. Our results of electronic structure calculations are reported and charge densities, electronic bands, densities of states and Fermi surfaces are discussed, focusing on the effects of spin–orbit coupling and electronic property anisotropy. Furthermore, we find a mixed quasi-2D + 3D character in the electronic structure, which reflects the layered crystal structure of the material.« less

Superconductivity in CaBi 2

DOE PAGES

Winiarski, M. J.; Wiendlocha, B.; Golba, S.; ...

2016-07-12

We observed superconductivity with critical temperature T c = 2.0 K in self-flux-grown single crystals of CaBi 2. This material adopts the ZrSi 2 structure type with lattice parameters a = 4.696(1) Å, b = 17.081(2) Å and c = 4.611(1) Å. The crystals of CaBi 2 were studied by means of magnetic susceptibility, specific heat and electrical resistivity measurements. The heat capacity jump at T c is ΔC/γT c = 1.41, confirming bulk superconductivity; the Sommerfeld coefficient γ = 4.1 mJ mol -1 K -2 and the Debye temperature Θ D = 157 K. The electron–phonon coupling strength ismore » λ el–ph = 0.59, and the thermodynamic critical field H c is low, between 111 and 124 Oe CaBi 2 is a moderate coupling type-I superconductor. Our results of electronic structure calculations are reported and charge densities, electronic bands, densities of states and Fermi surfaces are discussed, focusing on the effects of spin–orbit coupling and electronic property anisotropy. Furthermore, we find a mixed quasi-2D + 3D character in the electronic structure, which reflects the layered crystal structure of the material.« less

Implications of room temperature oxidation on crystal structure and exchange bias effect in Co/CoO nanoparticles

DOE PAGES

Feygenson, Mikhail; Formo, Eric V.; Freeman, Katherine; ...

2015-11-02

In this study, we describe how the exchange bias effect in Co/CoO nanoparticles depends on the size focusing and temperature treatment of precursor Co nanoparticles before oxidation at ambient conditions. By appealing to magnetization, microscopy, neutron and synchrotron x-ray measurements we found that as-synthesized Co nanoparticles readily oxidize in air only after 20 days. The highest exchange bias field of 814 Oe is observed at T = 2K. When the same nanoparticles are centrifuged and annealed at 70 °C in vacuum prior to oxidation, the exchange bias field is increased to 2570 Oe. Annealing of Co nanoparticles in vacuum improvesmore » their crystallinity and prevents complete oxidation, so that Co-core/CoO-shell structure is preserved even after 120 days. The crystal structure of CoO shell in both samples is different from its bulk counterpart. Implications of such distorted CoO shells on exchange bias are discussed. Coating of Co nanoparticles with amorphous silica shell makes them resistant to oxidation, but ultimately modifies the crystal structure of both Co core and SiO 2 shell.« less

Ultralong copper phthalocyanine nanowires with new crystal structure and broad optical absorption.

PubMed

Wang, Hai; Mauthoor, Soumaya; Din, Salahud; Gardener, Jules A; Chang, Rio; Warner, Marc; Aeppli, Gabriel; McComb, David W; Ryan, Mary P; Wu, Wei; Fisher, Andrew J; Stoneham, Marshall; Heutz, Sandrine

2010-07-27

The development of molecular nanostructures plays a major role in emerging organic electronic applications, as it leads to improved performance and is compatible with our increasing need for miniaturization. In particular, nanowires have been obtained from solution or vapor phase and have displayed high conductivity or large interfacial areas in solar cells. In all cases however, the crystal structure remains as in films or bulk, and the exploitation of wires requires extensive postgrowth manipulation as their orientations are random. Here we report copper phthalocyanine (CuPc) nanowires with diameters of 10-100 nm, high directionality, and unprecedented aspect ratios. We demonstrate that they adopt a new crystal phase, designated eta-CuPc, where the molecules stack along the long axis. The resulting high electronic overlap along the centimeter length stacks achieved in our wires mediates antiferromagnetic couplings and broadens the optical absorption spectrum. The ability to fabricate ultralong, flexible metal phthalocyanine nanowires opens new possibilities for applications of these simple molecules.

Nanoscale Cu{sub 2}O films: Radio-frequency magnetron sputtering and structural and optical studies

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

Kudryashov, D. A., E-mail: kudryashovda@apbau.ru; Gudovskikh, A. S.; Babichev, A. V.

2017-01-15

Nanoscale copper (I) oxide layers are formed by magnetron-assisted sputtering onto glassy and silicon substrates in an oxygen-free environment at room temperature, and the structural and optical properties of the layers are studied. It is shown that copper oxide formed on a silicon substrate exhibits a lower degree of disorder than that formed on a glassy substrate, which is supported by the observation of a higher intensity and a smaller half-width of reflections in the diffraction pattern. The highest intensity of reflections in the diffraction pattern is observed for Cu{sub 2}O films grown on silicon at a magnetron power ofmore » 150 W. The absorption and transmittance spectra of these Cu{sub 2}O films are in agreement with the well-known spectra of bulk crystals. In the Raman spectra of the films, phonons inherent in the crystal lattice of cubic Cu{sub 2}O crystals are identified.« less

High phase-purity 1T'-MoS2- and 1T'-MoSe2-layered crystals

NASA Astrophysics Data System (ADS)

Yu, Yifu; Nam, Gwang-Hyeon; He, Qiyuan; Wu, Xue-Jun; Zhang, Kang; Yang, Zhenzhong; Chen, Junze; Ma, Qinglang; Zhao, Meiting; Liu, Zhengqing; Ran, Fei-Rong; Wang, Xingzhi; Li, Hai; Huang, Xiao; Li, Bing; Xiong, Qihua; Zhang, Qing; Liu, Zheng; Gu, Lin; Du, Yonghua; Huang, Wei; Zhang, Hua

2018-06-01

Phase control plays an important role in the precise synthesis of inorganic materials, as the phase structure has a profound influence on properties such as conductivity and chemical stability. Phase-controlled preparation has been challenging for the metallic-phase group-VI transition metal dichalcogenides (the transition metals are Mo and W, and the chalcogens are S, Se and Te), which show better performance in electrocatalysis than their semiconducting counterparts. Here, we report the large-scale preparation of micrometre-sized metallic-phase 1T'-MoX2 (X = S, Se)-layered bulk crystals in high purity. We reveal that 1T'-MoS2 crystals feature a distorted octahedral coordination structure and are convertible to 2H-MoS2 following thermal annealing or laser irradiation. Electrochemical measurements show that the basal plane of 1T'-MoS2 is much more active than that of 2H-MoS2 for the electrocatalytic hydrogen evolution reaction in an acidic medium.

Enhancement of visible light photocatalytic activity over bistructural SnO2 nanobelts

NASA Astrophysics Data System (ADS)

Wang, Lihua; Wang, Yongli; Su, Dezhi; Zhao, Yongjie

2018-02-01

SnO2 nanobelts were synthesized by hydrothermal method. The structure and morphology were investigated by XRD, Raman spectra, SEM and TEM. The results revealed that the synthesized SnO2 nanobelts were covered with amorphous surface. For the photocatalytic efficiency of methylene blue, the none-fully crystallized SnO2 nanobelts were over four times higher than bulk SnO2. Moreover, the photo-degradation rate constant with SnO2 nanobelts as photocatalysts was over six times higher than bulk SnO2. It was considered that the subtle structure of SnO2 nanobelts not only lowered the band gap but also improved the transfer of charge carriers and trapping effect of solar light. Furthermore, this strategy of enhancing photocatalytic performance could be extended to the other kinds of metal oxide photocatalyst.

Modeling Calculation and Synthesis of Alumina Whiskers Based on the Vapor Deposition Process.

PubMed

Gong, Wei; Li, Xiangcheng; Zhu, Boquan

2017-10-17

This study simulated the bulk structure and surface energy of Al₂O₃ based on the density of states (DOS) and studied the synthesis and microstructure of one-dimensional Al₂O₃ whiskers. The simulation results indicate that the (001) surface has a higher surface energy than the others. The growth mechanism of Al₂O₃ whiskers follows vapor-solid (VS) growth. For the (001) surface with the higher surface energy, the driving force of crystal growth would be more intense in the (001) plane, and the alumina crystal would tend to grow preferentially along the direction of the (001) plane from the tip of the crystal. The Al₂O₃ grows to the shape of whisker with [001] orientation, which is proved both through modeling and experimentation.

Polypeptide Liquid Crystal Assisted Assembly of Cylindrically Symmetric Silica-Polypeptide Hybrid Microparticles

NASA Astrophysics Data System (ADS)

Russo, Paul; Rosu, Cornelia; Jacobeen, Shane; Park, Katherine; Yunker, Peter; Reichmanis, Elsa

Liquid crystals can organize dispersed particles into exotic structures. Matching the particle surface coating to the chemistry of the mesogenic phase permits a tight focus on factors such as extended particle shape. The colloidal particles developed for this work consist of a magnetic and fluorescent cylinder-like silica core. One end of the silica is rounded, almost hemispherical, giving the particles a bullet-like shape. These particles are functionalized with helical poly(γ-stearyl-L-glutamate) and dispersed, at different concentrations in cholesteric liquid crystals (ChLC) of the same polymer in tetrahydrofuran. Defects introduced by the particles to the director field of the bulk PSLG/THF host led to a variety of phases, including a quasi-hexagonal alignment of the particles. National Science Foundation.

Effects of Mass Fluctuation on Thermal Transport Properties in Bulk Bi2Te3

NASA Astrophysics Data System (ADS)

Huang, Ben; Zhai, Pengcheng; Yang, Xuqiu; Li, Guodong

2017-05-01

In this paper, we applied large-scale molecular dynamics and lattice dynamics to study the influence of mass fluctuation on thermal transport properties in bulk Bi2Te3, namely thermal conductivity ( K), phonon density of state (PDOS), group velocity ( v g), and mean free path ( l). The results show that total atomic mass change can affect the relevant vibrational frequency on the micro level and heat transfer rate in the macro statistic, hence leading to the strength variation of the anharmonic phonon processes (Umklapp scattering) in the defect-free Bi2Te3 bulk. Moreover, it is interesting to find that the anharmonicity of Bi2Te3 can be also influenced by atomic differences of the structure such as the mass distribution in the primitive cell. Considering the asymmetry of the crystal structure and interatomic forces, it can be concluded by phonon frequency, lifetime, and velocity calculation that acoustic-optical phonon scattering shows the structure-sensitivity to the mass distribution and complicates the heat transfer mechanism, hence resulting in the low lattice thermal conductivity of Bi2Te3. This study is helpful for designing the material with tailored thermal conductivity via atomic substitution.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

2018-05-01

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

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

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

DOE PAGES

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.; ...

2018-05-09

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Crystallization of Polymers in Confined Environments: Structural Development of Semi-crystalline Polymer-Layered Silicate Nanocomposites

NASA Astrophysics Data System (ADS)

Vaia, Richard A.; Lincoln, Derek M.; Wang, Zhi-Gang; Hsiao, Benjamin S.; Krishnamoorti, Ramanan

2000-03-01

Over the last decade, the utility of ultrafine dispersions of inorganic nanoparticles to enhance polymer performance and function as precursors to form self-passivating / self-healing inorganic coatings on the polymer surface has been established. Before developing the fundamental structure-property relationships though, a detailed understanding of processing / morphology relationships is necessary. As with other multiphase systems exhibiting nano (1-100 nm) and meso (100-500 nm) order (such as biopolymers, block-copolymers, colloidal suspensions, liquid crystals), physical properties ranging from toughness to optical clarity are determined by morphology on various length scales which in turn arise from processing history. This is anticipated to be especially important for blends containing two or more constituents with fundamental structural features on the nanoscale, such as crystal lamellae and aluminosilicate sheets. Small-angle x-ray scattering experiments with synchrotron radiation reveal the presence of ultra-long range (20-60 nm) mesoscopic ordering of the layered silicate in molten polyamide 6-layered silicate nanocomposites. This superstructure of these semi-rigid inorganic sheets provides a confined environment to examine the crystallization of polyamide 6 with traditional bulk characterization techniques. In addition to a change lamellae organization and lamellae size, the presence of the aluminosilicate layers and extent of interfacial interactions (end-tethered v. physiadsorbed chains) substantially alters the nucleation rate, growth kinetics and Brill transition of the crystal phase as revealed by isothermal crystallization experiments monitored in-situ with synchrotron radiation. These exfoliated nanocomposites provide new opportunities to investigate confined polymer crystallization as well as provide insight into the origin of various property enhancements in these systems.

Chain Stretching and Order-Disorder Transitions in Block Copolymer Monolayers and Multilayers

NASA Astrophysics Data System (ADS)

Kramer, Edward J.; Mishra, Vindhya; Stein, Gila E.; Sohn, Karen E.; Hur, Sumi; Fredrickson, Glenn H.; Cochran, Eric W.

2009-03-01

Both monolayers of block copolymer cylinders and spheres undergo order to disorder transitions (ODT) at temperatures well below those of the bulk. Monolayers of PS-b-P2VP cylinders undergo a ``nematic'' to ``isotropic'' transition at temperatures about 20 K below the bulk ODT while monolayers of PS-b-P2VP with P2VP spheres undergo a 2D crystal to hexatic transition at least 10 K below the bulk ODT. Bilayers of each structure disorder at temperatures well above that of the monolayers. While one is tempted to attribute all of the difference to the fact that ordered monolayers are quasi 2 dimensional while bilayers are not, an alternative explanation exists. In the cylinder monolayer the corona PS chains must stretch to fill a nearly square cross-section domain rather than a hexagonal one in the bulk, while the corona PS chains in a sphere monolayer must stretch to fill a hexagonal prism rather than an octahedron in the bulk. The more non-uniform stretching of the chains in the monolayer should increase its free energy and decrease its order-disorder temperature.

Pressure-induced nano-crystallization of silicate garnets from glass

PubMed Central

Irifune, T.; Kawakami, K.; Arimoto, T.; Ohfuji, H.; Kunimoto, T.; Shinmei, T.

2016-01-01

Transparent ceramics are important for scientific and industrial applications because of the superior optical and mechanical properties. It has been suggested that optical transparency and mechanical strength are substantially enhanced if transparent ceramics with nano-crystals are available. However, synthesis of the highly transparent nano-crystalline ceramics has been difficult using conventional sintering techniques at relatively low pressures. Here we show direct conversion from bulk glass starting material in mutianvil high-pressure apparatus leads to pore-free nano-polycrystalline silicate garnet at pressures above ∼10 GPa in a limited temperature range around 1,400 °C. The synthesized nano-polycrystalline garnet is optically as transparent as the single crystal for almost the entire visible light range and harder than the single crystal by ∼30%. The ultrahigh-pressure conversion technique should provide novel functional ceramics having various crystal structures, including those of high-pressure phases, as well as ideal specimens for some mineral physics applications. PMID:27924866

Photonic crystals possessing multiple Weyl points and the experimental observation of robust surface states

PubMed Central

Chen, Wen-Jie; Xiao, Meng; Chan, C. T.

2016-01-01

Weyl points, as monopoles of Berry curvature in momentum space, have captured much attention recently in various branches of physics. Realizing topological materials that exhibit such nodal points is challenging and indeed, Weyl points have been found experimentally in transition metal arsenide and phosphide and gyroid photonic crystal whose structure is complex. If realizing even the simplest type of single Weyl nodes with a topological charge of 1 is difficult, then making a real crystal carrying higher topological charges may seem more challenging. Here we design, and fabricate using planar fabrication technology, a photonic crystal possessing single Weyl points (including type-II nodes) and multiple Weyl points with topological charges of 2 and 3. We characterize this photonic crystal and find nontrivial 2D bulk band gaps for a fixed kz and the associated surface modes. The robustness of these surface states against kz-preserving scattering is experimentally observed for the first time. PMID:27703140

Lithium niobate bulk crystallization promoted by CO2 laser radiation

NASA Astrophysics Data System (ADS)

Ferreira, N. M.; Costa, F. M.; Nogueira, R. N.; Graça, M. P. F.

2012-09-01

The crystallization induced by laser radiation is a very promising technique to promote glass/ceramic transformation, being already used to produce crystalline patterns on glass surfaces. In this work, a SiO2-Li2O-Nb2O5 glass, prepared by the sol-gel route, was submitted to CO2 laser radiation and conventional heat-treatments in order to induce the LiNbO3 crystallization. The structure and morphology of the samples prepared by both routes was analyzed as a function of exposure time, radiation power and heat-treatment temperatures by XRD, Raman spectroscopy and SEM. The results reveal a correlation between the crystallization degree of LiNbO3 particles and glass matrix with the heat treatment type and experimental parameters. An heat-treatment at 650 °C/4 h was necessary to induce crystallization in heat treatments samples while 4 W/500 s was enough for laser radiation ones, corresponding a reduction time processing of ˜14 000 s.

Communication: Orientational structure manipulation in nematic liquid crystal droplets induced by light excitation of azodendrimer dopant

NASA Astrophysics Data System (ADS)

Shvetsov, Sergey A.; Emelyanenko, Alexander V.; Boiko, Natalia I.; Liu, Jui-Hsiang; Khokhlov, Alexei R.

2017-06-01

Reversible orientational transitions in the droplets of a nematic liquid crystal (NLC) caused by the change of boundary conditions under the low intensity diode illumination are investigated. Photosensitivity of NLC is achieved by the addition of the dendrimer compound with azobenzene terminal groups. Two types of NLC droplets in glycerol are considered: the spherical droplets in the bulk of glycerol and the droplets laid-down onto the solid substrate. In the second case, the first order phase transition is revealed. The effects described can be useful for the development of highly sensitive chemical detectors and microsized photo-tunable optical devices.

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

Liu, Yu; Petrovic, C.

CrI 3 is a promising candidate for the van der Waals bonded ferromagnetic devices since its ferromagnetism can be maintained upon exfoliating of bulk crystals down to single layer. In this work we studied critical properties of bulk CrI 3 single crystals around the paramagnetic to ferromagnetic phase transition. Critical exponents β= 0.260(4) with a critical temperature T c= 60.05(13) K and γ= 1.136(6) with T c= 60.43(4) K are obtained by the Kouvel-Fisher method, whereas δ= 5.32(2) is obtained by a critical isotherm analysis at T c= 60 K. In conclusion, the critical exponents determined in bulk CrI 3more » single crystals suggest a three-dimensional long-range magnetic coupling with the exchange distance decaying as J(r)≈r -4:69« less

Shubnikov-de Haas oscillations in bulk ZrT e5 single crystals: Evidence for a weak topological insulator

NASA Astrophysics Data System (ADS)

Lv, Yang-Yang; Zhang, Bin-Bin; Li, Xiao; Zhang, Kai-Wen; Li, Xiang-Bing; Yao, Shu-Hua; Chen, Y. B.; Zhou, Jian; Zhang, Shan-Tao; Lu, Ming-Hui; Li, Shao-Chun; Chen, Yan-Feng

2018-03-01

The study of ZrT e5 crystals is revived because of the recent theoretical prediction of topological phase in bulk ZrT e5 . However, the current conclusions for the topological character of bulk ZrT e5 are quite contradictory. To resolve this puzzle, we here identify the Berry phase on both b - and c planes of high-quality ZrT e5 crystals by the Shubnikov-de-Hass (SdH) oscillation under tilted magnetic field at 2 K. The angle-dependent SdH oscillation frequency, both on b - and c planes of ZrT e5 , demonstrates the two-dimensional feature. However, phase analysis of SdH verifies that a nontrivial π-Berry phase is observed in the c -plane SdH oscillation, but not in the b -plane one. Compared to bulk Fermi surface predicted by the first-principle calculation, the two-dimensional-like behavior of SdH oscillation measured at b plane comes from the bulk electron. Based on these analyses, it is suggested that bulk ZrT e5 at low temperature (˜2 K) belongs to a weak topological insulator, rather than Dirac semimetal or strong topological insulator as reported previously.

Doping of Czochralski-grown bulk β-Ga2O3 single crystals with Cr, Ce and Al

NASA Astrophysics Data System (ADS)

Galazka, Zbigniew; Ganschow, Steffen; Fiedler, Andreas; Bertram, Rainer; Klimm, Detlef; Irmscher, Klaus; Schewski, Robert; Pietsch, Mike; Albrecht, Martin; Bickermann, Matthias

2018-03-01

We experimentally evaluated segregation of Cr, Ce and Al in bulk β-Ga2O3 single crystals grown by the Czochralski method, as well as the impact of these dopants on optical properties. The segregation of Cr and Ce and their incorporation into the β-Ga2O3 crystal structure strongly depends on O2 concentration in the growth atmosphere which has a noticeable impact on decomposition of Ga2O3 and Cr2O3, as well as on the charge state of Cr and Ce. Effective segregation coefficients for Cr are in the range of 3.1-1.5 at 7-24 vol% O2, while for Ce they are roughly below 0.01 at 1.5-34 vol% O2. The effective segregation coefficient for Al is 1.1 at 1.5-21 vol% O2. Both dopants Ce and Al have a thermodynamically stabilizing effect on β-Ga2O3 crystal growth by supressing decomposition. While Ce has no impact on the optical transmittance in the ultraviolet and visible regions, in Cr doped crystals we observe three absorption bands due to Cr3+ on octahedral Ga sites, one in the ultraviolet merging with the band edge absorption of β-Ga2O3 and two in the visible spectrum, for which we estimate the absorption cross sections. Al doping also does not induce dopant related absorption bands but clearly shifts the absorption edge as one expects for a solid-solution crystal Ga2(1-x)Al2xO3 still in the monoclinic phase. For the highest doping concentration (Ga1.9Al0.1O3) we estimate an increase of the energy gap by 0.11 eV.

Magnesium Vacancy Segregation and Fast Pipe Diffusion for the ½<110>{110} Edge Dislocation in MgO

NASA Astrophysics Data System (ADS)

Walker, A. M.; Zhang, F.; Wright, K.; Gale, J. D.

2009-12-01

The movement of point defects in minerals plays a key role in determining their rheological properties, both by permitting diffusional creep and by allowing recovery by dislocation climb. Point defect diffusion can also control the kinetics of phase transitions and grain growth, and can determine the rate of chemical equilibration between phases. Because of this, and the difficulties associated with experimental studies of diffusion, the simulation of point defect formation and migration has been a subject of considerable interest in computational mineral physics. So far, studies have concentrated on point defects moving through otherwise perfect crystals. In this work we examine the behavior of magnesium vacancies close to the core of an edge dislocation in MgO and find that the dislocation dramatically changes the behavior of the point defect. An atomic scale model of the ½<110>{110} edge dislocation in MgO was constructed by applying the anisotropic linear elastic displacement field to the crystal structure and subsequently minimizing the energy of the crystal close to the dislocation core using a parameterized potential model. This process yielded the structure of an isolated edge dislocation in an otherwise perfect crystal. The energy cost associated with introducing magnesium vacancies around the dislocation was then mapped and compared to the formation energy of an isolated magnesium vacancy in bulk MgO. We find that the formation energy of magnesium vacancies around the dislocation mirrors the elastic strain field. Above the dislocation line σxx and σyy are negative and the strain field is compressional. Atoms are squeezed together to make room for the extra half plane effectively increasing the pressure in this region. Below the dislocation line σxx and σyy are positive and the strain field is dilatational. Planes of atoms are pulled apart to avoid a discontinuity across the glide plane and the effective pressure is decreased. In the region with a compressional strain field the vacancies become less stable than those in perfect MgO. In contrast, the region with a dilatational strain field hosts vacancies which are stabilized compared to the perfect crystal. This is in agreement with the previously observed tendency for increasing pressure to decrease the stability of vacancies in MgO. The most stable position for a magnesium vacancy was found to be 1.7 eV more stable than the vacancy in the bulk crystal, suggesting that vacancies will strongly partition to dislocations in MgO. Finally, the energy profile traced out by a vacancy moving through the bulk crystal was compared with that experienced by a vacancy moving along the dislocation core. A low energy pathway for vacancy migration along the dislocation line was found with a migration energy of 1.6 eV compared with a migration energy in the perfect crystal of 1.9 eV. This shows that vacancies segregated to the dislocation line will be significantly more mobile than vacancies in the perfect crystal. Dislocations will act as pipes, allowing material to be rapidly transported through crystals of MgO.

Calcium aluminate in alumina

NASA Astrophysics Data System (ADS)

Altay, Arzu

The properties of ceramic materials are determined not only by the composition and structure of the phases present, but also by the distribution of impurities, intergranular films and second phases. The phase distribution and microstructure both depend on the fabrication techniques, the raw materials used, the phase-equilibrium relations, grain growth and sintering processes. In this dissertation research, various approaches have been employed to understand fundamental phenomena such as grain growth, impurity segregation, second-phase formation and crystallization. The materials system chosen was alumina intentionally doped with calcium. Atomic-scale structural analyses of grain boundaries in alumina were carried on the processed samples. It was found that above certain calcium concentrations, CA6 precipitated as a second phase at all sintering temperatures. The results also showed that abnormal grain growth can occur after precipitation and it is not only related to the calcium level, but it is also temperature dependent. In order to understand the formation mechanism of CA6 precipitates in calcium doped alumina samples, several studies have been carried out using either bulk materials or thin films The crystallization of CA2 and CA6 powders has been studied. Chemical processing techniques were used to synthesize the powders. It was observed that CA2 powders crystallized directly, however CA6 powders crystallized through gamma-Al 2O3 solid solution. The results of energy-loss near-edge spectrometry confirmed that gamma-Al2O3 can dissolve calcium. Calcium aluminate/alumina reaction couples have also been investigated. All reaction couples were heat treated following deposition. It was found that gamma-Al2O3 was formed at the interface as a result of the interfacial reaction between the film and the substrate. gamma-Al 2O3 at the interface was stable at much higher temperatures compared to the bulk gamma-Al2O3 formed prior to the CA6 crystallization. In order to complement the studies carried out on the calcium aluminate phases, energy-loss near-edge structure (ELNES) fingerprints of CA2 and CA6 were obtained. It was shown that it is possible to distinguish these phases from each other by comparing the ELNES fingerprints. Theoretical calculations of ELNES were used to assign spectral features to certain symmetry environments that can later be used to understand the structures of unknown materials.

The Nature of Bonding in Bulk Tellurium Composed of One-Dimensional Helical Chains.

PubMed

Yi, Seho; Zhu, Zhili; Cai, Xiaolin; Jia, Yu; Cho, Jun-Hyung

2018-05-07

Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.

Lunar Magma Ocean Crystallization: Constraints from Fractional Crystallization Experiments

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Draper, D. S.

2015-01-01

The currently accepted paradigm of lunar formation is that of accretion from the ejecta of a giant impact, followed by crystallization of a global scale magma ocean. This model accounts for the formation of the anorthosite highlands crust, which is globally distributed and old, and the formation of the younger mare basalts which are derived from a source region that has experienced plagioclase extraction. Several attempts at modelling the crystallization of such a lunar magma ocean (LMO) have been made, but our ever-increasing knowledge of the lunar samples and surface have raised as many questions as these models have answered. Geodynamic models of lunar accretion suggest that shortly following accretion the bulk of the lunar mass was hot, likely at least above the solidus]. Models of LMO crystallization that assume a deep magma ocean are therefore geodynamically favorable, but they have been difficult to reconcile with a thick plagioclase-rich crust. A refractory element enriched bulk composition, a shallow magma ocean, or a combination of the two have been suggested as a way to produce enough plagioclase to account for the assumed thickness of the crust. Recently however, geophysical data from the GRAIL mission have indicated that the lunar anorthositic crust is not as thick as was initially estimated, which allows for both a deeper magma ocean and a bulk composition more similar to the terrestrial upper mantle. We report on experimental simulations of the fractional crystallization of a deep (approximately 100km) LMO with a terrestrial upper mantle-like (LPUM) bulk composition. Our experimental results will help to define the composition of the lunar crust and mantle cumulates, and allow us to consider important questions such as source regions of the mare basalts and Mg-suite, the role of mantle overturn after magma ocean crystallization and the nature of KREEP

Size effects on rhodium nanoparticles related to hydrogen-storage capability.

PubMed

Song, Chulho; Yang, Anli; Sakata, Osami; Kumara, L S R; Hiroi, Satoshi; Cui, Yi-Tao; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi

2018-06-06

To unveil the origin of the hydrogen-storage properties of rhodium nanoparticles (Rh NPs), we investigated the electronic and crystal structures of the Rh NPs using various synchrotron based X-ray techniques. Electronic structure studies revealed that the hydrogen-storage capability of Rh NPs could be attributed to their more unoccupied d-DOSs than that of the bulk near the Fermi level. Crystal structure studies indicated that lattice distortion and mean-square displacement increase while coordination number decreases with decreasing particle size and the hydrogen-absorption capability of Rh NPs improves to a greater extent with increased structural disorder in the local structure than with that in the mean structure. The smallest Rh NPs, having the largest structural disorder/increased vacancy spaces and the smallest coordination number, exhibited excellent hydrogen-storage capacity. Finally, from the bond-orientational order analysis, we confirmed that the localized disordering is distributed more over the surface part than the core part and hydrogen can be trapped on the surface part of Rh NPs which increases with a decrease in NP diameter.

Simulation study of light transport in laser-processed LYSO:Ce detectors with single-side readout

NASA Astrophysics Data System (ADS)

Bläckberg, L.; El Fakhri, G.; Sabet, H.

2017-11-01

A tightly focused pulsed laser beam can locally modify the crystal structure inside the bulk of a scintillator. The result is incorporation of so-called optical barriers with a refractive index different from that of the crystal bulk, that can be used to redirect the scintillation light and control the light spread in the detector. We here systematically study the scintillation light transport in detectors fabricated using the laser induced optical barrier technique, and objectively compare their potential performance characteristics with those of the two mainstream detector types: monolithic and mechanically pixelated arrays. Among countless optical barrier patterns, we explore barriers arranged in a pixel-like pattern extending all-the-way or half-way through a 20 mm thick LYSO:Ce crystal. We analyze the performance of the detectors coupled to MPPC arrays, in terms of light response functions, flood maps, line profiles, and light collection efficiency. Our results show that laser-processed detectors with both barrier patterns constitute a new detector category with a behavior between that of the two standard detector types. Results show that when the barrier-crystal interface is smooth, no DOI information can be obtained regardless of barrier refractive index (RI). However, with a rough barrier-crystal interface we can extract multiple levels of DOI. Lower barrier RI results in larger light confinement, leading to better transverse resolution. Furthermore we see that the laser-processed crystals have the potential to increase the light collection efficiency, which could lead to improved energy resolution and potentially better timing resolution due to higher signals. For a laser-processed detector with smooth barrier-crystal interfaces the light collection efficiency is simulated to  >42%, and for rough interfaces  >73%. The corresponding numbers for a monolithic crystal is 39% with polished surfaces, and 71% with rough surfaces, and for a mechanically pixelated array 35% with polished pixel surfaces and 59% with rough surfaces.

Simulation study of light transport in laser-processed LYSO:Ce detectors with single-side readout.

PubMed

Bläckberg, L; El Fakhri, G; Sabet, H

2017-10-19

A tightly focused pulsed laser beam can locally modify the crystal structure inside the bulk of a scintillator. The result is incorporation of so-called optical barriers with a refractive index different from that of the crystal bulk, that can be used to redirect the scintillation light and control the light spread in the detector. We here systematically study the scintillation light transport in detectors fabricated using the laser induced optical barrier technique, and objectively compare their potential performance characteristics with those of the two mainstream detector types: monolithic and mechanically pixelated arrays. Among countless optical barrier patterns, we explore barriers arranged in a pixel-like pattern extending all-the-way or half-way through a 20 mm thick LYSO:Ce crystal. We analyze the performance of the detectors coupled to MPPC arrays, in terms of light response functions, flood maps, line profiles, and light collection efficiency. Our results show that laser-processed detectors with both barrier patterns constitute a new detector category with a behavior between that of the two standard detector types. Results show that when the barrier-crystal interface is smooth, no DOI information can be obtained regardless of barrier refractive index (RI). However, with a rough barrier-crystal interface we can extract multiple levels of DOI. Lower barrier RI results in larger light confinement, leading to better transverse resolution. Furthermore we see that the laser-processed crystals have the potential to increase the light collection efficiency, which could lead to improved energy resolution and potentially better timing resolution due to higher signals. For a laser-processed detector with smooth barrier-crystal interfaces the light collection efficiency is simulated to  >42%, and for rough interfaces  >73%. The corresponding numbers for a monolithic crystal is 39% with polished surfaces, and 71% with rough surfaces, and for a mechanically pixelated array 35% with polished pixel surfaces and 59% with rough surfaces.

Wafer-scale plasmonic and photonic crystal sensors

NASA Astrophysics Data System (ADS)

George, M. C.; Liu, J.-N.; Farhang, A.; Williamson, B.; Black, M.; Wangensteen, T.; Fraser, J.; Petrova, R.; Cunningham, B. T.

2015-08-01

200 mm diameter wafer-scale fabrication, metrology, and optical modeling results are reviewed for surface plasmon resonance (SPR) sensors based on 2-D metallic nano-dome and nano-hole arrays (NHA's) as well as 1-D photonic crystal sensors based on a leaky-waveguide mode resonance effect, with potential applications in label free sensing, surface enhanced Raman spectroscopy (SERS), and surface-enhanced fluorescence spectroscopy (SEFS). Potential markets include micro-arrays for medical diagnostics, forensic testing, environmental monitoring, and food safety. 1-D and 2-D nanostructures were fabricated on glass, fused silica, and silicon wafers using optical lithography and semiconductor processing techniques. Wafer-scale optical metrology results are compared to FDTD modeling and presented along with application-based performance results, including label-free plasmonic and photonic crystal sensing of both surface binding kinetics and bulk refractive index changes. In addition, SEFS and SERS results are presented for 1-D photonic crystal and 2-D metallic nano-array structures. Normal incidence transmittance results for a 550 nm pitch NHA showed good bulk refractive index sensitivity, however an intensity-based design with 665 nm pitch was chosen for use as a compact, label-free sensor at both 650 and 632.8 nm wavelengths. The optimized NHA sensor gives an SPR shift of about 480 nm per refractive index unit when detecting a series of 0-40% glucose solutions, but according to modeling shows about 10 times greater surface sensitivity when operating at 532 nm. Narrow-band photonic crystal resonance sensors showed quality factors over 200, with reasonable wafer-uniformity in terms of both resonance position and peak height.

Electronic Transport Properties of Bismuth Microwire Arrays

NASA Astrophysics Data System (ADS)

Solomon, S.; Huber, T. E.; Bouffard, M.; Graf, M. J.

2002-03-01

Bulk Bi, a semimetal, and Bi-Sb, have the highest thermoelectric figure of merit Z at 100 K. The thermoelectric properties of these materials are strongly anisotropic. The best thermoelectric performance is observed when the electrical current flows along the trigonal axis. However, Bi single crystals are easily cleaved along the trigonal planes. This lack of strength has largely prevented the use of these materials in practical thermoelectric coolers. Composite technology offers the opportunity to increase the toughness of Bi and Bi-Sb. Also, microengineering Bi into composites may lead to a significant improvement in their thermoelectric performance, because of the reduction of phonon conductivity from phonon scattering at the grain boundaries and interfaces. X-ray diffraction studies show that the microwires in the array are highly oriented along the crystal direction normal to the (003) lattice plane of the rombohedral crystal structure of Bi . Measurements of the resistance of arrays of 3 mm and 10 mm diameter wires have been carried out over a wide range of temperatures (1.8 K 300 K) and magnetic fields (0-8 T), and orientations of the sample with respect to the magnetic field (0-90o) which includes the magnetic and transverse orientation. The zero field resistivity was studied and it was found that, at low temperatures, the wire boundary scattering is the dominant process. The longitudinal magnetoresistance is negative, in contrast to the longitudinal magnetoresistance of bulk crystals oriented in direction perpendicular to the trigonal plane of the rhombohedral crystal lattice who exhibit negligible magnetoresistance. This results are interpreted in terms of a size effect. Research supported by NASA and NSF.

Crystal growth and characterization of bulk Sb2Te3 topological insulator

NASA Astrophysics Data System (ADS)

Sultana, Rabia; Gurjar, Ganesh; Patnaik, S.; Awana, V. P. S.

2018-04-01

The Sb2Te3 crystals are grown using the conventional self flux method via solid state reaction route, by melting constituent elements (Sb and Te) at high temperature (850 °C), followed by slow cooling (2 °C/h). As grown Sb2Te3 crystals are analysed for various physical properties by x-ray diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) coupled with Energy Dispersive x-ray Spectroscopy (EDAX) and electrical measurements under magnetic field (6 Tesla) down to low temperature (2.5 K). The XRD pattern revealed the growth of synthesized Sb2Te3 sample along (00l) plane, whereas the SEM along with EDAX measurements displayed the layered structure with near stoichiometric composition, without foreign contamination. The Raman scattering studies displayed known ({{{{A}}}1{{g}}}1, {{{{E}}}{{g}}}2 and {{{{A}}}1{{g}}}2) vibrational modes for the studied Sb2Te3. The temperature dependent electrical resistivity measurements illustrated the metallic nature of the as grown Sb2Te3 single crystal. Further, the magneto—transport studies represented linear positive magneto-resistance (MR) reaching up to 80% at 2.5 K under an applied field of 6 Tesla. The weak anti localization (WAL) related low field (±2 Tesla) magneto-conductance at low temperatures (2.5 K and 20 K) has been analysed and discussed using the Hikami—Larkin—Nagaoka (HLN) model. Summarily, the short letter reports an easy and versatile method for crystal growth of bulk Sb2Te3 topological insulator (TI) and its brief physical property characterization.

Collection of Ni-bearing material from electroless plating waste by magnetic separation with HTS bulk magnet

NASA Astrophysics Data System (ADS)

Oka, T.; Fukazawa, H.; Fukui, S.; Ogawa, J.; Sato, T.; Ooizumi, M.; Tsujimura, M.; Yokoyama, K.

2014-01-01

The magnetic separation experiment to collect the Ni compounds from the waste liquid of electroless plating processes was conducted in the open-gradient magnetic separation process with the high temperature superconducting bulk magnet system. The magnetic pole containing Gd-based bulk superconductors was activated to 3.45 T at 35 K in the static magnetic field of 5 T with use of a superconducting solenoid magnet. The coarse Ni-sulfate crystals were formed by adding the concentrated sulfuric acid to the Ni-phosphite precipitates which yielded from the plating waste liquid by controlling the temperature and the pH value. The open-gradient magnetic separation technique was employed to separate the Ni-sulfate crystals from the mixture of the Ni-sulfate and Ni-phosphite compounds by the difference between their magnetic properties. And we succeeded in collecting Ni-sulfate crystals preferentially to the Ni-phosphite by attracting them to the magnetic pole soon after the Ni-sulfate crystals began to grow.

Bulk Superconductivity Induced by Se Substitution in BiCh2-Based Layered Compounds Eu0.5Ce0.5FBiS2-xSex

NASA Astrophysics Data System (ADS)

Goto, Yosuke; Sogabe, Ryota; Mizuguchi, Yoshikazu

2017-10-01

We report the effect of Se substitution on the crystal structure and superconductivity of BiCh2-based (Ch: S, Se) layered compounds Eu0.5Ce0.5FBiS2-xSex (x = 0-1). Crystal structure analysis showed that both lattice constants, a and c, increased with increasing x, which is different from the related La-doped system Eu0.5La0.5FBiS2-xSex. This is due to Se substitution at both in-plane and out-of-plane Ch sites in the present Ce-doped system. Zero resistivity was observed for x = 0.2-1 above 2 K. The superconducting properties of Eu0.5Ce0.5FBiS2-xSex were investigated by magnetic susceptibility measurement, and the highest superconducting transition temperature of 3.5 K was obtained for x = 0.6 with a large shielding volume fraction. The emergence of bulk superconductivity and metallic conductivity can be qualitatively described in terms of the increased in-plane chemical pressure effect. A magnetic anomaly below 8 K, probably because of the ferromagnetic order of the magnetic moment of Ce3+ ions, coexists with bulk superconductivity in the BiCh2 layer. Since the effect of Se substitution on the magnetic transition temperature is ignorable, we suggest that the coupling between the magnetic order at the (Eu,Ce)F layer and the superconductivity at the Bi(S,Se)2 layer is weak.

Magneto-phonon polaritons in two-dimension antiferromagnetic/ion-crystalic photonic crystals

NASA Astrophysics Data System (ADS)

Ta, J. X.; Song, Y. L.; Wang, X. Z.

2012-01-01

Magneto-phonon polaritons in a two-dimension photonic crystal (PC) are discussed. This PC is constructed by embedding a periodical square lattice of ionic-crystal cylinders into an antiferromagnet. The two media are dispersive, with their individual resonant frequencies near each other. We first set up an effective-medium method to obtain the effective magnetic permeability and dielectric permittivity of the PC, followed by the dispersion relations of surface and bulk polaritons. There are a number of new surface polaritons, and two new distinctive bulk polariton bands in which the negative refraction and left-handedness can appear. The numerical calculations are based on the example, FeF2/TlBr PC.

Growth of 1.5-In Eu : SrI2 Single Crystal and Scintillation Properties

NASA Astrophysics Data System (ADS)

Yokota, Yuui; Ito, Tomoki; Yasuhiro, Shoji; Kurosawa, Shunsuke; Ohashi, Yuji; Kamada, Kei; Yoshikawa, Akira

2016-04-01

We grew 1.5-in Eu doped SrI2 (Eu : SrI2) bulk single crystal by a modified vertical Bridgman (VB) method using a removable chamber and high-frequency induction heating. Asgrown 1.5-in Eu : SrI2 bulk single crystal had no visible crack and inclusion in the crystal. In the transmittance and α-ray radioluminescence spectra, large absorption below 433 nm and emission peak at 433 nm were observed, respectively. Each polished Eu : SrI2 specimen indicated 56 000 62 000 ph/MeV light yield and 3.3 3.9% energy resolution. The decay times of the specimens were 0.61 0.67 μs.

In-plane chemical pressure essential for superconductivity in BiCh2-based (Ch: S, Se) layered structure

PubMed Central

Mizuguchi, Yoshikazu; Miura, Akira; Kajitani, Joe; Hiroi, Takafumi; Miura, Osuke; Tadanaga, Kiyoharu; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2015-01-01

BiCh2-based compounds (Ch: S, Se) are a new series of layered superconductors, and the mechanisms for the emergence of superconductivity in these materials have not yet been elucidated. In this study, we investigate the relationship between crystal structure and superconducting properties of the BiCh2-based superconductor family, specifically, optimally doped Ce1−xNdxO0.5F0.5BiS2 and LaO0.5F0.5Bi(S1−ySey)2. We use powder synchrotron X-ray diffraction to determine the crystal structures. We show that the structure parameter essential for the emergence of bulk superconductivity in both systems is the in-plane chemical pressure, rather than Bi-Ch bond lengths or in-plane Ch-Bi-Ch bond angle. Furthermore, we show that the superconducting transition temperature for all REO0.5F0.5BiCh2 superconductors can be determined from the in-plane chemical pressure. PMID:26447333

Structural, electronic and elastic properties of heavy fermion YbRh2 Laves phase compound

NASA Astrophysics Data System (ADS)

Pawar, Harsha; Shugani, Mani; Aynyas, Mahendra; Sanyal, Sankar P.

2018-05-01

The structural, electronic and elastic properties of YbRh2 Laves phase intermetallic compound which crystallize in cubic (MgCu2-type) structure have been investigated using ab-initio full potential linearized augmented plane wave (FP- LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B') are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for this compound which obeys the stability criteria for cubic system.

Silicide surface phases on gold

NASA Technical Reports Server (NTRS)

Green, A. K.; Bauer, E.

1981-01-01

The crystalline silicide layers formed on (111) and (100) surfaces of Au films on various Si single-crystal substrates are studied by LEED and AES in conjunction with sputter-depth profiling as a function of annealing temperature. On the (111) surface, three basic silicide structures are obtained corresponding to layers of various thicknesses as obtained by different preparation conditions. The (100) surface shows only two different structures. None of the structures is compatible with the various bulk silicide structures deduced from X-ray diffraction. Using LEED as a criterion for the presence or absence of silicide on the surface, smaller layer thicknesses are obtained than reported previously on the basis of AES studies.

Studies on the growth, structural, optical, mechanical properties of 8-hydroxyquinoline single crystal by vertical Bridgman technique

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

Prabhakaran, SP.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in; Velusamy, P.

2011-11-15

Highlights: {yields} Growth of bulk single crystal of 8-hydroxyquinoline (8-HQ) by vertical Bridgman technique for the first time. {yields} The crystalline perfection is reasonably good. {yields} The photoluminescence spectrum shows that the material is suitable for blue light emission. -- Abstract: Single crystal of organic nonlinear optical material, 8-hydroxyquinoline (8-HQ) of dimension 52 mm (length) x 12 mm (dia.) was grown from melt using vertical Bridgman technique. The crystal system of the material was confirmed by powder X-ray diffraction analysis. The crystalline perfection of the grown crystal was examined by high-resolution X-ray diffraction study. Low angular spread around 400'' ofmore » the diffraction curve and the low full width half maximum values show that the crystalline perfection is reasonably good. The recorded photoluminescence spectrum shows that the material is suitable for blue light emission. Optical transmittance for the UV and visible region was measured and mechanical strength was estimated from Vicker's microhardness test along the growth face of the grown crystal.« less

Quantitative crystallinity determination for E1010, a novel carbapenem antibiotic, using differential scanning calorimetry.

PubMed

Kushida, Ikuo

2012-03-01

The objective of this study was to develop a quantitative crystallinity analysis method for the bulk drug of E1010 ((+)-(4R,5S,6S)-6-[(R)-1-hydroxyethyl]-3-[(2S,4S)-2-[(R)-1-hydroxy-1-[(R)-pyrrolidin-3 -yl]methyl]pyrrolidin-4-yl]thio-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid monohydrochloride), a novel carbapenem antibiotic. X-ray analyses, thermal analyses and hygroscopicity measurements were used to elucidate the crystal structure and the solid state properties. To develop a quantitative method for the crystallinity of E1010 bulk drug, the relationship between enthalpy change obtained by differential scanning calorimetry (DSC) and crystalline form ratio was investigated. E1010 bulk drug was found to exist in a crystalline trihydrate formed in two layers, i.e. a layer of E1010 free form, and a layer consisting of chloride ions and water molecules. The thermal analysis showed an endothermic peak derived from dehydration with the loss of crystal lattices at around 100°C as an onset. The enthalpy change value for the endothermic peak correlated well with crystalline content in binary physical mixtures of the crystalline trihydrate and the amorphous form. In addition, for nine lots of the bulk drug, a positive correlation between the enthalpy change and chemical stability in the solid state was observed. This quantitative analysis of crystallinity using DSC could be applicable for the quality control of the bulk drug to detect variability among manufacturing batches and to estimate the chemical stability of partially amorphous samples. © 2011 The Author. JPP © 2011 Royal Pharmaceutical Society.

Synthesis and solid-state characterisation of 4-substituted methylidene oxindoles

PubMed Central

2013-01-01

Background 4-substituted methylidene oxindoles are pharmacologically important. Detailed analysis and comparison of all the interactions present in crystal structures is necessary to understand how these structures arise. The XPac procedure allows comparison of complete crystal structures of related families of compounds to identify assemblies that are mainly the result of close-packing as well as networks of directed interactions. Results Five 4-substituted methylidene oxindoles have been synthesized by the Knoevenagel condensation of oxindole with para-substituted aromatic aldehydes and were characterized in the solid state by x-ray crystallography. Hence, the structures of (3E)-3-(4-Bromobenzylidene)-1,3-dihydro-2H-indol-2-one, 3a, (3E)-3-(4-Chlorobenzylidene)-1,3-dihydro-2H-indol-2-one, 3b, (3E)-3-(4-Methoxybenzylidene)-1,3-dihydro-2H-indol-2-one, 3c, (3E)-3-(4-Methylbenzylidene)-1,3-dihydro-2H-indol-2-one, 3d and (3E)-3-(4-Nitrobenzylidene)-1,3-dihydro-2H-indol-2-one, 3e, were elucidated using single crystal X-ray crystallography. Conclusions A hydrogen bonded dimer molecular assembly or supramolecular construct was identified in all the crystal structures examined along with a further four 1D supramolecular constructs which were common to at least two of the family of structures studied. The 1D supramolecular constructs indicate that once the obvious strong interaction is satisfied to form hydrogen bonded dimer it is the conventionally weaker interactions, such as steric bulk and edge-to-face interactions which compete to influence the final structure formation. PMID:24517531

Electrochemical Induced Calcium Phosphate Precipitation: Importance of Local pH

PubMed Central

2017-01-01

Phosphorus (P) is an essential nutrient for living organisms and cannot be replaced or substituted. In this paper, we present a simple yet efficient membrane free electrochemical system for P removal and recovery as calcium phosphate (CaP). This method relies on in situ formation of hydroxide ions by electro mediated water reduction at a titanium cathode surface. The in situ raised pH at the cathode provides a local environment where CaP will become highly supersaturated. Therefore, homogeneous and heterogeneous nucleation of CaP occurs near and at the cathode surface. Because of the local high pH, the P removal behavior is not sensitive to bulk solution pH and therefore, efficient P removal was observed in three studied bulk solutions with pH of 4.0 (56.1%), 8.2 (57.4%), and 10.0 (48.4%) after 24 h of reaction time. While P removal efficiencies are not generally affected by bulk solution pH, the chemical-physical properties of CaP solids collected on the cathode are still related to bulk solution pH, as confirmed by structure characterizations. High initial solution pH promotes the formation of more crystalline products with relatively high Ca/P molar ratio. The Ca/P molar ratio increases from 1.30 (pH 4.0) to 1.38 (pH 8.2) and further increases to 1.55 (pH 10.0). The formation of CaP precipitates was a typical crystallization process, with an amorphous phase formed at the initial stage which then transforms to the most stable crystal phase, hydroxyapatite, which is inferred from the increased Ca/P molar ratio from 1.38 (day 1) to the theoretical 1.76 (day 11) and by the formation of needle-like crystals. Finally, we demonstrated the efficiency of this system for real wastewater. This, together with the fact that the electrochemical method can work at low bulk pH, without dosing chemicals and a need for a separation process, highlights the potential application of the electrochemical method for P removal and recovery. PMID:28872838

Development of an Evolutionary Algorithm for the ab Initio Discovery of Two-Dimensional Materials

NASA Astrophysics Data System (ADS)

Revard, Benjamin Charles

Crystal structure prediction is an important first step on the path toward computational materials design. Increasingly robust methods have become available in recent years for computing many materials properties, but because properties are largely a function of crystal structure, the structure must be known before these methods can be brought to bear. In addition, structure prediction is particularly useful for identifying low-energy structures of subperiodic materials, such as two-dimensional (2D) materials, which may adopt unexpected structures that differ from those of the corresponding bulk phases. Evolutionary algorithms, which are heuristics for global optimization inspired by biological evolution, have proven to be a fruitful approach for tackling the problem of crystal structure prediction. This thesis describes the development of an improved evolutionary algorithm for structure prediction and several applications of the algorithm to predict the structures of novel low-energy 2D materials. The first part of this thesis contains an overview of evolutionary algorithms for crystal structure prediction and presents our implementation, including details of extending the algorithm to search for clusters, wires, and 2D materials, improvements to efficiency when running in parallel, improved composition space sampling, and the ability to search for partial phase diagrams. We then present several applications of the evolutionary algorithm to 2D systems, including InP, the C-Si and Sn-S phase diagrams, and several group-IV dioxides. This thesis makes use of the Cornell graduate school's "papers" option. Chapters 1 and 3 correspond to the first-author publications of Refs. [131] and [132], respectively, and chapter 2 will soon be submitted as a first-author publication. The material in chapter 4 is taken from Ref. [144], in which I share joint first-authorship. In this case I have included only my own contributions.

On the induction of homogeneous bulk crystallization in Eu-doped calcium aluminosilicate glass by applying simultaneous high pressure and temperature

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

Muniz, R. F., E-mail: robsonfmuniz@yahoo.com.br; Departamento de Física, Universidade Estadual de Maringá, 87020900, Maringá, PR; Ligny, D. de

2016-06-28

From initial calcium aluminosilicate glass, transparent glass-ceramics have been successfully synthesized under simultaneous high pressure and temperature (SHPT). Possible homogeneous volumetric crystallization of this glassy system, which was not achieved previously by means of conventional heat treatment, has been put in evidence with a SHPT procedure. Structural, mechanical, and optical properties of glass and glass-ceramic obtained were investigated. Raman spectroscopy and X-ray diffraction allowed to identify two main crystalline phases: merwinite [Ca{sub 3}Mg(SiO{sub 4}){sub 2}] and diopside [CaMgSi{sub 2}O{sub 6}]. A Raman scanning profile showed that the formation of merwinite is quite homogeneous over the bulk sample. However, the samplemore » surface also contains significant diopside crystals. Instrumented Berkovich nanoindentation was applied to determine the effect of SHPT on hardness from glass to glass-ceramic. For Eu-doped samples, the broadband emission due to 4f{sup 6}5d{sup 1} → 4f{sup 7} transition of Eu{sup 2+} was studied in both host systems. Additionally, the {sup 5}D{sub 0} → {sup 7}F{sub J} transition of Eu{sup 3+} was used as an environment probe in the pristine glass and the glass-ceramic.« less

Effect of Copper and Zirconium Addition on Properties of Fe-Co-Si-B-Nb Bulk Metallic Glasses

NASA Astrophysics Data System (ADS)

Ikram, Haris; Khalid, Fazal Ahmad; Akmal, Muhammad; Abbas, Zameer

2017-07-01

In this research work, iron-based bulk metallic glasses (BMGs) have been fabricated, characterized and compared with Fe-Si alloy. BMG alloys of composition ((Fe0.6Co0.4)0.75B0.20Si0.05)96Nb4) were synthesized by suction casting technique using chilled copper die. Effect of copper and zirconium addition on magnetic, mechanical, thermal and electrochemical behavior of ((Fe0.6Co0.4)0.75B0.20Si0.05)96Nb4 BMGs was investigated. Furthermore, effect of annealing on nano-crystallization and subsequently on magnetic and mechanical behavior was also analyzed. Amorphousness of structure was evidenced by XRD analysis and microscopic visualization, whereas nano-crystallization behavior was identified by peak broadening of XRD patterns. Magnetic properties, measured by vibrating sample magnetometer, were found to be improved for as-cast BMG alloys by copper addition and further enhanced by nano-crystallization after annealing. Mechanical properties were observed to be increased by zirconium addition while slightly declined by copper addition. Potentiodynamic polarization analysis manifested the positive role of zirconium in enhancing corrosion resistance of BMGs in acidic, basic and brine mediums. Moreover, mechanical properties and corrosion analysis results affirmed the superiority of BMG alloys over Fe-Si alloy.

Ab initio DFT+U study of He atom incorporation into UO(2) crystals.

PubMed

Gryaznov, Denis; Heifets, Eugene; Kotomin, Eugene

2009-09-07

We present and discuss results of the density functional theory (DFT) for perfect UO(2) crystals with He atoms in octahedral interstitial positions therein. We have calculated basic bulk crystal properties and He incorporation energies into the low temperature anti-ferromagnetic UO(2) phase using several exchange-correlation functionals within the spin-polarized local density (LDA) and generalized gradient (GGA) approximations. In all DFT calculations we included the on-site correlation corrections using the Hubbard model (DFT+U approach). We analysed a potential crystalline symmetry reduction from tetragonal down to orthorhombic structure and confirmed the presence of the Jahn-Teller effect in a perfect UO(2). We discuss also the problem of a conducting electronic state arising when He is placed into a tetragonal antiferromagnetic phase of UO(2) commonly used in defect modelling. Consequently, we found a specific monoclinic lattice distortion which allowed us to restore the semiconducting state and properly estimate He incorporation energies. Unlike the bulk properties, the He incorporation energy strongly depends on several factors, including the supercell size, the use of spin polarization, the exchange-correlation functionals and on-site correlation corrections. We compare our results for the He incorporation with the previous shell model and ab initio DFT calculations.

A quantized microwave quadrupole insulator with topologically protected corner states

NASA Astrophysics Data System (ADS)

Peterson, Christopher W.; Benalcazar, Wladimir A.; Hughes, Taylor L.; Bahl, Gaurav

2018-03-01

The theory of electric polarization in crystals defines the dipole moment of an insulator in terms of a Berry phase (geometric phase) associated with its electronic ground state. This concept not only solves the long-standing puzzle of how to calculate dipole moments in crystals, but also explains topological band structures in insulators and superconductors, including the quantum anomalous Hall insulator and the quantum spin Hall insulator, as well as quantized adiabatic pumping processes. A recent theoretical study has extended the Berry phase framework to also account for higher electric multipole moments, revealing the existence of higher-order topological phases that have not previously been observed. Here we demonstrate experimentally a member of this predicted class of materials—a quantized quadrupole topological insulator—produced using a gigahertz-frequency reconfigurable microwave circuit. We confirm the non-trivial topological phase using spectroscopic measurements and by identifying corner states that result from the bulk topology. In addition, we test the critical prediction that these corner states are protected by the topology of the bulk, and are not due to surface artefacts, by deforming the edges of the crystal lattice from the topological to the trivial regime. Our results provide conclusive evidence of a unique form of robustness against disorder and deformation, which is characteristic of higher-order topological insulators.

Mesoscale hybrid calibration artifact

DOEpatents

Tran, Hy D.; Claudet, Andre A.; Oliver, Andrew D.

2010-09-07

A mesoscale calibration artifact, also called a hybrid artifact, suitable for hybrid dimensional measurement and the method for make the artifact. The hybrid artifact has structural characteristics that make it suitable for dimensional measurement in both vision-based systems and touch-probe-based systems. The hybrid artifact employs the intersection of bulk-micromachined planes to fabricate edges that are sharp to the nanometer level and intersecting planes with crystal-lattice-defined angles.

Electronic shell structure in Ga12 icosahedra and the relation to the bulk forms of gallium.

PubMed

Schebarchov, D; Gaston, N

2012-07-28

The electronic structure of known cluster compounds with a cage-like icosahedral Ga(12) centre is studied by first-principles theoretical methods, based on density functional theory. We consider these hollow metalloid nanostructures in the context of the polymorphism of the bulk, and identify a close relation to the α phase of gallium. This previously unrecognised connection is established using the electron localisation function, which reveals the ubiquitous presence of radially-pointing covalent bonds around the Ga(12) centre--analogous to the covalent bonds between buckled deltahedral planes in α-Ga. Furthermore, we find prominent superatom shell structure in these clusters, despite their hollow icosahedral motif and the presence of covalent bonds. The exact nature of the electronic shell structure is contrasted with simple electron shell models based on jellium, and we demonstrate how the interplay between gallium dimerisation, ligand- and crystal-field effects can alter the splitting of the partially filled 1F shell. Finally, in the unique compound where the Ga(12) centre is bridged by six phosphorus ligands, the electronic structure most closely resembles that of δ-Ga and there are no well-defined superatom orbitals. The results of this comprehensive study bring new insights into the nature of chemical bonding in metalloid gallium compounds and the relation to bulk gallium metal, and they may also guide the development of more general models for ligand-protected clusters.

TEM study of {beta} Prime precipitate interaction mechanisms with dislocations and {beta} Prime interfaces with the aluminium matrix in Al-Mg-Si alloys

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

Teichmann, Katharina; Marioara, Calin D.; Andersen, Sigmund J.

The interaction mechanisms between dislocations and semi-coherent, needle-shaped {beta} Prime precipitates in Al-Mg-Si alloys have been studied by High Resolution Transmission Electron Microscopy (HRTEM). Dislocation loops appearing as broad contrast rings around the precipitate cross-sections were identified in the Al matrix. A size dependency of the interaction mechanism was observed; the precipitates were sheared when the longest dimension of their cross-section was shorter than approximately 15 nm, and looped otherwise. A more narrow ring located between the Al matrix and bulk {beta} Prime indicates the presence of a transition interface layer. Together with the bulk {beta} Prime structure, this wasmore » further investigated by High Angle Annular Dark Field Scanning TEM (HAADF-STEM). In the bulk {beta} Prime a higher intensity could be correlated with a third of the Si-columns, as predicted from the published structure. The transition layer incorporates Si columns in the same arrangement as in bulk {beta} Prime , although it is structurally distinct from it. The Z-contrast information and arrangement of these Si-columns demonstrate that they are an extension of the Si-network known to structurally connect all the precipitate phases in the Al-Mg-Si(-Cu) system. The width of the interface layer was estimated to about 1 nm. - Highlights: Black-Right-Pointing-Pointer {beta} Prime is found to be looped at sizes larger than 15 nm (cross section diameter). Black-Right-Pointing-Pointer {beta} Prime is found to be sheared at sizes smaller than 15 nm (cross section diameter). Black-Right-Pointing-Pointer The recently determined crystal structure of {beta} Prime is confirmed by HAADF-STEM. Black-Right-Pointing-Pointer Between {beta} Prime and the Al-matrix a transition layer of about 1 nm is existent. Black-Right-Pointing-Pointer The {beta} Prime /matrix layer is structurally distinct from bulk {beta} Prime and the aluminium matrix.« less

In-Depth View of the Structure and Growth of SnO2 Nanowires and Nanobrushes.

PubMed

Stuckert, Erin P; Geiss, Roy H; Miller, Christopher J; Fisher, Ellen R

2016-08-31

Strategic application of an array of complementary imaging and diffraction techniques is critical to determine accurate structural information on nanomaterials, especially when also seeking to elucidate structure-property relationships and their effects on gas sensors. In this work, SnO2 nanowires and nanobrushes grown via chemical vapor deposition (CVD) displayed the same tetragonal SnO2 structure as revealed via powder X-ray diffraction bulk crystallinity data. Additional characterization using a range of electron microscopy imaging and diffraction techniques, however, revealed important structure and morphology distinctions between the nanomaterials. Tailoring scanning transmission electron microscopy (STEM) modes combined with transmission electron backscatter diffraction (t-EBSD) techniques afforded a more detailed view of the SnO2 nanostructures. Indeed, upon deeper analysis of individual wires and brushes, we discovered that, despite a similar bulk structure, wires and brushes grew with different crystal faces and lattice spacings. Had we not utilized multiple STEM diffraction modes in conjunction with t-EBSD, differences in orientation related to bristle density would have been overlooked. Thus, it is only through a methodical combination of several structural analysis techniques that precise structural information can be reliably obtained.

Three-dimensional magnetic critical behavior in CrI 3

DOE PAGES

Liu, Yu; Petrovic, C.

2018-01-18

CrI 3 is a promising candidate for the van der Waals bonded ferromagnetic devices since its ferromagnetism can be maintained upon exfoliating of bulk crystals down to single layer. In this work we studied critical properties of bulk CrI 3 single crystals around the paramagnetic to ferromagnetic phase transition. Critical exponents β= 0.260(4) with a critical temperature T c= 60.05(13) K and γ= 1.136(6) with T c= 60.43(4) K are obtained by the Kouvel-Fisher method, whereas δ= 5.32(2) is obtained by a critical isotherm analysis at T c= 60 K. In conclusion, the critical exponents determined in bulk CrI 3more » single crystals suggest a three-dimensional long-range magnetic coupling with the exchange distance decaying as J(r)≈r -4:69« less

Annealing induced structural changes in amorphous Co{sub 23}Fe{sub 60}B{sub 17} film on Mo buffer layer

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

Dwivedi, Jagrati, E-mail: jdwivedi.phy@gmail.com; Mishra, Ashutosh; Gupta, Ranjeeta

2016-05-23

Structural changes occurring in a thin amorphous Co{sub 23}Fe{sub 60}B{sub 17} film sandwiched between two Mo layers, as a function of thermal annealing has been studied. Thermal stability of the Co{sub 23}Fe{sub 60}B{sub 17} film is found to be significantly lower than the bulk ribbons. SIMS measurements show that during crystallization, boron which is expelled out of the crystallites, has a tendency to move towards the surface. No significant diffusion of boron in Mo buffer layer is observed. This result is in contrast with some earlier studies where it was proposed that the role of buffer layer of refractory metalmore » is to absorb boron which is expelled out of the bcc FeCo phase during crystallization.« less

Effect of the Crystal Structure on the Electrical Properties of Thin-Film PZT Structures

NASA Astrophysics Data System (ADS)

Delimova, L. A.; Gushchina, E. V.; Zaitseva, N. V.; Seregin, D. S.; Vorotilov, K. A.; Sigov, A. S.

2018-03-01

A new method of two-stage crystallization of lead zirconate-titanate (PZT) films using a seed sublayer with a low excess lead content has been proposed and realized. A seed layer with a strong texture of perovskite Pe(111) grains is formed from a solution with a lead excess of 0-5 wt %; the fast growth of the grains is provided by the deposition of the main film from a solution with high lead content. As a result, a strong Pe(111) texture with complete suppression of the Pe(100) orientation forms. An analysis of current-voltage dependences of the transient currents and the distributions of the local conductivity measured by the contact AFM method reveals two various mechanisms of current percolation that are determined by traps in the bulk and at the perovskite grain interfaces.

Robust manipulation of light using topologically protected plasmonic modes.

PubMed

Liu, Chenxu; Gurudev Dutt, M V; Pekker, David

2018-02-05

We propose using a topological plasmonic crystal structure composed of an array of nearly parallel nanowires with unequal spacing for manipulating light. In the paraxial approximation, the Helmholtz equation that describes the propagation of light along the nanowires maps onto the Schrödinger equation of the Su-Schrieffer-Heeger (SSH) model. Using a full three-dimensional finite difference time domain solution of the Maxwell equations, we verify the existence of topological defect modes, with sub-wavelength localization, bound to domain walls of the plasmonic crystal. We show that by manipulating domain walls we can construct spatial mode filters that couple bulk modes to topological defect modes, and topological beam-splitters that couple two topological defect modes. Finally, we show that the structures are tolerant to fabrication errors with an inverse length-scale smaller than the topological band gap.

Crystallization Kinetics of Barium and Strontium Aluminosilicate Glasses of Feldspar Composition

NASA Technical Reports Server (NTRS)

Hyatt, Mark J.; Bansal, Narottam P.

1994-01-01

Crystallization kinetics of BaO.Al2O3.2SiO2 (BAS) and SrO.Al2O3.2SiO2 (SAS) glasses in bulk and powder forms have been studied by non-isothermal differential scanning calorimetry (DSC). The crystal growth activation energies were evaluated to be 473 and 451 kJ/mol for bulk samples and 560 and 534 kJ/mol for powder specimens in BAS and SAS glasses, respectively. Development of crystalline phases on thermal treatments of glasses at various temperatures has been followed by powder x-ray diffraction. Powder samples crystallized at lower temperatures than the bulk and the crystallization temperature was lower for SAS glass than BAS. Crystallization in both glasses appeared to be surface nucleated. The high temperature phase hexacelsian, MAl2Si2O8 (M = Ba or Sr), crystallized first by nucleating preferentially on the glass surface. Also, monoclinic celsian does not nucleate directly in the glass, but is formed at higher temperatures from the transformation of the metastable hexagonal phase. In SAS the transformation to monoclinic celsian occurred rapidly after 1 h at 1100 C. In contrast, in BAS this transformation is sluggish and difficult and did not go to completion even after 10 h heat treatment at 1400 C. The crystal growth morphologies in the glasses have been observed by optical microscopy. Some of the physical properties of the two glasses are also reported.

Nanoparticles in liquid crystals, and liquid crystals in nanoparticles

NASA Astrophysics Data System (ADS)

de Pablo, Juan

2015-03-01

Liquid crystals are remarkably sensitive to interfacial interactions. Small perturbations at a liquid crystal interface, for example, can be propagated over relatively long length scales, thereby providing the basis for a wide range of applications that rely on amplification of molecular events into macroscopic observables. Our recent research efforts have focused on the reverse phenomenon; that is, we have sought to manipulate the interfacial assembly of nanoparticles or the organization of surface active molecules by controlling the structure of a liquid crystal. This presentation will consist of a review of the basic principles that are responsible for liquid crystal-mediated interactions, followed by demonstrations of those principles in the context of two types of systems. In the first, a liquid crystal is used to direct the assembly of nanoparticles; through a combination of molecular and continuum models, it is found that minute changes in interfacial energy and particle size lead to liquid-crystal induced attractions that can span multiple orders of magnitude. Theoretical predictions are confirmed by experimental observations, which also suggest that LC-mediated assembly provides an effective means for fabrication of plasmonic devices. In the second type of system, the structure of a liquid crystal is controlled by confinement in submicron droplets. The morphology of the liquid crystal in a drop depends on a delicate balance between bulk and interfacial contributions to the free energy; that balance can be easily perturbed by adsorption of analytes or nanoparticles at the interface, thereby providing the basis for development of hierarchical assembly of responsive, anisotropic materials. Theoretical predictions also indicate that the three-dimensional order of a liquid crystal can be projected onto a two-dimensional interface, and give rise to novel nanostructures that are not found in simple isotropic fluids.

Chemical disorder influence on magnetic state of optimally-doped La0.7Ca0.3MnO3

NASA Astrophysics Data System (ADS)

Rozenberg, E.; Auslender, M.; Shames, A. I.; Jung, G.; Felner, I.; Tsindlekht, M. I.; Mogilyansky, D.; Sominski, E.; Gedanken, A.; Mukovskii, Ya. M.; Gorodetsky, G.

2011-10-01

X-band electron magnetic resonance and dc/ac magnetic measurements have been employed to study the effects of chemical disorder on magnetic ordering in bulk and nanometer-sized single crystals and bulk ceramics of optimally-doped La0.7Ca0.3MnO3 manganite. The magnetic ground state of bulk samples appeared to be ferromagnetic with the lower Curie temperature and higher magnetic homogeneity in the vicinity of the ferromagnetic-paramagnetic phase transition in the crystal, as compared with those characteristics in the ceramics. The influence of technological driven "macroscopic" fluctuations of Ca-dopant level in crystal and "mesoscopic" disorder within grain boundary regions in ceramics was proposed to be responsible for these effects. Surface spin disorder together with pronounced inter-particle interactions within agglomerated nano-sample results in well defined core/shell spin configuration in La0.7Ca0.3MnO3 nano-crystals. The analysis of the electron paramagnetic resonance data enlightened the reasons for the observed difference in the magnetic order. Lattice effects dominate the first-order nature of magnetic phase transition in bulk samples. However, mesoscale chemical disorder seems to be responsible for the appearance of small ferromagnetic polarons in the paramagnetic state of bulk ceramics. The experimental results and their analysis indicate that a chemical/magnetic disorder has a strong impact on the magnetic state even in the case of mostly stable optimally hole-doped manganites.

Direct Observation of Twisted Surface skyrmions in Bulk Crystals

NASA Astrophysics Data System (ADS)

Zhang, S. L.; van der Laan, G.; Wang, W. W.; Haghighirad, A. A.; Hesjedal, T.

2018-06-01

Magnetic skyrmions in noncentrosymmetric helimagnets with Dn symmetry are Bloch-type magnetization swirls with a helicity angle of ±9 0 ° . At the surface of helimagnetic thin films below a critical thickness, a twisted skyrmion state with an arbitrary helicity angle has been proposed; however, its direct experimental observation has remained elusive. Here, we show that circularly polarized resonant elastic x-ray scattering is able to unambiguously measure the helicity angle of surface skyrmions, providing direct experimental evidence that a twisted skyrmion surface state also exists in bulk systems. The exact surface helicity angles of twisted skyrmions for both left- and right-handed chiral bulk Cu2 OSeO3 , in the single as well as in the multidomain skyrmion lattice state, are determined, revealing their detailed internal structure. Our findings suggest that a skyrmion surface reconstruction is a universal phenomenon, stemming from the breaking of translational symmetry at the interface.

KDP crystal doped with L-arginine amino acid: growth, structure perfection, optical and strength characteristics

NASA Astrophysics Data System (ADS)

Pritula, I. M.; Kostenyukova, E. I.; Bezkrovnaya, O. N.; Kolybaeva, M. I.; Sofronov, D. S.; Dolzhenkova, E. F.; Kanaev, A.; Tsurikov, V.

2016-07-01

Potassium Dihydrogen Phosphate (KDP) crystal doped with L-arginine (L-arg) amino acid with 1.4 wt% concentration in the solution was grown onto a point seed by the method of temperature reduction. For the first time an attempt was made to grow large-size (7 × 6 × 8 cm3) optically transparent crystals, which allowed to analyze the effect of L-arg additive on the physical properties of the different growth sectors ({100} and {101}) of KDP. The incorporation of L-arg into both growth sectors of the crystal was confirmed by the methods of optical and IR spectroscopy and found to be caused by the ability of the amino acid to form hydrogen bonds with the face {100} and electrostatically interact with the positively charged face {101} of KDP crystal. A slight variation in the unit cell parameters was reported, the elementary cell volume of KDP:L-arg crystal increased in comparison with the one of pure KDP by 2·10-2 and 2.07·10-2 Å3 in the sectors {100} and {101}, respectively. It was found that the doping of L-arg enhanced the SHG efficiency of KDP and depended on the crystal growth sectors. The SHG efficiency of KDP:L-arg was by a factor 2.53 and 3.95 higher in comparison with those of pure KDP for {101} and {100} growth sector, respectively. The doping was found to lead to softening of both faces by ∼3-10% and ∼14-17% in the sectors {101} and {100}, respectively. Investigation of the influence of L-arg molecules on the bulk laser damage threshold of the crystals showed that the bulk laser damage threshold of the samples of KDP:L-arg crystal was higher than the one of the pure crystal in the sector {101} and lower in the sector {100}. The correlation between microhardness and laser damage threshold were discussed. The study is helpful for further searching, designing and simulation of hybrid NLO materials.

Defect formation energy in pyrochlore: the effect of crystal size

NASA Astrophysics Data System (ADS)

Wang, Jianwei; Ewing, Rodney C.; Becker, Udo

2014-09-01

Defect formation energies of point defects of two pyrochlores Gd2Ti2O7 and Gd2Zr2O7 as a function of crystal size were calculated. Density functional theory with plane-wave basis sets and the projector-augmented wave method were used in the calculations. The results show that the defect formation energies of the two pyrochlores diverge as the size decreases to the nanometer range. For Gd2Ti2O7 pyrochlore, the defect formation energy is higher at nanometers with respect to that of the bulk, while it is lower for Gd2Zr2O7. The lowest defect formation energy for Gd2Zr2O7 is found at 15-20 Å. The different behaviors of the defect formation energies as a function of crystal size are caused by different structural adjustments around the defects as the size decreases. For both pyrochlore compositions at large sizes, the defect structures are similar to those of the bulk. As the size decreases, for Gd2Ti2O7, additional structure distortions appear at the surfaces, which cause the defect formation energy to increase. For Gd2Zr2O7, additional oxygen Frenkel pair defects are introduced, which reduce the defect formation energy. As the size further decreases, increased structure distortions occur at the surfaces, which cause the defect formation energy to increase. Based on a hypothesis that correlates the energetics of defect formation and radiation response for complex oxides, the calculated results suggest that at nanometer range Gd2Ti2O7 pyrochlore is expected to have a lower radiation tolerance, and those of Gd2Zr2O7 pyrochlore to have a higher radiation tolerance. The highest radiation tolerance for Gd2Zr2O7 pyrochlore is expected to be found at ˜2 nanometers.

The steady-state and transient electron transport within bulk zinc-blende indium nitride: The impact of crystal temperature and doping concentration variations

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

Siddiqua, Poppy; O'Leary, Stephen K., E-mail: stephen.oleary@ubc.ca

2016-03-07

Within the framework of a semi-classical three-valley Monte Carlo electron transport simulation approach, we analyze the steady-state and transient aspects of the electron transport within bulk zinc-blende indium nitride, with a focus on the response to variations in the crystal temperature and the doping concentration. We find that while the electron transport associated with zinc-blende InN is highly sensitive to the crystal temperature, it is not very sensitive to the doping concentration selection. The device consequences of these results are then explored.

In-situ study of crystallization kinetics in ternary bulk metallic glass alloys with different glass forming abilities

DOE PAGES

Lan, Si; Wei, Xiaoya; Zhou, Jie; ...

2014-11-18

In-situ transmission electron microcopy and time-resolved neutron diffraction were used to study crystallization kinetics of two ternary bulk metallic glasses during isothermal annealing in the supercooled liquid region. It is found that the crystallization of Zr 56Cu 36Al 8, an average glass former, follows continuous nucleation and growth, while that of Zr 46Cu 46Al 8, a better glass former, is characterized by site-saturated nucleation, followed by slow growth. Possible mechanisms for the observed differences and the relationship to the glass forming ability are discussed.

Two-dimensional photonic crystal slab nanocavities on bulk single-crystal diamond

NASA Astrophysics Data System (ADS)

Wan, Noel H.; Mouradian, Sara; Englund, Dirk

2018-04-01

Color centers in diamond are promising spin qubits for quantum computing and quantum networking. In photon-mediated entanglement distribution schemes, the efficiency of the optical interface ultimately determines the scalability of such systems. Nano-scale optical cavities coupled to emitters constitute a robust spin-photon interface that can increase spontaneous emission rates and photon extraction efficiencies. In this work, we introduce the fabrication of 2D photonic crystal slab nanocavities with high quality factors and cubic wavelength mode volumes—directly in bulk diamond. This planar platform offers scalability and considerably expands the toolkit for classical and quantum nanophotonics in diamond.

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

DOE PAGES

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung; ...

2017-04-25

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

Room-temperature spin-orbit torque in NiMnSb

NASA Astrophysics Data System (ADS)

Ciccarelli, C.; Anderson, L.; Tshitoyan, V.; Ferguson, A. J.; Gerhard, F.; Gould, C.; Molenkamp, L. W.; Gayles, J.; Železný, J.; Šmejkal, L.; Yuan, Z.; Sinova, J.; Freimuth, F.; Jungwirth, T.

2016-09-01

Materials that crystallize in diamond-related lattices, with Si and GaAs as their prime examples, are at the foundation of modern electronics. Simultaneously, inversion asymmetries in their crystal structure and relativistic spin-orbit coupling led to discoveries of non-equilibrium spin-polarization phenomena that are now extensively explored as an electrical means for manipulating magnetic moments in a variety of spintronic structures. Current research of these relativistic spin-orbit torques focuses primarily on magnetic transition-metal multilayers. The low-temperature diluted magnetic semiconductor (Ga, Mn)As, in which spin-orbit torques were initially discovered, has so far remained the only example showing the phenomenon among bulk non-centrosymmetric ferromagnets. Here we present a general framework, based on the complete set of crystallographic point groups, for identifying the potential presence and symmetry of spin-orbit torques in non-centrosymmetric crystals. Among the candidate room-temperature ferromagnets we chose to use NiMnSb, which is a member of the broad family of magnetic Heusler compounds. By performing all-electrical ferromagnetic resonance measurements in single-crystal epilayers of NiMnSb we detect room-temperature spin-orbit torques generated by effective fields of the expected symmetry and of a magnitude consistent with our ab initio calculations.

Altering the Polymorphic Accessibility of Polycyclic Aromatic Hydrocarbons with Fluorination

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

Hiszpanski, Anna M.; Woll, Arthur R.; Kim, Bumjung

Here, substituting hydrogen with fluorine is an extensively employed strategy to improve the macroscopic properties of compounds for use in fields as diverse as pharmaceutics and optoelectronics. The role fluorine substitution plays on polymorphism—the ability of a compound to adopt more than one crystal structure—has not been previously studied. Yet, this understanding is important as different polymorphs of the same compound can result in drastically different bulk properties (e.g., solubility, absorptivity, and conductivity). Strategies to either promote or suppress the crystallization of particular polymorphs are thus desired. Here, we show that substituting hydrogen with fluorine affects the polymorphic behavior ofmore » contorted hexabenzocoronene (cHBC). A polycyclic aromatic hydrocarbon and molecular semiconductor, cHBC exhibits two polymorphs (i.e., P2 1/c crystal structure which we refer to as polymorph I and a triclinic crystal structure which we refer to as polymorph II) that are accessible through postdeposition processing of amorphous films. While the same two polymorphs remain accessible in fluorinated derivatives of cHBC, fluorination appears to favor the formation of polymorph I, with progressively smaller energy barrier for transformation from polymorph II to polymorph I with fluorination.« less

Synchrotron powder X-ray diffraction and structural analysis of Eu0.5La0.5FBiS2-x Se x

NASA Astrophysics Data System (ADS)

Nagasaka, K.; Jinno, G.; Miura, O.; Miura, A.; Moriyoshi, C.; Kuroiwa, Y.; Mizuguchi, Y.

2017-07-01

Eu0.5La0.5FBiS2-x Se x is a new BiS2-based superconductor system. In Eu0.5La0.5FBiS2-x Se x , electron carriers are doped to the BiS2 layer by the substitution of Eu by La. Bulk superconductivity in this system is induced by increasing the in-plane chemical pressure, which is controlled by the Se concentration (x). In this study, we have analysed the crystal structure of Eu0.5La0.5FBiS2-x Se x using synchrotron powder diffraction and the Rietveld refinement. The precise determination of the structural parameters and thermal factors suggest that the emergence of bulk superconductivity in Eu0.5La0.5FBiS2-x Se x is achieved by the enhanced in-plane chemical pressure and the decrease in in-plane disorder.

High-pressure structural, elastic, and electronic properties of the scintillator host material KMgF3

NASA Astrophysics Data System (ADS)

Vaitheeswaran, G.; Kanchana, V.; Kumar, Ravhi S.; Cornelius, A. L.; Nicol, M. F.; Svane, A.; Delin, A.; Johansson, B.

2007-07-01

The high-pressure structural behavior of the fluoroperovskite KMgF3 is investigated by theory and experiment. Density functional calculations were performed within the local density approximation and the generalized gradient approximation for exchange and correlation effects, as implemented within the full-potential linear muffin-tin orbital method. In situ high-pressure powder x-ray diffraction experiments were performed up to a maximum pressure of 40GPa using synchrotron radiation. We find that the cubic Pm3¯m crystal symmetry persists throughout the pressure range studied. The calculated ground state properties—the equilibrium lattice constant, bulk modulus, and elastic constants—are in good agreement with experimental results. By analyzing the ratio between the bulk and shear moduli, we conclude that KMgF3 is brittle in nature. Under ambient conditions, KMgF3 is found to be an indirect gap insulator, with the gap increasing under pressure.

Magnetic skin layer of NiO(100) probed by polarization-dependent spectromicroscopy

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

Mandal, Suman, E-mail: suman.mandal@sscu.iisc.ernet.in; Menon, Krishnakumar S. R., E-mail: krishna.menon@saha.ac.in; Belkhou, Rachid

2014-06-16

Using polarization-dependent x-ray photoemission electron microscopy, we have investigated the surface effects on antiferromagnetic (AFM) domain formation. Depth-resolved information obtained from our study indicates the presence of strain-induced surface AFM domains on some of the cleaved NiO(100) crystals, which are unusually thinner than bulk AFM domain wall widths (∼150 nm). Existence of such magnetic skin layer is substantiated by exchange-coupled ferromagnetic Fe domains in Fe/NiO(100), thereby evidencing the influence of this surface AFM domains on interfacial magnetic coupling. Our observations demonstrate a depth evolution of AFM structure in presence of induced surface strain, while the surface symmetry-breaking in absence of inducedmore » strain does not modify the bulk AFM domain structure. Realization of such thin surface AFM layer will provide better microscopic understanding of the exchange bias phenomena.« less

Valley photonic crystals for control of spin and topology

NASA Astrophysics Data System (ADS)

Dong, Jian-Wen; Chen, Xiao-Dong; Zhu, Hanyu; Wang, Yuan; Zhang, Xiang

2017-03-01

Photonic crystals offer unprecedented opportunity for light manipulation and applications in optical communication and sensing. Exploration of topology in photonic crystals and metamaterials with non-zero gauge field has inspired a number of intriguing optical phenomena such as one-way transport and Weyl points. Recently, a new degree of freedom, valley, has been demonstrated in two-dimensional materials. Here, we propose a concept of valley photonic crystals with electromagnetic duality symmetry but broken inversion symmetry. We observe photonic valley Hall effect originating from valley-dependent spin-split bulk bands, even in topologically trivial photonic crystals. Valley-spin locking behaviour results in selective net spin flow inside bulk valley photonic crystals. We also show the independent control of valley and topology in a single system that has been long pursued in electronic systems, resulting in topologically-protected flat edge states. Valley photonic crystals not only offer a route towards the observation of non-trivial states, but also open the way for device applications in integrated photonics and information processing using spin-dependent transportation.

Valley photonic crystals for control of spin and topology.

PubMed

Dong, Jian-Wen; Chen, Xiao-Dong; Zhu, Hanyu; Wang, Yuan; Zhang, Xiang

2017-03-01

Photonic crystals offer unprecedented opportunity for light manipulation and applications in optical communication and sensing. Exploration of topology in photonic crystals and metamaterials with non-zero gauge field has inspired a number of intriguing optical phenomena such as one-way transport and Weyl points. Recently, a new degree of freedom, valley, has been demonstrated in two-dimensional materials. Here, we propose a concept of valley photonic crystals with electromagnetic duality symmetry but broken inversion symmetry. We observe photonic valley Hall effect originating from valley-dependent spin-split bulk bands, even in topologically trivial photonic crystals. Valley-spin locking behaviour results in selective net spin flow inside bulk valley photonic crystals. We also show the independent control of valley and topology in a single system that has been long pursued in electronic systems, resulting in topologically-protected flat edge states. Valley photonic crystals not only offer a route towards the observation of non-trivial states, but also open the way for device applications in integrated photonics and information processing using spin-dependent transportation.

Phononic crystal diffraction gratings

NASA Astrophysics Data System (ADS)

Moiseyenko, Rayisa P.; Herbison, Sarah; Declercq, Nico F.; Laude, Vincent

2012-02-01

When a phononic crystal is interrogated by an external source of acoustic waves, there is necessarily a phenomenon of diffraction occurring on the external enclosing surfaces. Indeed, these external surfaces are periodic and the resulting acoustic diffraction grating has a periodicity that depends on the orientation of the phononic crystal. This work presents a combined experimental and theoretical study on the diffraction of bulk ultrasonic waves on the external surfaces of a 2D phononic crystal that consists of a triangular lattice of steel rods in a water matrix. The results of transmission experiments are compared with theoretical band structures obtained with the finite-element method. Angular spectrograms (showing frequency as a function of angle) determined from diffraction experiments are then compared with finite-element simulations of diffraction occurring on the surfaces of the crystal. The experimental results show that the diffraction that occurs on its external surfaces is highly frequency-dependent and has a definite relation with the Bloch modes of the phononic crystal. In particular, a strong influence of the presence of bandgaps and deaf bands on the diffraction efficiency is found. This observation opens perspectives for the design of efficient phononic crystal diffraction gratings.

Experimental Study of Sr Partitioning into Calcite at Various Linear Growth Rates and Temperatures: Preliminary Results.

NASA Astrophysics Data System (ADS)

Gabitov, R. I.; Watson, B. E.

2004-05-01

The surface of a crystal in equilibrium with surrounding fluid can have a composition that differs from the bulk crystal. If growth rate of the crystal exceeds a minimum value at which partitioning-equilibrium can be maintained, then the crystal surface composition may be "captured" by the newly-formed lattice. The degree of this entrapment increases with increasing crystal growth rate. Non-equlibrium partitioning of Sr into calcite probably occurs by this entrapment mechanism. Sr and calcite are geochemically significant in understanding the thermal history of the ocean because the substitution of Sr for Ca in calcite is temperature dependent. To improve our understanding of the partitioning of Sr into calcite, we conducted two different types of experiment: 1) calcite growth from Sr-bearing solution with analysis of the crystal cross-section by electron microprobe (bulk crystal-liquid runs); and 2) treatment of calcite cleavage surfaces with Sr-bearing solutions and examination of the top few nm surface layer by X-ray photoelectron spectroscopy (surface-liquid runs). In the series of bulk-liquid experiments crystals were grown by three different procedures: 1) precipitation on glass slide (pre-coated with calcite), where a steady flow of CaCl2 - SrCl2 and Na2CO3 solutions were mixed just before passage through a tube and allowed to drip onto a slide ("cave"-type experiments, ionic strength I=0.01); 2) growth from a CaCl2 - NH4Cl - SrCl2 solution by diffusion of CO2 from an ammonium carbonate source ("drift" experiments, I=0.52); 3) coarsening of small calcite crystals in the CaCO3-SrCO3-NaCl-H2O system at 800-950° C and 0.5-1 kb in a cold seal apparatus. The growth rate of individual crystals was determined by periodic monitoring of crystal size with time or roughly by comparison of final size with duration of the experiment. Surface-liquid experiments were performed by treatment of cleavage surfaces of natural calcite fragments in a Sr(ClO4)2 solution for 1 minute. After treatment the remaining solution was blown out by a stream of nitrogen to preclude the precipitation of Sr phase. We observed that the precipitated calcite crystals can be very different in size even if the runs have the same input rate of calcite components. The cave-type and cold-seal runs yielded 15-40 μ m calcites, but in the drift experiments crystal size varied between 60 μ m and 1 mm. Electron microprobe analysis across the large crystals show that the concentration of Sr is higher in the center and decreases toward the edge. This is probably due to the cube-root dependence of radial growth on the volume change of the growing crystals. Like previous workers who measured bulk uptake of Sr as a function of precipitation rate, we observed that increased growth rate (V, nm/s) enhances Sr uptake into the crystal, raising Kdbulk/liquid=(Sr/Ca)bulk/(Sr/Ca)liquid. Kdbulk/liquid = 0.03 to 0.06 when log(V)=-1.1 to -0.6 at 25° C in the cave-type runs (I=0.01). At higher ionic strength (I=0.52) and T=55° C, Kdbulk/liquid=0.11 to 0.15 when log(V)=-0.6 to 0.4 in the drift experiments. XPS analysis of surface-liquid experiments yielded higher Kdsurface/liquid=(Sr/Ca)surface/(Sr/Ca)liquid values compared with Kdbulk/liquid. This combined evidence supports the idea that Sr is enriched at the calcite surface relative to the bulk crystal during crystal growth.

Bimolecular crystals with an intercalated structure improve poly(p-phenylenevinylene)-based organic photovoltaic cells.

PubMed

Lim, Kyung-Geun; Park, Jun-Mo; Mangold, Hannah; Laquai, Frédéric; Choi, Tae-Lim; Lee, Tae-Woo

2015-01-01

The exciton dissociation, recombination, and charge transport of bulk heterojunction organic photovoltaic cells (OPVs) is influenced strongly by the nanomorphology of the blend, such as the grain size and the molecular packing. Although it is well known that polymers based on amorphous poly(p-phenylenevinylene) (PPV) have a fundamental limit to their efficiency because of low carrier mobility, which leads to increased recombination and unbalanced charge extraction, herein, we demonstrate that the issue can be overcome by forming bimolecular crystals of an amorphous PPV-based polymer:phenyl-C61 -butyric acid methyl ester (PCBM) intercalated structure. We used amorphous poly(2,5-dioctyloxy-p-phenylene vinylene-alt-2',5'-thienylene vinylene) (PPVTV), which has a simple chemical structure. A reasonably high power conversion efficiency (∼3.5 %) was obtained, although the material has an intrinsically amorphous structure and a relatively large band gap (2.0 eV). We demonstrate a correlation between a well-ordered bimolecular crystal of PPVTV:PCBM and an improved hole mobility of a PPVTV:PCBM film compared to a pristine PPVTV film by using 2 D grazing incidence XRD and space-charge-limited current measurements. Furthermore, we show that the bimolecular crystal structure in high-performance OPVs is related to an optimum molecular packing, which is influenced by the PPVTV:PCBM blending ratio, side-chain length, and molecular weight of the PPVTV polymer. Improved charge transport in PPVTV:PCBM bimolecular crystals leads to a fast sweep out of charges and thus suppression of nongeminate recombination under the operating conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terahertz Spectroscopy and Solid-State Density Functional Theory Calculations of Cyanobenzaldehyde Isomers.

PubMed

Dash, Jyotirmayee; Ray, Shaumik; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin; Gonnade, Rajesh G; Ambade, Ashootosh V; Joshi, Kavita; Pesala, Bala

2015-07-23

Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

Topological Valley Transport in Two-dimensional Honeycomb Photonic Crystals.

PubMed

Yang, Yuting; Jiang, Hua; Hang, Zhi Hong

2018-01-25

Two-dimensional photonic crystals, in analogy to AB/BA stacking bilayer graphene in electronic system, are studied. Inequivalent valleys in the momentum space for photons can be manipulated by simply engineering diameters of cylinders in a honeycomb lattice. The inequivalent valleys in photonic crystal are selectively excited by a designed optical chiral source and bulk valley polarizations are visualized. Unidirectional valley interface states are proved to exist on a domain wall connecting two photonic crystals with different valley Chern numbers. With the similar optical vortex index, interface states can couple with bulk valley polarizations and thus valley filter and valley coupler can be designed. Our simple dielectric PC scheme can help to exploit the valley degree of freedom for future optical devices.

In situ observation of defect annihilation in Kr ion-irradiated bulk Fe/amorphous-Fe 2 Zr nanocomposite alloy

DOE PAGES

Yu, K. Y.; Fan, Z.; Chen, Y.; ...

2014-08-26

Enhanced irradiation tolerance in crystalline multilayers has received significant attention lately. However, little is known on the irradiation response of crystal/amorphous nanolayers. We report on in situ Kr ion irradiation studies of a bulk Fe 96Zr 4 nanocomposite alloy. Irradiation resulted in amorphization of Fe 2Zr and formed crystal/amorphous nanolayers. α-Fe layers exhibited drastically lower defect density and size than those in large α-Fe grains. In situ video revealed that mobile dislocation loops in α-Fe layers were confined by the crystal/amorphous interfaces and kept migrating to annihilate other defects. This study provides new insights on the design of irradiation-tolerant crystal/amorphousmore » nanocomposites.« less

Chondritic Models of 4 Vesta: Comparison of Data from the Dawn Mission with Predicted Internal Structure and Surface Composition/Mineralogy

NASA Technical Reports Server (NTRS)

Toplis, M. J.; Mizzon, H.; Forni, O.; Monnereau, M.; Barrat, J-A.; Prettyman, T. H.; McSween, H. Y.; McCoy, T. J.; Mittlefehldt, D. W.; De Sanctis, M. C.;

3-D phononic crystals with ultra-wide band gaps

PubMed Central

Lu, Yan; Yang, Yang; Guest, James K.; Srivastava, Ankit

2017-01-01

In this paper gradient based topology optimization (TO) is used to discover 3-D phononic structures that exhibit ultra-wide normalized all-angle all-mode band gaps. The challenging computational task of repeated 3-D phononic band-structure evaluations is accomplished by a combination of a fast mixed variational eigenvalue solver and distributed Graphic Processing Unit (GPU) parallel computations. The TO algorithm utilizes the material distribution-based approach and a gradient-based optimizer. The design sensitivity for the mixed variational eigenvalue problem is derived using the adjoint method and is implemented through highly efficient vectorization techniques. We present optimized results for two-material simple cubic (SC), body centered cubic (BCC), and face centered cubic (FCC) crystal structures and show that in each of these cases different initial designs converge to single inclusion network topologies within their corresponding primitive cells. The optimized results show that large phononic stop bands for bulk wave propagation can be achieved at lower than close packed spherical configurations leading to lighter unit cells. For tungsten carbide - epoxy crystals we identify all angle all mode normalized stop bands exceeding 100%, which is larger than what is possible with only spherical inclusions. PMID:28233812

3-D phononic crystals with ultra-wide band gaps.

PubMed

Lu, Yan; Yang, Yang; Guest, James K; Srivastava, Ankit

2017-02-24

In this paper gradient based topology optimization (TO) is used to discover 3-D phononic structures that exhibit ultra-wide normalized all-angle all-mode band gaps. The challenging computational task of repeated 3-D phononic band-structure evaluations is accomplished by a combination of a fast mixed variational eigenvalue solver and distributed Graphic Processing Unit (GPU) parallel computations. The TO algorithm utilizes the material distribution-based approach and a gradient-based optimizer. The design sensitivity for the mixed variational eigenvalue problem is derived using the adjoint method and is implemented through highly efficient vectorization techniques. We present optimized results for two-material simple cubic (SC), body centered cubic (BCC), and face centered cubic (FCC) crystal structures and show that in each of these cases different initial designs converge to single inclusion network topologies within their corresponding primitive cells. The optimized results show that large phononic stop bands for bulk wave propagation can be achieved at lower than close packed spherical configurations leading to lighter unit cells. For tungsten carbide - epoxy crystals we identify all angle all mode normalized stop bands exceeding 100%, which is larger than what is possible with only spherical inclusions.

Magnetic anisotropy on the single crystal UNi4B probed by 11B NMR

NASA Astrophysics Data System (ADS)

Kishimoto, Yasuki; Matsuno, Haruki; Kotegawa, Hisashi; Tou, Hideki; Saito, Hiraku; Amitsuka, Hiroshi; Homma, Yoshiya; Nakamura, Ai; Li, Dexin; Honda, Fuminori; Aoki, Dai

2018-05-01

We have performed a susceptibility M / H and 11B NMR measurements to investigate the static magnetic anisotropy of a single crystal UNi4B. The Knight shift 11K and the hyperfine coupling constant Ahf evaluated by 11K- M / H plot show anisotropic behavior between H ∥ [ 11 2 bar 0 ] and H ∥ [ 0001 ] , reflecting the bulk susceptibility. The evaluated transferred term Atr of Ahf for H ∥ [ 11 2 bar 0 ] is much larger than the one for H ∥ [ 0001 ] . The strong hybridization in the [0001]-plane due to a itinerant 5f-electron is strongly associated with the unique magnetic structure in this compound.

Structural investigation of LaAlO3 up to 63 GPa

NASA Astrophysics Data System (ADS)

Guennou, Mael; Bouvier, Pierre; Garbarino, Gaston; Kreisel, Jens

2011-10-01

We report a high-pressure synchrotron x-ray diffraction on a LaAlO3 single crystal. The transition from rhombohedral to cubic at 14.8 GPa is confirmed by the loss of the superstructure reflections, whose intensity shows a linear pressure dependence, characteristic of a second-order transition. The crystal remains cubic up to 63 GPa, the highest pressure reached, which provides a confirmation over a very large pressure range of the general rules for the evolution of distortions of perovskites under pressure. We report the parameters of the Birch-Murnaghan equations of state in the low- and high-pressure phases and discuss the evolution of the bulk modulus.

Buffering capability and limitations in low dispersion photonic crystal waveguides with elliptical airholes.

PubMed

Long, Fang; Tian, Huiping; Ji, Yuefeng

2010-09-01

A low dispersion photonic crystal waveguide with triangular lattice elliptical airholes is proposed for compact, high-performance optical buffering applications. In the proposed structure, we obtain a negligible-dispersion bandwidth with constant group velocity ranging from c/41 to c/256, by optimizing the major and minor axes of bulk elliptical holes and adjusting the position and the hole size of the first row adjacent to the defect. In addition, the limitations of buffer performance in a dispersion engineering waveguide are well studied. The maximum buffer capacity and the maximum data rate can reach as high as 262bits and 515 Gbits/s, respectively. The corresponding delay time is about 255.4ps.

Infrared spectroscopy of molecular submonolayers on surfaces by infrared scanning tunneling microscopy: tetramantane on Au111.

PubMed

Pechenezhskiy, Ivan V; Hong, Xiaoping; Nguyen, Giang D; Dahl, Jeremy E P; Carlson, Robert M K; Wang, Feng; Crommie, Michael F

2013-09-20

We have developed a new scanning-tunneling-microscopy-based spectroscopy technique to characterize infrared (IR) absorption of submonolayers of molecules on conducting crystals. The technique employs a scanning tunneling microscope as a precise detector to measure the expansion of a molecule-decorated crystal that is irradiated by IR light from a tunable laser source. Using this technique, we obtain the IR absorption spectra of [121]tetramantane and [123]tetramantane on Au(111). Significant differences between the IR spectra for these two isomers show the power of this new technique to differentiate chemical structures even when single-molecule-resolved scanning tunneling microscopy (STM) images look quite similar. Furthermore, the new technique was found to yield significantly better spectral resolution than STM-based inelastic electron tunneling spectroscopy, and to allow determination of optical absorption cross sections. Compared to IR spectroscopy of bulk tetramantane powders, infrared scanning tunneling microscopy (IRSTM) spectra reveal narrower and blueshifted vibrational peaks for an ordered tetramantane adlayer. Differences between bulk and surface tetramantane vibrational spectra are explained via molecule-molecule interactions.

Persistent photoconductivity in oxygen-ion implanted KNbO3 bulk single crystal

NASA Astrophysics Data System (ADS)

Tsuruoka, R.; Shinkawa, A.; Nishimura, T.; Tanuma, C.; Kuriyama, K.; Kushida, K.

2016-12-01

Persistent Photoconductivity (PPC) in oxygen-ion implanted KNbO3 ([001] oriented bulk single crystals; perovskite structure; ferroelectric with a band gap of 3.16 eV)　is studied in air at room temperature to prevent the degradation of its crystallinity caused by the phase transition. The residual hydrogens in un-implanted samples are estimated to be 5×1014 cm-2 from elastic recoil detection analysis (ERDA). A multiple-energy implantation of oxygen ions into KNbO3 is performed using energies of 200, 400, and 600 keV (each ion fluence:1.0×1014 cm-2). The sheet resistance varies from >108 Ω/□ for an un-implanted sample to 1.9×107 Ω/□ for as-implanted one, suggesting the formation of donors due to hydrogen interstitials and oxygen vacancies introduced by the ion implantation. The PPC is clearly observed with ultraviolet and blue LEDs illumination rather than green, red, and infrared, suggesting the release of electrons from the metastable conductive state below the conduction band relating to the charge states of the oxygen vacancy.

Comparative study of initial stages of copper immersion deposition on bulk and porous silicon

NASA Astrophysics Data System (ADS)

Bandarenka, Hanna; Prischepa, Sergey L.; Fittipaldi, Rosalba; Vecchione, Antonio; Nenzi, Paolo; Balucani, Marco; Bondarenko, Vitaly

2013-02-01

Initial stages of Cu immersion deposition in the presence of hydrofluoric acid on bulk and porous silicon were studied. Cu was found to deposit both on bulk and porous silicon as a layer of nanoparticles which grew according to the Volmer-Weber mechanism. It was revealed that at the initial stages of immersion deposition, Cu nanoparticles consisted of crystals with a maximum size of 10 nm and inherited the orientation of the original silicon substrate. Deposited Cu nanoparticles were found to be partially oxidized to Cu2O while CuO was not detected for all samples. In contrast to porous silicon, the crystal orientation of the original silicon substrate significantly affected the sizes, density, and oxidation level of Cu nanoparticles deposited on bulk silicon.

Discotic columnar liquid crystal studied in the bulk and nanoconfined states by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Busselez, Rémi; Cerclier, Carole V.; Ndao, Makha; Ghoufi, Aziz; Lefort, Ronan; Morineau, Denis

2014-10-01

A prototypical Gay Berne discotic liquid crystal was studied by means of molecular dynamics simulations both in the bulk state and under confinement in a nanoporous channel. The phase behavior of the confined system strongly differs from its bulk counterpart: the bulk isotropic-to-columnar transition is replaced by a continuous ordering from a paranematic to a columnar phase. Moreover, a new transition is observed at a lower temperature in the confined state, which corresponds to a reorganization of the intercolumnar order. It reflects the competing effects of pore surface interaction and genuine hexagonal packing of the columns. The translational molecular dynamics in the different phases has been thoroughly studied and discussed in terms of collective relaxation modes, non-Gaussian behavior, and hopping processes.

Effect of precipitation inhibitors on indomethacin supersaturation maintenance: mechanisms and modeling.

PubMed

Patel, Dhaval D; Anderson, Bradley D

2014-05-05

This study quantitatively explores the mechanisms underpinning the effects of model pharmaceutical polymeric precipitation inhibitors (PPIs) on the crystal growth and, in turn, maintenance of supersaturation of indomethacin, a model poorly water-soluble drug. A recently developed second-derivative UV spectroscopy method and a first-order empirical crystal growth model were used to determine indomethacin crystal growth rates in the presence of model PPIs. All three model PPIs including HP-β-CD, PVP, and HPMC inhibited indomethacin crystal growth at both high and low degrees of supersaturation (S). The bulk viscosity changes in the presence of model PPIs could not explain their crystal growth inhibitory effects. At 0.05% w/w, PVP (133-fold) and HPMC (28-fold) were better crystal growth inhibitors than HP-β-CD at high S. The inhibitory effect of HP-β-CD on the bulk diffusion-controlled indomethacin crystal growth at high S was successfully modeled using reactive diffusion layer theory, which assumes reversible complexation in the diffusion layer. Although HP-β-CD only modestly inhibited indomethacin crystal growth at either high S (∼15%) or low S (∼2-fold), the crystal growth inhibitory effects of PVP and HPMC were more dramatic, particularly at high S (0.05% w/w). The superior crystal growth inhibitory effects of PVP and HPMC as compared with HP-β-CD at high S were attributed to a change in the indomethacin crystal growth rate-limiting step from bulk diffusion to surface integration. Indomethacin crystal growth inhibitory effects of all three model PPIs at low S were attributed to retardation of the rate of surface integration of indomethacin, a phenomenon that may reflect the adsorption of PPIs onto the growing crystal surface. The quantitative approaches outlined in this study should be useful in future studies to develop tools to predict supersaturation maintenance effects of PPIs.

Effect of Sn addition on glassy Si-Te bulk sample

NASA Astrophysics Data System (ADS)

Babanna, Jagannatha K.; Roy, Diptoshi; Varma, Sreevidya G.; Asokan, Sundarrajan; Das, Chandasree

2018-05-01

Bulk Si20Te79Sn1 glass is prepared by melt-quenching method, amorphous nature of the as-quenched glass is confirmed by XRD. I-V characteristics reveals that Si20Te79Sn1 bulk sample exhibits threshold type electrical switching behavior. The thermal parameters such as crystallization temperature, glass transition temperature are obtained using differential scanning calorimetry. The crystalline peak study of the sample annealed at crystallization temperature for 2 hr shows that the Sn atom interact with Si or Te but do not interact with the Si-Te matrix in a greater extent and it forms a separate phase network individually.

Mechanisms limiting the performance of large grain polycrystalline silicon solar cells

NASA Technical Reports Server (NTRS)

Culik, J. S.; Alexander, P.; Dumas, K. A.; Wohlgemuth, J. W.

1984-01-01

The open-circuit voltage and short-circuit current of large-grain (1 to 10 mm grain diameter) polycrystalline silicon solar cells is determined by the minority-carrier diffusion length within the bulk of the grains. This was demonstrated by irradiating polycrystalline and single-crystal (Czochralski) silicon solar cells with 1 MeV electrons to reduce their bulk lifetime. The variation of short-circuit current with minority-carrier diffusion length for the polycrystalline solar cells is identical to that of the single-crystal solar cells. The open-circuit voltage versus short-circuit current characteristic of the polycrystalline solar cells for reduced diffusion lengths is also identical to that of the single-crystal solar cells. The open-circuit voltage of the polycrystalline solar cells is a strong function of quasi-neutral (bulk) recombination, and is reduced only slightly, if at all, by grain-boundary recombination.

New structural phase obtained by exerting high pressure on (Br2)n@AFI composite material

NASA Astrophysics Data System (ADS)

Yao, Zhen; Lv, Jia-Yin; Liu, Bo; Liu, Bing-Bing; Yang, Bai

2018-06-01

In this paper, we present a theoretical study on the high-pressure behaviors of a (Br2)n@AlPO4-5 (AFI) peapod structure. The influence of the encapsulated Br2 molecule on the structural deformation of AFI crystal is analyzed using the volume-pressure function. The bonding process of the linearly arrayed Br2 molecule transferring to the bromine atomic chain is analyzed by the electron density distribution. A new high-pressure phase with P2 point group symmetry is obtained as the pressure increases to 34 GPa. In addition, electron density difference calculations are used to study the systematic charge transformation. Further analysis indicates that the encapsulated Br2 molecules can significantly modify the electronic structure of the AFI crystal. The band gap of the (Br2)n@AFI decreases with pressure and closes at 9 GPa. Moreover, the calculated bulk modulus and electronic properties indicate that the new structural phase is metallic with a high hardness, providing a new strategy for exploring novel nanomaterials.

Surface Structure as a Foundation of Nanotechnology

NASA Astrophysics Data System (ADS)

Robinson, Ian

2007-03-01

The three generations of synchrotron sources achieved to date, parasitic, dedicated and undulator-based, have each time revolutionized the field of X-ray diffraction. Surface structure determination, demonstrated (but very difficult) already with Coolidge tube sources, benefited from the enormous flux gain in the first generation, such as SSRL. Dedicated 2nd-generation sources, such as NSLS, allowed in-situ surface preparation and reliable steady beams to be available when a surface was ready to measure. Third generation sources, such as APS, enormously improved the brightness, hence coherence, and thus allowed access to the surfaces of nanoparticles. This talk will illustrate how these technological advances led to two significant scientific breakthroughs. The concept of crystal truncation rods (CTR) led to new views of how the surface is a modification of, but still an extension of the bulk crystal structure. The development of lensless coherent x-ray diffraction (CXD) imaging has allowed access to the structure of nanocrystalline materials by three-dimensional phase mapping of the particle interiors. The structural principles of these new nano materials are being investigated at present using these new methods.

A facile strategy to design zeolite L crystals with tunable morphology and surface architecture.

PubMed

Lupulescu, Alexandra I; Kumar, Manjesh; Rimer, Jeffrey D

2013-05-01

Tailoring the anisotropic growth rates of materials to achieve desired structural outcomes is a pervasive challenge in synthetic crystallization. Here we discuss a method to selectively control the growth of zeolite crystals, which are used extensively in a wide range of industrial applications. This facile method cooperatively tunes crystal properties, such as morphology and surface architecture, through the use of inexpensive, commercially available chemicals with specificity for binding to crystallographic surfaces and mediating anisotropic growth. We examined over 30 molecules as potential zeolite growth modifiers (ZGMs) of zeolite L (LTL type) crystallization. ZGM efficacy was quantified through a combination of macroscopic (bulk) and microscopic (surface) investigations that identified modifiers capable of dramatically altering the cylindrical morphology of LTL crystals. We demonstrate an ability to tailor properties critical to zeolite performance, such as external porous surface area, crystal shape, and pore length, which can enhance sorbate accessibility to LTL pores, tune the supramolecular organization of guest-host composites, and minimize the diffusion path length, respectively. We report that a synergistic combination of ZGMs and the judicious adjustment of synthesis parameters produce LTL crystals with unique surface features, and a range of length-to-diameter aspect ratios spanning 3 orders of magnitude. A systematic examination of different ZGM structures and molecular compositions (i.e., hydrophobicity and binding moieties) reveal interesting physicochemical properties governing their efficacy and specificity. Results of this study suggest this versatile strategy may prove applicable for a host of framework types to produce unrivaled materials that have eluded more conventional techniques.

Synthesis optimisation and characterisation of the organic-inorganic layered materials ZnS(m-xylylenediamine){sub 1/2} and ZnS(p-xylylenediamine){sub 1/2}

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

Luberda-Durnaś, K.; Guillén, A. González; Łasocha, W., E-mail: lasocha@chemia.uj.edu.pl

2016-06-15

Hybrid organic-inorganic layered materials of the type ZnS(amine){sub 1/2}, where amine=m-xylylenediamine (MXDA) or p-xylylenediamine (PXDA), were synthesised using a simple solvothermal method. Since the samples crystallised in the form of very fine powder, X-ray powder diffraction techniques were used for structural characterisation. The crystal structure studies, involving direct methods, show that both compounds crystallised in the orthorhombic crystal system, but in different space groups: ZnS(MXDA){sub 1/2} in non-centrosymmetric Ccm2{sub 1}, ZnS(PXDA){sub 1/2} in centrosymmetric Pcab. The obtained materials are built according to similar orders: semiconducting monolayers with the formula ZnS, parallel to the (010) plane, are separated by diamines. Themore » organic and inorganic fragments are connected by covalent bonds between metal atoms of the layers and nitrogen atoms of the amino groups. The optical properties of the hybrid materials differ from those of their bulk counterpart. In both compounds a blue-shift of about 0.8 or 0.9 eV was observed with reference to the bulk phase of ZnS. - Highlights: • New hybrid compounds: ZnS(MXDA){sub 1/2} and ZnS(PXDA){sub 1/2} were obtained. • Hybrids were studied using XRD, TG/DSC, XRK, SEM, UV–vis spectroscopy. • Structures of both materials were solved by powder diffraction methods.« less

Time-lapse 3D imaging of calcite precipitation in a microporous column

NASA Astrophysics Data System (ADS)

Godinho, Jose R. A.; Withers, Philip J.

2018-02-01

Time-lapse X-ray computed tomography is used to image the evolution of calcite precipitation during flow through microporous quartz over the course of 400 h. The growth rate decreases by more than seven times, which is linked to the clogging of flow paths that restricts flow to some regions of the column. Fewer precipitates are observed as a function of column depth, which is found to be related to a differential nucleation density along the sample. A higher nucleation density closer to the inlet implies more crystal volume increase per unit of time without affecting the rate if normalized to the surface area of crystals. Our overall growth rates measured in porous media are orders of magnitude slower than growth rates derived from traditional precipitation experiments on free surfaces. Based on our time-lapse results we hypothesize a scenario where the evolving distribution of precipitates within a pore structure during precipitation progressively modifies the local transport through the pores. Within less permeable regions the saturation index may be lower than along the main flow paths. Therefore, the reactive crystal surfaces within those regions grow at a slower rate than that expected from the bulk fluid composition. Since the amount of reactive surface area within these less permeable regions increases over time, the overall growth rate decreases without a necessary significant change of the bulk fluid composition along more permeable flow paths. In conclusion, the overall growth rates in an evolving porous media expected from bulk fluid compositions alone can be overestimated due to the development of stagnant sub-regions where the reactive surface area is bath by a solution with lower saturation index. In this context we highlight the value of time-lapse 3D studies for understanding the dynamics of mineral precipitation in porous media.

Improving the Representation of Snow Crystal Properties Within a Single-Moment Microphysics Scheme

NASA Technical Reports Server (NTRS)

Molthan, Andrew L.; Petersen, Walter A.; Case, Jonathan L.; Dembek, S. R.

2010-01-01

As computational resources continue their expansion, weather forecast models are transitioning to the use of parameterizations that predict the evolution of hydrometeors and their microphysical processes, rather than estimating the bulk effects of clouds and precipitation that occur on a sub-grid scale. These parameterizations are referred to as single-moment, bulk water microphysics schemes, as they predict the total water mass among hydrometeors in a limited number of classes. Although the development of single moment microphysics schemes have often been driven by the need to predict the structure of convective storms, they may also provide value in predicting accumulations of snowfall. Predicting the accumulation of snowfall presents unique challenges to forecasters and microphysics schemes. In cases where surface temperatures are near freezing, accumulated depth often depends upon the snowfall rate and the ability to overcome an initial warm layer. Precipitation efficiency relates to the dominant ice crystal habit, as dendrites and plates have relatively large surface areas for the accretion of cloud water and ice, but are only favored within a narrow range of ice supersaturation and temperature. Forecast models and their parameterizations must accurately represent the characteristics of snow crystal populations, such as their size distribution, bulk density and fall speed. These properties relate to the vertical distribution of ice within simulated clouds, the temperature profile through latent heat release, and the eventual precipitation rate measured at the surface. The NASA Goddard, single-moment microphysics scheme is available to the operational forecast community as an option within the Weather Research and Forecasting (WRF) model. The NASA Goddard scheme predicts the occurrence of up to six classes of water mass: vapor, cloud ice, cloud water, rain, snow and either graupel or hail.

An Nmr Study of Supercooled Water Under Nanoconfinement by Hydrophobic Surfaces

NASA Astrophysics Data System (ADS)

Ling, Yan-Chun

The main focus of this dissertation is studying the properties of bulk water, confined water, and interfacial water. The thermodynamics, dynamics and state of water are investigated by DSC and 1H NMR methods. Hydrophobic slit-shaped pores with tunable pore size from 0.5 nm to 1.6 nm are applied as confinement media in our experiments. By confining water in nanopores, we are able to cool the water lower than its homogeneous nucleation temperature 235 K at ambient pressure and access the "no man's land". Both experimental and simulation results show water has heterogeneity property, with two "phases", one is high-density liquid (HDL) "phase" which has dense-packing structure, the other is low-density liquid (LDL) "phase" which has more tetrahedral structure. At room temperature, HDL and LDL two "phases" can coexist in millisecond time scale and 10 nanometer length scale. The room temperature water structure is dominated by HDL structure. By decreasing the temperature, HDL could convert to LDL gradually. At 200 K, LDL dominates the liquid state of water. It is of importance to emphasis, for water confined in nanopores there is no crystallization above 200 K. A dynamic crossover at 225 K in the liquid state is observed in our hydrophobic system, similar to that observed in hydrophilic system. This proves such dynamic crossover is not induced by crystallization or surface effect, but originally from the intrinsic properties of water. At 190 K, we find a second change of rotational correlation time, which resembles the glassification process of supercooled confined water, suggesting a higher rotational glass transition temperature for bulk water. In the lower temperature range 145 K water. In the lower temperature range 145 K < T < 165 K, the interfacial water induced glass transition is observed. At sufficient low temperature, confinement plays an important role for the induced glass transition. We also study the properties of interfacial water by confining water in smaller hydrophobic pores. It shows the interfacial water remains liquid state at 140 K. There is an Arrhenius to Arrhenius dynamic crossover at 170 K due to the rotational motion slowing down. Comparing to bulk water, interfacial water has fast rotation but effectively immobile. Our studies thus provide a complete picture for the rather controversial supercooled region and also differentiate the properties of bulk water, confined water and interfacial water using different techniques.

Positron Interactions with Oriented Polymers and with Chiral Quartz Crystals

NASA Astrophysics Data System (ADS)

Wu, Fei

Positron annihilation in various materials has been applied to characterize microstructure for decades. In this work, PALS was used to study material nanostructure, with a focus on the size and density of free volume and hole relaxation properties in polycarbonate (PC) and polymethylmethacrylate (PMMA); fundamental studies of polarized positron interaction with chiral crystals were also studied. Free volume relaxation in PC and PMMA with different levels of simple shear orientation was studied by PALS. Effects of applied pressure on the free volume recovery were evaluated. Combining the bulk- and pressure-dependent PALS analyses, the removal of applied pressure led to free-volume relaxation in all samples studied. The alignment of the polymer chains and free-volume holes imposes molecular restrictions on the molecular mobility of both PC and PMMA in their glassy states. Results indicated that the relaxation of the free volume holes at temperatures below glass transition is mostly reversible. Longitudinally polarized positron particles were used to reveal asymmetric interactions in chiral quartz crystals. Experimental results showed a significant intensity difference in free positronium annihilation for left handed (LH) and right handed (RH) chiral quartz crystals. Doppler broadening energy spectra (DBES) of z-cut LH or RH quartz disks at different angles were also measured by an "S parameter" to probe the observed difference. It was found that obtained annihilation energy difference of DBES was in agreement with the result of positron annihilation in bulk chiral crystals. PALS was used to compare different orientations and confirm asymmetric interactions in natural versus synthetic quartz LH and RH crystals in z and non-z orientations. Significant lifetime and intensity differences in free positronium annihilation for LH and RH quartz crystals were observed. The trend was found to be same in the related crystallographic orientations of the LH or RH crystals; the direction of incident positrons, z or non-z, did not affect the observed differences in lifetime and intensity trends. The results confirmed the existence of differential interactions of positronium with the asymmetric lattice structures of LH and RH quartz crystals.

Interface and Electronic Characterization of Thin Epitaxial Co3O4 Films

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

Vaz, C.A.; Zhu, Y.; Wang, H.-Q.

2009-01-15

The interface and electronic structure of thin ({approx} 20-74 nm) Co{sub 3}O{sub 4}(1 1 0) epitaxial films grown by oxygen-assisted molecular beam epitaxy on MgAl{sub 2}O{sub 4}(1 1 0) single crystal substrates have been investigated by means of real and reciprocal space techniques. As-grown film surfaces are found to be relatively disordered and exhibit an oblique low energy electron diffraction (LEED) pattern associated with the O-rich CoO{sub 2} bulk termination of the (1 1 0) surface. Interface and bulk film structure are found to improve significantly with post-growth annealing at 820 K in air and display sharp rectangular LEED patterns,more » suggesting a surface stoichiometry of the alternative Co{sub 2}O{sub 2} bulk termination of the (1 1 0) surface. Non-contact atomic force microscopy demonstrates the presence of wide terraces separated by atomic steps in the annealed films that are not present in the as-grown structures; the step height of {approx}2.7 {angstrom} corresponds to two atomic layers and confirms a single termination for the annealed films, consistent with the LEED results. A model of the (1 x 1) surfaces that allows for compensation of the polar surfaces is presented.« less

Free-standing nanomechanical and nanophotonic structures in single-crystal diamond

NASA Astrophysics Data System (ADS)

Burek, Michael John

Realizing complex three-dimensional structures in a range of material systems is critical to a variety of emerging nanotechnologies. This is particularly true of nanomechanical and nanophotonic systems, both relying on free-standing small-scale components. In the case of nanomechanics, necessary mechanical degrees of freedom require physically isolated structures, such as suspended beams, cantilevers, and membranes. For nanophotonics, elements like waveguides and photonic crystal cavities rely on light confinement provided by total internal reflection or distributed Bragg reflection, both of which require refractive index contrast between the device and surrounding medium (often air). Such suspended nanostructures are typically fabricated in a heterolayer structure, comprising of device (top) and sacrificial (middle) layers supported by a substrate (bottom), using standard surface nanomachining techniques. A selective, isotropic etch is then used to remove the sacrificial layer, resulting in free-standing devices. While high-quality, crystalline, thin film heterolayer structures are readily available for silicon (as silicon-on-insulator (SOI)) or III-V semiconductors (i.e. GaAs/AlGaAs), there remains an extensive list of materials with attractive electro-optic, piezoelectric, quantum optical, and other properties for which high quality single-crystal thin film heterolayer structures are not available. These include complex metal oxides like lithium niobate (LiNbO3), silicon-based compounds such as silicon carbide (SiC), III-V nitrides including gallium nitride (GaN), and inert single-crystals such as diamond. Diamond is especially attractive for a variety of nanoscale technologies due to its exceptional physical and chemical properties, including high mechanical hardness, stiffness, and thermal conductivity. Optically, it is transparent over a wide wavelength range (from 220 nm to the far infrared), has a high refractive index (n ~ 2.4), and is host to a vast inventory of luminescent defect centers (many with direct optical access to highly coherent electron and nuclear spins). Diamond has many potential applications ranging from radio frequency nanoelectromechanical systems (RF-NEMS), to all-optical signal processing and quantum optics. Despite the commercial availability of wafer-scale nanocrystalline diamond thin films on foreign substrates (namely SiO2), this diamond-on-insulator (DOI) platform typically exhibits inferior material properties due to friction, scattering, and absorption losses at grain boundaries, significant surface roughness, and large interfacial stresses. In the absence of suitable heteroepitaxial diamond growth, substantial research and development efforts have focused on novel processing techniques to yield nanoscale single-crystal diamond mechanical and optical elements. In this thesis, we demonstrate a scalable 'angled-etching' nanofabrication method for realizing nanomechanical systems and nanophotonic networks starting from bulk single-crystal diamond substrates. Angled-etching employs anisotropic oxygen-based plasma etching at an oblique angle to the substrate surface, resulting in suspended optical structures with triangular cross-sections. Using this approach, we first realize single-crystal diamond nanomechanical resonant structures. These nanoscale diamond resonators exhibit high mechanical quality-factors (approaching Q ~ 105) with mechanical resonances up to 10 MHz. Next, we demonstrate engineered nanophotonic structures, specifically racetrack resonators and photonic crystal cavities, in bulk single-crystal diamond. Our devices feature large optical Q-factors, in excess of 10 5, and operate over a wide wavelength range, spanning visible and telecom. These newly developed high-Q diamond optical nanocavities open the door for a wealth of applications, ranging from nonlinear optics and chemical sensing, to quantum information processing and cavity optomechanics. Beyond isolated nanophotonic devices, we also developed free-standing angled-etched diamond waveguides which efficiently route photons between optical nanocavities, realizing true on-chip diamond nanophotonic networks. A high efficiency fiber-optical interface with aforementioned on-chip diamond nanophotonic networks, achieving > 90% power coupling, is also demonstrated. Lastly, we demonstrate a cavity-optomechanical system in single-crystal diamond, which builds upon previously realized diamond nanobeam photonic crystal cavities fabricated by angled-etching. Specifically, we demonstrate diamond optomechanical crystals (OMCs), where the engineered co-localization of photons and phonons in a quasi-periodic diamond nanostructure leads to coupling of an optical cavity field to a mechanical mode via the radiation pressure of light. In contrast to other material systems, diamond OMCs possess large intracavity photon capacity and sufficient optomechanical coupling rates to exceed a cooperativity of ~ 1 at room temperature and realize large amplitude optomechanical self-oscillations.

Low temperature growth of Ga 1- xIn xP bulk crystals from InSb-rich melt

NASA Astrophysics Data System (ADS)

Gennett, A.; Lewis, D.; Dutta, P. S.

2010-04-01

Bulk growth of phosphorus and arsenic based ternary III-V semiconductor crystals using pseudo-binary melts such as GaP-InP, GaP-GaAs, AlAs-GaAs, etc. is significantly challenging due to the high vapor pressures of group V species in conjunction with slow growth rates and the need for melt replenishment and mixing during growth. Lowering the growth temperature is desirable such that the vapor pressures of P and As can be easily handled. Low growth temperatures could be achieved by using Ga or In rich solutions. However, this approach is less attractive for growing bulk crystals due to several experimental difficulties including sticking of the growth solution to the crucible wall and to the grown crystal, making it challenging for crystal extraction. Growth of ternary crystals from low temperature quaternary melts has been found to be attractive. In this paper, we will present a new method for the growth of Ga 1- xIn xP from InSb rich Ga 1- xIn xP ySb 1- y melts at low growth temperatures in the range of 800-1050 °C. Thermodynamic phase diagrams calculated at various temperatures using a Gibbs free energy minimization software and materials databases commercially available from Thermo-Calc software will be presented along with experimental validation for Ga 1- xIn xP crystals grown at 1000 °C.

Laser stimulated third harmonic generation studies in ZnO-Ta2O5-B2O3 glass ceramics entrenched with Zn3Ta2O8 crystal phases

NASA Astrophysics Data System (ADS)

Siva Sesha Reddy, A.; Jedryka, J.; Ozga, K.; Ravi Kumar, V.; Purnachand, N.; Kityk, I. V.; Veeraiah, N.

2018-02-01

In this study zinc borate glasses doped with different concentrations Ta2O5 were synthesized and were crystallized by heat treatment for prolonged times. The samples were characterized by XRD, SEM, IR and Raman spectroscopy techniques. The SEM images of the crystallized samples have indicated that the samples contain randomly distributed crystal grains with size ∼1 μm entrenched in the residual amorphous phase. XRD studies have exhibited diffraction peaks identified as being due to the reflections from (1 1 1) planes of monoclinic Zn3Ta2O8 crystal phase that contains intertwined tetrahedral zinc and octahedral tantalate structural units. The concentration of such crystal phases in the bulk samples is observed to increase with increase of Ta2O5 up to 3.0 mol%. The IR and Raman spectroscopy studies have confirmed the presence of ZnO4 and TaO6 structural units in the glass network in addition to the conventional borate structural units. For measuring third harmonic generation (THG) in the samples, the samples were irradiated with 532 nm laser beam and the intensity of THG of probing beam (Nd:YAG λ = 1064 nm 20 ns pulsed laser (ω)) is measured as a function of fundamental beam power varying up to 200 J/m2. The intensity of THG is found to be increasing with increase of fundamental beam power and found to be the maximal for the glass crystallized with 3.0 mol% of Ta2O5. The intensity of THG of the ceramicized samples is found to be nearly 5 times higher with respect to that of pre-crystallized samples. The generation of 3ω is attributed to the perturbation/interaction between Zn3Ta2O8 anisotropic crystal grains and the incident probing beam.

Manipulating Semicrystalline Polymers in Confinement.

PubMed

Shingne, Nitin; Geuss, Markus; Thurn-Albrecht, Thomas; Schmidt, Hans-Werner; Mijangos, Carmen; Steinhart, Martin; Martín, Jaime

2017-08-17

Because final properties of nanoscale polymeric structures are largely determined by the solid-state microstructure of the confined polymer, it is imperative not only to understand how the microstructure of polymers develops under nanoscale confinement but also to establish means to manipulate it. Here we present a series of processing strategies, adapted from methods used in bulk polymer processing, that allow us to control the solidification of polymer nanostructures. First, we show that supramolecular nucleating agents can be readily used to modify the crystallization kinetics of confined poly(vinylidene fluoride) (PVDF). In addition, we demonstrate that microstructural features that are not traditionally affected by nucleating agents, such as the orientation of crystals, can be tuned with the crystallization temperature applied. Interestingly, we also show that high crystallization temperatures and long annealing periods induce the formation of the γ modification of PVDF, hence enabling the simple production of ferro/piezoelectric nanostructures. We anticipate that the approaches presented here can open up a plethora of new possibilities for the processing of polymer-based nanostructures with tailored properties and functionalities.

Single crystal growth and anisotropic magnetic properties of HoAl2Ge2

NASA Astrophysics Data System (ADS)

Matin, Md.; Mondal, Rajib; Thamizhavel, A.; Provino, A.; Manfrinetti, P.; Dhar, S. K.

2018-05-01

We have grown a single crystal of HoAl2Ge2, which crystallizes in the hexagonal CaAl2Si2 type structure with Ho ions in the trigonal coordination in the ab plane. The data obtained from the bulk measurement techniques of magnetization, heat capacity and transport reveal that HoAl2Ge2 orders antiferromagnetically at TN ˜6.5 K. The susceptibility below TN and isothermal magnetization at 2 K indicate the ab plane as the easy plane of magnetization. Heat capacity data reveal a prominent Schottky anomaly with a broad peak centered around 25 K, suggesting a relatively low crystal electric field (CEF) splitting. The electrical resistivity reveals the occurrence of a superzone gap below TN. The point charge model of the CEF is applied to the magnetization and the heat capacity data. While a good fit to the paramagnetic susceptibility is obtained, the CEF parameters do not provide a satisfactory fit to the isothermal magnetization at 2 K and the Schottky anomaly.

Gelatinized wheat starch influences crystallization behaviour and structure of roll-in shortenings in laminated bakery products.

PubMed

Mattice, Kristin D; Marangoni, Alejandro G

2018-03-15

One hydrogenated and one non-hydrogenated shortening were baked with isolated components of a croissant matrix, including crystalline wheat starch, gelatinized wheat starch, gluten, and formed gluten network. The impact of the matrix components on fat crystallization was analyzed for polymorphism using powder X-ray diffraction, solid fat content by pulsed nuclear magnetic resonance and thermal behaviour by differential scanning calorimetry. When compared to results obtained from croissants prepared with the respective shortenings, samples containing gelatinized wheat starch displayed notably similar results: polymorphic conversion, from the β' to β form over storage, and visually broader peaks in the melting endotherms indicating a greater temperature was required to completely melt all of the fat. All other component mixtures behaved similar to the respective fats in bulk. The measured rate of crystallization was greater in samples containing gelatinized wheat starch, indicating that the gelatinized starch could act as a nucleation site to speed crystallization. Copyright © 2017 Elsevier Ltd. All rights reserved.

Flexible Semitransparent Energy Harvester with High Pressure Sensitivity and Power Density Based on Laterally Aligned PZT Single-Crystal Nanowires.

PubMed

Zhao, Quan-Liang; He, Guang-Ping; Di, Jie-Jian; Song, Wei-Li; Hou, Zhi-Ling; Tan, Pei-Pei; Wang, Da-Wei; Cao, Mao-Sheng

2017-07-26

A flexible semitransparent energy harvester is assembled based on laterally aligned Pb(Zr 0.52 Ti 0.48 )O 3 (PZT) single-crystal nanowires (NWs). Such a harvester presents the highest open-circuit voltage and a stable area power density of up to 10 V and 0.27 μW/cm 2 , respectively. A high pressure sensitivity of 0.14 V/kPa is obtained in the dynamic pressure sensing, much larger than the values reported in other energy harvesters based on piezoelectric single-crystal NWs. Furthermore, theoretical and finite element analyses also confirm that the piezoelectric voltage constant g 33 of PZT NWs is competitive to the lead-based bulk single crystals and ceramics, and the enhanced pressure sensitivity and power density are substantially linked to the flexible structure with laterally aligned PZT NWs. The energy harvester in this work holds great potential in flexible and transparent sensing and self-powered systems.

Lattice dynamics and thermomechanical properties of zirconium(IV) chloride: Evidence for low-temperature negative thermal expansion

NASA Astrophysics Data System (ADS)

Kim, Eunja; Weck, Philippe F.; Borjas, Rosendo; Poineau, Frederic

2018-01-01

The crystal structure, lattice dynamics and themomechanical properties of bulk monoclinic zirconium tetrachloride (ZrCl4) have been investigated using zero-damping dispersion-corrected density functional theory [DFT-D3(zero)]. Phonon analysis reveals that ZrCl4 (cr) undergoes negative thermal expansion (NTE) near T ≈ 10 K, with a coefficient of thermal expansion of α = - 1.2 ppm K-1 and a Grüneisen parameter of γ = - 1.1 . The bulk modulus is predicted to vary from K0 = 8.7 to 7.0 GPa in the temperature range 0-550 K. The isobaric molar heat capacity derived from phonon calculations within the quasi-harmonic approximation is in fair agreement with existing calorimetric data.

The high-pressure behavior of spherocobaltite (CoCO3): a single crystal Raman spectroscopy and XRD study

NASA Astrophysics Data System (ADS)

Chariton, Stella; Cerantola, Valerio; Ismailova, Leyla; Bykova, Elena; Bykov, Maxim; Kupenko, Ilya; McCammon, Catherine; Dubrovinsky, Leonid

2018-01-01

Magnesite (MgCO3), calcite (CaCO3), dolomite [(Ca, Mg)CO3], and siderite (FeCO3) are among the best-studied carbonate minerals at high pressures and temperatures. Although they all exhibit the calcite-type structure ({R}\\bar{3}{c}) at ambient conditions, they display very different behavior at mantle pressures. To broaden the knowledge of the high-pressure crystal chemistry of carbonates, we studied spherocobaltite (CoCO3), which contains Co2+ with cation radius in between those of Ca2+ and Mg2+ in calcite and magnesite, respectively. We synthesized single crystals of pure spherocobaltite and studied them using Raman spectroscopy and X-ray diffraction in diamond anvil cells at pressures to over 55 GPa. Based on single crystal diffraction data, we found that the bulk modulus of spherocobaltite is 128 (2) GPa and K' = 4.28 (17). CoCO3 is stable in the calcite-type structure up to at least 56 GPa and 1200 K. At 57 GPa and after laser heating above 2000 K, CoCO3 partially decomposes and forms CoO. In comparison to previously studied carbonates, our results suggest that at lower mantle conditions carbonates can be stable in the calcite-type structure if the radius of the incorporated cation(s) is equal or smaller than that of Co2+ (i.e., 0.745 Å).

Praseodymium Cuprate Thin Film Cathodes for Intermediate Temperature Solid Oxide Fuel Cells: Roles of Doping, Orientation, and Crystal Structure.

PubMed

Mukherjee, Kunal; Hayamizu, Yoshiaki; Kim, Chang Sub; Kolchina, Liudmila M; Mazo, Galina N; Istomin, Sergey Ya; Bishop, Sean R; Tuller, Harry L

2016-12-21

Highly textured thin films of undoped, Ce-doped, and Sr-doped Pr 2 CuO 4 were synthesized on single crystal YSZ substrates using pulsed laser deposition to investigate their area-specific resistance (ASR) as cathodes in solid-oxide fuel cells (SOFCs). The effects of T' and T* crystal structures, donor and acceptor doping, and a-axis and c-axis orientation on ASR were systematically studied using electrochemical impedance spectroscopy on half cells. The addition of both Ce and Sr dopants resulted in improvements in ASR in c-axis oriented films, as did the T* crystal structure with the a-axis orientation. Pr 1.6 Sr 0.4 CuO 4 is identified as a potential cathode material with nearly an order of magnitude faster oxygen reduction reaction kinetics at 600 °C compared to thin films of the commonly studied cathode material La 0.6 Sr 0.4 Co 0.8 Fe 0.2 O 3-δ . Orientation control of the cuprate films on YSZ was achieved using seed layers, and the anisotropy in the ASR was found to be less than an order of magnitude. The rare-earth doped cuprate was found to be a versatile system for study of relationships between bulk properties and the oxygen reduction reaction, critical for improving SOFC performance.

Fabrication and characterization of non-Brownian particle-based crystals.

PubMed

Lash, Melissa H; Fedorchak, Morgan V; Little, Steven R; McCarthy, Joseph J

2015-01-27

Particle-based crystals have been explored in the literature for applications in molecular electronics, photonics, sensors, and drug delivery. However, much of the research on these crystals has been focused on particles of nano- and submicrometer dimensions (so-called colloidal crystals) with limited attention directed toward building blocks with dimensions ranging from tens to hundreds of micrometers. This can be attributed, in part, to the fact that the underlying thermal effects in these larger systems typically cannot naturally overcome kinetic barriers at the meso- and macroscales so that many of the methods used for nanoscale particle assembly cannot be directly applied to larger components, as they become kinetically arrested in nonequilibrium states. In this work, ultrasonic agitation is being explored as a means of allowing large, non-Brownian microparticles (18-750 μm) to overcome the kinetic barriers to packing in the creation of close-packed, highly ordered, crystalline structures. In addition, we study how the energy input affects bulk particle behavior and describe several new ways to characterize particle-based crystals made from microparticles.

Structural, Electronic and Elastic Properties of Heavy Fermion YbTM2 (TM= Ir and Pt) Laves Phase Compounds

NASA Astrophysics Data System (ADS)

Pawar, H.; Shugani, M.; Aynyas, M.; Sanyal, S. P.

2018-02-01

The structural, electronic and elastic properties of YbTM2 (TM = Ir and Pt) Laves phase intermetallic compounds which crystallize in cubic (MgCu2-type) structure, have been investigated using ab-initio full potential linearized augmented plane wave (FP-LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B‧) are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for these compounds which obey the stability criteria for cubic system.

Microstructure and properties of single crystal BaTiO3 thin films synthesized by ion implantation-induced layer transfer

NASA Astrophysics Data System (ADS)

Park, Young-Bae; Ruglovsky, Jennifer L.; Atwater, Harry A.

2004-07-01

Single crystal BaTiO3 thin films have been transferred onto Pt-coated and Si3N4-coated substrates by the ion implantation-induced layer transfer method using H + and He+ ion coimplantation and subsequent annealing. The transferred BaTiO3 films are single crystalline with root mean square roughness of 17nm. Polarized optical and piezoresponse force microscopy (PFM) indicate that the BaTiO3 film domain structure closely resembles that of bulk tetragonal BaTiO3 and atomic force microscopy shows a 90° a -c domain structure with a tetragonal angle of 0.5°-0.6°. Micro-Raman spectroscopy indicates that the local mode intensity is degraded in implanted BaTiO3 but recovers during anneals above the Curie temperature. The piezoelectric coefficient, d33, is estimated from PFM to be 80-100pm/V and the coercive electric field (Ec) is 12-20kV/cm, comparable to those in single crystal BaTiO3.

Sustainable thermoelectric materials fabricated by using Cu2Sn1-xZnxS3 nanoparticles as building blocks

NASA Astrophysics Data System (ADS)

Zhou, Wei; Shijimaya, Chiko; Takahashi, Mari; Miyata, Masanobu; Mott, Derrick; Koyano, Mikio; Ohta, Michihiro; Akatsuka, Takeo; Ono, Hironobu; Maenosono, Shinya

2017-12-01

Uniform Cu2Sn1-xZnxS3 (x = 0-0.2) nanoparticles (NPs) with a characteristic size of about 40 nm were chemically synthesized. The primary crystal phase of the NPs was wurtzite (WZ) with a mean crystalline size of about 20 nm. The NPs were sintered to form nanostructured pellets with different compositions preserving the composition and grain size of the original NPs by the pulse electric current sintering technique. The pellets had a zinc blende (ZB) structure with a residual WZ phase, and the mean crystalline size was found to remain virtually unchanged for all pellets. Among all samples, the pellets of Cu2Sn0.95Zn0.05S3 and Cu2Sn0.85Zn0.15S3 exhibited the highest ZT value (0.37 at 670 K) which is 10 times higher than that of a non-nanostructured Cu2SnS3 bulk crystal thanks to effective phonon scattering by nanograins, the phase-pure ZB crystal structure, and the increase in hole carrier density by Zn doping.

Sodium doping in ZnO crystals

NASA Astrophysics Data System (ADS)

Parmar, N. S.; Lynn, K. G.

2015-01-01

ZnO bulk single crystals were doped with sodium by thermal diffusion. Positron annihilations spectroscopy confirms the filling of zinc vacancies, to >6 μm deep in the bulk. Secondary-ion mass spectrometry measurement shows the diffusion of sodium up to 8 μm with concentration (1-3.5) × 1017 cm-3. Broad photoluminescence excitation peak at 3.1 eV, with onset appearance at 3.15 eV in Na:ZnO, is attributed to an electronic transition from a NaZn level at ˜(220-270) meV to the conduction band. Resistivity in Na doped ZnO crystals increases up to (4-5) orders of magnitude at room temperature.

Sodium Flux Growth of Bulk Gallium Nitride

NASA Astrophysics Data System (ADS)

Von Dollen, Paul Martin

This dissertation focused on development of a novel apparatus and techniques for crystal growth of bulk gallium nitride (GaN) using the sodium flux method. Though several methods exist to produce bulk GaN, none have been commercialized on an industrial scale. The sodium flux method offers potentially lower cost production due to relatively mild process conditions while maintaining high crystal quality. But the current equipment and methods for sodium flux growth of bulk GaN are generally not amenable to large-scale crystal growth or in situ investigation of growth processes, which has hampered progress. A key task was to prevent sodium loss or migration from the sodium-gallium growth melt while permitting N2 gas to access the growing crystal, which was accomplished by implementing a reflux condensing stem along with a reusable sealed capsule. The reflux condensing stem also enabled direct monitoring and control of the melt temperature, which has not been previously reported for the sodium flux method. Molybdenum-based materials were identified from a corrosion study as candidates for direct containment of the corrosive sodium-gallium melt. Successful introduction of these materials allowed implementation of a crucible-free containment system, which improved process control and can potentially reduce crystal impurity levels. Using the new growth system, the (0001) Ga face (+c plane) growth rate was >50 mum/hr, which is the highest bulk GaN growth rate reported for the sodium flux method. Omega X-ray rocking curve (?-XRC) measurements indicated the presence of multiple grains, though full width at half maximum (FWHM) values for individual peaks were <100 arcseconds. Oxygen impurity concentrations as measured by secondary ion mass spectroscopy (SIMS) were >1020 atoms/cm3, possibly due to reactor cleaning and handling procedures. This dissertation also introduced an in situ technique to correlate changes in N2 pressure with dissolution of nitrogen and precipitation of GaN from the sodium-gallium melt. Different stages of N2 pressure decay were identified and linked to distinct modes of GaN crystal growth. Based on this analysis, the highest growth rate may have up to 90 mum/hr, and did not appear to be mass-transport limited, in contrast to previous reports. Several refinements and improvements of the novel equipment and methods introduced were also explored, all of which have potential to further advance state of the art sodium flux growth of bulk GaN.

Liquid Between Macromolecules in Protein Crystals: Static Versus Dynamics

NASA Technical Reports Server (NTRS)

Chernov, A. A.

2005-01-01

Protein crystals are so fragile that they often can not be handled by tweezers. Indeed, measurements of the Young modulus, E, of lysozyme crystals resulted in E approx. equals 0.1 - 1 GPa, the lower figures, 0.1 - 0.5 GPa, being obtained from triple point bending of as-grown and not cross-linked crystals sitting in solution. The bending strength was found to be approx.10(exp -2) E. On the other hand, ultrasound speed and Mandelstam-Raman-Brilloin light scattering experiments led to much higher figures, E approx. equals 2.7 GPa. The lower figures for E were found from static or low frequency crystal deformations measurements, while the higher moduli are based on high frequency lattice vibrations, 10(exp 7) - 10(exp 10) 1/s. The physical reason for the about an order of magnitude discrepancy is in different behavior of water filling space between protein molecules. At slow lattice deformation, the not-bound intermolecular water has enough time to flow from the compressed to expanded regions of the deformed crystal. At high deformation frequencies in the ultra- and hypersound waves, the water is confined in the intermolecular space and, on that scale, behaves like a solid, thus contributing to the elastic crystal moduli. In this case, the reciprocal crystal modulus is expected to be an average of the water protein and water compressibilities (reciprocal compressibilities): the bulk modulus for lysozyme is 26 GPa, for water it is 7 GPa. Anisotropy of the crystal moduli comes from intermolecular contacts within the lattice while the high frequency hardness comes from the bulk of protein molecules and water bulk moduli. These conclusions are based on the analysis of liquid flow in porous medium to be presented.

Structural and dynamic properties of liquid tin from a new modified embedded-atom method force field

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

Vella, Joseph R.; Chen, Mohan; Stillinger, Frank H.

We developed a new modified embedded-atom method (MEAM) force field for liquid tin. Starting from the Ravelo and Baskes force field [Phys. Rev. Lett. 79, 2482 (1997)], the parameters are adjusted using a simulated annealing optimization procedure in order to obtain better agreement with liquid-phase data. The predictive capabilities of the new model and the Ravelo and Baskes force field are evaluated using molecular dynamics by comparing to a wide range of first-principles and experimental data. The quantities studied include crystal properties (cohesive energy, bulk modulus, equilibrium density, and lattice constant of various crystal structures), melting temperature, liquid structure, liquidmore » density, self-diffusivity, viscosity, and vapor-liquid surface tension. We show that although the Ravelo and Baskes force field generally gives better agreement with the properties related to the solid phases of tin, the new MEAM force field gives better agreement with liquid tin properties.« less

Structural and dynamic properties of liquid tin from a new modified embedded-atom method force field

NASA Astrophysics Data System (ADS)

Vella, Joseph R.; Chen, Mohan; Stillinger, Frank H.; Carter, Emily A.; Debenedetti, Pablo G.; Panagiotopoulos, Athanassios Z.

2017-02-01

A new modified embedded-atom method (MEAM) force field is developed for liquid tin. Starting from the Ravelo and Baskes force field [Phys. Rev. Lett. 79, 2482 (1997), 10.1103/PhysRevLett.79.2482], the parameters are adjusted using a simulated annealing optimization procedure in order to obtain better agreement with liquid-phase data. The predictive capabilities of the new model and the Ravelo and Baskes force field are evaluated using molecular dynamics by comparing to a wide range of first-principles and experimental data. The quantities studied include crystal properties (cohesive energy, bulk modulus, equilibrium density, and lattice constant of various crystal structures), melting temperature, liquid structure, liquid density, self-diffusivity, viscosity, and vapor-liquid surface tension. It is shown that although the Ravelo and Baskes force field generally gives better agreement with the properties related to the solid phases of tin, the new MEAM force field gives better agreement with liquid tin properties.

Structural and dynamic properties of liquid tin from a new modified embedded-atom method force field

DOE PAGES

Vella, Joseph R.; Chen, Mohan; Stillinger, Frank H.; ...

2017-02-01

We developed a new modified embedded-atom method (MEAM) force field for liquid tin. Starting from the Ravelo and Baskes force field [Phys. Rev. Lett. 79, 2482 (1997)], the parameters are adjusted using a simulated annealing optimization procedure in order to obtain better agreement with liquid-phase data. The predictive capabilities of the new model and the Ravelo and Baskes force field are evaluated using molecular dynamics by comparing to a wide range of first-principles and experimental data. The quantities studied include crystal properties (cohesive energy, bulk modulus, equilibrium density, and lattice constant of various crystal structures), melting temperature, liquid structure, liquidmore » density, self-diffusivity, viscosity, and vapor-liquid surface tension. We show that although the Ravelo and Baskes force field generally gives better agreement with the properties related to the solid phases of tin, the new MEAM force field gives better agreement with liquid tin properties.« less

A unified relation for the solid-liquid interface free energy of pure FCC, BCC, and HCP metals

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

Wilson, S. R.; Mendelev, M. I., E-mail: mendelev@ameslab.gov

2016-04-14

We study correlations between the solid-liquid interface (SLI) free energy and bulk material properties (melting temperature, latent heat, and liquid structure) through the determination of SLI free energies for bcc and hcp metals from molecular dynamics (MD) simulation. Values obtained for the bcc metals in this study were compared to values predicted by the Turnbull, Laird, and Ewing relations on the basis of previously published MD simulation data. We found that of these three empirical relations, the Ewing relation better describes the MD simulation data. Moreover, whereas the original Ewing relation contains two constants for a particular crystal structure, wemore » found that the first coefficient in the Ewing relation does not depend on crystal structure, taking a common value for all three phases, at least for the class of the systems described by embedded-atom method potentials (which are considered to provide a reasonable approximation for metals).« less

A colloidal quantum dot photonic crystal phosphor: nanostructural engineering of the phosphor for enhanced color conversion.

PubMed

Min, Kyungtaek; Jung, Hyunho; Park, Yeonsang; Cho, Kyung-Sang; Roh, Young-Geun; Hwang, Sung Woo; Jeon, Heonsu

2017-06-29

Phosphors, long-known color-converting photonic agents, are gaining increasing attention owing to the interest in white LEDs and related applications. Conventional material-based approaches to phosphors focus on obtaining the desired absorption/emission wavelengths and/or improving quantum efficiency. Here, we report a novel approach for enhancing the performance of phosphors: structural modification of phosphors. We incorporated inorganic colloidal quantum dots (CQDs) into a lateral one-dimensional (1D) photonic crystal (PhC) thin-film structure, with its photonic band-edge (PBE) modes matching the energy of 'excitation photons' (rather than 'emitted photons', as in most other PBE application devices). At resonance, we observed an approximately 4-fold enhancement of fluorescence over the reference bulk phosphor, which reflects an improved absorption of the excitation photons. This nano-structural engineering approach is a paradigm shift in the phosphor research area and may help to develop next-generation higher efficiency phosphors with novel characteristics.

The 2D Selfassembly of Benzimidazole and its Co-crystallization

NASA Astrophysics Data System (ADS)

Costa, Paulo; Teeter, Jacob; Kunkel, Donna; Sinitskii, Alexander; Enders, Axel

Benzimidazoles (BI) are organic molecules that form ferroelectric crystals. Key to their ferroelectric behavior are the switchable N . . . HN type bonds and how they couple to the electron system of the molecules. We attempted to crystallize BI on various metal surfaces and studied them using STM. We observed that on Au and Ag, BI joins into zipper chains characteristic of its bulk structure that can pack into a continuous 2D layer. Because the dipole of BI lies in the direction of its switchable hydrogen bond, these zippers should in principle have reversible polarizations that point along the direction they run. BI's crystallization is reminiscent to how croconic acid (CA) crystallizes in 2D using O . . . HO bonding, suggesting that these molecules may be able to co-crystallize through OH . . . N bonds. This would present the opportunity to modify BI's properties, such as the energy needed to switch a hydrogen from a donor to acceptor site. When co-deposited, CA and BI successfully combine into a co-crystal formed by building blocks consisting of 2 CA and 2 BI molecules. These findings demonstrate the usefulness of using STM as a preliminary check to verify if two molecules are compatible with each other without having to attempt crystallization with multiple solvents and mixing methods.

Shuttle Mission STS-50: Orbital Processing of High-Quality CdTe Compound Semiconductors Experiment: Final Flight Sample Characterization Report

NASA Technical Reports Server (NTRS)

Larson, David J.; Casagrande, Luis G.; DiMarzio, Don; Alexander, J. Iwan D.; Carlson, Fred; Lee, Taipo; Dudley, Michael; Raghathamachar, Balaji

1998-01-01

The Orbital Processing of High-Quality Doped and Alloyed CdTe Compound Semiconductors program was initiated to investigate, quantitatively, the influences of gravitationally dependent phenomena on the growth and quality of bulk compound semiconductors. The objective was to improve crystal quality (both structural and compositional) and to better understand and control the variables within the crystal growth production process. The empirical effort entailed the development of a terrestrial (one-g) experiment baseline for quantitative comparison with microgravity (mu-g) results. This effort was supported by the development of high-fidelity process models of heat transfer, fluid flow and solute redistribution, and thermo-mechanical stress occurring in the furnace, safety cartridge, ampoule, and crystal throughout the melting, seeding, crystal growth, and post-solidification processing. In addition, the sensitivity of the orbital experiments was analyzed with respect to the residual microgravity (mu-g) environment, both steady state and g-jitter. CdZnTe crystals were grown in one-g and in mu-g. Crystals processed terrestrially were grown at the NASA Ground Control Experiments Laboratory (GCEL) and at Grumman Aerospace Corporation (now Northrop Grumman Corporation). Two mu-g crystals were grown in the Crystal Growth Furnace (CGF) during the First United States Microgravity Laboratory Mission (USML-1), STS-50, June 24 - July 9, 1992.

Large-scale ordering of nanoparticles using viscoelastic shear processing.

PubMed

Zhao, Qibin; Finlayson, Chris E; Snoswell, David R E; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P; Petukhov, Andrei V; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J

2016-06-03

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Effect of annealing under tensile loading on the structure of nanocrystals in the Finemet alloy

NASA Astrophysics Data System (ADS)

Ershov, N. V.; Chernenkov, Yu. P.; Fedorov, V. I.; Lukshina, V. A.; Potapov, A. P.

2014-11-01

The effect of nanocrystallization annealing under tensile loading on the structure of nanocrystals in the soft magnetic alloy Fe-Si-Nb-B-Cu (Finemet) has been investigated. It has been shown that the body-centered cubic (bcc) lattice of α-FeSi nanocrystals is extended along the direction of the application of the load upon annealing and is compressed in the transverse direction. Nanocrystals in the Finemet alloy have a higher degree of anisotropy of mechanical properties as compared to bulk crystals of α-FeSi, so that agreement between the measured and calculated values of the elongation is achieved only with a significant increase in the elastic moduli. Substantial changes in mechanical properties of the crystals with a decrease in their size to the nanometer scale are caused by the influence of the rigid amorphous matrix of the Fe(Nb)-B phase surrounding the nanocrystals.

Annealing of gallium nitride under high-N 2 pressure

NASA Astrophysics Data System (ADS)

Porowski, S.; Jun, J.; Krukowski, S.; Grzegory, I.; Leszczynski, M.; Suski, T.; Teisseyre, H.; Foxon, C. T.; Korakakis, D.

1999-04-01

GaN is the key material for blue and ultraviolet optoelectronics. It is a strongly bonded wurztite structure semiconductor with the direct energy gap 3.5 eV. Due to strong bonding, the diffusion processes require high temperatures, above 1300 K. However at this temperature range at ambient pressure, GaN becomes unstable and dissociates into Ga and N 2. Therefore high pressure of N 2 is required to study the diffusion and other annealing related processes. We studied annealing of bulk GaN nitride single crystals grown under high pressure and also annealing of homo- and heteroepitaxial GaN layers grown by MOCVD technique. Annealing at temperatures above 1300 K influences strongly the structural and optical properties of GaN crystals and layers. At this temperature diffusion of the Mg and Zn acceptors have been observed. In spite of very interesting experimental observations the understanding of microscopic mechanisms of these processes is limited.

Scanning Tunneling Microscopy Study on Dirac Nodal-line Semimetal ZrSiS

NASA Astrophysics Data System (ADS)

Su, Chih-Chuan; Guan, Syu-You; Wang, Tzu-Cheng; Sankar, Raman; Guo, Guang-Yu; Chou, Fangcheng; Chang, Chia-Seng; Chuang, Tien-Ming

The discovery of 3D Dirac nodal-line protected by non-symmophic symmetry in ZrSiS family has been reported by angle resolved photoemission spectroscopy (ARPES) and quantum oscillation measurements. ZrSiS also exhibits a butterfly shaped titanic angular magnetoresistance and strong Zeeman splitting in quantum oscillation. These observations with its layered crystal structure make the ZrSiS family an interesting candidate to understand the novel properties of the nodal-line semimetals. Here, we study the electronic structures of the single crystal ZrSiS by using spectroscopic-imaging scanning tunneling microscope at T= 4.2K. Our quasiparticle scattering interference imaging reveals the characteristic wave vectors with linear dispersion from Dirac line nodes in the bulk and its surface states. Our results are in excellent agreement with the first principle calculation, and also in consistent with ARPES and quantum oscillation measurements.

Full open-framework batteries for stationary energy storage

NASA Astrophysics Data System (ADS)

Pasta, Mauro; Wessells, Colin D.; Liu, Nian; Nelson, Johanna; McDowell, Matthew T.; Huggins, Robert A.; Toney, Michael F.; Cui, Yi

2014-01-01

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Large-scale ordering of nanoparticles using viscoelastic shear processing

PubMed Central

Zhao, Qibin; Finlayson, Chris E.; Snoswell, David R. E.; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P.; Petukhov, Andrei V.; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A.; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J.

2016-01-01

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles. PMID:27255808

The controlled growth of GaN microrods on Si(111) substrates by MOCVD

NASA Astrophysics Data System (ADS)

Foltynski, Bartosz; Garro, Nuria; Vallo, Martin; Finken, Matthias; Giesen, Christoph; Kalisch, Holger; Vescan, Andrei; Cantarero, Andrés; Heuken, Michael

2015-03-01

In this paper, a selective area growth (SAG) approach for growing GaN microrods on patterned SiNx/Si(111) substrates by metal-organic chemical vapor deposition (MOCVD) is studied. The surface morphology, optical and structural properties of vertical GaN microrods terminated by pyramidal shaped facets (six { 10 1 bar 1} planes) were characterized using scanning electron microscopy (SEM), room temperature photoluminescence (PL) and Raman spectroscopy, respectively. Measurements revealed high-quality GaN microcolumns grown with silane support. Characterized structures were grown nearly strain-free (central frequency of Raman peak of 567±1 cm-1) with crystal quality comparable to bulk crystals (FWHM=4.2±1 cm-1). Such GaN microrods might be used as a next-generation device concept for solid-state lighting (SSL) applications by realizing core-shell InGaN/GaN multi-quantum wells (MQWs) on the n-GaN rod base.

Full open-framework batteries for stationary energy storage.

PubMed

Pasta, Mauro; Wessells, Colin D; Liu, Nian; Nelson, Johanna; McDowell, Matthew T; Huggins, Robert A; Toney, Michael F; Cui, Yi

2014-01-01

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Pressure induced Ag 2Te polymorphs in conjunction with topological non trivial to metal transition

DOE PAGES

Zhu, J.; Oganov, A. R.; Feng, W. X.; ...

2016-08-01

Silver telluride (Ag 2Te) is well known as superionic conductor and topologica insulator with polymorphs. Pressure induced three phase transitions in Ag 2Te hav been reported in previous. Here, we experimentally identified high pressure phas above 13 GPa of Ag 2Te by using high pressure synchrotron x ray diffraction metho in combination with evolutionary crystal structure prediction, showing it crystallize into a monoclinic structure of space group C2/m with lattice parameters a = 6.081Å b = 5.744Å, c = 6.797 Å, β = 105.53°. The electronic properties measurements of Ag 2Te reveal that the topologically non-trivial semiconducting phase I andmore » semimetalli phase II previously predicated by theory transformed into bulk metals fo high pressure phases in consistent with the first principles calculations« less