A low thermal impact annealing process for SiO2-embedded Si nanocrystals with optimized interface quality

NASA Astrophysics Data System (ADS)

Hiller, Daniel; Gutsch, Sebastian; Hartel, Andreas M.; Löper, Philipp; Gebel, Thoralf; Zacharias, Margit

2014-04-01

Silicon nanocrystals (Si NCs) for 3rd generation photovoltaics or optoelectronic applications can be produced by several industrially compatible physical or chemical vapor deposition technologies. A major obstacle for the integration into a fabrication process is the typical annealing to form and crystallize these Si quantum dots (QDs) which involves temperatures ≥1100 °C for 1 h. This standard annealing procedure allows for interface qualities that correspond to more than 95% dangling bond defect free Si NCs. We study the possibilities to use rapid thermal annealing (RTA) and flash lamp annealing to crystallize the Si QDs within seconds or milliseconds at high temperatures. The Si NC interface of such samples exhibits huge dangling bond defect densities which makes them inapplicable for photovoltaics or optoelectronics. However, if the RTA high temperature annealing is combined with a medium temperature inert gas post-annealing and a H2 passivation, luminescent Si NC fractions of up to 90% can be achieved with a significantly reduced thermal load. A new figure or merit, the relative dopant diffusion length, is introduced as a measure for the impact of a Si NC annealing procedure on doping profiles of device structures.

Ultrathin silicon oxynitride layer on GaN for dangling-bond-free GaN/insulator interface.

PubMed

Nishio, Kengo; Yayama, Tomoe; Miyazaki, Takehide; Taoka, Noriyuki; Shimizu, Mitsuaki

2018-01-23

Despite the scientific and technological importance of removing interface dangling bonds, even an ideal model of a dangling-bond-free interface between GaN and an insulator has not been known. The formation of an atomically thin ordered buffer layer between crystalline GaN and amorphous SiO 2 would be a key to synthesize a dangling-bond-free GaN/SiO 2 interface. Here, we predict that a silicon oxynitride (Si 4 O 5 N 3 ) layer can epitaxially grow on a GaN(0001) surface without creating dangling bonds at the interface. Our ab initio calculations show that the GaN/Si 4 O 5 N 3 structure is more stable than silicon-oxide-terminated GaN(0001) surfaces. The electronic properties of the GaN/Si 4 O 5 N 3 structure can be tuned by modifying the chemical components near the interface. We also propose a possible approach to experimentally synthesize the GaN/Si 4 O 5 N 3 structure.

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

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Nature of electron trap states under inversion at In0.53Ga0.47As/Al2O3 interfaces

NASA Astrophysics Data System (ADS)

Colleoni, Davide; Pourtois, Geoffrey; Pasquarello, Alfredo

2017-03-01

In and Ga impurities substitutional to Al in the oxide layer resulting from diffusion out of the substrate are identified as candidates for electron traps under inversion at In0.53Ga0.47As/Al2O3 interfaces. Through density-functional calculations, these defects are found to be thermodynamically stable in amorphous Al2O3 and to be able to capture two electrons in a dangling bond upon breaking bonds with neighboring O atoms. Through a band alignment based on hybrid functional calculations, it is inferred that the corresponding defect levels lie at ˜1 eV above the conduction band minimum of In0.53Ga0.47As, in agreement with measured defect densities. These results support the technological importance of avoiding cation diffusion into the oxide layer.

Microwave plasma induced surface modification of diamond-like carbon films

NASA Astrophysics Data System (ADS)

Rao Polaki, Shyamala; Kumar, Niranjan; Gopala Krishna, Nanda; Madapu, Kishore; Kamruddin, Mohamed; Dash, Sitaram; Tyagi, Ashok Kumar

2017-12-01

Tailoring the surface of diamond-like carbon (DLC) film is technically relevant for altering the physical and chemical properties, desirable for useful applications. A physically smooth and sp3 dominated DLC film with tetrahedral coordination was prepared by plasma-enhanced chemical vapor deposition technique. The surface of the DLC film was exposed to hydrogen, oxygen and nitrogen plasma for physical and chemical modifications. The surface modification was based on the concept of adsorption-desorption of plasma species and surface entities of films. Energetic chemical species of microwave plasma are adsorbed, leading to desorbtion of the surface carbon atoms due to energy and momentum exchange. The interaction of such reactive species with DLC films enhanced the roughness, surface defects and dangling bonds of carbon atoms. Adsorbed hydrogen, oxygen and nitrogen formed a covalent network while saturating the dangling carbon bonds around the tetrahedral sp3 valency. The modified surface chemical affinity depends upon the charge carriers and electron covalency of the adsorbed atoms. The contact angle of chemically reconstructed surface increases when a water droplet interacts either through hydrogen or van dear Waals bonding. These weak interactions influenced the wetting property of the DLC surface to a great extent.

a-SiNx:H-based ultra-low power resistive random access memory with tunable Si dangling bond conduction paths

PubMed Central

Jiang, Xiaofan; Ma, Zhongyuan; Xu, Jun; Chen, Kunji; Xu, Ling; Li, Wei; Huang, Xinfan; Feng, Duan

2015-01-01

The realization of ultra-low power Si-based resistive switching memory technology will be a milestone in the development of next generation non-volatile memory. Here we show that a high performance and ultra-low power resistive random access memory (RRAM) based on an Al/a-SiNx:H/p+-Si structure can be achieved by tuning the Si dangling bond conduction paths. We reveal the intrinsic relationship between the Si dangling bonds and the N/Si ratio x for the a-SiNx:H films, which ensures that the programming current can be reduced to less than 1 μA by increasing the value of x. Theoretically calculated current-voltage (I–V ) curves combined with the temperature dependence of the I–V characteristics confirm that, for the low-resistance state (LRS), the Si dangling bond conduction paths obey the trap-assisted tunneling model. In the high-resistance state (HRS), conduction is dominated by either hopping or Poole–Frenkel (P–F) processes. Our introduction of hydrogen in the a-SiNx:H layer provides a new way to control the Si dangling bond conduction paths, and thus opens up a research field for ultra-low power Si-based RRAM. PMID:26508086

a-SiNx:H-based ultra-low power resistive random access memory with tunable Si dangling bond conduction paths.

PubMed

Jiang, Xiaofan; Ma, Zhongyuan; Xu, Jun; Chen, Kunji; Xu, Ling; Li, Wei; Huang, Xinfan; Feng, Duan

2015-10-28

The realization of ultra-low power Si-based resistive switching memory technology will be a milestone in the development of next generation non-volatile memory. Here we show that a high performance and ultra-low power resistive random access memory (RRAM) based on an Al/a-SiNx:H/p(+)-Si structure can be achieved by tuning the Si dangling bond conduction paths. We reveal the intrinsic relationship between the Si dangling bonds and the N/Si ratio x for the a-SiNx:H films, which ensures that the programming current can be reduced to less than 1 μA by increasing the value of x. Theoretically calculated current-voltage (I-V) curves combined with the temperature dependence of the I-V characteristics confirm that, for the low-resistance state (LRS), the Si dangling bond conduction paths obey the trap-assisted tunneling model. In the high-resistance state (HRS), conduction is dominated by either hopping or Poole-Frenkel (P-F) processes. Our introduction of hydrogen in the a-SiNx:H layer provides a new way to control the Si dangling bond conduction paths, and thus opens up a research field for ultra-low power Si-based RRAM.

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

Di, Jun; Chen, Chao; Yang, Shi -Ze

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

Reaction of Si(100) with NH3: Rate-limiting steps and reactivity enhancement via electronic excitation

NASA Astrophysics Data System (ADS)

Bozso, F.; Avouris, Ph.

1986-09-01

We report on the low-temperature reaction of ammonia with Si(100)-(2×1). The dangling bonds in the clean Si surface promote NH3 dissociation even at temperatures as low as 90 K. The N atoms thus produced occupy subsurface sites, while the H atoms bind to surface Si atoms, tie up the dangling bonds, and inactivate the surface. Thermal or electronic-excitation-induced hydrogen desorption restores the dangling bonds and the reactivity of the surface. Silicon nitride film growth is achieved at 90 K by simultaneous exposure of the Si surface to NH3 and an electron beam.

Forming-free performance of a-SiN x :H-based resistive switching memory obtained by oxygen plasma treatment.

PubMed

Zhang, Xinxin; Ma, Zhongyuan; Zhang, Hui; Liu, Jian; Yang, Huafeng; Sun, Yang; Tan, Dinwen; Li, Wei; Xu, Ling; Chen, Kuiji; Feng, Duan

2018-06-15

An a-SiN x -based resistive random access memory (RRAM) device with a forming-free characteristic has significant potentials for the industrialization of the next-generation memories. We demonstrate that a forming-free a-SiN x O y RRAM device can be achieved by an oxygen plasma treatment of ultra-thin a-SiN x :H films. Electron spin resonance spectroscopy reveals that Si dangling bonds with a high density (10 19 cm -3 ) are distributed in the initial state, which exist in the forms of Si 2 N≡Si·, SiO 2 ≡Si·, O 3 ≡Si·, and N 3 ≡Si·. X-ray photoelectron spectroscopy and temperature-dependent current analyses reveal that the silicon dangling bonds induced by the oxygen plasma treatment and external electric field contribute to the low resistance state (LRS). For the high resistance state (HRS), the rupture of the silicon dangling bond pathway is attributed to the partial passivation of Si dangling bonds by H + and O 2- . Both LRS and HRS transmissions obey the hopping conduction model. The proposed oxygen plasma treatment, introduced to generate a high density of Si dangling bonds in the SiN x O y :H films, provides a new approach to forming-free RRAM devices.

Laboratory Investigations of Mesospheric Ice Surfaces: Absence of Dangling Bonds in the Presence of Atomic Oxygen

NASA Astrophysics Data System (ADS)

Boulter, J. E.; Morgan, C. G.; Marschall, J.

2006-05-01

Remote observations of PMCs have become more sophisticated and have increased in geographic and temporal coverage, while numerical models have advanced in detail and predictive power. Together, these advances enable new questions of PMC morphology, optical properties, and microphysical processes in their formation and dissipation. Laboratory investigations also advance this understanding, simulating physical and chemical processes unique to this atmospheric region under comparable conditions. In this work, ice deposition experiments in the presence of microwave discharge-dissociated molecular oxygen suggest heterogeneous interactions between dangling OH bonds on the ice surface and atomic oxygen. Ice films deposited on a gold substrate at temperatures of 115, 130, and 140 K from oxygen/water gas mixtures representative of the summertime polar mesosphere exhibit infrared absorption features characteristic of dangling bonds, whereas films grown in the presence of atomic oxygen do not. Dangling bond spectral features are shown to diminish rapidly when the microwave discharge is activated during ice deposition. Similar decreases were not seen when the gas stream was heated or when the ice film was slowly annealed from 130 to 160 K. One interpretation of these results is that atomic oxygen binds to dangling bond sites during ice growth, a phenomenon that may also occur during the formation of ice particles observed just below the cold summertime mesopause.

Forming-free performance of a-SiN x :H-based resistive switching memory obtained by oxygen plasma treatment

NASA Astrophysics Data System (ADS)

Zhang, Xinxin; Ma, Zhongyuan; Zhang, Hui; Liu, Jian; Yang, Huafeng; Sun, Yang; Tan, Dinwen; Li, Wei; Xu, Ling; Chen, Kuiji; Feng, Duan

2018-06-01

An a-SiN x -based resistive random access memory (RRAM) device with a forming-free characteristic has significant potentials for the industrialization of the next-generation memories. We demonstrate that a forming-free a-SiN x O y RRAM device can be achieved by an oxygen plasma treatment of ultra-thin a-SiN x :H films. Electron spin resonance spectroscopy reveals that Si dangling bonds with a high density (1019 cm‑3) are distributed in the initial state, which exist in the forms of Si2N≡Si·, SiO2≡Si·, O3≡Si·, and N3≡Si·. X-ray photoelectron spectroscopy and temperature-dependent current analyses reveal that the silicon dangling bonds induced by the oxygen plasma treatment and external electric field contribute to the low resistance state (LRS). For the high resistance state (HRS), the rupture of the silicon dangling bond pathway is attributed to the partial passivation of Si dangling bonds by H+ and O2‑. Both LRS and HRS transmissions obey the hopping conduction model. The proposed oxygen plasma treatment, introduced to generate a high density of Si dangling bonds in the SiN x O y :H films, provides a new approach to forming-free RRAM devices.

Intercalation of P atoms in Fullerene-like CP x

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Czigány, Zs.; Furlan, A.; Stafström, S.; Hultman, L.

2011-01-01

The energy cost for P atom intercalation and corresponding structural implications during formation of Fullerene-like Phosphorus carbide (FL-CPx) were evaluated within the framework of Density Functional Theory. Single P atom interstitial defects in FL-CPx are energetically feasible and exhibit energy cost of 0.93-1.21 eV, which is comparable to the energy cost for experimentally confirmed tetragon defects and dangling bonds in CPx. A single P atom intercalation event in FL-CPx can increase the inter-sheet distance from 3.39-3.62 Å to 5.81-7.04 Å. These theoretical results are corroborated by Selected Area Electron Diffraction characterization of FL-CPx samples.

OPTOELECTRONIC PROPERTIES AND THE GAP STATE DISTRIBUTION IN a-Si, Ge ALLOYS

NASA Astrophysics Data System (ADS)

Aljishi, S.; Smith, Z. E.; Wagner, S.

In this article we review optical and electronic transport data measured in amorphous silicon-germanium alloys with the goal of identifying the density of states as a function of alloy composition. The results show that while alloying a-Si:H with germanium has little effect on the valence band tail, the conduction band tail density of states is increased dramatically. Defect distributions both above and below midgap are detected and identified with the dangling bond D+/° and D°/- states. The density of deep defects below midgap increases exponentially with germanium content. Above midgap, a large concentration of defects lying between 0.3 and 0.5 eV below the conduction band edge has a strong effect on transient electron transport.

Magnetism on a Boron-doped Si(111)-√ 3 × √ 3 Surface

NASA Astrophysics Data System (ADS)

Moon, Chang-Youn; Eom, Daejin; Koo, Ja-Yong

2018-03-01

We perform first-principles calculation to investigate the possible magnetism on the Si(111)-√ 3 × √ 3 surface, which is stabilized for highly boron-doped samples. When the silicon adatom on top of a boron atom is removed to form a defect structure, three silicon dangling bonds are exposed, generating half-filled doubly degenerate energy levels in the band gap, which stabilizes a local magnetic moment of 2 μ B . When many such defect structures are adjacent to one another, they are found to align antiferromagnetically. However, we demonstrate that the ferromagnetism can be stabilized by adjusting the number of electrons in the defects, suggesting a possibility towards spintronic applications for this unique silicon surface structure.

First principles study of the effect of hydrogen annealing on SiC MOSFETs

NASA Astrophysics Data System (ADS)

Chokawa, Kenta; Shiraishi, Kenji

2018-04-01

The high interfacial defect density at SiC/SiO2 interfaces formed by thermal oxidation is a crucial problem. Although post-oxidation annealing with H2 can reduce the defect density, some defects still remain at the interface. We investigate the termination of vacancy defects by H atoms at the 4H-SiC(0001)/SiO2 interface and discuss the stability of these H termination structures. Si vacancy defects can be terminated with H atoms to reduce the defect density, and the termination structure is stable even at high temperatures. On the other hand, it is difficult to terminate C vacancy defects with H atoms because the H atoms desorb from the dangling bonds and form H2 molecules below room temperature. However, we confirm that N atoms are effective for reducing the C vacancy defect states. Therefore, a defect-less interface can be achieved by post-oxidation annealing with H2 and N2.

Gold atoms and dimers on amorphous SiO(2): calculation of optical properties and cavity ringdown spectroscopy measurements.

PubMed

Del Vitto, Annalisa; Pacchioni, Gianfranco; Lim, Kok Hwa; Rösch, Notker; Antonietti, Jean-Marie; Michalski, Marcin; Heiz, Ulrich; Jones, Harold

2005-10-27

We report on the optical absorption spectra of gold atoms and dimers deposited on amorphous silica in size-selected fashion. Experimental spectra were obtained by cavity ringdown spectroscopy. Issues on soft-landing, fragmentation, and thermal diffusion are discussed on the basis of the experimental results. In parallel, cluster and periodic supercell density functional theory (DFT) calculations were performed to model atoms and dimers trapped on various defect sites of amorphous silica. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [[triple bond]Si(.-)], nonbridging oxygen [[triple bond]Si-O(.-)], and the silanolate group [[triple bond]Si-O(-)] act as trapping centers for the gold particles. The results are not only important for understanding the chemical bonding of atoms and clusters on oxide surfaces, but they will also be of fundamental interest for photochemical studies of size-selected clusters on surfaces.

Molecular dynamics study on welding a defected graphene by a moving fullerene

NASA Astrophysics Data System (ADS)

Cai, Kun; Wan, Jing; Yu, Jingzhou; Cai, Haifang; Qin, Qinghua

2016-07-01

When a composite nanostructure is fabricated through van der Waals interaction only, the interaction among components may be sensitive to environmental conditions. To endow such a structure with relative stability, new covalent bonds should be applied. In this paper, a welding method for welding a circular graphene with a defect gap through a moving fullerene (C240 or C540 buckyball) is presented. When the buckyball moves above the gap, the two faces of the gap are attracted to each other and the distance between the two faces is shortened. When the dangling carbon atoms on both faces of the gap are excited to form new normal sp2-sp2 carbon bonds, the gap can be sewn up quickly. Molecular dynamics simulations are presented to demonstrate the welding process. When the gap is a sector, an ideal cone can be fabricated using the present method.

Defect engineering in atomically-thin bismuth oxychloride towards photocatalytic oxygen evolution

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

Di, Jun; Chen, Chao; Yang, Shi -Ze

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

Defect engineering in atomically-thin bismuth oxychloride towards photocatalytic oxygen evolution

DOE PAGES

Di, Jun; Chen, Chao; Yang, Shi -Ze; ...

2017-06-26

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds,more » defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. As a result, this successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.« less

Structural, optical, and spin properties of hydrogenated amorphous silicon-germanium alloys

NASA Astrophysics Data System (ADS)

Stutzmann, M.; Street, R. A.; Tsai, C. C.; Boyce, J. B.; Ready, S. E.

1989-07-01

We report on a detailed study of structural and electronic properties of hydrogenated amorphous silicon-germanium alloys deposited by rf glow discharge from SiH4 and GeH4 in a diode reactor. The chemical composition of the alloys is related to the deposition conditions, with special emphasis on preferential incorporation of Ge into the solid phase and on the role of inert dilutant gases. Hydrogen bonding in the alloys is investigated with nuclear magnetic resonance and vibrational (Raman and infrared) spectroscopy. The optical properties of a-SiGe:H samples deposited under optimal conditions are analyzed with the help of subgap absorption measurements and band-tail luminescence for the entire range of alloy composi-tions. A large part of the article describes an investigation of the electron-spin-resonance response of undoped alloys. The spin density associated with dangling bond defects localized on Si and Ge atoms has been measured as a function of alloy composition for optimized material. In addition, the dependence of the two defect densities on the detailed deposition conditions (rf power, substrate temperature, and dilution) has been determined in a systematic way for alloys deposited from a plasma with a fixed SiH4/GeH4ratio. The results of this study, especially the preferential creation of Ge dangling bonds, are discussed in the context of our structural data. Furthermore, spin resonance is employed to investigate the light-induced degradation (Staebler-Wronski effect) of a-SiGe:H. Finally, the changes of the spin-resonance spectra of a-Si0.7 Ge0.3 :H upon substitutional doping with phosphorus and boron have been obtained experimentally, and are used to construct a model for the electronic density of states in this material.

Observation of structure transition as a function of temperature in depositing hydrogenated sp2-rich carbon films

NASA Astrophysics Data System (ADS)

Wang, Yongfu; Gao, Kaixiong; Zhang, Junyan

2018-05-01

In this study, we carried out the transition experiments of graphite-like (GL) to fullerene-like (FL) structures by placing high temperature steel substrates in the depositing environment which can form FL hydrogenated carbon films. We investigated the changes of bond mixtures, H content, aromatic clusters and internal stress at the transition process, and proposed the transformation mechanism inferred from Raman, TEM cross-section, FTIR and XPS results. It was found that the size of aromatic clusters and accordingly graphene planes and the formation of edge dangling bonds were the key steps. H+ bombardment leaded to the splitting of large graphene planes (at GL stage) into more and smaller planes (at FL stage) and the formation of edge dangling bonds; Some of these dangling bonds were reduced by the formation of pentagons and subsequent curving of the smaller planes, which were an indicator of FL structures.

Large magnetoresistance of nickel-silicide nanowires: non-equilibrium heating of magnetically-coupled dangling bonds.

PubMed

Kim, T; Chamberlin, R V; Bird, J P

2013-03-13

We demonstrate large (>100%) time-dependent magnetoresistance in nickel-silicide nanowires and develop a thermodynamic model for this behavior. The model describes nonequilibrium heating of localized spins in an increasing magnetic field. We find a strong interaction between spins but no long-range magnetic order. The spins likely come from unpaired dangling bonds in the interfacial layers of the nanowires. The model indicates that although these bonds couple weakly to a thermal bath, they dominate the nanowire resistance.

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

PubMed

Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

2015-05-26

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

An investigation of hydrogenized amorphous Si structures with Doppler broadening positron annihilation techniques

NASA Astrophysics Data System (ADS)

Petkov, M. P.; Marek, T.; Asoka-Kumar, P.; Lynn, K. G.; Crandall, R. S.; Mahan, A. H.

1998-07-01

In this letter, we examine the feasibility of applying positron annihilation spectroscopy to the study of hydrogenized amorphous silicon (a-Si:H)-based structures produced by chemical vapor deposition techniques. The positron probe, sensitive to open volume formations, is used to characterize neutral and negatively charged silicon dangling bonds, typical for undoped and n-doped a-Si:H, respectively. Using depth profiling along the growth direction a difference was observed in the electronic environment of these defects, which enables their identification in a p-i-n device.

Fast synthesize ZnO quantum dots via ultrasonic method.

PubMed

Yang, Weimin; Zhang, Bing; Ding, Nan; Ding, Wenhao; Wang, Lixi; Yu, Mingxun; Zhang, Qitu

2016-05-01

Green emission ZnO quantum dots were synthesized by an ultrasonic sol-gel method. The ZnO quantum dots were synthesized in various ultrasonic temperature and time. Photoluminescence properties of these ZnO quantum dots were measured. Time-resolved photoluminescence decay spectra were also taken to discover the change of defects amount during the reaction. Both ultrasonic temperature and time could affect the type and amount of defects in ZnO quantum dots. Total defects of ZnO quantum dots decreased with the increasing of ultrasonic temperature and time. The dangling bonds defects disappeared faster than the optical defects. Types of optical defects first changed from oxygen interstitial defects to oxygen vacancy and zinc interstitial defects. Then transformed back to oxygen interstitial defects again. The sizes of ZnO quantum dots would be controlled by both ultrasonic temperature and time as well. That is, with the increasing of ultrasonic temperature and time, the sizes of ZnO quantum dots first decreased then increased. Moreover, concentrated raw materials solution brought larger sizes and more optical defects of ZnO quantum dots. Copyright © 2015 Elsevier B.V. All rights reserved.

Theoretical Study of Diamond-Like Carbons and Nucleation of Diamond

NASA Astrophysics Data System (ADS)

Lee, Choon-Heung

Different forms of amorphous carbon and hydrocarbons with varying elastic and optical properties, hardness, density and hydrogen content exist depending on the preparation technique. The structure can vary from graphitic to diamond -like, i.e., from mainly threefold coordinated to mainly four-fold coordinated. In order to study the properties of such materials, microscopic models must be developed. These studies include the modelling of crosslinked defective graphite, diamond nucleation along the graphite edges, and diamond-like carbons. Tamor's proposed structure for diamondlike carbon consists of crosslinked graphitic regions. We studied a concrete realization of this model in which the cross -links are produced by shortening the interplanar bond lengths. The model study was accomplished with a pure rhombohedral graphite cell. For this study we used a semi-empirical potential based on Tersoff's environment-dependent potential which contains angular terms. It is enhanced by a long-range potential which describes the interplanar interactions. We found a configuration corresponding to a local minimum. More general features such as the randomness of the distribution of cross-links are needed for a realistic model. A model study of diamond/graphite interfaces was motivated by recent observations by Li and Angus. They observed a significant enhancement of diamond nucleation on the graphite edge planes with the preferential orientation relationship: {0001} _{g} | {111 }_{d}, < 1120 >_{g} | < 101>_{d}. Two possible interface structures were studied using the Tersoff potential. We found that the models have comparable low interface energies even if they contain some dangling bonds. Moreover, lower interface energies were found when the dangling bonds of the non-bonded diamond layer were satisfied with hydrogen. We have proposed a growth mechanism based on this study. Finally, we constructed realistic models of dense amorphous carbon. The WWW (introduced earlier for a-Si by Wooten, Winer and Weaire) model was the starting structure. The effects of clustering of the threefold coordinated atoms in pairs, chains, or graphitic (planar hexagonal clusters) were studied. The resulting models were relaxed using the Tersoff potential. Their electronic structures were studied using an empirical tight-binding scheme with parameters adjusted to reproduce the diamond and graphite band-structures. The models were found to have densities of ~ 3 g/cm^3 and bulk moduli of ~3.1 Mbar. Localized dangling bonds and pi - pi^* states were found within the wide gap of the WWW model consistent with optical gaps of the order of 0.5-2 eV. Hydrogen atoms were introduced to remove some of the dangling bonds. The models were found to account for the essential features of ion-beam deposited amorphous carbon and hydrogenated amorphous carbon.

Anisotropic electrical conduction and reduction in dangling-bond density for polycrystalline Si films prepared by catalytic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Niikura, Chisato; Masuda, Atsushi; Matsumura, Hideki

1999-07-01

Polycrystalline Si (poly-Si) films with high crystalline fraction and low dangling-bond density were prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD. Directional anisotropy in electrical conduction, probably due to structural anisotropy, was observed for Cat-CVD poly-Si films. A novel method to separately characterize both crystalline and amorphous phases in poly-Si films using anisotropic electrical conduction was proposed. On the basis of results obtained by the proposed method and electron spin resonance measurements, reduction in dangling-bond density for Cat-CVD poly-Si films was achieved using the condition to make the quality of the included amorphous phase high. The properties of Cat-CVD poly-Si films are found to be promising in solar-cell applications.

Hydrogen-related defects in hydrogenated amorphous semiconductors

NASA Astrophysics Data System (ADS)

Jin, Shu; Ley, Lothar

1991-07-01

One of the key steps in the formation of glow-discharge-deposited (GD) a-Si:H or a-Ge:H films by plasma deposition from the gas phase is the elimination of excess hydrogen from the growth surface which is necessary for the cross linking of the Si or Ge network and the reduction of the defect density associated with the hydrogen-rich surface layer. The high defect density (~1018 cm-3) in a growing surface layer can, depending on preparation conditions, be either reduced (to ~1016 cm-3) or be trapped in the bulk upon subsequent growth, as evidenced by a great deal of data. However, little is known about its origin and implication. We have investigated the change in electronic structure related with this process using UHV-evaporated a-Ge as a model system, subjected to thermal hydrogenation, plasma hydrogenation, and various annealing cycles. The density of occupied states in the pseudogap of the a-Ge(:H) surface (probing depth ~50 Å) was determined with total-yield photoelectron spectroscopy. In this way, effects of thermal annealing, hydrogenation, and ion bombarding on the near-surface defect density could be studied. We identify in room-temperature (RT) hydrogenated a-Ge:H another defect at about Ev+0.45 eV in addition to the dangling-bond defect. This defect exists at the initial stage of hydrogen incorporation, decreases upon ~250 °C annealing, and is restored upon RT rehydrogenation. Therefore we suspect that this defect is hydrogen induced and concomitant with the formation of unexpected bondings [both multiply bonded XHx (X=Si or Ge and x=2 and 3) and polyhydride (XH2)n configurations] favored at RT hydrogenation. As a possible candidate we suggest the Ge-H-Ge three-center bond in which one electron is placed in a nonbonding orbital that gives rise to the paramagnetic state in the gap of a-Ge:H observed here. This defect also accounts for the large defect density at the growing surface in the optimized plasma chemical-vapor-deposition process, where the special bonding configurations mentioned above are the predominant species. The formation and annealing of this defect will be discussed.

Effect of Ge atoms on crystal structure and optoelectronic properties of hydrogenated Si-Ge films

NASA Astrophysics Data System (ADS)

Li, Tianwei; Zhang, Jianjun; Ma, Ying; Yu, Yunwu; Zhao, Ying

2017-07-01

Optoelectronic and structural properties of hydrogenated microcrystalline silicon-germanium (μc-Si1-xGex:H) alloys prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) were investigated. When the Ge atoms were predominantly incorporated in amorphous matrix, the dark and photo-conductivity decreased due to the reduced crystalline volume fraction of the Si atoms (XSi-Si) and the increased Ge dangling bond density. The photosensitivity decreased monotonously with Ge incorporation under higher hydrogen dilution condition, which was attributed to the increase in both crystallization of Ge and the defect density.

Device physics of hydrogenated amorphous silicon solar cells

NASA Astrophysics Data System (ADS)

Liang, Jianjun

This dissertation reports measurements on and modeling of hydrogenated amorphous silicon (a-Si:H) nip solar cells. Cells with thicknesses from 200-900 nm were prepared at United Solar Ovonic LLC. The current density-voltage (J-V) relations were measured under laser illumination (685 nm wavelength, up to 200 mW/cm2) over the temperature range 240 K--350 K. The changes in the cells' open-circuit voltage during extended laser illumination (light-soaking) were measured, as were the cell properties in several light-soaked states. The J-V properties of cells in their as-deposited and light-soaked states converge at low-temperatures. Electromodulation spectra for the cells were also measured over the range 240 K--350 K to determine the temperature-dependent bandgap. These experimental results were compared to computer calculations of J-V relations using the AMPS ((c)Pennsylvania State University) computer code. Bandtail parameters (for electron and hole mobility and recombination) were consistent with published drift-mobility and transient photocurrent measurements on a-Si:H. The open-circuit voltage and power density measurements on as-deposited cells, as a function of temperature and thickness, were predicted well. The calculations support a general "hole mobility limited" approach to analyzing a-Si:H solar cells, and indicate that the doped electrode layers, the as-deposited density of dangling bonds, and the electron mobility are of secondary importance to as-deposited cells. For light-soaked a-Si:H solar cells, incorporation of a density of dangling bonds in the computer calculations accounted satisfactorily for the power and open-circuit voltage measurements, including the low-temperature convergence effect. The calculations indicate that, in the light-soaked state at room-temperature, electron recombination is split nearly evenly between holes trapped in the valence bandtail and holes trapped on dangling bonds. The result supports Stutzmann, Jackson, and Tsai's 1985 conjecture that dangling bond creation results only from bandtail recombination events. We compared the predictions of the hydrogen-collision model proposed by Branz with the kinetics of the open-circuit voltage as light-soaking progressed. We obtained satisfactory agreement for the initial phases of light-soaking with the conjecture that only bandtail recombination leads to dangling bond creation, and the computer calculations for this recombination channel's diminishment in the cell as the dangling bond density grows.

Ab initio investigation of the structural and electronic properties of amorphous HgTe.

PubMed

Zhao, Huxian; Chen, Xiaoshuang; Lu, Jianping; Shu, Haibo; Lu, Wei

2014-01-29

We present the structure and electronic properties of amorphous mercury telluride obtained from first-principle calculations. The initial configuration of amorphous mercury telluride is created by computation alchemy. According to different exchange–correlation functions in our calculations, we establish two 256-atom models. The topology of both models is analyzed in terms of radial and bond angle distributions. It is found that both the Te and the Hg atoms tend to be fourfold, but with a wrong bond rate of about 10%. The fraction of threefold and fivefold atoms also shows that there are a significant number of dangling and floating bonds in our models. The electronic properties are also obtained. It is indicated that there is a bandgap in amorphous HgTe, in contrast to the zero bandgap for crystalline HgTe. The structures of the band tail and defect states are also discussed.

The effects of surface polarity and dangling bonds on the electronic properties of MoS2 on SiO2

NASA Astrophysics Data System (ADS)

Sung, Ha-Jun; Choe, Duk-Hyun; Chang, Kee Joo

2015-03-01

MoS2 has recently attracted much attention due to its intriguing physical phenomena and possible applications for the next generation electronic devices. In pristine monolayer MoS2, strong spin-orbit coupling and inversion symmetry breaking allow for an effective coupling between the spin and valley degrees of freedom, inducing valley polarization at the K valleys. However, the spin-valley coupling disappears in bilayer MoS2 because the inversion symmetry is restored. In this work, we investigate the effects of surface polarity and dangling bonds on the electronic properties of MoS2 on α-quartz SiO2 through first-principles calculations. In monolayer MoS2, a transition can take place from the direct-gap to indirect-gap semiconductor in the presence of O dangling bonds. In bilayer MoS2, O dangling bonds induce dipole fields across the interface and thus break the inversion symmetry, resulting in the valley polarization, similar to that of pristine monolayer MoS2. Based on the results, we discuss the origin of the valley polarization observed in MoS2 deposited on SiO2 This work was supported by National Research Foundation of Korea (NRF) under Grant No. NRF-2005-0093845 and by Samsung Science and Technology Foundation under Grant No. SSTFBA1401-08.

DFT studies on the Al, B, and P doping of silicene

NASA Astrophysics Data System (ADS)

Hernández Cocoletzi, H.; Castellanos Águila, J. E.

2018-02-01

The search for efficient adsorbents of atoms and molecules has motivated the study of systems in the presence of defects. For this reason, we have investigated theoretically the creation of mono- and di-vacancies on single layer silicene, as well as the Al, B, and P doping of silicene. Using the first-principles method with the generalized gradient approximation in the parameterization of Perdew-Burke-Ernzerhof, we have found that Al, B, and P interact strongly with Si atoms. Besides, when the vacancies are generated, the dangling bonds are saturated in pairs to form new bonds. Optimal geometries, binding energies, density of states (DOS) and charge density are reported. The results suggest that new chemical modifications can be used to modify the electronic properties of single-layer silicene.

Subatomic electronic feature from dynamic motion of Si dimer defects in Bi nanolines on Si(001)

NASA Astrophysics Data System (ADS)

Kirkham, C. J.; Longobardi, M.; Köster, S. A.; Renner, Ch.; Bowler, D. R.

2017-08-01

Scanning tunneling microscopy (STM) reveals unusual sharp features in otherwise defect-free Bi nanolines self-assembled on Si(001). They appear as subatomic thin lines perpendicular to the Bi nanoline at positive biases and as atomic size beads at negative biases. Density functional theory (DFT) simulations show that these features can be attributed to buckled Si dimers substituting for Bi dimers in the nanoline, where the sharp feature is the counterintuitive signature of these dimers flipping during scanning. The perfect correspondence between the STM data and the DFT simulation demonstrated in this paper highlights the detailed understanding we have of the complex Bi-Si(001) Haiku system. This discovery has applications in the patterning of Si dangling bonds for nanoscale electronics.

Theoretical characterisation of point defects on a MoS2 monolayer by scanning tunnelling microscopy.

PubMed

González, C; Biel, B; Dappe, Y J

2016-03-11

Different S and Mo vacancies as well as their corresponding antisite defects in a free-standing MoS2 monolayer are analysed by means of scanning tunnelling microscopy (STM) simulations. Our theoretical methodology, based on the Keldysh nonequilibrium Green function formalism within the density functional theory (DFT) approach, is applied to simulate STM images for different voltages and tip heights. Combining the geometrical and electronic effects, all features of the different STM images can be explained, providing a valuable guide for future experiments. Our results confirm previous reports on S atom imaging, but also reveal a strong dependence on the applied bias for vacancies and antisite defects that include extra S atoms. By contrast, when additional Mo atoms cover the S vacancies, the MoS2 gap vanishes and a bias-independent bright protrusion is obtained in the STM image. Finally, we show that the inclusion of these point defects promotes the emergence of reactive dangling bonds that may act as efficient adsorption sites for external adsorbates.

Interactions between plasma-treated carbon nanotubes and electrically neutral materials

NASA Astrophysics Data System (ADS)

Ogawa, Daisuke; Nakamura, Keiji

2014-10-01

A plasma treatment can create dangling bonds on the surface of carbon nanotubes (CNTs). The dangling bonds are so reactive that the bonds possibly interact with other neutral species even out of the plasma if the lifetime of the bonds is effectively long. In order to have good understandings with the interactions, we placed multi-wall CNTs (MWCNTs) in atmospheric dielectric barrier discharge that was created in a closed environment with the voltage at 5 kV. We set 50 W for the operating power and 15 minutes for the process time for this plasma treatment. Our preliminary results showed that the reaction between dangling bonds and neutrals likely occurred in the situation when CNTs were treated with argon plasma, and then exposed in a nitrogen-rich dry box. We did Fourier transform infrared (FTIR) spectroscopy after the treatments. The measurement showed that the spectrum with plasma-treated CNTs was different from pristine CNTs. This is an indication that the plasma-treated CNTs have reactive cites on the surface even after the discharge (~ minutes), and then the CNTs likely reacted with the neutral species that causes the different spectrum. In this poster, we will show more details from our results and further progresses from this research.

Dangling bond energetics in carbon nitride and phosphorus carbide thin films with fullerene-like and amorphous structure

NASA Astrophysics Data System (ADS)

Gueorguiev, G. K.; Broitman, E.; Furlan, A.; Stafström, S.; Hultman, L.

2009-11-01

The energy cost for dangling bond formation in Fullerene-like Carbon Nitride (FL-CN x) and Phosphorus carbide (FL-CP x) as well as their amorphous counterparts: a-CN x, a-CP x, and a-C has been calculated within the framework of Density Functional Theory and compared with surface water adsorption measurements. The highest energy cost is found in the FL-CN x (about 1.37 eV) followed by FL-CP x compounds (0.62-1.04 eV).

Analytic method for calculating properties of random walks on networks

NASA Technical Reports Server (NTRS)

Goldhirsch, I.; Gefen, Y.

1986-01-01

A method for calculating the properties of discrete random walks on networks is presented. The method divides complex networks into simpler units whose contribution to the mean first-passage time is calculated. The simplified network is then further iterated. The method is demonstrated by calculating mean first-passage times on a segment, a segment with a single dangling bond, a segment with many dangling bonds, and a looplike structure. The results are analyzed and related to the applicability of the Einstein relation between conductance and diffusion.

Surface Structure and Surface Electronic States Related to Plasma Cleaning of Silicon and Germanium

NASA Astrophysics Data System (ADS)

Cho, Jaewon

This thesis discusses the surface structure and the surface electronic states of Si and Ge(100) surfaces as well as the effects of oxidation process on the silicon oxide/Si(100) interface structure. The H-plasma exposure was performed in situ at low temperatures. The active species, produced in the H-plasma by the rf-excitation of H_2 gas, not only remove microcontaminants such as oxygen and carbon from the surface, but also passivate the surface with atomic hydrogen by satisfying the dangling bonds of the surface atoms. The surfaces were characterized by Angle Resolved UV-Photoemission Spectroscopy (ARUPS) and Low Energy Electron Diffraction (LEED). In the case of Si(100), H-plasma exposure produced ordered H-terminated crystallographic structures with either a 2 x 1 or 1 x 1 LEED pattern. The hydride phases, found on the surfaces of the cleaned Si(100), were shown to depend on the temperature of the surface during H-plasma cleaning. The electronic states for the monohydride and dihydride phases were identified by ARUPS. When the plasma cleaned surface was annealed, the phase transition from the dihydride to monohydride was observed. The monohydride Si-H surface bond was stable up to 460^circC, and the dangling bond surface states were identified after annealing at 500^circC which was accompanied by the spectral shift. The H-terminated surface were characterized to have a flat band structure. For the Ge(100) surface, an ordered 2 x 1 monohydride phase was obtained from the surface cleaned at 180 ^circC. After plasma exposure at <=170^circC a 1 x 1 surface was observed, but the ARUPS indicated that the surface was predominantly composed of disordered monohydride structures. After annealing above the H-dissociation temperatures, the shift in the spectrum was shown to occur with the dangling bond surface states. The H-terminated surfaces were identified to be unpinned. The interface structure of silicon oxide/Si(100) was studied using ARUPS. Spectral shifts were observed, which were dependent on the processes of surface preparation and oxidation. The shift was characterized in association with the band bending. The origins of the spectral shifts were discussed, including defects at interface and H-passivation in Si. The interface structure is considered to be dependent on the surface preparation and oxidation process.

Inhibition of quantum size effects from surface dangling bonds: The first principles study on different morphology SiC nanowires

NASA Astrophysics Data System (ADS)

Li, Yan-Jing; Li, Shu-Long; Gong, Pei; Li, Ya-Lin; Fang, Xiao-Yong; Jia, Ya-Hui; Cao, Mao-Sheng

2018-06-01

In recent years, we investigated the structure and photoelectric properties of Silicon carbide nanowires (SiCNWs) with different morphologies and sizes by using the first-principle in density functional theory, and found a phenomenon that is opposite to quantum size effect, namely, the band gap of nanowires increases with the increase of the diameter. To reveal the nature of this phenomenon, we further carry out the passivation of SiCNWs. The results show that the hydrogenated SiCNWs are direct band gap semiconductors, and the band gap decreases with the diameter increasing, which indicates the dangling bonds of the SiCNWs suppress its quantum size effect. The optical properties of SiCNWs with different diameters before and after hydrogenated are compared, we found that these surface dangling bonds lead to spectral shift which is different with quantum size effect of SiCNWs. These results have potential scientific value to deepen the understanding of the photoelectric properties of SiCNWs and to promote the development of optoelectronic devices.

Strong Photoluminescence Enhancement of Silicon Oxycarbide through Defect Engineering

PubMed Central

Ford, Brian; Tabassum, Natasha; Nikas, Vasileios; Gallis, Spyros

2017-01-01

The following study focuses on the photoluminescence (PL) enhancement of chemically synthesized silicon oxycarbide (SiCxOy) thin films and nanowires through defect engineering via post-deposition passivation treatments. SiCxOy materials were deposited via thermal chemical vapor deposition (TCVD), and exhibit strong white light emission at room-temperature. Post-deposition passivation treatments were carried out using oxygen, nitrogen, and forming gas (FG, 5% H2, 95% N2) ambients, modifying the observed white light emission. The observed white luminescence was found to be inversely related to the carbonyl (C=O) bond density present in the films. The peak-to-peak PL was enhanced ~18 and ~17 times for, respectively, the two SiCxOy matrices, oxygen-rich and carbon-rich SiCxOy, via post-deposition passivations. Through a combinational and systematic Fourier transform infrared spectroscopy (FTIR) and PL study, it was revealed that proper tailoring of the passivations reduces the carbonyl bond density by a factor of ~2.2, corresponding to a PL enhancement of ~50 times. Furthermore, the temperature-dependent and temperature-dependent time resolved PL (TDPL and TD-TRPL) behaviors of the nitrogen and forming gas passivated SiCxOy thin films were investigated to acquire further insight into the ramifications of the passivation on the carbonyl/dangling bond density and PL yield. PMID:28772802

Super-hydrophobic coatings with nano-size roughness prepared with simple PECVD method

NASA Astrophysics Data System (ADS)

Choi, Yoon S.; Lee, Joon S.; Jin, Su B.; Han, Jeon G.

2013-08-01

A simple and conventional method to synthesize nearly flat super-hydrophobic coatings was studied. Conventional plasma enhanced chemical vapour deposition (PECVD) was adopted to synthesize hydrophobic coatings on plastic and glass substrates at room temperature. Hexamethyldisilane was used as a precursor, and hydrogen gas was added to modulate the surface roughness and passivate defects, such as dangling bond and electrically uncovered polar sites rendering non-hydrophobicity. The static water contact angle (WCA) was controlled in the range 120°-160° by adjusting process parameters, especially the hydrogen flow rate and power. AFM showed that the film with a WCA of 145° has as small as 2.5 nm roughness in rms value. In the resistance test of salt water and cosmetics, this film showed excellent results owing to super-hydrophobicity and defect passivation which keeps the surface isolated from external agents. In order to exploit these results, Rare gas analysis was used to examine the process plasma and Fourier transform infrared (FTIR) was used to analyse the chemical structures of the super-hydrophobic films. In the FTIR results, the remarkable increase in the modes of Si-Hx and Si-C bonds as well as Si-CH2-Si in the film was observed indicating the defect passivation and closely packed dense film structure.

Defect-induced room temperature ferromagnetism in silicon carbide nanosheets

NASA Astrophysics Data System (ADS)

Yang, Guijin; Wu, Yanyan; Ma, Shuyi; Fu, Yujun; Gao, Daqiang; Zhang, Zhengmei; Li, Jinyun

2018-07-01

Silicon carbide (SiC) nanosheets with different sizes and thickness were synthesized by a liquid exfoliation method by varying the exfoliating time in the N, N-dimethylformamide organic solvent. During the exfoliating time increasing from 4 to 16 h, the size of the SiC nanosheets decreases gradually from 500 to 200 nm, and the thickness decreases from 9 to 3.5 nm. Results showed that all prepared SiC nanosheets show intrinsic room temperature ferromagnetism, which is greatly different to the diamagnetism nature of virgin bulk SiC. Moreover, the saturation magnetization of the SiC nanosheets increases monotonously from 0.005 to 0.018 emu/g as the size and thickness decrease. Further studies via transmission electron microscopy, superconducting quantum interference device, and electron spin resonance revealed that the origin of the ferromagnetism in SiC nanosheets might be attributed to the defects with carbon dangling bond on the surface of nanosheets.

Effects of Vacancy Cluster Defects on Electrical and Thermodynamic Properties of Silicon Crystals

PubMed Central

Huang, Pei-Hsing; Lu, Chi-Ming

2014-01-01

A first-principle plane-wave pseudopotential method based on the density function theory (DFT) was employed to investigate the effects of vacancy cluster (VC) defects on the band structure and thermoelectric properties of silicon (Si) crystals. Simulation results showed that various VC defects changed the energy band and localized electron density distribution of Si crystals and caused the band gap to decrease with increasing VC size. The results can be ascribed to the formation of a defect level produced by the dangling bonds, floating bonds, or high-strain atoms surrounding the VC defects. The appearance of imaginary frequencies in the phonon spectrum of defective Si crystals indicates that the defect-region structure is dynamically unstable and demonstrates phase changes. The phonon dispersion relation and phonon density of state were also investigated using density functional perturbation theory. The obtained Debye temperature (θ D) for a perfect Si crystal had a minimum value of 448 K at T = 42 K and a maximum value of 671 K at the high-temperature limit, which is consistent with the experimental results reported by Flubacher. Moreover, the Debye temperature decreased with increases in the VC size. VC defects had minimal effects on the heat capacity (C v) value when temperatures were below 150 K. As the temperature was higher than 150 K, the heat capacity gradually increased with increasing temperature until it achieved a constant value of 11.8 cal/cell·K. The heat capacity significantly decreased as the VC size increased. For a 2 × 2 × 2 superlattice Si crystal containing a hexagonal ring VC (HRVC10), the heat capacity decreased by approximately 17%. PMID:24526923

Theoretical insights into the energetics and electronic properties of MPt12 (M = Fe, Co, Ni, Cu, and Pd) nanoparticles supported by N-doped defective graphene

NASA Astrophysics Data System (ADS)

Wang, Qing; Tian, Yu; Chen, Guangju; Zhao, Jingxiang

2017-03-01

Enhancing the catalytic activity and decreasing the usage of Pt catalysts has been a major target in widening their applications for developing proton-exchange membrane fuel cells. In this work, the adsorption energetics, structural features, and electronic properties of several MPt12 (M = Fe, Co, Ni, Cu, and Pd) nanoparticles (NPs) deposited on N-doped defective graphene were systemically explored by means of comprehensive density functional theory (DFT) computations. The computations revealed that the defective N-doped graphene substrate can provide anchoring site for these Pt-based alloying NPs due to their strong hybridization with the sp2 dangling bonds at the defect sites of substrate. Especially, these deposited MPt12 NPs exhibit reduced magnetic moment and their average d-band centers are shifted away from the Fermi level, as compared with the freestanding NPs, leading to the reduction of the adsorption energies of the O species. Thus, the defective N-doped graphene substrate not only enhances the stability of the deposited MPt12 NPs, but also endows them higher catalytic performance for the oxygen reduction reaction.

Interactions of atomic hydrogen with amorphous SiO2

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Tritiated amorphous silicon films and devices

NASA Astrophysics Data System (ADS)

Kosteski, Tome

The do saddle-field glow discharge deposition technique has been used to bond tritium within an amorphous silicon thin film network using silane and elemental tritium in the glow discharge. The concentration of tritium is approximately 7 at. %. Minimal outgassing of tritium from tritiated hydrogenated amorphous silicon (a-Si:H:T) at room temperature suggests that tritium is bonded stably. Tritium effusion only occurred at temperatures above the film's growth temperature. The radioactive decay of tritium results in the production of high-energy beta particles. Each beta particle can generate on average approximately 1300 electron-hole pairs in a-Si:H:T. Electrical conductivity of a-Si:H:T is shown to be due to a thermally activated process and due to the generation of excess carriers by the beta particles. p-i-n betavoltaic devices have been made with a-Si:H:T in the intrinsic (i-) region. The i-region consisted of either a-Si:H:T, or a thin section of a-Si:H:T (a Delta layer) sandwiched between undoped hydrogenated amorphous silicon (a-Si:H). The excess carriers generated in the i-region are separated by the device's built-in electric field. Short-circuit currents (Isc ), open-circuit voltages (Voc), and power have been measured and correlated to the generation of excess carriers in the i-region. Good devices were made at a substrate temperature of 250°C and relatively large flow rates of silane and tritium; this ensures that there are more monohydride bonds than dihydride bonds. Under dark conditions, Isc, and Voc have been found to decrease rapidly. This is consistent with the production of silicon neutral dangling bonds (5 x 1017cm-3 per day) from the loss of tritium due to its transmutation into helium. Dangling bonds reduce carrier lifetime and weaken the electric field in the i-region. The short-circuit current from Delta layer devices decreased more slowly and settled to higher values for narrower Delta layers. This is because the dangling bonds are isolated to the Delta layer and the lifetime of excess carriers generated in the a-Si:H remains unaffected. Annealing a-Si:H:T at 120°C for approximately one hour is shown to remove dangling bonds produced from the decay of bonded tritium.

Mechanical response of transient telechelic networks with many-part stickers

NASA Astrophysics Data System (ADS)

Sing, Michelle K.; Ramírez, Jorge; Olsen, Bradley D.

2017-11-01

A central question in soft matter is understanding how several individual, weak bonds act together to produce collective interactions. Here, gel-forming telechelic polymers with multiple stickers at each chain end are studied through Brownian dynamics simulations to understand how collective interaction of the bonds affects mechanical response of the gels. These polymers are modeled as finitely extensible dumbbells using an explicit tau-leap algorithm and the binding energy of these associations was kept constant regardless of the number of stickers. The addition of multiple bonds to the associating ends of telechelic polymers increases or decreases the network relaxation time depending on the relative kinetics of association but increases both shear stress and extensional viscosity. The relationship between the rate of association and the Rouse time of dangling chains results in two different regimes for the equilibrium stress relaxation of associating physical networks. In case I, a dissociated dangling chain is able to fully relax before re-associating to the network, resulting in two characteristic relaxation times and a non-monotonic terminal relaxation time with increasing number of bonds per polymer endgroup. In case II, the dissociated dangling chain is only able to relax a fraction of the way before it re-attaches to the network, and increasing the number of bonds per endgroup monotonically increases the terminal relaxation time. In flow, increasing the number of stickers increases the steady-state shear and extensional viscosities even though the overall bond kinetics and equilibrium constant remain unchanged. Increased dissipation in the simulations is primarily due to higher average chain extension with increasing bond number. These results indicate that toughness and dissipation in physically associating networks can both be increased by breaking single, strong bonds into smaller components.

Surface Dangling-Bond States and Band Lineups in Hydrogen-Terminated Si, Ge, and Ge/Si Nanowires

NASA Astrophysics Data System (ADS)

Kagimura, R.; Nunes, R. W.; Chacham, H.

2007-01-01

We report an ab initio study of the electronic properties of surface dangling-bond (SDB) states in hydrogen-terminated Si and Ge nanowires with diameters between 1 and 2 nm, Ge/Si nanowire heterostructures, and Si and Ge (111) surfaces. We find that the charge transition levels ɛ(+/-) of SDB states behave as a common energy reference among Si and Ge wires and Si/Ge heterostructures, at 4.3±0.1eV below the vacuum level. Calculations of ɛ(+/-) for isolated atoms indicate that this nearly constant value is a periodic-table atomic property.

Characterization of point defects in monolayer arsenene

NASA Astrophysics Data System (ADS)

Liang, Xiongyi; Ng, Siu-Pang; Ding, Ning; Wu, Chi-Man Lawrence

2018-06-01

Topological defects that are inevitably found in 2D materials can dramatically affect their properties. Using density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) method, the structural, thermodynamic, electronic and magnetic properties of six types of typical point defects in arsenene, i.e. the Stone-Wales defect, single and double vacancies and adatoms, were systemically studied. It was found that these defects were all more easily generated in arsenene with lower formation energies than those with graphene and silicene. Stone-Wales defects can be transformed from pristine arsenene by overcoming a barrier of 2.19 eV and single vacancy defects tend to coalesce into double vacancy defects by diffusion. However, a type of adatom defect does not exhibit kinetic stability at room temperature. In addition, SV defects and another type of adatom defect can remarkably affect the electronic and magnetic properties of arsenene, e.g. they can introduce localized states near the Fermi level, as well as a strongly local magnetic moment due to dangling bond and unpaired electron. Furthermore, the simulated scanning tunneling microscopy (STM) and Raman spectroscopy were computed and the types of point defects can be fully characterized by correlating the STM images and Raman spectra to the defective atomistic structures. The results provide significant insights to the effect of defects in arsenene for potential applications, as well as identifications of two helpful tools (STM and Raman spectroscopy) to distinguish the type of defects in arsenene for future experiments.

High-frequency EPR of surface impurities on nanodiamond

NASA Astrophysics Data System (ADS)

Peng, Zaili; Stepanov, Viktor; Takahashi, Susumu

Diamond is a fascinating material, hosting nitrogen-vacancy (NV) defect centers with unique magnetic and optical properties. There have been many reports that suggest the existence of paramagnetic impurities near surface of various kinds of diamonds. Electron paramagnetic resonance (EPR) investigation of mechanically crushed nanodiamonds (NDs) as well as detonation NDs revealed g 2 like signals that are attributed to structural defects and dangling bonds near the diamond surface. In this presentation, we investigate paramagnetic impurities in various sizes of NDs using high-frequency (HF) continuous wave (cw) and pulsed EPR spectroscopy. Strong size dependence on the linewidth of HF cw EPR spectra reveals the existence of paramagnetic impurities in the vicinity of the diamond surface. We also study the size dependence of the spin-lattice and spin-spin relaxation times (T1 and T2) of single substitutional nitrogen defects in NDs Significant deviations from the temperature dependence of the phonon-assisted T1 process were observed in the ND samples, and were attributed to the contribution from the surface impurities. This work was supported by the Searle Scholars Program and the National Science Foundation (DMR-1508661 and CHE-1611134).

Molecular dynamics study of radiation damage and microstructure evolution of zigzag single-walled carbon nanotubes under carbon ion incidence

NASA Astrophysics Data System (ADS)

Li, Huan; Tang, Xiaobin; Chen, Feida; Huang, Hai; Liu, Jian; Chen, Da

2016-07-01

The radiation damage and microstructure evolution of different zigzag single-walled carbon nanotubes (SWCNTs) were investigated under incident carbon ion by molecular dynamics (MD) simulations. The radiation damage of SWCNTs under incident carbon ion with energy ranging from 25 eV to 1 keV at 300 K showed many differences at different incident sites, and the defect production increased to the maximum value with the increase in incident ion energy, and slightly decreased but stayed fairly stable within the majority of the energy range. The maximum damage of SWCNTs appeared when the incident ion energy reached 200 eV and the level of damage was directly proportional to incident ion fluence. The radiation damage was also studied at 100 K and 700 K and the defect production decreased distinctly with rising temperature because radiation-induced defects would anneal and recombine by saturating dangling bonds and reconstructing carbon network at the higher temperature. Furthermore, the stability of a large-diameter tube surpassed that of a thin one under the same radiation environments.

Organic Solar Cells: Degradation Processes and Approaches to Enhance Performance

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

Fungura, Fadzai

2016-12-17

Intrinsic photodegradation of organic solar cells, theoretically attributed to C-H bond rearrangement/breaking, remains a key commercialization barrier. This work presents, via dark electron paramagnetic resonance (EPR), the first experimental evidence for metastable C dangling bonds (DBs) (g=2.0029±0.0004) formed by blue/UV irradiation of polymer:fullerene blend films in nitrogen. The DB density increased with irradiation and decreased ~4 fold after 2 weeks in the dark. The dark EPR also showed increased densities of other spin-active sites in photodegraded polymer, fullerene, and polymer:fullerene blend films, consistent with broad electronic measurements of fundamental properties, including defect/gap state densities. The EPR enabled identification of defectmore » states, whether in the polymer, fullerene, or at the donor/acceptor (D/A) interface. Importantly, the EPR results indicate that the DBs are at the D/A interface, as they were present only in the blend films. The role of polarons in interface DB formation is also discussed.« less

Highly Sensitive and Reusable Membraneless Field-Effect Transistor (FET)-Type Tungsten Diselenide (WSe2) Biosensors.

PubMed

Lee, Hae Won; Kang, Dong-Ho; Cho, Jeong Ho; Lee, Sungjoo; Jun, Dong-Hwan; Park, Jin-Hong

2018-05-30

In recent years when the demand for high-performance biosensors has been aroused, a field-effect transistor (FET)-type biosensor (BioFET) has attracted great interest because of its high sensitivity, label-free detection, fast detection speed, and miniaturization. However, the insulating membrane in the conventional BioFET, which is essential in preventing the surface dangling bonds of typical semiconductors from nonspecific bindings, has limited the sensitivity of biosensors. Here, we present a highly sensitive and reusable membraneless BioFET based on a defect-free van der Waals material, tungsten diselenide (WSe 2 ). We intentionally generated a few surface defects that serve as extra binding sites for the bioreceptor immobilization through weak oxygen plasma treatment, consequently magnifying the sensitivity values to 2.87 × 10 5 A/A for 10 mM glucose. The WSe 2 BioFET also maintained its high sensitivity even after several cycles of rinsing and glucose application were repeated.

Discrete impurity band from surface danging bonds in nitrogen and phosphorus doped SiC nanowires

NASA Astrophysics Data System (ADS)

Li, Yan-Jing; Li, Shu-Long; Gong, Pei; Li, Ya-Lin; Cao, Mao-Sheng; Fang, Xiao-Yong

2018-04-01

The electronic structure and optical properties of the nitrogen and phosphorus doped silicon carbide nanowires (SiCNWs) are investigated using first-principle calculations based on density functional theory. The results show doping can change the type of the band gap and improve the conductivity. However, the doped SiCNWs form a discrete impurity levels at the Fermi energy, and the dispersion degree decreases with the diameter increasing. In order to reveal the root of this phenomenon, we hydrogenated the doped SiCNWs, found that the surface dangling bonds were saturated, and the discrete impurity levels are degeneracy, which indicates that the discrete impurity band of the doped SiCNWs is derived from the dangling bonds. The surface passivation can degenerate the impurity levels. Therefore, both doping and surface passivation can better improve the photoelectric properties of the SiCNWs. The result can provide additional candidates in producing nano-optoelectronic devices.

Hydrogen interaction kinetics of Ge dangling bonds at the Si0.25Ge0.75/SiO2 interface

NASA Astrophysics Data System (ADS)

Stesmans, A.; Nguyen Hoang, T.; Afanas'ev, V. V.

2014-07-01

The hydrogen interaction kinetics of the GePb1 defect, previously identified by electron spin resonance (ESR) as an interfacial Ge dangling bond (DB) defect occurring in densities ˜7 × 1012 cm-2 at the SiGe/SiO2 interfaces of condensation grown (100)Si/a-SiO2/Ge0.75Si0.25/a-SiO2 structures, has been studied as function of temperature. This has been carried out, both in the isothermal and isochronal mode, through defect monitoring by capacitance-voltage measurements in conjunction with ESR probing, where it has previously been demonstrated the defects to operate as negative charge traps. The work entails a full interaction cycle study, comprised of analysis of both defect passivation (pictured as GePb1-H formation) in molecular hydrogen (˜1 atm) and reactivation (GePb1-H dissociation) in vacuum. It is found that both processes can be suitably described separately by the generalized simple thermal (GST) model, embodying a first order interaction kinetics description based on the basic chemical reactions GePb1 + H2 → GePb1H + H and GePb1H → GePb1 + H, which are found to be characterized by the average activation energies Ef = 1.44 ± 0.04 eV and Ed = 2.23 ± 0.04 eV, and attendant, assumedly Gaussian, spreads σEf = 0.20 ± 0.02 eV and σEd = 0.15 ± 0.02 eV, respectively. The substantial spreads refer to enhanced interfacial disorder. Combination of the separately inferred kinetic parameters for passivation and dissociation results in the unified realistic GST description that incorporates the simultaneous competing action of passivation and dissociation, and which is found to excellently account for the full cycle data. For process times ta ˜ 35 min, it is found that even for the optimum treatment temperature ˜380 °C, only ˜60% of the GePb1 system can be electrically silenced, still far remote from device grade level. This ineffectiveness is concluded, for the major part, to be a direct consequence of the excessive spreads in the activation energies, ˜2-3 times larger than for the Si DB Pb defects at the standard thermal (111)Si/SiO2 interface which may be easily passivated to device grade levels, strengthened by the reduced difference between the average Ef and Ed values. Exploring the guidelines of the GST model indicates that passivation can be improved by decreasing Tan and attendant enlarging of ta, however, at best still leaving ˜2% defects unpassivated even for unrealistically extended anneal times. The average dissociation energy Ed ˜ 2.23 eV, concluded as representing the GePb1-H bond strength, is found to be smaller than the SiPb-H one, characterized by Ed ˜ 2.83 eV. An energy deficiency is encountered regarding the energy sum rule inherent to the GST-model, the origin of which is substantiated to lie with a more complex nature of the forward passivation process than basically depicted in the GST model. The results are discussed within the context of theoretical considerations on the passivation of interfacial Ge DBs by hydrogen.

Atomic-scale analysis of deposition and characterization of a-Si:H thin films grown from SiH radical precursor

NASA Astrophysics Data System (ADS)

Sriraman, Saravanapriyan; Aydil, Eray S.; Maroudas, Dimitrios

2002-07-01

Growth of hydrogenated amorphous silicon films (a-Si:H) on an initial H-terminated Si(001)(2 x1) substrate at T=500 K was studied through molecular-dynamics (MD) simulations of repeated impingement of SiH radicals to elucidate the effects of reactive minority species on the structural quality of the deposited films. The important reactions contributing to film growth were identified through detailed visualization of radical-surface interaction trajectories. These reactions include (i) insertion of SiH into Si-Si bonds, (ii) adsorption onto surface dangling bonds, (iii) surface H abstraction by impinging SiH radicals through an Eley-Rideal mechanism, (iv) surface adsorption by penetration into subsurface layers or dissociation leading to interstitial atomic hydrogen, (v) desorption of interstitial hydrogen into the gas phase, (vi) formation of higher surface hydrides through the exchange of hydrogen, and (vii) dangling-bond-mediated dissociation of surface hydrides into monohydrides. The MD simulations of a-Si:H film growth predict an overall surface reaction probability of 95% for the SiH radical that is in good agreement with experimental measurements. Structural and chemical characterization of the deposited films was based on the detailed analysis of evolution of the films' structure, surface morphology and roughness, surface reactivity, and surface composition. The analysis revealed that the deposited films exhibit high dangling bond densities and rough surface morphologies. In addition, the films are abundant in voids and columnar structures that are detrimental to producing device-quality a-Si:H thin films.

Investigation of 3C-SiC/SiO2 interfacial point defects from ab initio g-tensor calculations and electron paramagnetic resonance measurements

NASA Astrophysics Data System (ADS)

Nugraha, T. A.; Rohrmueller, M.; Gerstmann, U.; Greulich-Weber, S.; Stellhorn, A.; Cantin, J. L.; von Bardeleben, J.; Schmidt, W. G.; Wippermann, S.

SiC is widely used in high-power, high-frequency electronic devices. Recently, it has also been employed as a building block in nanocomposites used as light absorbers in solar energy conversion devices. Analogous to Si, SiC features SiO2 as native oxide that can be used for passivation and insulating layers. However, a significant number of defect states are reported to form at SiC/SiO2 interfaces, limiting mobility and increasing recombination of free charge carriers. We investigated the growth of oxide on different 3C-SiC surfaces from first principles. Carbon antisite Csi defects are found to be strongly stabilized in particular at the interface, because carbon changes its hybridization from sp3 in the SiC-bulk to sp2 at the interface, creating a dangling bond inside a porous region of the SiO2 passivating layer. Combining ab initio g-tensor calculations and electron paramagnetic resonance (EPR) measurements, we show that Csi defects explain the measured EPR signatures, while the hyperfine structure allows to obtain local structural information of the oxide layer. Financial support from BMBF NanoMatFutur Grant 13N12972 and DFG priority program SPP-1601 is gratefully acknowledged.

Interaction of a single acetophenone molecule with group III-IV elements mediated by Si(001)

NASA Astrophysics Data System (ADS)

Racis, A.; Jurczyszyn, L.; Radny, M. W.

2018-03-01

A theoretical study of an influence of the acetophenone molecule adsorbed on the Si(001) on the local chemical reactivity of silicon surface is presented. The obtained results indicate that the interaction of the molecule with silicon substrate breaks the intra-dimer π bonds in four surface silicon dimers interacting directly with adsorbed molecule. This leads to the formation of two pairs of unpaired dangling bonds at two opposite sides of the molecule. It is demonstrated that these dangling bonds increase considerably the local chemical reactivity of the silicon substrate in the vicinity of the adsorbed molecule. Consequently, it is shown that such molecule bonded with Si(001) can stabilize the position of In and Pb adatoms diffusing on silicon substrate at two sides and initiate the one-dimensional aggregation of the metallic adatoms on the Si(001) substrate anchored at both sides of the adsorbed molecule. This type of aggregation leads to the growth of chain-like atomic structures in opposite directions, pinned to adsorbed molecule and oriented perpendicular to the rows of surface silicon dimers.

Time-dependent vibrational spectral analysis of first principles trajectory of methylamine with wavelet transform.

PubMed

Biswas, Sohag; Mallik, Bhabani S

2017-04-12

The fluctuation dynamics of amine stretching frequencies, hydrogen bonds, dangling N-D bonds, and the orientation profile of the amine group of methylamine (MA) were investigated under ambient conditions by means of dispersion-corrected density functional theory-based first principles molecular dynamics (FPMD) simulations. Along with the dynamical properties, various equilibrium properties such as radial distribution function, spatial distribution function, combined radial and angular distribution functions and hydrogen bonding were also calculated. The instantaneous stretching frequencies of amine groups were obtained by wavelet transform of the trajectory obtained from FPMD simulations. The frequency-structure correlation reveals that the amine stretching frequency is weakly correlated with the nearest nitrogen-deuterium distance. The frequency-frequency correlation function has a short time scale of around 110 fs and a longer time scale of about 1.15 ps. It was found that the short time scale originates from the underdamped motion of intact hydrogen bonds of MA pairs. However, the long time scale of the vibrational spectral diffusion of N-D modes is determined by the overall dynamics of hydrogen bonds as well as the dangling ND groups and the inertial rotation of the amine group of the molecule.

Column-by-column observation of dislocation motion in CdTe: Dynamic scanning transmission electron microscopy

NASA Astrophysics Data System (ADS)

Li, Chen; Zhang, Yu-Yang; Pennycook, Timothy J.; Wu, Yelong; Lupini, Andrew R.; Paudel, Naba; Pantelides, Sokrates T.; Yan, Yanfa; Pennycook, Stephen J.

2016-10-01

The dynamics of partial dislocations in CdTe have been observed at the atomic scale using aberration-corrected scanning transmission electron microscopy (STEM), allowing the mobility of different dislocations to be directly compared: Cd-core Shockley partial dislocations are more mobile than Te-core partials, and dislocation cores with unpaired columns have higher mobility than those without unpaired columns. The dynamic imaging also provides insight into the process by which the dislocations glide. Dislocations with dangling bonds on unpaired columns are found to be more mobile because the dangling bonds mediate the bond exchanges required for the dislocations to move. Furthermore, a screw dislocation has been resolved to dissociate into a Shockley partial-dislocation pair along two different directions, revealing a way for the screw dislocation to glide in the material. The results show that dynamic STEM imaging has the potential to uncover the details of dislocation motion not easily accessible by other means.

A magnetic resonance study of MoS(2) fullerene-like nanoparticles.

PubMed

Panich, A M; Shames, A I; Rosentsveig, R; Tenne, R

2009-09-30

We report on the first nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) investigation of inorganic fullerene-like MoS(2) nanoparticles. Spectra of bulk 2H-MoS(2) samples have also been measured for comparison. The similarity between the measured quadrupole coupling constants and chemical shielding anisotropy parameters for bulk and fullerene-like MoS(2) reflects the nearly identical local crystalline environments of the Mo atoms in these two materials. EPR measurements show that fullerene-like MoS(2) exhibits a larger density of dangling bonds carrying unpaired electrons, indicative of them having a more defective structure than the bulk sample. The latter observation explains the increase in the spin-lattice relaxation rate observed in the NMR measurements for this sample in comparison with the bulk 2H- MoS(2) ones.

A magnetic resonance study of MoS2 fullerene-like nanoparticles

NASA Astrophysics Data System (ADS)

Panich, A. M.; Shames, A. I.; Rosentsveig, R.; Tenne, R.

2009-09-01

We report on the first nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) investigation of inorganic fullerene-like MoS2 nanoparticles. Spectra of bulk 2H-MoS2 samples have also been measured for comparison. The similarity between the measured quadrupole coupling constants and chemical shielding anisotropy parameters for bulk and fullerene-like MoS2 reflects the nearly identical local crystalline environments of the Mo atoms in these two materials. EPR measurements show that fullerene-like MoS2 exhibits a larger density of dangling bonds carrying unpaired electrons, indicative of them having a more defective structure than the bulk sample. The latter observation explains the increase in the spin-lattice relaxation rate observed in the NMR measurements for this sample in comparison with the bulk 2H- MoS2 ones.

First-principles study of Ga-vacancy induced magnetism in β-Ga2O3.

PubMed

Yang, Ya; Zhang, Jihua; Hu, Shunbo; Wu, Yabei; Zhang, Jincang; Ren, Wei; Cao, Shixun

2017-11-01

First principles calculations based on density functional theory were performed to study the electronic structure and magnetic properties of β-Ga 2 O 3 in the presence of cation vacancies. We investigated two kinds of Ga vacancies at different symmetry sites and the consequent structural distortion and defect states. We found that both the six-fold coordinated octahedral site and the four-fold coordinated tetrahedral site vacancies can lead to a spin polarized ground state. Furthermore, the calculation identified a relationship between the spin polarization and the charge states of the vacancies, which might be explained by a molecular orbital model consisting of uncompensated O 2- 2p dangling bonds. The calculations for the two vacancy systems also indicated a potential long-range ferromagnetic order which is beneficial for spintronics application.

Quantum efficiencies exceeding unity in amorphous silicon solar cells

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

Vanmaekelbergh, D.; Lagemaat, J. van de; Schropp, R.E.I.

1994-12-31

The experimental observation of internal quantum efficiencies above unity in crystalline silicon solar cells has brought up the question whether the generation of multiple electron/hole pairs has to be taken into consideration also in solar cells based on direct gap amorphous semiconductors. To study photogenerated carrier dynamics, the authors have applied Intensity Modulated Photocurrent Spectroscopy (IMPS) to hydrogenated amorphous silicon p-i-n solar cells. In the reverse voltage bias region at low illumination intensities it has been observed that the low frequency limit of the AC quantum yield Y increases significantly above unit with decreasing light intensity, indicating that more thanmore » one electron per photon is detected in the external circuit. This phenomenon can be explained by considering trapping and thermal emission of photogenerated carriers at intragap atmospheric dangling bond defect centers.« less

Synthesis of SnS2/SnS fullerene-like nanoparticles: a superlattice with polyhedral shape.

PubMed

Hong, Sung You; Popovitz-Biro, Ronit; Prior, Yehiam; Tenne, Reshef

2003-08-27

Tin disulfide pellets were laser ablated in an inert gas atmosphere, and closed cage fullerene-like (IF) nanoparticles were produced. The nanoparticles had various polyhedra and short tubular structures. Some of these forms contained a periodic pattern of fringes resulting in a superstructure. These patterns could be assigned to a superlattice created by periodic stacking of layered SnS(2) and SnS. Such superlattices are reminiscent of misfit layer compounds, which are known to form tubular morphologies. This mechanism adds up to the established mechanism for IF formation, namely, the annihilation of reactive dangling bonds at the periphery of the nanoparticles. Additionally, it suggests that one of the driving forces to form tubules in misfit compounds is the annihilation of dangling bonds at the rim of the layered structure.

Studies of electronic structure of ZnO grain boundary and its proximity by using spatially resolved electron energy loss spectroscopy

NASA Astrophysics Data System (ADS)

Ong, H. C.; Dai, J. Y.; Du, G. T.

2002-07-01

The low electron energy loss and complex dielectric functions of an arbitrary grain boundary and its proximity in ZnO thin films have been studied by using the spatially resolved electron energy loss spectroscopy. The critical point parameters have been determined by fitting the dielectric functions simultaneously with analytical line shape model. Gradual changes have been observed in the dielectric functions spectra. The critical points are found to redshift and then blueshift when the electron beam scanned across the grain boundary, which suggest the distinctive electronic structure not only of the grain boundary but also of the depletion region. In addition, comparison has been made between the experiment and the recent theoretical studies to account for the interband transitions that occur in the grain boundaries. Several features predicted by the theory are qualitatively found to be consistent with our results. The presence of dangling bonds instead of bond distortion is attributed to be the major cause of defects in the grain boundaries of ZnO.

Surface Defect Passivation and Reaction of c-Si in H2S.

PubMed

Liu, Hsiang-Yu; Das, Ujjwal K; Birkmire, Robert W

2017-12-26

A unique passivation process of Si surface dangling bonds through reaction with hydrogen sulfide (H 2 S) is demonstrated in this paper. A high-level passivation quality with an effective minority carrier lifetime (τ eff ) of >2000 μs corresponding to a surface recombination velocity of <3 cm/s is achieved at a temperature range of 550-650 °C. X-ray photoelectron spectroscopy (XPS) confirmed the bonding states of Si and S and provides insights into the reaction pathway of Si with H 2 S and other impurity elements both during and after the reaction. Quantitative analysis of XPS spectra showed that the τ eff increases with an increase in the surface S content up to ∼3.5% and stabilizes thereafter, indicative of surface passivation by monolayer coverage of S on the Si surface. However, S passivation of the Si surface is highly unstable because of thermodynamically favorable reaction with atmospheric H 2 O and O 2 . This instability can be eliminated by capping the S-passivated Si surface with a protective thin film such as low-temperature-deposited amorphous silicon nitride.

Hydrogen passivation of polycrystalline silicon thin films

NASA Astrophysics Data System (ADS)

Scheller, L.-P.; Weizman, M.; Simon, P.; Fehr, M.; Nickel, N. H.

2012-09-01

The influence of post-hydrogenation on the electrical and optical properties of solid phase crystallized polycrystalline silicon (poly-Si) was examined. The passivation of grain-boundary defects was measured as a function of the passivation time. The silicon dangling-bond concentration decreases with increasing passivation time due to the formation of Si-H complexes. In addition, large H-stabilized platelet-like clusters are generated. The influence of H on the electrical properties was investigated using temperature dependent conductivity and Hall-effect measurements. For poly-Si on Corning glass, the dark conductivity decreases upon hydrogenation, while it increases when the samples are fabricated on silicon-nitride covered Borofloat glass. Hall-effect measurements reveal that for poly-Si on Corning glass the hole concentration and the mobility decrease upon post-hydrogenation, while a pronounced increase is observed for poly-Si on silicon-nitride covered Borofloat glass. This indicates the formation of localized states in the band gap, which is supported by sub band-gap absorption measurments. The results are discussed in terms of hydrogen-induced defect passivation and generation mechanisms.

Myotonic Dystrophy Type 1 RNA Crystal Structures Reveal Heterogeneous 1×1 Nucleotide UU Internal Loop Conformations⊥

PubMed Central

Kumar, Amit; Park, HaJeung; Fang, Pengfei; Parkesh, Raman; Guo, Min; Nettles, Kendall W.; Disney, Matthew D.

2011-01-01

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5′CUG/3′GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures are disclosed of a model DM1 triplet repeating construct, 5′r(UUGGGC(CUG)3GUCC)2, refined to 2.20 Å and 1.52 Å resolution. Here, differences in orientation of the 5′ dangling UU end between the two structures induce changes in the backbone groove width, which reveals that non-canonical 1×1 nucleotide UU internal loops can display an ensemble of pairing conformations. In the 2.20 Å structure, CUGa, the 5′UU forms one hydrogen-bonded pairs with a 5′UU of a neighboring helix in the unit cell to form a pseudo-infinite helix. The central 1×1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1×1 nucleotide UU internal loops each form a one hydrogen-bonded pair. In the 1.52 Å structure, CUGb, the 5′ UU dangling end is tucked into the major groove of the duplex. While the canonical paired bases show no change in base pairing, in CUGb the terminal 1×1 nucleotide UU internal loops form now two hydrogen-bonded pairs. Thus, the shift in major groove induced by the 5′UU dangling end alters non-canonical base patterns. Collectively, these structures indicate that 1×1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands. PMID:21988728

Myotonic dystrophy type 1 RNA crystal structures reveal heterogeneous 1 × 1 nucleotide UU internal loop conformations.

PubMed

Kumar, Amit; Park, HaJeung; Fang, Pengfei; Parkesh, Raman; Guo, Min; Nettles, Kendall W; Disney, Matthew D

2011-11-15

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5'CUG/3'GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures of a model DM1 triplet repeating construct, 5'r[UUGGGC(CUG)(3)GUCC](2), refined to 2.20 and 1.52 Å resolution are disclosed. Here, differences in the orientation of the 5' dangling UU end between the two structures induce changes in the backbone groove width, which reveals that noncanonical 1 × 1 nucleotide UU internal loops can display an ensemble of pairing conformations. In the 2.20 Å structure, CUGa, the 5' UU forms a one hydrogen-bonded pair with a 5' UU of a neighboring helix in the unit cell to form a pseudoinfinite helix. The central 1 × 1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1 × 1 nucleotide UU internal loops each form a one-hydrogen bond pair. In the 1.52 Å structure, CUGb, the 5' UU dangling end is tucked into the major groove of the duplex. While the canonically paired bases show no change in base pairing, in CUGb the terminal 1 × 1 nucleotide UU internal loops now form two hydrogen-bonded pairs. Thus, the shift in the major groove induced by the 5' UU dangling end alters noncanonical base patterns. Collectively, these structures indicate that 1 × 1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands.

Myotonic Dystrophy Type 1 RNA Crystal Structures Reveal Heterogeneous 1 × 1 Nucleotide UU Internal Loop Conformations

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

Kumar, Amit; Park, HaJeung; Fang, Pengfei

2012-03-27

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5'CUG/3'GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures of a model DM1 triplet repeating construct, 5'r[{und UU}GGGC(C{und U}G){sub 3}GUCC]{sub 2}, refined to 2.20 and 1.52 {angstrom} resolution are disclosed. Here, differences in the orientation of the 5' dangling UU end between the two structures induce changes in the backbone groove width, which reveals that noncanonical 1 x 1 nucleotide UU internal loops can display an ensemble of pairing conformations.more » In the 2.20 {angstrom} structure, CUGa, the 5' UU forms a one hydrogen-bonded pair with a 5' UU of a neighboring helix in the unit cell to form a pseudoinfinite helix. The central 1 x 1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1 x 1 nucleotide UU internal loops each form a one-hydrogen bond pair. In the 1.52 {angstrom} structure, CUGb, the 5' UU dangling end is tucked into the major groove of the duplex. While the canonically paired bases show no change in base pairing, in CUGb the terminal 1 x 1 nucleotide UU internal loops now form two hydrogen-bonded pairs. Thus, the shift in the major groove induced by the 5' UU dangling end alters noncanonical base patterns. Collectively, these structures indicate that 1 x 1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands.« less

Synchrotron Radiation Damage Mechanism of X-Ray Mask Membranes Irradiated in Helium Environment

NASA Astrophysics Data System (ADS)

Arakawa, Tomiyuki; Okuyama, Hiroshi; Okada, Koichi; Nagasawa, Hiroyuki; Syoki, Tsutomu; Yamaguchi, Yoh-ichi

1992-12-01

The mechanism of X-ray mask membrane displacement induced by synchrotron radiation (SR) has been discussed. Silicon nitride (SiN) and silicon carbide (SiC) membranes were irradiated by SR in a 1 atm helium ambient. SR-induced displacement for both membranes was 25-97 nm (σ). Oxygen concentration in both SiN and SiC was below 0.01 in O/Si atomic ratio. Although an increase in dangling bond density of SiN was observed, no remarkable increase in spin density was detected in SiC. Moreover, the most important finding was that thin oxides were grown on the membrane surface after SR irradiation. From these results, it is considered that the oxide growth on SiC membrane surfaces, and both the oxide growth and the increase of dangling bond density in SiN play an important role in the SR-induced displacement for the X-ray mask membranes.

Universal behavior of surface-dangling bonds in hydrogen-terminated Si, Ge, and Si/Ge nanowires.

NASA Astrophysics Data System (ADS)

Nunes, Ricardo; Kagimura, Ricardo; Chacham, Hélio

2007-03-01

We report an ab initio study of the electronic properties of surface dangling bond (SDB) states in hydrogen-terminated Si, Ge, and Si/Ge nanowires with diameters between 1 and 2 nm. We find that the charge transition levels ɛ(+/-) of SDB states are deep in the bandgap for Si wires, and shallow (near the valence band edge) for Ge wires. In both Si and Ge wires, the SDB states are localized. We also find that the SDB ɛ(+/-) levels behave as a ``universal" energy reference level among Si, Ge, and Si/Ge wires within a precision of 0.1 eV. By computing the average bewteen the electron affinity and ionization energy in the atomi limit of several atoms from the III, IV and V columns, we conjecture that the universality is a periodic-table atomic property.

Single Grain Boundary Modeling and Design of Microcrystalline Si Solar Cells.

PubMed

Lin, Chu-Hsuan; Hsu, Wen-Tzu; Tai, Cheng-Hung

2013-01-21

For photovoltaic applications, microcrystalline silicon has a lot of advantages, such as the ability to absorb the near-infrared part of the solar spectrum. However, there are many dangling bonds at the grain boundary in microcrystalline Si. These dangling bonds would lead to the recombination of photo-generated carriers and decrease the conversion efficiency. Therefore, we included the grain boundary in the numerical study in order to simulate a microcrystalline Si solar cell accurately, designing new three-terminal microcrystalline Si solar cells. The 3-μm-thick three-terminal cell achieved a conversion efficiency of 10.8%, while the efficiency of a typical two-terminal cell is 9.7%. The three-terminal structure increased the J SC but decreased the V OC , and such phenomena are discussed. High-efficiency and low-cost Si-based thin film solar cells can now be designed based on the information provided in this paper.

Single Grain Boundary Modeling and Design of Microcrystalline Si Solar Cells

PubMed Central

Lin, Chu-Hsuan; Hsu, Wen-Tzu; Tai, Cheng-Hung

2013-01-01

For photovoltaic applications, microcrystalline silicon has a lot of advantages, such as the ability to absorb the near-infrared part of the solar spectrum. However, there are many dangling bonds at the grain boundary in microcrystalline Si. These dangling bonds would lead to the recombination of photo-generated carriers and decrease the conversion efficiency. Therefore, we included the grain boundary in the numerical study in order to simulate a microcrystalline Si solar cell accurately, designing new three-terminal microcrystalline Si solar cells. The 3-μm-thick three-terminal cell achieved a conversion efficiency of 10.8%, while the efficiency of a typical two-terminal cell is 9.7%. The three-terminal structure increased the JSC but decreased the VOC, and such phenomena are discussed. High-efficiency and low-cost Si-based thin film solar cells can now be designed based on the information provided in this paper. PMID:28809309

Dynamics behavior of lithium in graphite lattice: MD calculation approach

NASA Astrophysics Data System (ADS)

Shimizu, A.; Tachikawa, H.

2000-12-01

In order to investigate the diffusion process of Li atom in graphite, molecular dynamics simulation was achieved on the basis of molecular mechanics 2 (MM2) method using four layers cluster model one of which is composed of C150H30 with terminating hydrogen atoms. According to the simulations at 500 K, Li atom stabilizes initially around the center of mass, gets out of the graphite layers after 3.0 ps through diffusion, which is different from the movement of Li+ ion captured by the dangling bonds of the edge carbon atoms. The diffusion process of Li atom is found to be composed of following four steps in series: (1) vibration around the stabilization point; (2) bulk diffusion; (3) vibration under influence of the dangling bonds of edge carbon atoms; and (4) escape from the graphite layers. The diffusivity for step (3) is smaller than that for step (2).

Impact of recess etching and surface treatments on ohmic contacts regrown by molecular-beam epitaxy for AlGaN/GaN high electron mobility transistors

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

Joglekar, S.; Azize, M.; Palacios, T.

Ohmic contacts fabricated by regrowth of n{sup +} GaN are favorable alternatives to metal-stack-based alloyed contacts in GaN-based high electron mobility transistors. In this paper, the influence of reactive ion dry etching prior to regrowth on the contact resistance in AlGaN/GaN devices is discussed. We demonstrate that the dry etch conditions modify the surface band bending, dangling bond density, and the sidewall depletion width, which influences the contact resistance of regrown contacts. The impact of chemical surface treatments performed prior to regrowth is also investigated. The sensitivity of the contact resistance to the surface treatments is found to depend uponmore » the dangling bond density of the sidewall facets exposed after dry etching. A theoretical model has been developed in order to explain the observed trends.« less

Dangling-bond logic gates on a Si(100)-(2 × 1)-H surface.

PubMed

Kawai, Hiroyo; Ample, Francisco; Wang, Qing; Yeo, Yong Kiat; Saeys, Mark; Joachim, Christian

2012-03-07

Atomic-scale Boolean logic gates (LGs) with two inputs and one output (i.e. OR, NOR, AND, NAND) were designed on a Si(100)-(2 × 1)-H surface and connected to the macroscopic scale by metallic nano-pads physisorbed on the Si(100)-(2 × 1)-H surface. The logic inputs are provided by saturating and unsaturating two surface Si dangling bonds, which can, for example, be achieved by adding and extracting two hydrogen atoms per input. Quantum circuit design rules together with semi-empirical elastic-scattering quantum chemistry transport calculations were used to determine the output current intensity of the proposed switches and LGs when they are interconnected to the metallic nano-pads by surface atomic-scale wires. Our calculations demonstrate that the proposed devices can reach ON/OFF ratios of up to 2000 for a running current in the 10 µA range.

Magnetic resonance force microscopy of paramagnetic electron spins at millikelvin temperatures.

PubMed

Vinante, A; Wijts, G; Usenko, O; Schinkelshoek, L; Oosterkamp, T H

2011-12-06

Magnetic resonance force microscopy (MRFM) is a powerful technique to detect a small number of spins that relies on force detection by an ultrasoft magnetically tipped cantilever and selective magnetic resonance manipulation of the spins. MRFM would greatly benefit from ultralow temperature operation, because of lower thermomechanical noise and increased thermal spin polarization. Here we demonstrate MRFM operation at temperatures as low as 30 mK, thanks to a recently developed superconducting quantum interference device (SQUID)-based cantilever detection technique, which avoids cantilever overheating. In our experiment, we detect dangling bond paramagnetic centres on a silicon surface down to millikelvin temperatures. Fluctuations of such defects are supposedly linked to 1/f magnetic noise and decoherence in SQUIDs, as well as in several superconducting and single spin qubits. We find evidence that spin diffusion has a key role in the low-temperature spin dynamics.

Annealing effects on capacitance-voltage characteristics of a-Si/SiN(x) multilayer prepared using hot-wire chemical vapour deposition.

PubMed

Panchal, A K; Rai, D K; Solanki, C S

2011-04-01

Post-deposition annealing of a-Si/SiN(x) multilayer films at different temperature shows varying shift in high frequency (1 MHz) capacitance-voltage (HFCV) characteristics. Various a-Si/SiN(x) multilayer films were deposited using hot wire chemical vapor deposition (HWCVD) and annealed in the temperature range of 800 to 900 degrees C to precipitate Si quantum dots (Si-QD) in a-Si layers. HFCV measurements of the as-deposited and annealed films in metal-insulator-semiconductor (MIS) structures show hysterisis in C-V curves. The hysteresis in the as-deposited films and annealed films is attributed to charge trapping in Si-dangling bonds in a-Si layer and in Si-QD respectively. The charge trapping density in Si-QD increases with temperature while the interface defects density (D(it)) remains constant.

Hydrogen interaction kinetics of Ge dangling bonds at the Si{sub 0.25}Ge{sub 0.75}/SiO{sub 2} interface

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

Stesmans, A., E-mail: andre.stesmans@fys.kuleuven.be; Nguyen Hoang, T.; Afanas'ev, V. V.

2014-07-28

The hydrogen interaction kinetics of the GeP{sub b1} defect, previously identified by electron spin resonance (ESR) as an interfacial Ge dangling bond (DB) defect occurring in densities ∼7 × 10{sup 12} cm{sup −2} at the SiGe/SiO{sub 2} interfaces of condensation grown (100)Si/a-SiO{sub 2}/Ge{sub 0.75}Si{sub 0.25}/a-SiO{sub 2} structures, has been studied as function of temperature. This has been carried out, both in the isothermal and isochronal mode, through defect monitoring by capacitance-voltage measurements in conjunction with ESR probing, where it has previously been demonstrated the defects to operate as negative charge traps. The work entails a full interaction cycle study, comprised of analysis ofmore » both defect passivation (pictured as GeP{sub b1}-H formation) in molecular hydrogen (∼1 atm) and reactivation (GeP{sub b1}-H dissociation) in vacuum. It is found that both processes can be suitably described separately by the generalized simple thermal (GST) model, embodying a first order interaction kinetics description based on the basic chemical reactions GeP{sub b1} + H{sub 2} → GeP{sub b1}H + H and GeP{sub b1}H → GeP{sub b1} + H, which are found to be characterized by the average activation energies E{sub f} = 1.44 ± 0.04 eV and E{sub d} = 2.23 ± 0.04 eV, and attendant, assumedly Gaussian, spreads σE{sub f} = 0.20 ± 0.02 eV and σE{sub d} = 0.15 ± 0.02 eV, respectively. The substantial spreads refer to enhanced interfacial disorder. Combination of the separately inferred kinetic parameters for passivation and dissociation results in the unified realistic GST description that incorporates the simultaneous competing action of passivation and dissociation, and which is found to excellently account for the full cycle data. For process times t{sub a} ∼ 35 min, it is found that even for the optimum treatment temperature ∼380 °C, only ∼60% of the GeP{sub b1} system can be electrically silenced, still far remote from device grade level. This ineffectiveness is concluded, for the major part, to be a direct consequence of the excessive spreads in the activation energies, ∼2–3 times larger than for the Si DB P{sub b} defects at the standard thermal (111)Si/SiO{sub 2} interface which may be easily passivated to device grade levels, strengthened by the reduced difference between the average E{sub f} and E{sub d} values. Exploring the guidelines of the GST model indicates that passivation can be improved by decreasing T{sub an} and attendant enlarging of t{sub a}, however, at best still leaving ∼2% defects unpassivated even for unrealistically extended anneal times. The average dissociation energy E{sub d} ∼ 2.23 eV, concluded as representing the GeP{sub b1}-H bond strength, is found to be smaller than the SiP{sub b}-H one, characterized by E{sub d} ∼ 2.83 eV. An energy deficiency is encountered regarding the energy sum rule inherent to the GST-model, the origin of which is substantiated to lie with a more complex nature of the forward passivation process than basically depicted in the GST model. The results are discussed within the context of theoretical considerations on the passivation of interfacial Ge DBs by hydrogen.« less

Defect assisted coupling of a MoS2/TiO2 interface and tuning of its electronic structure.

PubMed

Chen, Guifeng; Song, Xiaolin; Guan, Lixiu; Chai, Jianwei; Zhang, Hui; Wang, Shijie; Pan, Jisheng; Tao, Junguang

2016-09-02

Although MoS2 based heterostructures have drawn increased attention, the van der Waals forces within MoS2 layers make it difficult for the layers to form strong chemical coupled interfaces with other materials. In this paper, we demonstrate the successful strong chemical attachment of MoS2 on TiO2 nanobelts after appropriate surface modifications. The etch-created dangling bonds on TiO2 surfaces facilitate the formation of a steady chemically bonded MoS2/TiO2 interface. With the aid of high resolution transmission electron microscope measurements, the in-plane structure registry of MoS2/TiO2 is unveiled at the atomic scale, which shows that MoS2[1-10] grows along the direction of TiO2[001] and MoS2[110] parallel to TiO2[100] with every six units of MoS2 superimposed on five units of TiO2. Electronically, type II band alignments are realized for all surface treatments. Moreover, the band offsets are delicately correlated to the surface states, which plays a significant role in their photocatalytic performance.

Charge Trapping Properties of Ge Nanocrystals Grown via Solid-State Dewetting

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

Johnston, Steven; Jadli, I.; Aouassa, M.

2018-05-04

In the present work, we report on the charge trapping properties of Germanium Nanocrystals (Ge NCs) self assembled on SiO2 thin layer for promising applications in next-generation non volatile memory by the means of Deep Level Transient Spectroscopy (DLTS) and high frequency C-V method. The Ge NCs were grown via dewetting phenomenon at solid state by Ultra-High Vacuum (UHV) annealing and passivated with silicon before SiO2 capping. The role of the surface passivation is to reduce the electrical defect density at the Ge NCs-SiO2 interface. The presence of the Ge NCs in the oxide of the MOS capacitors strongly affectsmore » the C-V characteristics and increases the accumulation capacitance, causes a negative flat band voltage (VFB) shift. The DLTS has been used to study the individual Ge NCs as a single point deep level defect in the oxide. DLTS reveals two main features: the first electron traps around 255 K could correspond to dangling bonds at the Si/SiO2 interface and the second, at high-temperature (>300 K) response, could be originated from minority carrier generation in Ge NCs.« less

The O-(Al2) centre in topaz and its relation to the blue colour

NASA Astrophysics Data System (ADS)

da Silva, D. N.; Guedes, K. J.; Pinheiro, M. V. B.; Schweizer, S.; Spaeth, J.-M.; Krambrock, K.

2005-01-01

Colour-enhanced blue topaz is one of the most traded gemstones. Naturally very rare, mostly topaz is irradiated by neutrons, electrons, gamma radiation and combinations of them. The colour centre is still not identified. It was speculated that it is related to a Si dangling bond defect occupied by two electrons with spin S = 0. We investigated natural blue as well as colourless topaz from different regions in Brazil by electron paramagnetic resonance (EPR), optical absorption and Raman spectroscopy. The results are compared with neutron and gamma-irradiated blue topaz. By EPR two paramagnetic defects are identified in all samples: (i) the peroxy radical (O2-) measured at room temperature and (ii) an (O-) hole centre interacting with two equivalent Al neighbours measured at low temperature. Blue samples show an absorption band centred at 620 nm which is responsible for the blue colour. From our investigation we find that the O-(Al2) hole centre has nearly the same thermal stability as the optical absorption band. However, we cannot say whether it is responsible for the absorption band and the blue colour. We suggest that at least it plays a dominant role in the stabilization of the blue colour.

Origin of magnetic properties in carbon implanted ZnO nanowires.

PubMed

Wang, Y F; Shao, Y C; Hsieh, S H; Chang, Y K; Yeh, P H; Hsueh, H C; Chiou, J W; Wang, H T; Ray, S C; Tsai, H M; Pao, C W; Chen, C H; Lin, H J; Lee, J F; Wu, C T; Wu, J J; Chang, Y M; Asokan, K; Chae, K H; Ohigashi, T; Takagi, Y; Yokoyama, T; Kosugi, N; Pong, W F

2018-05-17

Various synchrotron radiation-based spectroscopic and microscopic techniques are used to elucidate the room-temperature ferromagnetism of carbon-doped ZnO-nanowires (ZnO-C:NW) via a mild C + ion implantation method. The photoluminescence and magnetic hysteresis loops reveal that the implantation of C reduces the number of intrinsic surface defects and increases the saturated magnetization of ZnO-NW. The interstitial implanted C ions constitute the majority of defects in ZnO-C:NW as confirmed by the X-ray absorption spectroscopic studies. The X-ray magnetic circular dichroism spectra of O and C K-edge respectively indicate there is a reduction in the number of unpaired/dangling O 2p bonds in the surface region of ZnO-C:NW and the C 2p-derived states of the implanted C ions strongly affect the net spin polarization in the surface and bulk regions of ZnO-C:NW. Furthermore, these findings corroborate well with the first-principles calculations of C-implanted ZnO in surface and bulk regions, which highlight the stability of implanted C for the suppression and enhancement of the ferromagnetism of the ZnO-C:NW in the surface region and bulk phase, respectively.

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

Videla, Pablo E.; Rossky, Peter J.; Laria, D., E-mail: dhlaria@cnea.gov.ar

We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H{sub 2}O]{sub 3} and [D{sub 2}O]{sub 3}, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zeromore » point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H{sub 2}O]{sub 3} than in [D{sub 2}O]{sub 3}. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments.« less

First-principles simulation on Seebeck coefficient in silicon nanowires

NASA Astrophysics Data System (ADS)

Nakamura, Koichi

2017-06-01

The Seebeck coefficients of silicon nanowires (SiNWs) were simulated on the basis of first-principles calculation using various atomistic structure models. The electronic band structures of fully hydrogen-terminated SiNW models give the correct image of quantum mechanical confinement from bulk silicon to SiNW for each axial direction, and the change in the density of states by dimensional reduction to SiNW enhances the thermoelectric performance in terms of the Seebeck coefficient, compared with those of bulk silicon and silicon nanosheets. The uniaxial tensile strain for the SiNW models does not strongly affect the Seebeck coefficient even for the SiNW system with giant piezoresistivity. In contrast, dangling bonds on a wire wall sharply reduce the Seebeck coefficient of SiNW and totally degrade thermoelectric performance from the viewpoint of the power factor. The exclusion of dangling bonds is a key element for the design and application of high-performance thermoelectric nanowires of semiconducting materials.

Dye-sensitization of CdS nano-cage - A density functional theory approach

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

Jain, Kalpna; Singh, Kh. S.; Kishor, Shyam

2016-05-23

Quantum dots a few nanometer in size exhibit unique properties in comparison to bulk due to quantum confinement. Their properties can be tuned according to their sizes. Dye sensitized quantum dot (DSQD) solar cells are based on the same principle with surface dangling bonds as a challenge. Researches have shown the existence and stability of nano-cages which are assembled such as to minimize the surface dangling bonds and hence maximize stability. Here, we report a first principles DFT study of optical and electronic properties of CdS-cage (Cd{sub 34}S{sub 34}) sensitized with nkx-2388 dye in three different geometric configurations of dyemore » attachment. A significant distortion is found to occur in the geometric structure of the cage when it interacts strongly with the dye. The relative positioning of dye and cage energy levels is found to be different in different configurations. The absorption spectrum has been analyzed with the help of natural transition orbitals (NTO).« less

Communication: Isotopic effects on tunneling motions in the water trimer.

PubMed

Videla, Pablo E; Rossky, Peter J; Laria, D

2016-02-14

We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H2O]3 and [D2O]3, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O-O-O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H2O]3 than in [D2O]3. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments.

Realization of a Hole-Doped Mott Insulator on a Triangular Silicon Lattice

NASA Astrophysics Data System (ADS)

Ming, Fangfei; Johnston, Steve; Mulugeta, Daniel; Smith, Tyler S.; Vilmercati, Paolo; Lee, Geunseop; Maier, Thomas A.; Snijders, Paul C.; Weitering, Hanno H.

2017-12-01

The physics of doped Mott insulators is at the heart of some of the most exotic physical phenomena in materials research including insulator-metal transitions, colossal magnetoresistance, and high-temperature superconductivity in layered perovskite compounds. Advances in this field would greatly benefit from the availability of new material systems with a similar richness of physical phenomena but with fewer chemical and structural complications in comparison to oxides. Using scanning tunneling microscopy and spectroscopy, we show that such a system can be realized on a silicon platform. The adsorption of one-third monolayer of Sn atoms on a Si(111) surface produces a triangular surface lattice with half filled dangling bond orbitals. Modulation hole doping of these dangling bonds unveils clear hallmarks of Mott physics, such as spectral weight transfer and the formation of quasiparticle states at the Fermi level, well-defined Fermi contour segments, and a sharp singularity in the density of states. These observations are remarkably similar to those made in complex oxide materials, including high-temperature superconductors, but highly extraordinary within the realm of conventional s p -bonded semiconductor materials. It suggests that exotic quantum matter phases can be realized and engineered on silicon-based materials platforms.

Moessbauer study in thin films of FeSi2 and FeSe systems

NASA Technical Reports Server (NTRS)

Escue, W. J.; Aggarwal, K.; Mendiratta, R. G.

1978-01-01

Thin films of FeSi2 and FeSe were studied using Moessbauer spectroscopy information regarding dangling bond configuration and nature of crystal structure in thin films was derived. A significant influence of crystalline aluminum substrate on film structure was observed.

Fabrication of hierarchical porous hollow carbon spheres with few-layer graphene framework and high electrochemical activity for supercapacitor

NASA Astrophysics Data System (ADS)

Chen, Jing; Hong, Min; Chen, Jiafu; Hu, Tianzhao; Xu, Qun

2018-06-01

Porous amorphous carbons with large number of defects and dangling bonds indicate great potential application in energy storage due to high specific surface area and strong adsorption properties, but poor conductivity and pore connection limit their practical application. Here few-layer graphene framework with high electrical conductivity is embedded and meanwhile hierarchical porous structure is constructed in amorphous hollow carbon spheres (HCSs) by catalysis of Fe clusters of angstrom scale, which are loaded in the interior of crosslinked polystyrene via a novel method. These unique HCSs effectively integrate the inherent properties from two-dimensional sp2-hybridized carbon, porous amorphous carbon, hierarchical pore structure and thin shell, leading to high specific capacitance up to 561 F g-1 at a current density of 0.5 A g-1 as an electrode of supercapacitor with excellent recyclability, which is much higher than those of other reported porous carbon materials up to present.

Absolute surface energy calculations of Wurtzite (0001)/(000-1): a study of ZnO and GaN

NASA Astrophysics Data System (ADS)

Zhang, Jingzhao; Zhang, Yiou; Tse, Kinfai; Deng, Bei; Xu, Hu; Zhu, Junyi

The accurate absolute surface energies of (0001)/(000-1) surfaces of wurtzite structures are crucial in determining the thin film growth mode of important energy materials. However, the surface energies still remain to be solved due to the intrinsic difficulty of calculating dangling bond energy of asymmetrically bonded surface atoms. We used a pseudo-hydrogen passivation method to estimate the dangling bond energy and calculate the polar surfaces of ZnO and GaN. The calculations were based on the pseudo chemical potentials obtained from a set of tetrahedral clusters or simple pseudo-molecules, using density functional theory approaches, for both GGA and HSE. And the surface energies of (0001)/(000-1) surfaces of wurtzite ZnO and GaN we obtained showed relatively high self-consistencies. A wedge structure calculation with a new bottom surface passivation scheme of group I and group VII elements was also proposed and performed to show converged absolute surface energy of wurtzite ZnO polar surfaces. Part of the computing resources was provided by the High Performance Cluster Computing Centre, Hong Kong Baptist University. This work was supported by the start-up funding and direct Grant with the Project code of 4053134 at CUHK.

Surface electronic states of low-temperature H-plasma-exposed Ge(100)

NASA Astrophysics Data System (ADS)

Cho, Jaewon; Nemanich, R. J.

1992-11-01

The surface of low-temperature H-plasma-cleaned Ge(100) was studied by angle-resolved UV-photoemission spectroscopy and low-energy electron diffraction (LEED). The surface was prepared by an ex situ preclean followed by an in situ H-plasma exposure at a substrate temperature of 150-300 °C. Auger-electron spectroscopy indicated that the in situ H-plasma clean removed the surface contaminants (carbon and oxygen) from the Ge(100) surface. The LEED pattern varied from a 1×1 to a sharp 2×1, as the substrate temperature was increased. The H-induced surface state was identified at ~5.6 eV below EF, which was believed to be mainly due to the ordered or disordered monohydride phases. The annealing dependence of the spectra showed that the hydride started to dissociate at a temperature of 190 °C, and the dangling-bond surface state was identified. A spectral shift upon annealing indicated that the H-terminated surfaces were unpinned. After the H-plasma clean at 300 °C the dangling-bond surface state was also observed directly with no evidence of H-induced states.

Isotopic equilibria in aqueous clusters at low temperatures: Insights from the MB-pol many-body potential

NASA Astrophysics Data System (ADS)

Videla, Pablo E.; Rossky, Peter J.; Laria, Daniel

2018-02-01

By combining path-integrals molecular dynamics simulations with the accurate MB-pol potential energy surface, we investigate the role of alternative potential models on isotopic fractionation ratios between H and D atoms at dangling positions in water clusters at low temperatures. Our results show clear stabilizations of the lighter isotope at dangling sites, characterized by free energy differences ΔG that become comparable to or larger than kBT for temperatures below ˜75 K. The comparison between these results to those previously reported using the empirical q-TIP4P/F water model [P. E. Videla et al., J. Phys. Chem. Lett. 5, 2375 (2014)] reveals that the latter Hamiltonian overestimates the H stabilization by ˜25%. Moreover, predictions from the MB-pol model are in much better agreement with measured results reported for similar isotope equilibria at ice surfaces. The dissection of the quantum kinetic energies into orthogonal directions shows that the dominant differences between the two models are to be found in the anharmonic characteristics of the potential energy surfaces along OH bond directions involved in hydrogen bonds.

The Study of Electrical Properties for Multilayer La2O3/Al2O3 Dielectric Stacks and LaAlO3 Dielectric Film Deposited by ALD.

PubMed

Feng, Xing-Yao; Liu, Hong-Xia; Wang, Xing; Zhao, Lu; Fei, Chen-Xi; Liu, He-Lei

2017-12-01

The capacitance and leakage current properties of multilayer La 2 O 3 /Al 2 O 3 dielectric stacks and LaAlO 3 dielectric film are investigated in this paper. A clear promotion of capacitance properties is observed for multilayer La 2 O 3 /Al 2 O 3 stacks after post-deposition annealing (PDA) at 800 °C compared with PDA at 600 °C, which indicated the recombination of defects and dangling bonds performs better at the high-k/Si substrate interface for a higher annealing temperature. For LaAlO 3 dielectric film, compared with multilayer La 2 O 3 /Al 2 O 3 dielectric stacks, a clear promotion of trapped charges density (N ot ) and a degradation of interface trap density (D it ) can be obtained simultaneously. In addition, a significant improvement about leakage current property is observed for LaAlO 3 dielectric film compared with multilayer La 2 O 3 /Al 2 O 3 stacks at the same annealing condition. We also noticed that a better breakdown behavior for multilayer La 2 O 3 /Al 2 O 3 stack is achieved after annealing at a higher temperature for its less defects.

Perils of Neglecting Lattice Relaxation in the Pressure Dependence of Deep Luminescence Bands in Wide Gap Semiconductors

NASA Astrophysics Data System (ADS)

Iota, V.; Weinstein, B. A.

1998-03-01

Deep defect states are often assumed to be insensitive to pressure because of their localized atomic-like character. In apparent conflict with this, experiments on widegap II-VI materials find that the pressure shifts of many 'midgap' photoluminescence (PL) bands associated with large-lattice-relaxation defects are more rapid than the shift of the bandgap(B. Weinstein, T. Ritter, et. al., Phys. Stat. Sol. (b) 198), 167 (1996). To study this, we measured the effects of pressure on the PL and PL-excitation (PLE) bands arising from the Zn-vacancy (V_Zn) and the P_Se deep acceptor centers in ZnSe. Using the observed pressure variation of the Stokes shifts and the established 1 atm. configuration coordinate (CC) models( D.Y. Jeon, H.P Gislason, G.D. Watkins, Phys. Rev. B 48), 7872 (1993), we were able to infer quantitative CC-diagrams at any pressure. Our results show that the pressure dependence of the lattice relaxation contributes a substantial fraction (several meV/kbar) to the overall shift of the PL-bands, and, hence, must be included. For the case of the V_Zn, simple calculations of the Jahn-Teller splitting using dangling-bond orbitals support this conclusion. figures

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE PAGES

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching; ...

2017-11-14

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

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

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

C incorporation and segregation during Si 1- yC y/Si( 0 0 1 ) gas-source molecular beam epitaxy from Si 2H 6 and CH 3SiH 3

NASA Astrophysics Data System (ADS)

Foo, Y. L.; Bratland, K. A.; Cho, B.; Soares, J. A. N. T.; Desjardins, P.; Greene, J. E.

2002-08-01

We have used in situ D 2 temperature-programmed desorption (TPD) to probe C incorporation and surface segregation kinetics, as well as hydrogen desorption pathways, during Si 1- yC y(0 0 1) gas-source molecular beam epitaxy from Si 2H 6/CH 3SiH 3 mixtures at temperatures Ts between 500 and 650 °C. Parallel D 2 TPD results from C-adsorbed Si(0 0 1) wafers exposed to varying CH 3SiH 3 doses serve as reference data. Si 1- yC y(0 0 1) layer spectra consist of three peaks: first-order β 1 at 515 °C and second-order β 2 at 405 °C, due to D 2 desorption from Si monodeuteride and dideuteride phases, as well as a new second-order C-induced γ 1 peak at 480 °C. C-adsorbed Si(0 0 1) samples with very high CH 3SiH 3 exposures yielded a higher-temperature TPD feature, corresponding to D 2 desorption from surface C atoms, which was never observed in Si 1- yC y(0 0 1) layer spectra. The Si 1- yC y(0 0 1) γ 1 peak arises due to desorption from Si monodeuteride species with C backbonds. γ 1 occurs at a lower temperature than β 1 reflecting the lower D-Si * bond strength, where Si * represents surface Si atoms bonded to second-layer C atoms, as a result of charge transfer from dangling bonds. The total integrated monohydride (β 1+γ 1) intensity, and hence the dangling bond density, remains constant with y indicating that C does not deactivate surface dangling bonds as it segregates to the second-layer during Si 1- yC y(0 0 1) growth. Si * coverages increase with y at constant Ts and with Ts at constant y. The positive Ts-dependence shows that C segregation is kinetically limited at Ts⩽650 °C. D 2 desorption activation energies from β 1, γ 1 and β 2 sites are 2.52, 2.22 and 1.88 eV.

Mechanisms of boron diffusion in silicon and germanium

NASA Astrophysics Data System (ADS)

Mirabella, S.; De Salvador, D.; Napolitani, E.; Bruno, E.; Priolo, F.

2013-01-01

B migration in Si and Ge matrices raised a vast attention because of its influence on the production of confined, highly p-doped regions, as required by the miniaturization trend. In this scenario, the diffusion of B atoms can take place under severe conditions, often concomitant, such as very large concentration gradients, non-equilibrium point defect density, amorphous-crystalline transition, extrinsic doping level, co-doping, B clusters formation and dissolution, ultra-short high-temperature annealing. In this paper, we review a large amount of experimental work and present our current understanding of the B diffusion mechanism, disentangling concomitant effects and describing the underlying physics. Whatever the matrix, B migration in amorphous (α-) or crystalline (c-) Si, or c-Ge is revealed to be an indirect process, activated by point defects of the hosting medium. In α-Si in the 450-650 °C range, B diffusivity is 5 orders of magnitude higher than in c-Si, with a transient longer than the typical amorphous relaxation time. A quick B precipitation is also evidenced for concentrations larger than 2 × 1020 B/cm3. B migration in α-Si occurs with the creation of a metastable mobile B, jumping between adjacent sites, stimulated by dangling bonds of α-Si whose density is enhanced by B itself (larger B density causes higher B diffusivity). Similar activation energies for migration of B atoms (3.0 eV) and of dangling bonds (2.6 eV) have been extracted. In c-Si, B diffusion is largely affected by the Fermi level position, occurring through the interaction between the negatively charged substitutional B and a self-interstitial (I) in the neutral or doubly positively charged state, if under intrinsic or extrinsic (p-type doping) conditions, respectively. After charge exchanges, the migrating, uncharged BI pair is formed. Under high n-type doping conditions, B diffusion occurs also through the negatively charged BI pair, even if the migration is depressed by Coulomb pairing with n-type dopants. The interplay between B clustering and migration is also modeled, since B diffusion is greatly affected by precipitation. Small (below 1 nm) and relatively large (5-10 nm in size) BI clusters have been identified with different energy barriers for thermal dissolution (3.6 or 4.8 eV, respectively). In c-Ge, B motion is by far less evident than in c-Si, even if the migration mechanism is revealed to be similarly assisted by Is. If Is density is increased well above the equilibrium (as during ion irradiation), B diffusion occurs up to quite large extents and also at relatively low temperatures, disclosing the underlying mechanism. The lower B diffusivity and the larger activation barrier (4.65 eV, rather than 3.45 eV in c-Si) can be explained by the intrinsic shortage of Is in Ge and by their large formation energy. B diffusion can be strongly enhanced with a proper point defect engineering, as achieved with embedded GeO2 nanoclusters, causing at 650 °C a large Is supersaturation. These aspects of B diffusion are presented and discussed, modeling the key role of point defects in the two different matrices.

Depleted Nanocrystal-Oxide Heterojunctions for High-Sensitivity Infrared Detection

DTIC Science & Technology

2015-08-28

from surface dangling bonds and behave as effective nonradiative recombination centers.17 Upon the growth of CdSe, the main PL peak exhibits a redshift...as nonradiative recombination sites and cause PL degradation. With a 4.5 ML CdSe shell, the QY drops to 4%. As seen in Fig. 6, the PL QY is

Infrared, Raman and Magnetic Resonance Spectroscopic Study of SiO2:C Nanopowders.

PubMed

Savchenko, Dariya; Vorliček, Vladimir; Kalabukhova, Ekaterina; Sitnikov, Aleksandr; Vasin, Andrii; Kysil, Dmytro; Sevostianov, Stanislav; Tertykh, Valentyn; Nazarov, Alexei

2017-12-01

Optical and magnetic properties of SiO 2 :C nanopowders obtained by chemical and thermal modification of fumed silica were studied by Fourier transform infrared spectroscopy, Raman, continuous wave (CW) electron paramagnetic resonance (EPR), echo-detected EPR and pulsed electron nuclear double resonance (ENDOR) spectroscopy. Two overlapping signals of Lorentzian lineshape were detected in CW EPR spectra of the initial SiO 2 :C. The EPR signal at g = 2.0055(3) is due to the silicon dangling bonds, which vanishes after thermal annealing, and the second EPR signal at g = 2.0033(3) was attributed to the carbon-related defect (CRD). The annealing of the SiO 2 :C samples gives rise to the increase of the CRD spin density and shift to the higher g-values due to the appearance of the oxygen in the vicinity of the CRD. Based on the temperature-dependent behavior of the CRD EPR signal intensity, linewidth and resonance field position we have attributed it to the spin system with non-localized electrons hopping between neighboring carbon dangling bonds, which undergo a strong exchange interaction with a localized spin system of carbon nanodots. The observed motional narrowing of the CRD EPR signal in the temperature interval from 4 to 20 K indicates that electrons are mobile at 4 K which can be explained by a quantum character of the conductivity in the vicinity of the carbon layer. The electrons trapped in quantum wells move from one carbon nanodot to another by hopping process through the energy barrier. The fact that echo-detected EPR signal at g = 2.0035(3) was observed in SiO 2 :C sample annealed at T ann  ≥ 700 °C serves as evidence that non-localized electrons coexist with localized electrons that have the superhyperfine interaction with surrounding 13 C and 29 Si nuclei located at the SiO 2 :C interface. The presence of the superhyperfine interaction of CRD with 1 H nuclei indicates the existence of hydrogenated regions in SiO 2 :C sample.

Structure, bonding nature, and binding energy of alkanethiolate on As-rich GaAs (001) surface: a density functional theory study.

PubMed

Voznyy, Oleksandr; Dubowski, Jan J

2006-11-30

Chemisorption of alkanethiols on As-rich GaAs (001) surface under a low coverage condition was studied using first principles density functional calculations in a periodic supercell approach. The thiolate adsorption site, tilt angle and its direction are dictated by the high directionality of As dangling bond and sulfur 3p orbital participating in bonding and steric repulsion of the first three CH2 units from the surface. Small charge transfer between thiolate and surface, strong dependence of total energy on tilt angle, and a relatively short length of 2.28 A of the S-As bond indicate the highly covalent nature of the bonding. Calculated binding energy of 2.1 eV is consistent with the available experimental data.

Role of orbital overlap in atomic manipulation

NASA Astrophysics Data System (ADS)

Jarvis, Sam; Sweetman, Adam; Bamidele, Joseph; Kantorovich, Lev; Moriarty, Philip

2012-06-01

We conduct ab initio simulations illustrating that the ability to achieve atomic manipulation using a dynamic force microscope depends on the precise orientation of the dangling bond(s) at the tip apex and their charge density with respect to those of surface atoms. Using the Si(100)-c(4×2) surface as a prototype, we demonstrate that it is possible to select tip apices capable of performing atomic manipulation tasks which are unachievable using another choice of apex. Specific tip apices can be identified via examination of F(z) curves taken at different lateral positions.

Effect of ultraviolet illumination on the charge trapping behaviour in SiN(x)/InP metal-insulator-semiconductor structure provided by plasma enhanced chemical vapour deposition

NASA Astrophysics Data System (ADS)

Kim, C. H.; Han, I. K.; Lee, J. I.; Kang, K. N.; Kwon, S. D.; Choe, B.; Park, H. L.; Her, J.; Lim, H.

1994-04-01

In this work, we investigated the effect of ultraviolet illumination, which is known to generate silicon dangling bonds, on the charge trapping behaviors, utilizing the constant capacitance technique in SiN(x)/InP structure where conventional PE CVD was used to form the SiN films on InP. We found different behaviors of this structure with ultraviolet illumination compared to the case of SiN(x)/Si structure. Both the Si-rich condition during PE CVD and ultraviolet illumination seem to not only increase the number of traps but also broaden the energy level of the traps in the insulator near the SiN(x)/InP interface. In all cases (N-rich, Si-rich, with and without ultraviolet illumination) the amphoteric nature of the traps has been observed, which is a characteristic of Si-dangling bonds. Also, the effect of ultraviolet photons on the interface of SiN(x)/InP, especially in correlation with the deficiency of phosphorus at the interface, is discussed considering the existence of net negative fixed charges at the interface.

Peierls instability as the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers

NASA Astrophysics Data System (ADS)

Kang, Myung Ho; Kwon, Se Gab; Jung, Sung Chul

2018-03-01

Density functional theory (DFT) calculations are used to investigate the insulating origin of the Na/Si(111)-(3 × 1) surface with a Na coverage of 2/3 monolayers. In the coverage definition, one monolayer refers to one Na atom per surface Si atom, so this surface contains an odd number of electrons (i.e., three Si dangling-bond electrons plus two Na electrons) per 3 × 1 unit cell. Interestingly, this odd-electron surface has been ascribed to a Mott-Hubbard insulator to account for the measured insulating band structure with a gap of about 0.8 eV. Here, we instead propose a Peierls instability as the origin of the experimental band gap. The concept of Peierls instability is fundamental in one-dimensional metal systems but has not been taken into account in previous studies of this surface. Our DFT calculations demonstrate that the linear chain structure of Si dangling bonds in this surface is energetically unstable with respect to a × 2 buckling modulation, and the buckling-induced band gap of 0.79 eV explains well the measured insulating nature.

Tunneling spectroscopy of close-spaced dangling-bond pairs in Si(001):H

PubMed Central

Engelund, Mads; Zuzak, Rafał; Godlewski, Szymon; Kolmer, Marek; Frederiksen, Thomas; García-Lekue, Aran; Sánchez-Portal, Daniel; Szymonski, Marek

2015-01-01

We present a combined experimental and theoretical study of the electronic properties of close-spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called “cross” and “line” structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces. PMID:26404520

Structure of thin diamond films: A 1H and 13C nuclear-magnetic-resonance study

NASA Astrophysics Data System (ADS)

Pruski, M.; Lang, D. P.; Hwang, Son-Jong; Jia, H.; Shinar, J.

1994-04-01

The 1H and 13C nuclear magnetic resonance (NMR) of thin diamond films deposited from naturally abundant (1.1 at. %) as well as 50% and 100% 13enriched CH4 heavily diluted in H2 is described and discussed. Less than 0.6 at. % of hydrogen is found in the films which contain crystallites up to ~15 μm across. The 1H NMR consists of a broad 50-65-kHz-wide Gaussian line attributed to H atoms bonded to carbon and covering the crystallite surfaces. A narrow Lorentzian line was only occasionally observed and is found not to be intrinsic to the diamond structure. The 13C NMR demonstrates that >99.5% of the C atoms reside in a quaternary diamondlike configuration. 1-13C cross-polarization measurement indicates that, at the very least, the majority of 13C nuclei cross polarized by 1H, i.e., within three bond distances from a 1H at a crystallite surface, reside in sp3 diamondlike coordinated sites. The 13C relaxation rates of the films are four orders of magnitude faster than that of natural diamond and believed to be due to 13C spin diffusion to paramagnetic centers, presumably carbon dangling bonds. Analysis of the measured relaxation rates indicates that within the 13C spin-diffusion length of √DTc1 ~0.05 μm, these centers are uniformly distributed in the diamond crystallites. The possibility that the dangling bonds are located at internal nanovoid surfaces is discussed.

Quantum chemistry study on the open end of single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Hou, Shimin; Shen, Ziyong; Zhao, Xingyu; Xue, Zengquan

2003-05-01

Geometrical and electronic structures of open-ended single-walled carbon nanotubes (SWCNTs) are calculated using density functional theory (DFT) with hybrid functional (B3LYP) approximation. Due to different distances between carbon atoms along the edge, reconstruction occurs at the open end of the (4,4) armchair SWCNT, i.e., triple bonds are formed in the carbon atom pairs at the mouth; however, for the (6,0) zigzag SWCNT, electrons in dangling bonds still remain at 'no-bonding' states. The ionization potential (IP) of both (4,4) and (6,0) SWCNTs is increased by their negative intrinsic dipole moments, and localized electronic states existed at both of their open ends.

Positron annihilation studies of silicon-based materials

NASA Astrophysics Data System (ADS)

Petkov, Mihail Petkov

Positron Annihilation Spectroscopy (PAS) is used as a defect-profiling tool in the characterization of Si-based materials. PAS, in conjunction with variable energy positron beams, is a non-destructive depth-profiling probe, ideally suited for studying thin films, multi-layered structures, and buried interfaces. Its sensitivity to open-volume defects covers a wide range of defect sizes and concentrations, and surpasses that of most other techniques. This dissertation presents PAS investigations of electrical, chemical and mechanical properties of a number of advanced materials for future use by the semiconductor industry. Among the subjects of this work are: hydrogenated amorphous silicon (a-Si:H) for use in solar cells and flat-panel displays; low dielectric constant materials (low-k) for interlayer dielectrics; and thin-gate transistors, focusing on the defects at the Si/SiO 2 interface, which limit the device reliability. Results from extensive research on various possibilities to enhance the PAS capability by increasing its efficiency are presented in the appendices. The recognition of different dangling bond defects for low defect densities is achieved in these first PAS studies of void-free a-Si:H. Direct evidence of the existence of dopant-defect complexes is obtained for the first time. This research lays the foundation for future studies of the role of the impurities in light- and thermal degradation of a-Si:H PAS was applied to the characterization of porous low-k dielectrics. The annihilation observables are correlated with the dielectric properties of the material and their preparation conditions. PAS is the only non-destructive local k-probe, and the only tool for measuring void densities and sizes. The method is also sensitive to the chemical environment of the voids, seen during oxidation, water absorption, and forming gas anneal. Industrial research, partially based on these results, is currently in progress at IBM. A decade-old controversy, involving different models of defect states at Si/SiO2 interfaces, has been resolved. The two-defect model was confirmed and previous results were reevaluated. Research in this area will promote the use of PAS as an on-line diagnostic tool in the manufacturing of integrated circuits.

Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O₂ and O Adsorption: A First-Principles Investigation.

PubMed

Chu, Minmin; Liu, Xin; Sui, Yanhui; Luo, Jie; Meng, Changgong

2015-10-27

Taking the adsorption of CO, NO, O₂ and O as probes, we investigated the electronic structure of transition metal atoms (TM, TM = Fe, Co, Ni, Cu and Zn) embedded in graphene by first-principles-based calculations. We showed that these TM atoms can be effectively stabilized on monovacancy defects on graphene by forming plausible interactions with the C atoms associated with dangling bonds. These interactions not only give rise to high energy barriers for the diffusion and aggregation of the embedded TM atoms to withstand the interference of reaction environments, but also shift the energy levels of TM-d states and regulate the reactivity of the embedded TM atoms. The adsorption of CO, NO, O₂ and O correlates well with the weight averaged energy level of TM-d states, showing the crucial role of interfacial TM-C interactions on manipulating the reactivity of embedded TM atoms. These findings pave the way for the developments of effective monodispersed atomic TM composites with high stability and desired performance for gas sensing and catalytic applications.

Edge-spin-derived magnetism in few-layer MoS2 nanomeshes

NASA Astrophysics Data System (ADS)

Kondo, G.; Yokoyama, N.; Yamada, S.; Hashimoto, Y.; Ohata, C.; Katsumoto, S.; Haruyama, J.

2017-12-01

Magnetism arising from edge spins is highly interesting, particularly in 2D atomically thin materials in which the influence of edges becomes more significant. Among such materials, molybdenum disulfide (MoS2; one of the transition metal dichalcogenide (TMD) family) is attracting significant attention. The causes for magnetism observed in the TMD family, including in MoS2, have been discussed by considering various aspects, such as pure zigzag atomic-structure edges, grain boundaries, and vacancies. Here, we report the observation of ferromagnetism (FM) in few-layer MoS2 nanomeshes (NMs; honeycomb-like array of hexagonal nanopores with low-contamination and low-defect pore edges), which have been created by a specific non-lithographic method. We confirm robust FM arising from pore edges in oxygen(O)-terminated MoS2-NMs at room temperature, while it disappears in hydrogen(H)-terminated samples. The observed high-sensitivity of FM to NM structures and critical annealing temperatures suggest a possibility that the Mo-atom dangling bond in pore edge is a dominant factor for the FM.

Reaction mechanism of a PbS-on-ZnO heterostructure and enhanced photovoltaic diode performance with an interface-modulated heterojunction energy band structure.

PubMed

Li, Haili; Jiao, Shujie; Ren, Jinxian; Li, Hongtao; Gao, Shiyong; Wang, Jinzhong; Wang, Dongbo; Yu, Qingjiang; Zhang, Yong; Li, Lin

2016-02-07

A room temperature successive ionic layer adsorption and reaction (SILAR) method is introduced for fabricating quantum dots-on-wide bandgap semiconductors. Detailed exploration of how SILAR begins and proceeds is performed by analyzing changes in the electronic structure of related elements at interfaces by X-ray photoelectric spectroscopy, together with characterization of optical properties and X-ray diffraction. The distribution of PbS QDs on ZnO, which is critical for optoelectrical applications of PbS with a large dielectric constant, shows a close relationship with the dipping order. A successively deposited PbS QDs layer is obtained when the sample is first immersed in Na2S solution. This is reasonable because the initial formation of different chemical bonds on ZnO nanorods is closely related to dangling bonds and defect states on surfaces. Most importantly, dipping order also affects their optoelectrical characteristics greatly, which can be explained by the heterojunction energy band structure related to the interface. The formation mechanism for PbS QDs on ZnO is confirmed by the fact that the photovoltaic diode device performance is closely related to the dipping order. Our atomic-scale understanding emphasises the fundamental role of surface chemistry in the structure and tuning of optoelectrical properties, and consequently in devices.

Thin silicon foils produced by epoxy-induced spalling of silicon for high efficiency solar cells

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

Martini, R., E-mail: roberto.martini@imec.be; imec, Kapeldreef 75, 3001 Leuven; Kepa, J.

2014-10-27

We report on the drastic improvement of the quality of thin silicon foils produced by epoxy-induced spalling. In the past, researchers have proposed to fabricate silicon foils by spalling silicon substrates with different stress-inducing materials to manufacture thin silicon solar cells. However, the reported values of effective minority carrier lifetime of the fabricated foils remained always limited to ∼100 μs or below. In this work, we investigate epoxy-induced exfoliated foils by electron spin resonance to analyze the limiting factors of the minority carrier lifetime. These measurements highlight the presence of disordered dangling bonds and dislocation-like defects generated by the exfoliation process.more » A solution to remove these defects compatible with the process flow to fabricate solar cells is proposed. After etching off less than 1 μm of material, the lifetime of the foil increases by more than a factor of 4.5, reaching a value of 461 μs. This corresponds to a lower limit of the diffusion length of more than 7 times the foil thickness. Regions with different lifetime correlate well with the roughness of the crack surface which suggests that the lifetime is now limited by the quality of the passivation of rough surfaces. The reported values of the minority carrier lifetime show a potential for high efficiency (>22%) thin silicon solar cells.« less

Quasi-planar elemental clusters in pair interactions approximation

NASA Astrophysics Data System (ADS)

Chkhartishvili, Levan

2016-01-01

The pair-interactions approximation, when applied to describe elemental clusters, only takes into account bonding between neighboring atoms. According to this approach, isomers of wrapped forms of 2D clusters - nanotubular and fullerene-like structures - and truly 3D clusters, are generally expected to be more stable than their quasi-planar counterparts. This is because quasi-planar clusters contain more peripheral atoms with dangling bonds and, correspondingly, fewer atoms with saturated bonds. However, the differences in coordination numbers between central and peripheral atoms lead to the polarization of bonds. The related corrections to the molar binding energy can make small, quasi-planar clusters more stable than their 2D wrapped allotropes and 3D isomers. The present work provides a general theoretical frame for studying the relative stability of small elemental clusters within the pair interactions approximation.

Sticking and recombination of the SiH 3 radical on hydrogenated amorphous silicon: The catalytic effect of diborane

NASA Astrophysics Data System (ADS)

Perrin, Jérôme; Takeda, Yoshihiko; Hirano, Naoto; Takeuchi, Yoshiaki; Matsuda, Akihisa

1989-03-01

The deposition rate of hydrogenated amorphous silicon films in SiH 4 glow-discharge is drastically enhanced upon addition of B 2H 6 when the gas-phase concentration exceeds 10 -4. This cannot be attributed to gas-phase reactions and must be interpreted as an increase of the sticking probability of the dominant SiH 3 radical. However, the total surface loss probability ( β) of SiH 3 which includes both sticking ( s) and recombination ( γ) increases only above 10 -2 B 2H 6 concentration, which reveals that between 10 -4 and 10 -2 the ratio {s}/{β} increases. A precursor-state model is proposed in which SiH 3 first physisorbs on the H-covered surface and migrates until it recombines, or chemisorbs on a free dangling bond site. At a typical deposition temperature of 200° C, the only mechanism of creation of dangling bonds in the absence of B 2H 6 is precisely the recombination of SiH 3 as SiH 4 by H abstraction, which limits the sticking probability to a fraction of β. This restriction is overcome with the help of hydroboron radicals, presumably BH 3, which catalyze H 2 desorption.

Electronic, Magnetic, and Transport Properties of Polyacrylonitrile-Based Carbon Nanofibers of Various Widths: Density-Functional Theory Calculations

NASA Astrophysics Data System (ADS)

Partovi-Azar, P.; Panahian Jand, S.; Kaghazchi, P.

2018-01-01

Edge termination of graphene nanoribbons is a key factor in determination of their physical and chemical properties. Here, we focus on nitrogen-terminated zigzag graphene nanoribbons resembling polyacrylonitrile-based carbon nanofibers (CNFs) which are widely studied in energy research. In particular, we investigate magnetic, electronic, and transport properties of these CNFs as functions of their widths using density-functional theory calculations together with the nonequilibrium Green's function method. We report on metallic behavior of all the CNFs considered in this study and demonstrate that the narrow CNFs show finite magnetic moments. The spin-polarized electronic states in these fibers exhibit similar spin configurations on both edges and result in spin-dependent transport channels in the narrow CNFs. We show that the partially filled nitrogen dangling-bond bands are mainly responsible for the ferromagnetic spin ordering in the narrow samples. However, the magnetic moment becomes vanishingly small in the case of wide CNFs where the dangling-bond bands fall below the Fermi level and graphenelike transport properties arising from the π orbitals are recovered. The magnetic properties of the CNFs as well as their stability have also been discussed in the presence of water molecules and the hexagonal boron nitride substrate.

Coagulation of linear carbon molecules into nanoparticles: a molecular dynamics study

NASA Astrophysics Data System (ADS)

Yamaguchi, Yasutaka; Wakabayashi, Tomonari

2004-04-01

Using molecular dynamics (MD) simulations, the coagulation of carbon chain molecules that occurs on the subliming surface of a carbon-containing rare-gas matrix is investigated. Intermolecular connections with dangling bonds enhance the sublimation of the matrix and that results in the emission of a layer of nested carbon chains into vacuum at a velocity about 100 m/s. The following conversion from carbon sp- to more stable sp 2-type bonds heats up the carbon material above 3000 K. During this process, the nested carbon layer self-anneals via a graphitic mono-layer into a conjunct array of particles with a dimension about 10 nm.

Measuring the reactivity of a silicon-terminated probe

NASA Astrophysics Data System (ADS)

Sweetman, Adam; Stirling, Julian; Jarvis, Samuel Paul; Rahe, Philipp; Moriarty, Philip

2016-09-01

It is generally accepted that the exposed surfaces of silicon crystals are highly reactive due to the dangling bonds which protrude into the vacuum. However, surface reconstruction not only modifies the reactivity of bulk silicon crystals, but also plays a key role in determining the properties of silicon nanocrystals. In this study we probe the reactivity of silicon clusters at the end of a scanning probe tip by examining their interaction with closed-shell fullerene molecules. Counter to intuitive expectations, many silicon clusters do not react strongly with the fullerene cage, and we find that only specific highly oriented clusters have sufficient reactivity to break open the existing carbon-carbon bonds.

Stability and electronic structure of the low- Σ grain boundaries in CdTe: a density functional study

DOE PAGES

Park, Ji-Sang; Kang, Joongoo; Yang, Ji-Hui; ...

2015-01-15

Using first-principles density functional calculations, we investigate the relative stability and electronic structure of the grain boundaries (GBs) in zinc-blende CdTe. Among the low-Σ-value symmetric tilt Σ3 (111), Σ3 (112), Σ5 (120), and Σ5 (130) GBs, we show that the Σ3 (111)GB is always the most stable due to the absence of dangling bonds and wrong bonds. The Σ5 (120) GBs, however, are shown to be more stable than the Σ3 (112) GBs, even though the former has a higher Σ value, and the latter is often used as a model system to study GB effects in zinc-blende semiconductors. Furthermore,more » we find that although containing wrong bonds, the Σ5 (120) GBs are electrically benign due to the short wrong bond lengths, and thus are not as harmful as the Σ3 (112) GBs also having wrong bonds but with longer bond lengths.« less

X-ray photoelectron study of Si+ ion implanted polymers

NASA Astrophysics Data System (ADS)

Tsvetkova, T.; Balabanov, S.; Bischoff, L.; Krastev, V.; Stefanov, P.; Avramova, I.

2010-11-01

X-ray photoelectron spectroscopy was used to characterize different polymer materials implanted with low energy Si+ ions (E=30 keV, D= 1.1017 cm-2). Two kinds of polymers were studied - ultra-high-molecular-weight poly-ethylene (UHMWPE), and poly-methyl-methacrylate (PMMA). The non-implanted polymer materials show the expected variety of chemical bonds: carbon-carbon, carbon being three- and fourfold coordinated, and carbon-oxygen in the case of PMMA samples. The X-ray photoelectron and Raman spectra show that Si+ ion implantation leads to the introduction of additional disorder in the polymer material. The X-ray photoelectron spectra of the implanted polymers show that, in addition to already mentioned bonds, silicon creates new bonds with the host elements - Si-C and Si-O, together with additional Si dangling bonds as revealed by the valence band study of the implanted polymer materials.

DFT study of anisotropy effects on the electronic properties of diamond nanowires with nitrogen-vacancy center.

PubMed

Solano, Jesús Ramírez; Baños, Alejandro Trejo; Durán, Álvaro Miranda; Quiroz, Eliel Carvajal; Irisson, Miguel Cruz

2017-09-26

In the development of quantum computing and communications, improvements in materials capable of single photon emission are of great importance. Advances in single photon emission have been achieved experimentally by introducing nitrogen-vacancy (N-V) centers on diamond nanostructures. However, theoretical modeling of the anisotropic effects on the electronic properties of these materials is almost nonexistent. In this study, the electronic band structure and density of states of diamond nanowires with N-V defects were analyzed through first principles approach using the density functional theory and the supercell scheme. The nanowires were modeled on two growth directions [001] and [111]. All surface dangling bonds were passivated with hydrogen (H) atoms. The results show that the N-V introduces multiple trap states within the energy band gap of the diamond nanowire. The energy difference between these states is influenced by the growth direction of the nanowires, which could contribute to the emission of photons with different wavelengths. The presence of these trap states could reduce the recombination rate between the conduction and the valence band, thus favoring the single photon emission. Graphical abstract Diamond nanowires with nitrogen-vacancy centerᅟ.

Silicon homo-heterojunction solar cells: A promising candidate to realize high performance more stably

NASA Astrophysics Data System (ADS)

Tan, Miao; Zhong, Sihua; Wang, Wenjie; Shen, Wenzhong

2017-08-01

We have investigated the influences of diverse physical parameters on the performances of a silicon homo-heterojunction (H-H) solar cell, which encompasses both homojunction and heterojunction, together with their underlying mechanisms by the aid of AFORS-HET simulation. It is found that the performances of H-H solar cell are less sensitive to (i) the work function of the transparent conductive oxide layer, (ii) the interfacial density of states at the front hydrogenated amorphous silicon/crystalline silicon (a-Si:H/c-Si) interface, (iii) the peak dangling bond defect densities within the p-type a-Si:H (p-a-Si:H) layer, and (iv) the doping concentration of the p-a-Si:H layer, when compared to that of the conventional heterojunction with intrinsic thin layer (HIT) counterparts. These advantages are due to the fact that the interfacial recombination and the recombination within the a-Si:H region are less affected by all the above parameters, which fundamentally benefit from the field-effect passivation of the homojunction. Therefore, the design of H-H structure can provide an opportunity to produce high-efficiency solar cells more stably.

Thin-film Sb2Se3 photovoltaics with oriented one-dimensional ribbons and benign grain boundaries

NASA Astrophysics Data System (ADS)

Zhou, Ying; Wang, Liang; Chen, Shiyou; Qin, Sikai; Liu, Xinsheng; Chen, Jie; Xue, Ding-Jiang; Luo, Miao; Cao, Yuanzhi; Cheng, Yibing; Sargent, Edward H.; Tang, Jiang

2015-06-01

Solar cells based on inorganic absorbers, such as Si, GaAs, CdTe and Cu(In,Ga)Se2, permit a high device efficiency and stability. The crystals’ three-dimensional structure means that dangling bonds inevitably exist at the grain boundaries (GBs), which significantly degrades the device performance via recombination losses. Thus, the growth of single-crystalline materials or the passivation of defects at the GBs is required to address this problem, which introduces an added processing complexity and cost. Here we report that antimony selenide (Sb2Se3)—a simple, non-toxic and low-cost material with an optimal solar bandgap of ˜1.1 eV—exhibits intrinsically benign GBs because of its one-dimensional crystal structure. Using a simple and fast (˜1 μm min-1) rapid thermal evaporation process, we oriented crystal growth perpendicular to the substrate, and produced Sb2Se3 thin-film solar cells with a certified device efficiency of 5.6%. Our results suggest that the family of one-dimensional crystals, including Sb2Se3, SbSeI and Bi2S3, show promise in photovoltaic applications.

Understanding the synthesis, performance, and passivation of metal oxide photocathodes

NASA Astrophysics Data System (ADS)

Flynn, Cory James

Metal oxides are ubiquitous in semiconductor technologies for their ease of synthesis, chemical stability, and tunable optical/electronic properties. These properties are especially important to fabricating efficient photoelectrodes for solar-energy applications. To counter inherent problems in these materials, new strategies were developed and successfully implemented on the widely-utilized p-type semiconductor, NiO. As the size of semiconductor materials shrink, the surface-to-volume ratio increases and surface defects dominate the performance of the materials. Surface defects can alter the optical and electronic characteristics of materials by changing the Fermi level, charge-carrier mobility, and surface reactivity. We first present a strategy to increase the electrical mobility of mesoporous metal oxide electrode materials by optimizing shape morphology. Transitioning from nanospheres to hexagonal nanoplatelets increased the charge-carrier mobility by one order of magnitude. We then employed this improved material with a new vapor-phase deposition method termed targeted atomic deposition (TAD) to selectively passivate defect sites in semiconductor nanomaterials. We demonstrated the capabilities of this passivation method by applying a TAD of aluminum onto NiO. By exploiting a temperature-dependent deposition process, we selectively passivated the highly reactive sites in NiO: oxygen dangling bonds associated with Ni vacancies. The TAD treatment completely passivated all measurable surface defects, optically bleached the material, and significantly improved all photovoltaic performance metrics in dye-sensitized solar cells. The technique was proven to be generic to numerous forms of NiO. While the implementation of TAD of Al was successful, the process involved pulsing two precursors to passivate the material. Ideally, the TAD process should require only a single precursor and continuous exposure. We utilized a continuous flow of diborane to perform a TAD of B onto NiO. The TAD process was successfully implemented in a simplified manner. The treatment moderately increased DSSC performance and proved viability with a different vapor-phase precursor.

A Study of Electrical and Optical Stability of GSZO THin Film Transisitors

DTIC Science & Technology

2014-01-01

introduces an overview of the research carried out on IGZO , ZnO, and GSZO thin film transistors that is relevant to the work discussed in this...dangling bonds or electron trapping near the gate insulator interface in IGZO thin film transistors . Mathews et al. [13] indicated that subjecting TFTs to...Ping David Shieh, Hideo Hosono, and Jerzy Kanicki, Photofield-Effect in Amporphous In-Ga-Zn-O (a- IGZO ) Thin - Film Transistors . Journal of Information

Enhanced surface modification engineering (H, F, Cl, Br, and NO{sub 2}) of CdS nanowires with and without surface dangling bonds

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

Zeng, Yijie; Xing, Huaizhong, E-mail: xinghz@dhu.edu.cn; Lu, Aijiang

2015-08-07

Semiconductor nanowires (NWs) can be applied in gas sensing and cell detection, but the sensing mechanism is not clearly understood. In this study, surface modification effect on the electronic properties of CdS NWs for different diameters with several species (H, F, Cl, Br, and NO{sub 2}) is investigated by first principles calculations. The surface dangling bonds and halogen elements are chosen to represent the environment of the surface. Halogen passivation drastically changes the band gaps due to the strong electronegativity and the energy level of halogen atoms. Density of states analysis indicates that valence band maximum (VBM) of halogen-passivated NWsmore » is formed by the p states of halogen atoms, while VBM of H-passivated NWs is originated from Cd 4d and S 3p orbitals. To illustrate that surface modification can be applied in gas sensing, NO{sub 2}-absorbed NWs with different coverage are calculated. Low coverage of NO{sub 2} introduces a deep p-type dopant-like level, while high coverage introduces a shallow n-type dopant-like level into the band structure. The transformation is due to that at low coverage the adsorption is chemical while at high coverage is physical. These findings might promote the understanding of surface modification effect and the sensing mechanism of NWs as gas sensors.« less

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Study on the performance of 2.6 μm In0.83Ga0.17As detector with different etch gases

NASA Astrophysics Data System (ADS)

Li, Ping; Tang, Hengjing; Li, Tao; Li, Xue; Shao, Xiumei; Ma, Yingjie; Gong, Haimei

2017-09-01

In order to obtain a low-damage recipe in the ICP processing, ICP-induced damage using Cl2/CH4 etch gases in extended wavelength In0.83Ga0.17As detector materials was studied in this paper. The effect of ICP etching on In0.83Ga0.17As samples was characterized qualitatively by the photoluminescence (PL) technology. The etch damage of In0.83Ga0.17As samples was characterized quantitatively by the Transmission Line Model (TLM), current voltage (IV) measurement, signal and noise testing and the Fourier Transform Infrared Spectroscopy (FTIR) technologies. The results showed that the Cl2/CH4 etching processing could lead better detector performance than that Cl2/N2, such as a larger square resistance, a lower dark current, a lower noise voltage and a higher peak detectivity. The lower PL signal intensity and lower dark current could be attributed to the hydrogen decomposed by the CH4 etch gases in the plasma etching process. These hydrogen particles generated non-radiative recombination centers in inner materials to weaken the PL intensity and passivated dangling bond at the surface to reduce the dark current. The larger square resistance resulted from the lower etch damage. The lower dark current meant that the detectors have less dangling bonds and leakage channels.

Topological dynamics of gyroscopic and Floquet lattices from Newton's laws

NASA Astrophysics Data System (ADS)

Lee, Ching Hua; Li, Guangjie; Jin, Guliuxin; Liu, Yuhan; Zhang, Xiao

2018-02-01

Despite intense interest in realizing topological phases across a variety of electronic, photonic, and mechanical platforms, the detailed microscopic origin of topological behavior often remains elusive. To bridge this conceptual gap, we show how hallmarks of topological modes—boundary localization and chirality—emerge from Newton's laws in mechanical topological systems. We first construct a gyroscopic lattice with analytically solvable edge modes, and show how the Lorentz and spring restoring forces conspire to support very robust "dangling bond" boundary modes. The chirality and locality of these modes intuitively emerges from microscopic balancing of restoring forces and cyclotron tendencies. Next, we introduce the highlight of this work, an experimentally realistic mechanical nonequilibrium (Floquet) Chern lattice driven by ac electromagnets. Through appropriate synchronization of the ac driving protocol, the Floquet lattice is "pushed around" by a rotating potential analogous to an object washed ashore by water waves. Besides hosting "dangling bond" chiral modes analogous to the gyroscopic boundary modes, our Floquet Chern lattice also supports peculiar half-period chiral modes with no static analog, i.e., analogs of anomalous Floquet Chern insulators edge modes. With key parameters controlled electronically, our setup has the advantage of being dynamically tunable for applications involving arbitrary Floquet modulations. The physical intuition gleaned from our two prototypical topological systems is applicable not just to arbitrarily complicated mechanical systems, but also photonic and electrical topological setups.

Trade-off between quantum capacitance and thermodynamic stability of defected graphene: an implication for supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Srivastava, Anurag; SanthiBhushan, Boddepalli

2018-03-01

Defects are inevitable most of the times either at the synthesis, handling or processing stage of graphene, causes significant deviation of properties. The present work discusses the influence of vacancy defects on the quantum capacitance as well as thermodynamic stability of graphene, and the nitrogen doping pattern needs to be followed to attain a trade-off between these two. Density Functional Theory (DFT) calculations have been performed to analyze various vacancy defects and different possible nitrogen doping patterns at the vacancy site of graphene, with an implication for supercapacitor electrodes. The results signify that vacancy defect improves the quantum capacitance of graphene at the cost of thermodynamic stability, while the nitrogen functionalization at the vacancy improves thermodynamic stability and quantum capacitance both. It has been observed that functionalizing all the dangling carbons at the defect site with nitrogen is the key to attain high thermodynamic stability as well as quantum capacitance. Furthermore, the results signify the suitability of these functionalized graphenes for anode electrode of high energy density asymmetric supercapacitors.

Detection of subsurface core-level shifts in Si 2p core-level photoemission from Si(111)-(1x1):As

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

Paggel, J.J.; Hasselblatt, M.; Horn, K.

1997-04-01

The (7 x 7) reconstruction of the Si(111) surface arises from a lowering energy through the reduction of the number of dangling bonds. This reconstruction can be removed by the adsorption of atoms such as hydrogen which saturate the dangling bonds, or by the incorporation of atoms, such as arsenic which, because of the additional electron it possesses, can form three bonds and a nonreactive lone pair orbital from the remaining two electrons. Core and valence level photoemission and ion scattering data have shown that the As atoms replace the top silicon atoms. Previous core level spectra were interpreted inmore » terms of a bulk and a single surface doublet. The authors present results demonstrate that the core level spectrum contains two more lines. The authors assign these to subsurface silicon layers which also experience changes in the charge distribution when a silicon atom is replaced by an arsenic atom. Subsurface core level shifts are not unexpected since the modifications of the electronic structure and/or of photohole screening are likely to decay into the bulk and not just to affect the top-most substrate atoms. The detection of subsurface components suggests that the adsorption of arsenic leads to charge flow also in the second double layer of the Si(111) surface. In view of the difference in atomic radius between As and Si, it was suggested that the (1 x 1): As surface is strained. The presence of charge rearrangement up to the second double layer implies that the atomic coordinates also exhibit deviations from their ideal Si(111) counterparts, which might be detected through a LEED I/V or photoelectron diffraction analysis.« less

Changes in the hydrogen-bonding strength of internal water molecules and cysteine residues in the conductive state of channelrhodopsin-1

NASA Astrophysics Data System (ADS)

Lórenz-Fonfría, Víctor A.; Muders, Vera; Schlesinger, Ramona; Heberle, Joachim

2014-12-01

Water plays an essential role in the structure and function of proteins, particularly in the less understood class of membrane proteins. As the first of its kind, channelrhodopsin is a light-gated cation channel and paved the way for the new and vibrant field of optogenetics, where nerve cells are activated by light. Still, the molecular mechanism of channelrhodopsin is not understood. Here, we applied time-resolved FT-IR difference spectroscopy to channelrhodopsin-1 from Chlamydomonas augustae. It is shown that the (conductive) P2380 intermediate decays with τ ≈ 40 ms and 200 ms after pulsed excitation. The vibrational changes between the closed and the conductive states were analyzed in the X-H stretching region (X = O, S, N), comprising vibrational changes of water molecules, sulfhydryl groups of cysteine side chains and changes of the amide A of the protein backbone. The O-H stretching vibrations of "dangling" water molecules were detected in two different states of the protein using H218O exchange. Uncoupling experiments with a 1:1 mixture of H2O:D2O provided the natural uncoupled frequencies of the four O-H (and O-D) stretches of these water molecules, each with a very weakly hydrogen-bonded O-H group (3639 and 3628 cm-1) and with the other O-H group medium (3440 cm-1) to moderately strongly (3300 cm-1) hydrogen-bonded. Changes in amide A and thiol vibrations report on global and local changes, respectively, associated with the formation of the conductive state. Future studies will aim at assigning the respective cysteine group(s) and at localizing the "dangling" water molecules within the protein, providing a better understanding of their functional relevance in CaChR1.

International Conference on the Physics of Semiconductors (17th) Held in San Francisco, California on August 6-10, 1984

DTIC Science & Technology

1984-09-30

experimental probe of the Landau level density of states, which we find to be distinctly non -gaussian and in qualitative agreement with theoretical predictions...dispersion on the cleaved Si(111)2xi surface. For good single domain 2x1 surfaces different experimental groups agree on a highly dispersive dangling-bond...work underlies the operation of new devices proposed II] and realized experimentally : a gate controlled microwave generator (2,3J and a charge

Magnetic resonance tracking of fluorescent nanodiamond fabrication

NASA Astrophysics Data System (ADS)

Shames, A. I.; Osipov, V. Yu; Boudou, J. P.; Panich, A. M.; von Bardeleben, H. J.; Treussart, F.; Vul', A. Ya

2015-04-01

Magnetic resonance techniques (electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR)) are used for tracking the multi-stage process of the fabrication of fluorescent nanodiamonds (NDs) produced by high-energy electron irradiation, annealing, and subsequent nano-milling. Pristine commercial high pressure and high temperature microdiamonds (MDs) with mean size 150 μm contain ~5  ×  1018 spins/g of singlet (S = 1/2) substitutional nitrogen defects P1, as well as sp3 C-C dangling bonds in the crystalline lattice. The half-field X-band EPR clearly shows (by the appearance of the intense ‘forbidden’ g = 4.26 line) that high-energy electron irradiation and annealing of MDs induce a large amount (~5  ×  1017 spins/g) of triplet (S = 1) magnetic centers, which are identified as negatively charged nitrogen vacancy defects (NV-). This is supported by EPR observations of the ‘allowed’ transitions between Zeeman sublevels of the triplet state. After progressive milling of the fluorescent MDs down to an ultrasubmicron scale (≤100 nm), the relative abundance of EPR active NV- defects in the resulting fluorescent NDs (FND) substantially decreases and, vice versa, the content of C-inherited singlet defects correlatively increases. In the fraction of the finest FNDs (mean particle size <20 nm), which are contained in the dried supernatant of ultracentrifuged aqueous dispersion of FNDs, the NV- content is found to be reduced by one order of magnitude whereas the singlet defects content increases up to ~2  ×  1019 spins/g. In addition, another triplet-type defect, which is characterized by the g = 4.00 ‘forbidden’ line, appears. On reduction of the particle size below the 20 nm limit, the ‘allowed’ EPR lines become practically unobservable, whereas the ‘forbidden’ lines remain as a reliable fingerprint of the presence of NV- centers in small ND systems. The same size reduction causes the disappearance of the characteristic hyperfine satellites in the spectra of the P1 centers. We discuss the mechanisms that cause both the strong reduction of the peak intensity of the ‘allowed’ lines in EPR spectra of triplet defects and the transformation of the P1 spectra.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, J.R.; Thomas, T.M.; Czanderna, A.W.

1984-07-31

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, John R.; Thomas, Terence M.; Czanderna, Alvin W.

1985-01-01

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Passivation of InGaAs(001)-(2 × 4) by Self-Limiting Chemical Vapor Deposition of a Silicon Hydride Control Layer.

PubMed

Edmonds, Mary; Kent, Tyler; Chagarov, Evgueni; Sardashti, Kasra; Droopad, Ravi; Chang, Mei; Kachian, Jessica; Park, Jun Hong; Kummel, Andrew

2015-07-08

A saturated Si-Hx seed layer for gate oxide or contact conductor ALD has been deposited via two separate self-limiting and saturating CVD processes on InGaAs(001)-(2 × 4) at substrate temperatures of 250 and 350 °C. For the first self-limiting process, a single silicon precursor, Si3H8, was dosed at a substrate temperature of 250 °C, and XPS results show the deposited silicon hydride layer saturated at about 4 monolayers of silicon coverage with hydrogen termination. STS results show the surface Fermi level remains unpinned following the deposition of the saturated silicon hydride layer, indicating the InGaAs surface dangling bonds are electrically passivated by Si-Hx. For the second self-limiting process, Si2Cl6 was dosed at a substrate temperature of 350 °C, and XPS results show the deposited silicon chloride layer saturated at about 2.5 monolayers of silicon coverage with chlorine termination. Atomic hydrogen produced by a thermal gas cracker was subsequently dosed at 350 °C to remove the Si-Cl termination by replacing with Si-H termination as confirmed by XPS, and STS results confirm the saturated Si-Hx bilayer leaves the InGaAs(001)-(2 × 4) surface Fermi level unpinned. Density function theory modeling of silicon hydride surface passivation shows an Si-Hx monolayer can remove all the dangling bonds and leave a charge balanced surface on InGaAs.

Composition dependence of solid-phase epitaxy in silicon-germanium alloys: Experiment and theory

NASA Astrophysics Data System (ADS)

Haynes, T. E.; Antonell, M. J.; Lee, C. Archie; Jones, K. S.

1995-03-01

The rates of solid-phase epitaxy (SPE) in unstrained Si1-xGex alloys have been measured by time-resolved reflectivity for eight different alloy compositions, including both Si-rich and Ge-rich layers. Amorphous layers 300-400 nm thick were first formed in 8-μm-thick, relaxed, epitaxial Si1-xGex layers (0.02<=x<=0.87) by ion implantation of Si+. For each composition, the measured SPE rates spanned approximately two orders of magnitude. The alloy SPE rates are shown to be related to the regrowth rates of the two pure elements by a simple equation expressed in terms of the composition parameter x and having no adjustable parameters. The form of this equation implies that crystallization occurs by a serial attachment process at the amorphous-crystal interface and that the rate of attachment of each individual atom is determined by the identities of its four nearest neighbors. Such a process is consistent with the dangling-bond model proposed by Spaepen and Turnbull [in Laser-Solid Interactions and Laser Processing, edited by S. D. Ferris, H. J. Leamy, and J. M. Poate, AIP Conf. Proc. No. 50 (AIP, New York, 1979)] if the SPE rate is limited by the migration rate of dangling bonds rather than by their formation rate. Based on this analysis, an interpretation is proposed for the anomalously large activation energies that have been measured for SPE in some Si-rich compositions.

Improved Gate Dielectric Deposition and Enhanced Electrical Stability for Single-Layer MoS2 MOSFET with an AlN Interfacial Layer.

PubMed

Qian, Qingkai; Li, Baikui; Hua, Mengyuan; Zhang, Zhaofu; Lan, Feifei; Xu, Yongkuan; Yan, Ruyue; Chen, Kevin J

2016-06-09

Transistors based on MoS2 and other TMDs have been widely studied. The dangling-bond free surface of MoS2 has made the deposition of high-quality high-k dielectrics on MoS2 a challenge. The resulted transistors often suffer from the threshold voltage instability induced by the high density traps near MoS2/dielectric interface or inside the gate dielectric, which is detrimental for the practical applications of MoS2 metal-oxide-semiconductor field-effect transistor (MOSFET). In this work, by using AlN deposited by plasma enhanced atomic layer deposition (PEALD) as an interfacial layer, top-gate dielectrics as thin as 6 nm for single-layer MoS2 transistors are demonstrated. The AlN interfacial layer not only promotes the conformal deposition of high-quality Al2O3 on the dangling-bond free MoS2, but also greatly enhances the electrical stability of the MoS2 transistors. Very small hysteresis (ΔVth) is observed even at large gate biases and high temperatures. The transistor also exhibits a low level of flicker noise, which clearly originates from the Hooge mobility fluctuation instead of the carrier number fluctuation. The observed superior electrical stability of MoS2 transistor is attributed to the low border trap density of the AlN interfacial layer, as well as the small gate leakage and high dielectric strength of AlN/Al2O3 dielectric stack.

Systematic review: Early versus late dangling after free flap reconstruction of the lower limb.

PubMed

McGhee, J T; Cooper, L; Orkar, K; Harry, L; Cubison, T

2017-08-01

Dangling regimes after free flap surgery to the lower limb vary between centres and clinicians. There is currently no accepted gold standard. This review examines the evidence for early versus late post-operative dangling after free flap reconstruction of the lower limb. The secondary aim is to evaluate the regimes used. Medline, Embase and the Cochrane library were searched for all studies on dangling or rehabilitation after free flap reconstruction in the lower limb (December 2015). All studies outlining a clear dangling regime were included. Data were extracted by two authors independently and analysed using the software package Review Manager (RevMan 5). All authors were contacted for further information. 197 patients were included from 8 studies: 1 randomized, 6 cohort and 1 case-series. Although some studies did not state the aetiology, of those that did; 42% were trauma, 31% oncology, 20% complex wounds and 7% infection. The majority of flaps were latissimus dorsi, 18% parascapular, 15% anterolateral thigh and the remainder was mixed. Forty-eight percent of patients dangled on post-operative day (POD) 7, 29% on day 6, 4% on day 5 and 18% on day 3, with varying regimes. A meta-analysis of comparable studies showed circulatory benefit after 4 days of dangling using tissue oxygen saturation as a measure. Four flap failures (2.0%) were reported. There is physiological benefit in post-operative dangling. A 3-day flap training regime is sufficient for physiological training. However, the optimal flap training regime remains unclear. It may be appropriate to start dangling as early as POD 3. More research is needed to determine the optimal time to start dangling and the regime. Copyright © 2017 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

Electronic and Optical Properties of Core/Shell Pb16X16/Cd52X52 (X =S, Se, Te) Quantum Dots

NASA Astrophysics Data System (ADS)

Tamukong, Patrick; Mayo, Michael; Kilina, Svetlana

2015-03-01

The electronic and optoelectronic properties of semiconductor quantum dots (QDs) are mediated by surface defects due to the presence of dangling bonds producing trap states within the HOMO-LUMO energy gap, and contributing to fluorescence quenching. Surface capping ligands are generally used to alleviate this problem and increase the quantum yields of QDs. An alternative way is to synthesize core-shell QD structures; i.e., a QD core with a shell of another semiconductor material. We have investigated the effects of Cd52X52 shells on the photoexcited dynamics of Pb16X16 (X =S, Se, Te) QDs. The thin (~ 0.50 nm) shells were found to result largely in type I core/shell structures and a blue shift of the absorption spectra. Our studies revealed fairly strong core-shell hybridization in the electronic states close to the conduction band (CB) edge for Pb16S16andPb16Se16 cores, whereas for the Pb16Te16 core, such CB states were largely shell-like in nature. Nonadiabatic DFT-based dynamics, coupled with the surface hopping method, was used to study the effects of the core and shell compositions on energy relaxation rates in these systems.

Progress on Electronic and Optoelectronic Devices of 2D Layered Semiconducting Materials.

PubMed

Wang, Feng; Wang, Zhenxing; Jiang, Chao; Yin, Lei; Cheng, Ruiqing; Zhan, Xueying; Xu, Kai; Wang, Fengmei; Zhang, Yu; He, Jun

2017-09-01

2D layered semiconducting materials (2DLSMs) represent the thinnest semiconductors, holding many novel properties, such as the absence of surface dangling bonds, sizable band gaps, high flexibility, and ability of artificial assembly. With the prospect of bringing revolutionary opportunities for electronic and optoelectronic applications, 2DLSMs have prospered over the past twelve years. From materials preparation and property exploration to device applications, 2DLSMs have been extensively investigated and have achieved great progress. However, there are still great challenges for high-performance devices. In this review, we provide a brief overview on the recent breakthroughs in device optimization based on 2DLSMs, particularly focussing on three aspects: device configurations, basic properties of channel materials, and heterostructures. The effects from device configurations, i.e., electrical contacts, dielectric layers, channel length, and substrates, are discussed. After that, the affect of the basic properties of 2DLSMs on device performance is summarized, including crystal defects, crystal symmetry, doping, and thickness. Finally, we focus on heterostructures based on 2DLSMs. Through this review, we try to provide a guide to improve electronic and optoelectronic devices of 2DLSMs for achieving practical device applications in the future. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of incoherent twin boundaries on the electrical properties of β-Ga2O3 layers homoepitaxially grown by metal-organic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Fiedler, A.; Schewski, R.; Baldini, M.; Galazka, Z.; Wagner, G.; Albrecht, M.; Irmscher, K.

2017-10-01

We present a quantitative model that addresses the influence of incoherent twin boundaries on the electrical properties in β-Ga2O3. This model can explain the mobility collapse below a threshold electron concentration of 1 × 1018 cm-3 as well as partly the low doping efficiency in β-Ga2O3 layers grown homoepitaxially by metal-organic vapor phase epitaxy on (100) substrates of only slight off-orientation. A structural analysis by transmission electron microscopy (TEM) reveals a high density of twin lamellae in these layers. In contrast to the coherent twin boundaries parallel to the (100) plane, the lateral incoherent twin boundaries exhibit one dangling bond per unit cell that acts as an acceptor-like electron trap. Since the twin lamellae are thin, we consider the incoherent twin boundaries to be line defects with a density of 1011-1012 cm-2 as determined by TEM. We estimate the influence of the incoherent twin boundaries on the electrical transport properties by adapting Read's model of charged dislocations. Our calculations quantitatively confirm that the mobility reduction and collapse as well as partly the compensation are due to the presence of twin lamellae.

A Model Study of the Thermal Evolution of Astrophysical Ices

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Teolis, B. D.; Baragiola, R. A.

2006-01-01

We address the question of the evolution of ices that have been exposed to radiation from stellar sources and cosmic rays. We studied in the laboratory the thermal evolution of a model ice sample: a mixture of water, hydrogen peroxide, dioxygen, and ozone produced by irradiating solid H2O2 with 50 keV H(+) at 17 K. The changes in composition and release of volatiles during warming to 200 K were monitored by infrared spectroscopy, mass spectrometry, and microbalance techniques. We find evidence for voids in the water component from the infrared bands due to dangling H bonds. The absorption from these bands increases during heating and can be observed at temperatures as high as approx. 155 K. More O2 is stored in the radiolyzed film than can be retained by codeposition of O2 and H2O. This O2 remains trapped until approx. 155 K, where it desorbs in an outburst as water ice crystallizes. Warming of the ice also drastically decreases the intrinsic absorbance of O2 by annealing defects in the ice. We also observe loss of O3 in two stages during heating, which correlates with desorption and possibly chemical reactions with radicals stored in the ice, triggered by the temperature increase.

Pullout Performances of Grouted Rockbolt Systems with Bond Defects

NASA Astrophysics Data System (ADS)

Xu, Chang; Li, Zihan; Wang, Shanyong; Wang, Shuren; Fu, Lei; Tang, Chunan

2018-03-01

This paper presents a numerical study on the pullout behaviour of fully grouted rockbolts with bond defects. The cohesive zone model (CZM) is adopted to model the bond-slip behaviour between the rockbolt and grout material. Tensile tests were also conducted to validate the numerical model. The results indicate that the defect length can obviously influence the load and stress distributions along the rockbolt as well as the load-displacement response of the grouted system. Moreover, a plateau in the stress distribution forms due to the bond defect. The linear limit and peak load of the load-displacement response decrease as the defect length increases. A bond defect located closer to the loaded end leads to a longer nonlinear stage in the load-displacement response. However, the peak loads measured from the specimens made with various defect locations are almost approximately the same. The peak load for a specimen with the defects equally spaced along the bolt is higher than that for a specimen with defects concentrated in a certain zone, even with the same total defect length. Therefore, the dispersed pattern of bond defects would be much safer than the concentrated pattern. For the specimen with dispersed defects, the peak load increases with an increase in the defect spacing, even if the total defect length is the same. The peak load for a grouted rockbolt system with defects increases with an increases in the bolt diameter. This work leads to a better understanding of the load transfer mechanism for grouted rockbolt systems with bond defects, and paves the way towards developing a general evaluation method for damaged rockbolt grouted systems.

Resonant optical spectroscopy and coherent control of Cr4+ spin ensembles in SiC and GaN

NASA Astrophysics Data System (ADS)

Koehl, William

Spins bound to point defects have emerged as an important resource in quantum information and spintronic technologies, especially as new materials systems have been developed that enable robust and precise quantum state control via optical, electronic, or mechanical degrees of freedom. In an effort to broaden the range of materials platforms available to such defect-based quantum technologies, we have recently begun exploring optically active transition metal ion spins doped into common wide-bandgap semiconductors. The spins of such ions are derived in part from unpaired d orbital electron states, suggesting in some cases that they may be portable across multiple materials systems. This in contrast to many vacancy-related defect spins such as the diamond nitrogen vacancy center or silicon carbide divacancy, which are formed primarily from the dangling bond states of the host. Here we demonstrate ensemble optical spin polarization and time-resolved optically detected magnetic resonance (ODMR) of the S = 1 electronic ground state of chromium (Cr4+) impurities in silicon carbide (SiC) and gallium nitride (GaN). We find that these impurities possess narrow optical linewidths (<8.5 GHz at cryogenic temperatures) that allow us to optically resolve the magnetic sublevels of the spins even when probing a large ensemble of many ions simultaneously. This enables us to directly polarize and probe the Cr4+ spins using straightforward optical techniques, which we then combine with coherent microwave excitation in order to characterize the dynamical properties of the ensemble. Significantly, these near-infrared emitters also possess exceptionally weak phonon sidebands, ensuring that >73% of the overall optical emission is contained within the defects' zero-phonon lines. These characteristics make the Cr4+ ion system a promising target for further study in the ongoing effort to integrate optically active quantum states within common optoelectronic materials. In collaboration with B. Diler, S. J. Whiteley, A. Bourassa, N. T. Son, E. Janzén, and D. D. Awschalom. This work supported by AFOSR, ARO, NSF MRSEC, the Argonne LDRD Program, LiLi-NFM, and the Knut and Alice Wallenberg Foundation.

Donor ionization in size controlled silicon nanocrystals: The transition from defect passivation to free electron generation

NASA Astrophysics Data System (ADS)

Crowe, I. F.; Papachristodoulou, N.; Halsall, M. P.; Hylton, N. P.; Hulko, O.; Knights, A. P.; Yang, P.; Gwilliam, R. M.; Shah, M.; Kenyon, A. J.

2013-01-01

We studied the photoluminescence spectra of silicon and phosphorus co-implanted silica thin films on (100) silicon substrates as a function of isothermal annealing time. The rapid phase segregation, formation, and growth dynamics of intrinsic silicon nanocrystals are observed, in the first 600 s of rapid thermal processing, using dark field mode X-TEM. For short annealing times, when the nanocrystal size distribution exhibits a relatively small mean diameter, formation in the presence of phosphorus yields an increase in the luminescence intensity and a blue shift in the emission peak compared with intrinsic nanocrystals. As the mean size increases with annealing time, this enhancement rapidly diminishes and the peak energy shifts further to the red than the intrinsic nanocrystals. These results indicate the existence of competing pathways for the donor electron, which depends strongly on the nanocrystal size. In samples containing a large density of relatively small nanocrystals, the tendency of phosphorus to accumulate at the nanocrystal-oxide interface means that ionization results in a passivation of dangling bond (Pb-centre) type defects, through a charge compensation mechanism. As the size distribution evolves with isothermal annealing, the density of large nanocrystals increases at the expense of smaller nanocrystals, through an Ostwald ripening mechanism, and the majority of phosphorus atoms occupy substitutional lattice sites within the nanocrystals. As a consequence of the smaller band-gap, ionization of phosphorus donors at these sites increases the free carrier concentration and opens up an efficient, non-radiative de-excitation route for photo-generated electrons via Auger recombination. This effect is exacerbated by an enhanced diffusion in phosphorus doped glasses, which accelerates silicon nanocrystal growth.

Simulation of light-induced degradation of μc-Si in a-Si/μc-Si tandem solar cells by the diode equivalent circuit

NASA Astrophysics Data System (ADS)

Weicht, J. A.; Hamelmann, F. U.; Behrens, G.

2016-02-01

Silicon-based thin film tandem solar cells consist of one amorphous (a-Si) and one microcrystalline (μc-Si) silicon solar cell. The Staebler - Wronski effect describes the light- induced degradation and temperature-dependent healing of defects of silicon-based solar thin film cells. The solar cell degradation depends strongly on operation temperature. Until now, only the light-induced degradation (LID) of the amorphous layer was examined in a-Si/μc-Si solar cells. The LID is also observed in pc-Si single function solar cells. In our work we show the influence of the light-induced degradation of the μc-Si layer on the diode equivalent circuit. The current-voltage-curves (I-V-curves) for the initial state of a-Si/pc-Si modules are measured. Afterwards the cells are degraded under controlled conditions at constant temperature and constant irradiation. At fixed times the modules are measured at standard test conditions (STC) (AM1.5, 25°C cell temperature, 1000 W/m2) for controlling the status of LID. After the degradation the modules are annealed at dark conditions for several hours at 120°C. After the annealing the dangling bonds in the amorphous layer are healed, while the degradation of the pc-Si is still present, because the healing of defects in pc-Si solar cells needs longer time or higher temperatures. The solar cells are measured again at STC. With this laboratory measured I-V-curves we are able to separate the values of the diode model: series Rs and parallel resistance Rp, saturation current Is and diode factor n.

Optical properties of Si and Ge nanocrystals: Parameter-free calculations

NASA Astrophysics Data System (ADS)

Ramos, L. E.; Weissker, H.-Ch.; Furthmüller, J.; Bechstedt, F.

2005-12-01

The cover picture of the current issue refers to the Edi-tor's Choice article of Ramos et al. [1]. The paper gives an overview of the electronic and optical properties of silicon and germanium nanocrystals determined by state-of-the-art ab initio methods. Nanocrystals have promising applications in opto-electronic devices, since they can be used to confine electrons and holes and facilitate radiative recombination. Since meas-urements for single nanoparticles are difficult to make, ab initio theoretical investigations become important to understand the mechanisms of luminescence.The cover picture shows nanocrystals of four sizes with tetrahedral coordination whose dangling bonds at the surface are passivated with hydrogen. As often observed in experiments, the nanocrystals are not perfectly spherical, but contain facets. Apart from the size of the nanocrystals, which determines the quantum confinement, the way their dangling bonds are passivated is relevant for their electronic and optical properties. For instance, the passivation with hydroxyls reduces the quantum confine-ment. On the other hand, the oxidation of the silicon nanocrys-tals increases the quantum confinement and reduces the effect of single surface terminations on the gap. Due to the oscillator strengths of the lowest-energy optical transitions, Ge nanocrys-tals are in principle more suitable for opto-electronic applica-tions than Si nanocrystals.The first author, Luis E. Ramos, is a postdoc at the Institute of Solid-State Physics and Optics (IFTO), Friedrich-Schiller University Jena, Germany. He investigates electronic and optical properties of semiconductor nanocrystallites and is a member of the European Network of Excellence NANO-QUANTA and of the European Theoretical Spectroscopy Facility (ETSF).

Improved Gate Dielectric Deposition and Enhanced Electrical Stability for Single-Layer MoS2 MOSFET with an AlN Interfacial Layer

PubMed Central

Qian, Qingkai; Li, Baikui; Hua, Mengyuan; Zhang, Zhaofu; Lan, Feifei; Xu, Yongkuan; Yan, Ruyue; Chen, Kevin J.

2016-01-01

Transistors based on MoS2 and other TMDs have been widely studied. The dangling-bond free surface of MoS2 has made the deposition of high-quality high-k dielectrics on MoS2 a challenge. The resulted transistors often suffer from the threshold voltage instability induced by the high density traps near MoS2/dielectric interface or inside the gate dielectric, which is detrimental for the practical applications of MoS2 metal-oxide-semiconductor field-effect transistor (MOSFET). In this work, by using AlN deposited by plasma enhanced atomic layer deposition (PEALD) as an interfacial layer, top-gate dielectrics as thin as 6 nm for single-layer MoS2 transistors are demonstrated. The AlN interfacial layer not only promotes the conformal deposition of high-quality Al2O3 on the dangling-bond free MoS2, but also greatly enhances the electrical stability of the MoS2 transistors. Very small hysteresis (ΔVth) is observed even at large gate biases and high temperatures. The transistor also exhibits a low level of flicker noise, which clearly originates from the Hooge mobility fluctuation instead of the carrier number fluctuation. The observed superior electrical stability of MoS2 transistor is attributed to the low border trap density of the AlN interfacial layer, as well as the small gate leakage and high dielectric strength of AlN/Al2O3 dielectric stack. PMID:27279454

Differences in optoelectronic properties between H-saturated and unsaturated GaN nanowires with DFT method

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-05-01

To investigate the influences of dangling bonds on GaN nanowires surface, the differences in optoelectronic properties between H-saturated and unsaturated GaN nanowires are researched through first-principles study. The GaN nanowires along the [0001] growth direction with diameters of 3.7, 7.5 and 9.5 Å are considered. According to the results, H-saturated GaN nanowires are more stable than the unsaturated ones. With increasing nanowire diameter, unsaturated GaN nanowires become more stable, while the stability of H-saturated GaN nanowires has little change. After geometry optimization, the atomic displacements of unsaturated and H-saturated models are almost reversed. In (0001) crystal plane, Ga atoms tend to move inwards and N atoms tend to move outwards slightly for the unsaturated nanowires, while Ga atoms tend to move outwards and N atoms tend to move inwards slightly for the H-saturated nanowires. Besides, with increasing nanowire diameter, the conduction band minimum of H-saturated nanowire moves to the lower energy side, while that of the unsaturated nanowire changes slightly. The bandgaps of H-saturated nanowires are approaching to bulk GaN as the diameter increases. Absorption curves and reflectivity curves of the unsaturated and H-saturated nanowires exhibit the same trend with the change of energy except the H-saturated models which show larger variations. Through all the calculated results above, we can better understand the effects of dangling bonds on the optoelectronic properties of GaN nanowires and select more proper calculation models and methods for other calculations.

The Effects of Hydrogen on the Potential-Energy Surface of Amorphous Silicon

NASA Astrophysics Data System (ADS)

Joly, Jean-Francois; Mousseau, Normand

2012-02-01

Hydrogenated amorphous silicon (a-Si:H) is an important semiconducting material used in many applications from solar cells to transistors. In 2010, Houssem et al. [1], using the open-ended saddle-point search method, ART nouveau, studied the characteristics of the potential energy landscape of a-Si as a function of relaxation. Here, we extend this study and follow the impact of hydrogen doping on the same a-Si models as a function of doping level. Hydrogen atoms are first attached to dangling bonds, then are positioned to relieve strained bonds of fivefold coordinated silicon atoms. Once these sites are saturated, further doping is achieved with a Monte-Carlo bond switching method that preserves coordination and reduces stress [2]. Bonded interactions are described with a modified Stillinger-Weber potential and non-bonded Si-H and H-H interactions with an adapted Slater-Buckingham potential. Large series of ART nouveau searches are initiated on each model, resulting in an extended catalogue of events that characterize the evolution of potential energy surface as a function of H-doping. [4pt] [1] Houssem et al., Phys Rev. Lett., 105, 045503 (2010)[0pt] [2] Mousseau et al., Phys Rev. B, 41, 3702 (1990)

Stress relaxation at a gelatin hydrogel-glass interface in direct shear sliding

NASA Astrophysics Data System (ADS)

Gupta, Vinit; Singh, Arun K.

2018-01-01

In this paper, we study experimentally the stress relaxation behavior of soft solids such as gelatin hydrogels on a smooth glass surface in direct shear sliding. It is observed experimentally that irrespective of pulling velocity, the sliding block relaxes to the same level of nonzero residual stress. However, residual stress increases with increasing gelatin concentration in the hydrogels. We have also validated a friction model for strong bond formation during steady relaxation in light of the experimental observations. Our theoretical analysis establishes that population of dangling chains at the sliding interface significantly affects the relaxation process. As a result, residual stress increases with increasing gelatin concentration or decreasing mesh size of the three-dimensional structures in the hydrogels. It is also found that the transition time, at which a weak bond converts to strong bond, increases with increasing mesh size of the hydrogels. Moreover, relaxation time constant of a strong bond decreases with increasing mesh size. However, activation length of a strong bond increases with mesh size. Finally, this study signifies the role of residual strength in frictional shear sliding and it is believed that these results should be useful to understand the role of residual stress in stick-slip instability.

Infrared Absorption of Methanol-Water Clusters Mn(H2O), n = 1-4, Recorded with the Vuv-Ionization Techniques

NASA Astrophysics Data System (ADS)

Lee, Yu-Fang; Lee, Yuan-Pern

2016-06-01

We investigated IR spectra in the CH- and OH-stretching regions of size-selected methanol-water clusters, Mn(H_2O) with M representing CH_3OH and n = 1-4, in a pulsed supersonic jet by using the VUV (vacuum-ultraviolet)-ionization/IR-depletion technique. The VUV light at 118 nm served as the source of ionization in a time-of-flight mass spectrometer. The tunable IR laser served as a source of dissociation for clusters before ionization. Spectra of methanol-water clusters in the OH region show significant variations as the number of methanol molecules increase, whereas spectra in the CH region are similar. For M(H_2O), absorption of a structure with H_2O as a proton donor was observed at 3570, 3682, and 3722 wn, whereas that of methanol as a proton donor was observed at 3611 and 3753 wn. For M2(H_2O), the OH-stretching band of the dangling OH of H_2O was observed at 3721 wn, whereas overlapped bands near 3425, 3472, and 3536 wn correspond to the OH-stretching modes of three hydrogen-bonded OH in a cyclic structure. For M3(H_2O), the dangling OH shifts to 3715 wn, and the hydrogen-bonded OH-stretching bands become much broader, with a band near 3179 wn having the smallest wavenumber. Scaled harmonic vibrational wavenumbers and relative IR intensities predicted for the methanol-water clusters with the M06-2X/aug-cc-pVTZ method are consistent with our experimental results. For M4(H_2O), observed spectrum agree less with theoretical predictions, indicating the presence of isomers other than the most stable cyclic one. Spectra of Mn(H_2O) and Mn+1 are compared and the cooperative hydrogen-bonding is discussed.

Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

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

Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

2014-01-28

The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

Tip-induced reduction of the resonant tunneling current on semiconductor surfaces.

PubMed

Jelínek, Pavel; Svec, Martin; Pou, Pablo; Perez, Ruben; Cháb, Vladimír

2008-10-24

We report scanning tunneling microscope measurements showing a substantial decrease of the current, almost to zero, on the Si(111)-(7x7) reconstruction in the near-to-contact region under low bias conditions. First principles simulations for the tip-sample interaction and transport calculations show that this effect is driven by the substantial local modification of the atomic and electronic structure of the surface. The chemical reactivity of the adatom dangling bond states that dominate the electronic density of states close to the Fermi level and their spatial localization result in a strong modification of the electronic current.

Voc enhancement of a solar cell with doped Li+-PbS as the active layer

NASA Astrophysics Data System (ADS)

Chávez Portillo, M.; Alvarado Pulido, J.; Gallardo Hernández, S.; Soto Cruz, B. S.; Alcántara Iniesta, S.; Gutiérrez Pérez, R.; Portillo Moreno, O.

2018-06-01

In this report, we investigate the fabrication of solar cells obtained by chemical bath technique, based on CdS as window layer and PbS and PbS-Li+-doped as the active layer. We report open-circuit-voltage Voc values of ∼392 meV for PbS and ∼630 meV for PbSLi+-doped, a remarkable enhanced in the open circuit voltage is shown for solar cells with doped active layer. Li+ ion passivate the dangling bonds in PbS-metal layer interface in consequence reducing the recombination centers.

On the nature of the solvated electron in ice Ih.

PubMed

de Koning, Maurice; Fazzio, Adalberto; da Silva, Antônio José Roque; Antonelli, Alex

2016-02-14

The water-solvated excess electron (EE) is a key chemical agent whose hallmark signature, its asymmetric optical absorption spectrum, continues to be a topic of debate. While nearly all investigation has focused on the liquid-water solvent, the fact that the crystalline-water solvated EE shows a very similar visible absorption pattern has remained largely unexplored. Here, we present spin-polarized density-functional theory calculations subject to periodic boundary conditions of the interplay between an EE and a number of intrinsic lattice defects in ice Ih. Our results show that the optical absorption signatures in the presence of three unsaturated hydrogen bonds (HB) are very similar to those observed experimentally. Its low-energy side can be attributed to transitions between the EE ground state and a single localized excited level, in a picture that is different from that for the liquid solvent, where this portion has been associated with hydrogen-like s → p excitations. The blue tail, on the other hand, relates to transitions between the EE ground state and delocalized excited states, which is in line with the bound-to-continuum transition interpretations for the EE in liquid water. Finally, we find that, depending on the number of dangling HBs participating in the EE trap, its charge density may spontaneously break the spin degeneracy through exchange interactions with the surrounding electrons, displaying the many-electron quantum nature of the EE problem in ice Ih.

Solvothermal synthesis, electromagnetic and electrochemical properties of jellylike cylinder graphene-Mn3O4 composite with highly coupled effect

NASA Astrophysics Data System (ADS)

Long, Yuting; Xie, Junliang; Li, Hong; Liu, Zirui; Xie, Yahong

2017-12-01

Jellylike cylinder graphene-Mn3O4 composite with highly coupled effect was successfully synthesized by a simple solvothermal process. Without using toxic reducing agent and expensive equipment, this method is environmental compatible and suitable for low cost mass production. High capacitance Mn3O4 nanoparticles are homogeneously anchored on excellent conductivity graphene framework and a growth mechanism is hypothesized. Excellent electron conductivity and unique structure of Mn3O4-graphene composite give rise to various applications such as microwave absorber and electrode material. As a microwave absorber, the composite exhibits lowest reflection loss of -14.2 dB in the frequency range of 2-18 GHz. Good microwave absorption performance is due to the structure of the composite where conductive channels form between nano sized Mn3O4 and high conductivity graphene with defects and dangling bonds. As for electrochemical property, Mn3O4-graphene composite with coupled effect shows excellent performance with highest specific capacitance of 246.7 F g-1 in saturated K2SO4 at a scan rate of 5 mV s-1. Good electrochemical property is also attributed to the structure with high utilization of Mn3O4, fast charge carrier transmission, and excellent electronic conductivity. This composite shows a promising application in absorbing materials and electrodes.

Physical criteria for the interface passivation layer in hydrogenated amorphous/crystalline silicon heterojunction solar cell

NASA Astrophysics Data System (ADS)

Zhao, Lei; Wang, Guanghong; Diao, Hongwei; Wang, Wenjing

2018-01-01

AFORS-HET (automat for simulation of heterostructures) simulation was utilized to explore the physical criteria for the passivation layer in hydrogenated amorphous/crystalline silicon heterojunction (SHJ) solar cells, by systematically investigating the solar cell current density-voltage (J-V) performance as a function of the interface defect density (D it) at the passivation layer/c-Si hetero-interface, the thickness (t) of the passivation layer, the bandgap (E g) of the passivation layer, and the density of dangling bond states (D db)/band tail states (D bt) in the band gap of the passivation layer. The corresponding impact regulations were presented clearly. Except for D it, the impacts of D db, D bt and E g are strongly dependent on the passivation layer thickness t. While t is smaller than 4-5 nm, the solar cell performance is less sensitive to the variation of D db, D bt and E g. Low D it at the a-Si:H/c-Si interface and small thickness t are the critical criteria for the passivation layer in such a case. However, if t has to be relatively larger, the microstructure, i.e. the material quality, including D db, D bt and E g, of the passivation layer should be controlled carefully. The mechanisms involved were analyzed and some applicable methods to prepare the passivation layer were proposed.

A review of defects and disorder in multinary tetrahedrally bonded semiconductors [Defects and disorder in multinary tetrahedrally bonded semiconductors studied by experiment and theory

DOE PAGES

Baranowski, Lauryn L.; Zawadzki, Pawel; Lany, Stephan; ...

2016-11-10

Defects are critical to understanding the electronic properties of semiconducting compounds, for applications such as light-emitting diodes, transistors, photovoltaics, and thermoelectrics. In this review, we describe our work investigating defects in tetrahedrally bonded, multinary semiconductors, and discuss the place of our research within the context of publications by other groups. We applied experimental and theory techniques to understand point defects, structural disorder, and extended antisite defects in one semiconductor of interest for photovoltaic applications, Cu 2SnS 3. We contrast our findings on Cu 2SnS 3 with other chemically related Cu-Sn-S compounds, as well as structurally related compounds such as Cumore » 2ZnSnS 4 and Cu(In,Ga)Se 2. We find that evaluation of point defects alone is not sufficient to understand defect behavior in multinary tetrahedrally bonded semiconductors. In the case of Cu 2SnS 3 and Cu 2ZnSnS 4, structural disorder and entropy-driven cation clustering can result in nanoscale compositional inhomogeneities which detrimentally impact the electronic transport. Therefore, it is not sufficient to assess only the point defect behavior of new multinary tetrahedrally bonded compounds; effects such as structural disorder and extended antisite defects must also be considered. Altogether, this review provides a framework for evaluating tetrahedrally bonded semiconducting compounds with respect to their defect behavior for photovoltaic and other applications, and suggests new materials that may not be as prone to such imperfections.« less

A review of defects and disorder in multinary tetrahedrally bonded semiconductors [Defects and disorder in multinary tetrahedrally bonded semiconductors studied by experiment and theory

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

Baranowski, Lauryn L.; Zawadzki, Pawel; Lany, Stephan

Defects are critical to understanding the electronic properties of semiconducting compounds, for applications such as light-emitting diodes, transistors, photovoltaics, and thermoelectrics. In this review, we describe our work investigating defects in tetrahedrally bonded, multinary semiconductors, and discuss the place of our research within the context of publications by other groups. We applied experimental and theory techniques to understand point defects, structural disorder, and extended antisite defects in one semiconductor of interest for photovoltaic applications, Cu 2SnS 3. We contrast our findings on Cu 2SnS 3 with other chemically related Cu-Sn-S compounds, as well as structurally related compounds such as Cumore » 2ZnSnS 4 and Cu(In,Ga)Se 2. We find that evaluation of point defects alone is not sufficient to understand defect behavior in multinary tetrahedrally bonded semiconductors. In the case of Cu 2SnS 3 and Cu 2ZnSnS 4, structural disorder and entropy-driven cation clustering can result in nanoscale compositional inhomogeneities which detrimentally impact the electronic transport. Therefore, it is not sufficient to assess only the point defect behavior of new multinary tetrahedrally bonded compounds; effects such as structural disorder and extended antisite defects must also be considered. Altogether, this review provides a framework for evaluating tetrahedrally bonded semiconducting compounds with respect to their defect behavior for photovoltaic and other applications, and suggests new materials that may not be as prone to such imperfections.« less

Superhydrophilic TiO2 thin film by nanometer scale surface roughness and dangling bonds

NASA Astrophysics Data System (ADS)

Bharti, Bandna; Kumar, Santosh; Kumar, Rajesh

2016-02-01

A remarkable enhancement in the hydrophilic nature of titanium dioxide (TiO2) films is obtained by surface modification in DC-glow discharge plasma. Thin transparent TiO2 films were coated on glass substrate by sol-gel dip coating method, and exposed in DC-glow discharge plasma. The plasma exposed TiO2 film exhibited a significant change in its wetting property contact angle, which is a representative of wetting property, has reduced to considerable limits 3.02° and 1.85° from its initial value 54.40° and 48.82° for deionized water and ethylene glycol, respectively. It is elucidated that the hydrophilic property of plasma exposed TiO2 films dependent mainly upon nanometer scale surface roughness. Variation, from 4.6 nm to 19.8 nm, in the film surface roughness with exposure time was observed by atomic force microscopy (AFM). Analysis of variation in the values of contact angle and surface roughness with increasing plasma exposure time reveal that the surface roughness is the main factor which makes the modified TiO2 film superhydrophilic. However, a contribution of change in the surface states, to the hydrophilic property, is also observed for small values of the plasma exposure time. Based upon nanometer scale surface roughness and dangling bonds, a variation in the surface energy of TiO2 film from 49.38 to 88.92 mJ/m2 is also observed. X-ray photoelectron spectroscopy (XPS) results show change in the surface states of titanium and oxygen. The observed antifogging properties are the direct results of the development of the superhydrophilic wetting characteristics to TiO2 films.

Controlled formation of closed-edge nanopores in graphene

NASA Astrophysics Data System (ADS)

He, Kuang; Robertson, Alex W.; Gong, Chuncheng; Allen, Christopher S.; Xu, Qiang; Zandbergen, Henny; Grossman, Jeffrey C.; Kirkland, Angus I.; Warner, Jamie H.

2015-07-01

Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport.Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport. Electronic supplementary information (ESI) available: Low magnification images, image processing techniques employed, modelling and simulation of closed edge nanoribbon, comprehensive AC-TEM dataset, and supporting analysis. See DOI: 10.1039/c5nr02277k

Amorphous and crystalline silicon based heterojunction solar cells

NASA Astrophysics Data System (ADS)

Schüttauf, J. A.

2011-10-01

In this thesis, research on amorphous and crystalline silicon heterojunction (SHJ) solar cells is described. Probably the most important feature of SHJ solar cells is a thin intrinsic amorphous silicion (a-Si:H) layer that is deposited before depositing the doped emitter and back surface field. The passivation properties of such intrinsic layers made by three different chemical vapor deposition (CVD) techniques have been investigated. For layers deposited at 130°C, all techniques show a strong reduction in surface recombination velocity (SRV) after annealing. Modelling indicates that dangling bond saturation by atomic hydrogen is the predominant mechanism. We obtain outstanding carrier lifetimes of 10.3 ms, corresponding to SRVs of 0.56 cm/s. For a-Si:H films made at 250°C, an as-deposited minority carrier lifetime of 2.0 ms is observed. In contrast to a-Si:H films fabricated at 130°C, however, no change in passivation quality upon thermal annealing is observed. These films were fabricated for the first time using a continuous in-line HWCVD mode. Wafer cleaning before a-Si:H deposition is a crucial step for c-Si surface passivation. We tested the influence of an atomic hydrogen treatment before a-Si:H deposition on the c-Si surface. The treatments were performed in a new virgin chamber to exclude Si deposition from the chamber walls. Subsequently, we deposited a-Si:H layers onto the c-Si wafers and measured the lifetime for different H treatment times. We found that increasing hydrogen treatment times led to lower effective lifetimes. Modelling of the measured minority carrier lifetime data shows that the decreased passivation quality is caused by an increased defect density at the amorphous-crystalline interface. Furtheremore, the passivation of different a-Si:H containing layers have been tested. For intrinsic films and intrinsic/n-type stacks, an improvement in passivation up to 255°C and 270°C is observed. This improvement is attributed to dangling bond saturation by H, whereas the decrease at higher temperatures is caused by H effusion. For intrinsic/n-type a-Si:H layer stacks, a record minority carrier lifetime of 13.3 ms is obtained. In contrast, for intrinsic/p-type a-Si:H layer stacks, a deterioration in passivation is observed over the whole temperature range, due to the asymmetric Fermi-level dependent defect formation enthalpy in n- and p-type a-Si:H. Comparing the lifetime values and trends for the different layer stacks to the performance of the corresponding cells, it is observed that the intrinsic/p-layer stack is limiting device performance. Based on these findings, the solar cells were prepared in a modified order, reaching an efficiency of 16.7% (VOC = 681 mV), versus 15.8% (VOC = 659 mV) in the ‘standard’ order. Finally, transparent conductive oxide (TCO) layers are studied for application into solar cells. It is observed that both types of TCO deposition have no significant influence on the passivation properties of standard a-Si:H layer stacks forming the emitter structure in the used SHJ cells. On flat wafers, a conversion efficiency of 16.7% has been obtained when ITO is used as TCO, versus an efficiency of 16.3% for ZnO:Al; slightly lower due to increased electrical losses.

Isomers and energy landscapes of micro-hydrated sulfite and chlorate clusters

NASA Astrophysics Data System (ADS)

Hey, John C.; Doyle, Emily J.; Chen, Yuting; Johnston, Roy L.

2018-03-01

We present putative global minima for the micro-hydrated sulfite SO32-(H2O)N and chlorate ClO32(H2O)N systems in the range 3≤N≤15 found using basin-hopping global structure optimization with an empirical potential. We present a structural analysis of the hydration of a large number of minimized structures for hydrated sulfite and chlorate clusters in the range 3≤N≤50. We show that sulfite is a significantly stronger net acceptor of hydrogen bonding within water clusters than chlorate, completely suppressing the appearance of hydroxyl groups pointing out from the cluster surface (dangling OH bonds), in low-energy clusters. We also present a qualitative analysis of a highly explored energy landscape in the region of the global minimum of the eight water hydrated sulfite and chlorate systems. This article is part of the theme issue `Modern theoretical chemistry'.

A shear localization mechanism for lubricity of amorphous carbon materials

PubMed Central

Ma, Tian-Bao; Wang, Lin-Feng; Hu, Yuan-Zhong; Li, Xin; Wang, Hui

2014-01-01

Amorphous carbon is one of the most lubricious materials known, but the mechanism is not well understood. It is counterintuitive that such a strong covalent solid could exhibit exceptional lubricity. A prevailing view is that lubricity of amorphous carbon results from chemical passivation of dangling bonds on surfaces. Here we show instead that lubricity arises from shear induced strain localization, which, instead of homogeneous deformation, dominates the shearing process. Shear localization is characterized by covalent bond reorientation, phase transformation and structural ordering preferentially in a localized region, namely tribolayer, resulting in shear weakening. We further demonstrate an anomalous pressure induced transition from stick-slip friction to continuous sliding with ultralow friction, due to gradual clustering and layering of graphitic sheets in the tribolayer. The proposed shear localization mechanism sheds light on the mechanism of superlubricity, and would enrich our understanding of lubrication mechanism of a wide variety of amorphous materials. PMID:24412998

Highly selective covalent organic functionalization of epitaxial graphene

NASA Astrophysics Data System (ADS)

Bueno, Rebeca A.; Martínez, José I.; Luccas, Roberto F.; Del Árbol, Nerea Ruiz; Munuera, Carmen; Palacio, Irene; Palomares, Francisco J.; Lauwaet, Koen; Thakur, Sangeeta; Baranowski, Jacek M.; Strupinski, Wlodek; López, María F.; Mompean, Federico; García-Hernández, Mar; Martín-Gago, José A.

2017-05-01

Graphene functionalization with organics is expected to be an important step for the development of graphene-based materials with tailored electronic properties. However, its high chemical inertness makes difficult a controlled and selective covalent functionalization, and most of the works performed up to the date report electrostatic molecular adsorption or unruly functionalization. We show hereafter a mechanism for promoting highly specific covalent bonding of any amino-terminated molecule and a description of the operating processes. We show, by different experimental techniques and theoretical methods, that the excess of charge at carbon dangling-bonds formed on single-atomic vacancies at the graphene surface induces enhanced reactivity towards a selective oxidation of the amino group and subsequent integration of the nitrogen within the graphene network. Remarkably, functionalized surfaces retain the electronic properties of pristine graphene. This study opens the door for development of graphene-based interfaces, as nano-bio-hybrid composites, fabrication of dielectrics, plasmonics or spintronics.

Isomers and energy landscapes of micro-hydrated sulfite and chlorate clusters.

PubMed

Hey, John C; Doyle, Emily J; Chen, Yuting; Johnston, Roy L

2018-03-13

We present putative global minima for the micro-hydrated sulfite SO 3 2- (H 2 O) N and chlorate ClO 3 - (H 2 O) N systems in the range 3≤ N ≤15 found using basin-hopping global structure optimization with an empirical potential. We present a structural analysis of the hydration of a large number of minimized structures for hydrated sulfite and chlorate clusters in the range 3≤ N ≤50. We show that sulfite is a significantly stronger net acceptor of hydrogen bonding within water clusters than chlorate, completely suppressing the appearance of hydroxyl groups pointing out from the cluster surface (dangling OH bonds), in low-energy clusters. We also present a qualitative analysis of a highly explored energy landscape in the region of the global minimum of the eight water hydrated sulfite and chlorate systems.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Authors.

The assessment of orthodontic bonding defects: optical coherence tomography followed by three-dimensional reconstruction

NASA Astrophysics Data System (ADS)

Rominu, R.; Sinescu, C.; Rominu, M.; Negrutiu, M.; Petrescu, E.; Pop, D.; Podoleanu, A. Gh.

2011-10-01

Orthodontic bonding is a simple yet important procedure that can influence the outcome of treatment in case it is performed incorrectly. An orthodontic treatment shadowed by repeated bonding failures can become unduly long and will decrease patient trust and compliance. Optical coherence tomography has been widely used in ophtalmology but is relatively new to dentistry. Using OCT one can detect aerial inclusions within the orthodontic adhesive or even identify incongruence between the bracket base and the tooth surface. The aim of our study was to identify bonding defects and reconstruct them three-dimensionally in order to be able to characterize them more accurately. We bonded 30 sound human permanent teeth with ceramic orthodontic brackets using a no-mix self-curing orthodontic adhesive. Prior to bonding all teeth were stored in tap water at 4°C and then professionally cleaned with rotary brushes and pumice. The samples were processed by the same person and the rotary brushes were changed after every fifth tooth. All interfaces were investigated by means of OCT and 4 defects were found. Subsequently, the defects were reconstructed threedimensionally using an open-source program. By identifying and reconstructing bonding defects we could assess the quality of the bonding procedure. Since bonding tends to be more accurate in vitro where the environmental conditions are close to ideal, it is probable that defects found in vivo be even greater in number, which leads to the conclusion that this type of investigation is potentially valuable.

Defects in Amorphous Semiconductors: The Case of Amorphous Indium Gallium Zinc Oxide

NASA Astrophysics Data System (ADS)

de Jamblinne de Meux, A.; Pourtois, G.; Genoe, J.; Heremans, P.

2018-05-01

Based on a rational classification of defects in amorphous materials, we propose a simplified model to describe intrinsic defects and hydrogen impurities in amorphous indium gallium zinc oxide (a -IGZO). The proposed approach consists of organizing defects into two categories: point defects, generating structural anomalies such as metal—metal or oxygen—oxygen bonds, and defects emerging from changes in the material stoichiometry, such as vacancies and interstitial atoms. Based on first-principles simulations, it is argued that the defects originating from the second group always act as perfect donors or perfect acceptors. This classification simplifies and rationalizes the nature of defects in amorphous phases. In a -IGZO, the most important point defects are metal—metal bonds (or small metal clusters) and peroxides (O - O single bonds). Electrons are captured by metal—metal bonds and released by the formation of peroxides. The presence of hydrogen can lead to two additional types of defects: metal-hydrogen defects, acting as acceptors, and oxygen-hydrogen defects, acting as donors. The impact of these defects is linked to different instabilities observed in a -IGZO. Specifically, the diffusion of hydrogen and oxygen is connected to positive- and negative-bias stresses, while negative-bias illumination stress originates from the formation of peroxides.

Modulation of surface flatness and van der Waals bonding of two-dimensional materials to reduce contact resistance.

NASA Astrophysics Data System (ADS)

Yue, Dewu; Yoo, Won Jong

Despite that the novel quantum mechanical properties of two-dimension (2D) materials are well explored theoretically, their electronic performance is limited by the contact resistance of the metallic interface and therefore their inherent novel properties are rarely realized experimentally. In this study, we demonstrate that we can largely reduce the contact resistance induced between metal and 2D materials, by controlling the surface condition of 2D materials, eg. surface flatness and van der Waals bonding. To induce the number of more effective carrier conducting modes, we engineer the surface roughness and dangling bonds of the 2D interface in contact with metal. As a result, electrical contact resistance of the metal interface is significantly reduced and carrier mobility in the device level is enhanced correspondingly. This work was supported by the Global Research Laboratory and Global Frontier R&D Programs at the Center for Hybrid Interface Materials, both funded by the Ministry of Science, ICT & Future Planning via the National Research Foundation of Korea (NRF).

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide

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

Kerr, A. J.; Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093; Chagarov, E.

2014-09-14

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al{sub 2}O{sub 3} gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge.more » These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001)« less

Open circuit voltage-decay behavior in amorphous p-i-n solar due to injection

NASA Astrophysics Data System (ADS)

Smrity, Manu; Dhariwal, S. R.

2018-05-01

The paper deals with the basic recombination processes at the dangling bond and the band tail states at various levels of injection, expressed in terms of short-circuit current density and their role in the behavior of amorphous solar cells. As the level of injection increases the fill factor decreases whereas the open circuit voltage increases very slowly, showing a saturation tendency. Calculations have been done for two values of tail state densities and shows that with an increase in tail state densities both, the fill factor and open circuit voltage decreases, results an overall degradation of the solar cell.

Modification of Wetting Properties of PMMA by Immersion Plasma Ion Implantation

NASA Astrophysics Data System (ADS)

Mireault, N.; Ross, G. G.

Advancing and receding contact angles below 5° have been obtained on PMMA surfaces with the implantation of argon and oxygen ions. The ion implantations were performed by means of the Immersion Plasma Ion Implantation (IPII) technique, a hybrid between ion beams and immersion plasmas. Characterization of treated PMMA surfaces by means of XPS and its combination with chemical derivatization (CD-XPS) have revealed the depletion of oxygen and the creation of dangling bonds, together with the formation of new chemical functions such as -OOH, -COOH and C=C. These observations provide a good explanation for the strong increase of the wetting properties of the PMMA surfaces.

Inversion layer on the Ge(001) surface from the four-probe conductance measurements

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

Wojtaszek, Mateusz; Lis, Jakub, E-mail: j.lis@uj.edu.pl; Zuzak, Rafal

2014-07-28

We report four-probe conductance measurements with sub-micron resolution on atomically clean Ge(001) surfaces. A qualitative difference between n-type and p-type crystals is observed. The scaling behavior of the resistance on n-type samples indicates two-dimensional current flow, while for the p-type crystal a three-dimensional description is appropriate. We interpret this in terms of the formation of an inversion layer at the surface. This result points to the surface states, i.e., dangling bonds, as the driving force behind band bending in germanium. It also explains the intrinsic character of band bending in germanium.

Fluorine atom abstraction by Si(100). I. Experimental

NASA Astrophysics Data System (ADS)

Tate, M. R.; Gosalvez-Blanco, D.; Pullman, D. P.; Tsekouras, A. A.; Li, Y. L.; Yang, J. J.; Laughlin, K. B.; Eckman, S. C.; Bertino, M. F.; Ceyer, S. T.

1999-08-01

In the interaction of low energy F2 with Si(100) at 250 K, a dissociative chemisorption mechanism called atom abstraction is identified in which only one of the F atoms is adsorbed while the other F atom is scattered into the gas phase. The dynamics of atom abstraction are characterized via time-of-flight measurements of the scattered F atoms. The F atoms are translationally hyperthermal but only carry a small fraction (˜3%) of the tremendous exothermicity of the reaction. The angular distribution of F atoms is unusually broad for the product of an exothermic reaction. These results suggest an "attractive" interaction potential between F2 and the Si dangling bond with a transition state that is not constrained geometrically. These results are in disagreement with the results of theoretical investigations implying that the available potential energy surfaces are inadequate to describe the dynamics of this gas-surface interaction. In addition to single atom abstraction, two atom adsorption, a mechanism analogous to classic dissociative chemisorption in which both F atoms are adsorbed onto the surface, is also observed. The absolute probability of the three scattering channels (single atom abstraction, two atom adsorption, and unreactive scattering) for an incident F2 are determined as a function of F2 exposure. The fluorine coverage is determined by integrating the reaction probabilities over F2 exposure, and the reaction probabilities are recast as a function of fluorine coverage. Two atom adsorption is the dominant channel [P2=0.83±0.03(95%, N=9)] in the limit of zero coverage and decays monotonically to zero. Single atom abstraction is the minor channel (P1=0.13±0.03) at low coverage but increases to a maximum (P1=0.35±0.08) at about 0.5 monolayer (ML) coverage before decaying to zero. The reaction ceases at 0.94±0.11(95%, N=9) ML. Thermal desorption and helium diffraction confirm that the dangling bonds are the abstraction and adsorption sites. No Si lattice bonds are broken, in contrast to speculation by other investigators that the reaction exothermicity causes lattice disorder.

Molecular-dynamics simulation of polymethylene chain confined in cylindrical potentials. I. Nature of the conformational defects

NASA Astrophysics Data System (ADS)

Yamamoto, Takashi; Kimikawa, Yuichi

1992-10-01

The conformational motion of a polymethylene molecule constrained by a cylindrical potential is simulated up to 100 ps. The molecule consists of 60 CH2 groups and has variable bond lengths, bond angles, and dihedral angles. Our main concern here is the excitation and the dynamics of the conformational defects: kinks, jogs, etc. Under weaker constraint a number of gauche bonds are excited; they mostly form pairs such as gtḡ kinks or gtttḡ jogs. These conformational defects show no continuous drift in space. Instead they often annihilate and then recreate at different sites showing apparently random positional changes. The conformational defects produce characteristic strain fields around them. It seems that the conformational defects interact attractively through these strain fields. This is evidenced by remarkably correlated spatial distributions of the gauche bonds.

Detailed study of SiOxNy:H/Si interface properties for high quality surface passivation of crystalline silicon

NASA Astrophysics Data System (ADS)

Dong, Peng; Lei, Dong; Yu, Xuegong; Huang, Chunlai; Li, Mo; Dai, Gang; Zhang, Jian; Yang, Deren

2018-01-01

In this work, we present a detailed study on the interface and passivation properties of the hydrogenated silicon oxynitride (SiOxNy:H) on the crystalline silicon (c-Si) and their correlations with the film composition. The SiOxNy:H films were synthesized by plasma enhanced chemical vapor deposition (PECVD) at various N2O flow rates, which results in different film composition, in particular the different H-related bonds, such as Sisbnd H and Nsbnd H bonds. Fourier transform infrared spectroscopy measurements show that the concentration of Nsbnd H bonds increases with the N2O flows from 0 to 30 sccm, while drops below the detection limit at N2O flows above 30 sccm. This changing trend of Nsbnd H bonds correlates well with the evolution of carrier lifetime of silicon substrate passivated by SiOxNy:H film, indicating the crucial role of Nsbnd H bonds in surface passivation. It is inferred that during the film deposition and forming gas anneal (FGA) a considerable amount of hydrogen atoms are liberated from the weak type of Nsbnd H bonds rather than Sisbnd H bonds, and then passivate the dangling bonds at the interface, thus resulting in the significant reduction of interface state density and the improved passivation quality. In detail, the interface state density is reduced from ∼5 × 1012 to ∼2 × 1012 cm-2 eV-1 after the FGA, as derived from the high frequency capacitance-voltage (Csbnd V) measurements.

Nanometre-scale 3D defects in Cr2AlC thin films.

PubMed

Chen, Y T; Music, D; Shang, L; Mayer, J; Schneider, J M

2017-04-20

MAX-phase Cr 2 AlC containing thin films were synthesized by magnetron sputtering in an industrial system. Nanometre-scale 3D defects are observed near the boundary between regions of Cr 2 AlC and of the disordered solid solution (CrAl) x C y . Shrinkage of the Cr-Cr interplanar distance and elongation of the Cr-Al distance in the vicinity of the defects are detected using transmission electron microscopy. The here observed deformation surrounding the defects was described using density functional theory by comparing the DOS of bulk Cr 2 AlC with the DOS of a strained and unstrained Cr 2 AlC(0001) surface. From the partial density of states analysis, it can be learned that Cr-C bonds are stronger than Cr-Al bonds in bulk Cr 2 AlC. Upon Cr 2 AlC(0001) surface formation, both bonds are weakened. While the Cr-C bonds recover their bulk strength as Cr 2 AlC(0001) is strained, the Cr-Al bonds experience only a partial recovery, still being weaker than their bulk counterparts. Hence, the strain induced bond strengthening in Cr 2 AlC(0001) is larger for Cr d - C p bonds than for Cr d - Al p bonds. The here observed changes in bonding due to the formation of a strained surface are consistent with the experimentally observed elongation of the Cr-Al distance in the vicinity of nm-scale 3D defects in Cr 2 AlC thin films.

Efficient detection of dangling pointer error for C/C++ programs

NASA Astrophysics Data System (ADS)

Zhang, Wenzhe

2017-08-01

Dangling pointer error is pervasive in C/C++ programs and it is very hard to detect. This paper introduces an efficient detector to detect dangling pointer error in C/C++ programs. By selectively leave some memory accesses unmonitored, our method could reduce the memory monitoring overhead and thus achieves better performance over previous methods. Experiments show that our method could achieve an average speed up of 9% over previous compiler instrumentation based method and more than 50% over previous page protection based method.

Photoinduced Charge Transfer from Titania to Surface Doping Site

PubMed Central

Inerbaev, Talgat; Hoefelmeyer, James D.; Kilin, Dmitri S.

2013-01-01

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

Photoinduced Charge Transfer from Titania to Surface Doping Site.

PubMed

Inerbaev, Talgat; Hoefelmeyer, James D; Kilin, Dmitri S

2013-05-16

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO 2 . Charge transfer from the photo-excited TiO 2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO 2 nanorod and catalytic site. A slab of TiO 2 represents a fragment of TiO 2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO 2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO 2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting.

Real-time dangling objects sensing: A preliminary design of mobile headset ancillary device for visual impaired.

PubMed

Lin, C H; Cheng, P H; Shen, S T

2014-01-01

Blinds and severe visual impairments can utilize tactile sticks to assist their walking. However, they cannot fully understand the dangling objects in front of their walking routes. This research proposed a mobile real-time dangling objects sensing (RDOS) prototype, which is located on the cap to sense any front barrier. This device utilized cheap ultrasonic sensor to act as another complement eye for blinds to understand the front dangling objects. Meanwhile, the RDOS device can dynamically adjust the sensor's front angle that is depended on the user's body height and promote the sensing accuracy. Meanwhile, two major required algorithms, height-angle measurement and ultrasonic sensor alignment, are proposed with this prototype. The research team also integrated the RDOS device prototype with mobile Android devices by communicating with Bluetooth to record the walking route.

Limiting Size of Monolayer Graphene Flakes Grown on Silicon Carbide or via Chemical Vapor Deposition on Different Substrates

NASA Astrophysics Data System (ADS)

Alekseev, N. I.

2018-05-01

The maximum size of homogeneous monolayer graphene flakes that form during the high-temperature evaporation of silicon from a surface of SiC or during graphene synthesis via chemical vapor deposition is estimated, based on the theoretical calculations developed in this work. Conditions conducive to the fragmentation of a monolayer graphene sheet to form discrete fragments or terrace-type structures in which excess energy due to dangling bonds at the edges is compensated for by the lack of internal stress are indentified and described. The results from calculations for the sizes of graphene structures are compared with experimental findings for the most successful graphene syntheses reported in the literature.

Investigation into the origin of parasitic absorption in GaInP|GaAs double heterostructures

NASA Astrophysics Data System (ADS)

Giannini, Nathan; Yang, Zhou; Albrecht, Alexander R.; Sheik-Bahae, Mansoor

2017-02-01

Despite achievements of extremely high external quantum efficiency (EQE), 99.5%, the net cooling of GaInP|GaAs double heterostructures (DHS) has never been realized. This is due to an unknown source of parasitic absorption. Prior studies have ruled out the possibility of the bulk absorption from the GaAs layer. Thus it is thought to be either at the air- GaInP interface, through the presence of dangling bonds, or in bulk GaInP through impurities. Using two-color thermallens calorimetry (based on the Z-scan technique), this study indicates that that the parasitic absorption likely originates from the GaInP bulk layers.

Higher Order Multipole Potentials and Electrostatic Screening Effects on Cohesive Energy and Bulk Modulus of Metallic Nanoparticles

NASA Astrophysics Data System (ADS)

Barakat, T.

2011-12-01

Higher order multipole potentials and electrostatic screening effects are introduced to incorporate the dangling bonds on the surface of a metallic nanopaticle and to modify the coulomb like potential energy terms, respectively. The total interaction energy function for any metallic nanoparticle is represented in terms of two- and three-body potentials. The two-body part is described by dipole-dipole interaction potential, and in the three-body part, triple-dipole (DDD) and dipole-dipole-quadrupole (DDQ) terms are included. The size-dependent cohesive energy and bulk modulus are observed to decrease with decreasing sizes, a result which is in good agreement with the experimental values of Mo and W nanoparticles.

Ab initio and Molecular Dynamic models of displacement damage in crystalline and turbostratic graphite

NASA Astrophysics Data System (ADS)

McKenna, Alice

One of the functions of graphite is as a moderator in several nuclear reactor designs, including the Advanced Gas-cooled Reactor (AGR). In the reactor graphite is used to thermalise the neutrons produced in the fission reaction thus allowing a self-sustained reaction to occur. The graphite blocks, acting as the moderator, are constantly irradiated and consequently suffer damage. This thesis examines the types of damage caused using molecular dynamic (MD) simulations and ab intio calculations. Neutron damage starts with a primary knock-on atom (PKA), which is travelling so fast that it creates damage through electronic and thermal excitation (this is addressed with thermal spike simulations). When the PKA has lost energy the subsequent cascade is based on ballistic atomic displacement. These two types of simulations were performed on single crystal graphite and other carbon structures such as diamond and amorphous carbon as a comparison. The thermal spike in single crystal graphite produced results which varied from no defects to a small number of permanent defects in the structure. It is only at the high energy range that more damage is seen but these energies are less likely to occur in the nuclear reactor. The thermal spike does not create damage but it is possible that it can heal damaged sections of the graphite, which can be demonstrated with the motion of the defects when a thermal spike is applied. The cascade simulations create more damage than the thermal spike even though less energy is applied to the system. A new damage function is found with a threshold region that varies with the square root of energy in excess of the energy threshold. This is further broken down in to contributions from primary and subsequent knock-on atoms. The threshold displacement energy (TDE) is found to be Ed=25eV at 300K. In both these types of simulation graphite acts very differently to the other carbon structures. There are two types of polycrystalline graphite structures which simulations have been performed on. The difference between the two is at the grain boundaries with one having dangling bonds and the other one being bonded. The cascade showed the grain boundaries acting as a trap for the knock-on atoms which produces more damage compared with the single crystal. Finally the effects of turbostratic disorder on damage is considered. Density functional theory (DFT) was used to look at interstitials in (002) twist boundaries and how they act compared to AB stacked graphite. The results of these calculations show that the spiro interstitial is more stable in these grain boundaries, so at temperatures where the interstitial can migrate along the c direction they will segregate to (002) twist boundaries.

Self-Healing of Unentangled Polymer Networks with Reversible Bonds

PubMed Central

Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun; Leibler, Ludwik; Rubinstein, Michael

2013-01-01

Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. PMID:24347684

Reliability of the pair-defect-sum approximation for the strength of valence-bond orbitals

PubMed Central

Pauling, Linus; Herman, Zelek S.; Kamb, Barclay J.

1982-01-01

The pair-defect-sum approximation to the bond strength of a hybrid orbital (angular wave functions only) is compared to the rigorous value as a function of bond angle for seven types of bonding situations, with between three and eight bond directions equivalent by geometrical symmetry operations and with only one independent bond angle. The approximation is seen to be an excellent one in all cases, and the results provide a rationale for the application of this approximation to a variety of problems. PMID:16593167

Dynamics of Dangling Od-Stretch at the Air/water Interface by Heterodyne-Detected Sfg Spectroscopy

NASA Astrophysics Data System (ADS)

Stiopkin, I. V.; Weeraman, C.; Shalhout, F.; Benderskii, A. V.

2009-06-01

SFG spectra of dangling OD-stretch at the air/water interface contain information on vibrational dephasing dynamics, ultrafast reorientational molecular motion, and vibrational energy transfer. To better separate these processes we conducted heterodyne-detected SFG experiments to measure real and imaginary contributions of the SFG spectrum of the dangling OD-stretch at the air/D_2O interface for SSP, PPP, and SPS polarizations. Variations in the temporal profiles of the SFG signals for these three polarizations will be also discussed.

Vibrational characteristics of FRP-bonded concrete interfacial defects in a low frequency regime

NASA Astrophysics Data System (ADS)

Cheng, Tin Kei; Lau, Denvid

2014-04-01

As externally bonded fiber-reinforced polymer (FRP) is a critical load-bearing component of strengthened or retrofitted civil infrastructures, the betterment of structural health monitoring (SHM) methodology for such composites is imperative. Henceforth the vibrational characteristics of near surface interfacial defects involving delamination and trapped air pockets at the FRP-concrete interface are investigated in this study using a finite element approach. Intuitively, due to its lower interfacial stiffness compared with an intact interface, a damaged region is expected to have a set of resonance frequencies different from an intact region when excited by acoustic waves. It has been observed that, when excited acoustically, both the vibrational amplitudes and frequency peaks in the response spectrum of the defects demonstrate a significant deviation from an intact FRP-bonded region. For a thin sheet of FRP bonded to concrete with sizable interfacial defects, the fundamental mode under free vibration is shown to be relatively low, in the order of kHz. Due to the low resonance frequencies of the defects, the use of low-cost equipment for interfacial defect detection via response spectrum analysis is highly feasible.

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

PubMed

Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

2015-05-13

Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

First-principles study on C=C defects near SiC/SiO2 interface: Defect passivation by double-bond saturation

NASA Astrophysics Data System (ADS)

Tajima, Nobuo; Kaneko, Tomoaki; Yamasaki, Takahiro; Nara, Jun; Schimizu, Tatsuo; Kato, Koichi; Ohno, Takahisa

2018-04-01

Thermally produced SiC/SiO2 stacking in SiC MOSFETs creates defect-related interfacial states in and around the band gap of SiC. These interfacial states can cause serious reliability problems such as threshold voltage shift, as well as efficiency problems such as channel mobility degradation. Carbon species having C=C double bonds have been suggested as one of the origins of these interfacial states. We have theoretically shown that this type of defect produces interfacial states in and around the band gap of SiC, and that they can be removed by saturating the C=C double bond by reactions with H2 and F2. The single-bond products of these reactions are found to be stable at regular device operation temperatures.

Molecular Dynamics Modeling of PPTA Crystals in Aramid Fibers

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

Mercer, Brian Scott

2016-05-19

In this work, molecular dynamics modeling is used to study the mechanical properties of PPTA crystallites, which are the fundamental microstructural building blocks of polymer aramid bers such as Kevlar. Particular focus is given to constant strain rate axial loading simulations of PPTA crystallites, which is motivated by the rate-dependent mechanical properties observed in some experiments with aramid bers. In order to accommodate the covalent bond rupture that occurs in loading a crystallite to failure, the reactive bond order force eld ReaxFF is employed to conduct the simulations. Two major topics are addressed: The rst is the general behavior ofmore » PPTA crystallites under strain rate loading. Constant strain rate loading simulations of crystalline PPTA reveal that the crystal failure strain increases with increasing strain rate, while the modulus is not a ected by the strain rate. Increasing temperature lowers both the modulus and the failure strain. The simulations also identify the C N bond connecting the aromatic rings as weakest primary bond along the backbone of the PPTA chain. The e ect of chain-end defects on PPTA micromechanics is explored, and it is found that the presence of a chain-end defect transfers load to the adjacent chains in the hydrogen-bonded sheet in which the defect resides, but does not in uence the behavior of any other chains in the crystal. Chain-end defects are found to lower the strength of the crystal when clustered together, inducing bond failure via stress concentrations arising from the load transfer to bonds in adjacent chains near the defect site. The second topic addressed is the nature of primary and secondary bond failure in crystalline PPTA. Failure of both types of bonds is found to be stochastic in nature and driven by thermal uctuations of the bonds within the crystal. A model is proposed which uses reliability theory to model bonds under constant strain rate loading as components with time-dependent failure rate functions. The model is shown to work well for predicting the onset of primary backbone bond failure, as well as the onset of secondary bond failure via chain slippage for the case of isolated non-interacting chain-end defects.« less

Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

PubMed

Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

2016-12-28

Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride

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

Jimenez, I.; Jankowski, A.F.; Terminello, L.J.

1997-04-01

Boron nitride is an interesting material for technological applications and for fundamental solid state physics investigations. It is a compound isoelectronic with carbon and, like carbon can possess sp{sup 2} and sp{sup 3} bonded phases resembling graphite and diamond. BN crystallizes in the sp{sup 2}-bonded hexagonal (h-BN), rhombohedral (r-BN) and turbostratic phases, and in the sp{sup 3}-bonded cubic (c-BN) and wurtzite (w-BN) phases. A new family of materials is obtained when replacing C-C pairs in graphite with isoelectronic B-N pairs, resulting in C{sub 2}BN compounds. Regarding other boron compounds, BN is exceptional in the sense that it has standard two-centermore » bonds with conventional coordination numbers, while other boron compounds (e.g. B{sub 4}C) are based on the boron icosahedron unit with three-center bonds and high coordination numbers. The existence of several allotropic forms and fullerene-like structures for BN suggests a rich variety of local bonding and poses the questions of how this affects the local electronic structure and how the material accommodates the stress induced in the transition regions between different phases. One would expect point defects to play a crucial role in stress accommodation, but these must also have a strong influence in the electronic structure, since the B-N bond is polar and a point defect will thus be a charged structure. The study of point defects in relationship to the electronic structure is of fundamental interest in these materials. Recently, the authors have shown that Near-Edge X-ray Absorption Fine Structure (NEXAFS) is sensitive to point defects in h-BN, and to the formation of metastable phases even in amorphous materials. This is significant since other phase identification techniques like vibrational spectroscopies or x-ray diffraction yield ambiguous results for nanocrystalline and amorphous samples. Serendipitously, NEXAFS also combines chemical selectivity with point defect sensitivity.« less

Porous silicon nanoparticles as biocompatible contrast agents for magnetic resonance imaging

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

Gongalsky, M. B., E-mail: mgongalsky@gmail.com; Kargina, Yu. V.; Osminkina, L. A.

2015-12-07

We propose porous silicon nanoparticles (PSi NPs) with natural oxide coating as biocompatible and bioresorbable contrast agents for magnetic resonant imaging (MRI). A strong shortening of the transversal proton relaxation time (T{sub 2}) was observed for aqueous suspensions of PSi NPs, whereas the longitudinal relaxation time (T{sub 1}) changed moderately. The longitudinal and transversal relaxivities are estimated to be 0.03 and 0.4 l/(g·s), respectively, which are promising for biomedical studies. The proton relaxation is suggested to undergo via the magnetic dipole-dipole interaction with Si dangling bonds on surfaces of PSi NPs. MRI experiments with phantoms have revealed the remarkable contrastingmore » properties of PSi NPs for medical diagnostics.« less

Optical, photonic and optoelectronic properties of graphene, h-NB and their hybrid materials

NASA Astrophysics Data System (ADS)

Wang, Jingang; Ma, Fengcai; Liang, Wenjie; Wang, Rongming; Sun, Mengtao

2017-06-01

Because of the linear dispersion relation and the unique structure of graphene's Dirac electrons, which can be tuned the ultra-wide band, this enables more applications in photonics, electronics and plasma optics. As a substrate, hexagonal boron nitride (h-BN) has an atomic level flat surface without dangling bonds, a weak doping effect and a response in the far ultraviolet area. So the graphene/h-BN heterostructure is very attractive due to its unique optical electronics characteristics. Graphene and h-BN which are stacked in different ways could open the band gap of graphene, and form a moiré pattern for graphene on h-BN and the superlattice in the Brillouin zone, which makes it possible to build photoelectric devices.

Polycrystalline Si nanoparticles and their strong aging enhancement of blue photoluminescence

NASA Astrophysics Data System (ADS)

Yang, Shikuan; Cai, Weiping; Zeng, Haibo; Li, Zhigang

2008-07-01

Nearly spherical polycrystalline Si nanoparticles with 20 nm diameter were fabricated based on laser ablation of silicon wafer immersed in sodium dodecyl sulfate aqueous solution. Such Si nanoparticles consist of disordered areas and ultrafine grains of 3 nm in mean size and exhibit significant photoluminescence in blue region. Importantly, aging at ambient air leads to continuing enhancement of the emission (more than 130 times higher in 16 weeks) showing stable and strong blue emission. This aging enhancement is attributed to progressive passivation of nonradiative Pb centers corresponding to silicon dangling bonds on the particles' surface. This study could be helpful in pushing Si into optoelectronic field and Si-based full color display, biomedical tagging, and flash memories.

Autonomous Scanning Probe Microscopy in Situ Tip Conditioning through Machine Learning.

PubMed

Rashidi, Mohammad; Wolkow, Robert A

2018-05-23

Atomic-scale characterization and manipulation with scanning probe microscopy rely upon the use of an atomically sharp probe. Here we present automated methods based on machine learning to automatically detect and recondition the quality of the probe of a scanning tunneling microscope. As a model system, we employ these techniques on the technologically relevant hydrogen-terminated silicon surface, training the network to recognize abnormalities in the appearance of surface dangling bonds. Of the machine learning methods tested, a convolutional neural network yielded the greatest accuracy, achieving a positive identification of degraded tips in 97% of the test cases. By using multiple points of comparison and majority voting, the accuracy of the method is improved beyond 99%.

Non-Destructive Evaluation of Kissing Bonds using Local Defect Resonance (LDR) Spectroscopy: A Simulation Study

NASA Astrophysics Data System (ADS)

Delrue, S.; Tabatabaeipour, M.; Hettler, J.; Van Den Abeele, K.

With the growing demand from industry to optimize and further develop existing Non-Destructive Testing & Evaluation (NDT&E) techniques or new methods to detect and characterize incipient damage with high sensitivity and increased quality, ample efforts have been devoted to better understand the typical behavior of kissing bonds, such as delaminations and cracks. Recently, it has been shown experimentally that the nonlinear ultrasonic response of kissing bonds could be enhanced by using Local Defect Resonance (LDR) spectroscopy. LDR spectroscopy is an efficient NDT technique that takes advantage of the characteristic fre- quencies of the defect (defect resonances) in order to provide maximum acoustic wave-defect interaction. In fact, for nonlinear methodologies, the ultrasonic excitation of the sample should occur at either multiples or integer ratios of the characteristic defect resonance frequencies, in order to obtain the highest signal-to-noise response in the nonlinear LDR spectroscopy. In this paper, the potential of using LDR spectroscopy for the detection, localization and characterization of kissing bonds is illustrated using a 3D simulation code for elastic wave propagation in materials containing closed but dynamically active cracks or delaminations. Using the model, we are able to define an appropriate method, based on the Scaling Subtraction Method (SSM), to determine the local defect resonance frequencies of a delamination in a composite plate and to illustrate an increase in defect nonlinearity due to LDR. The simulation results will help us to obtain a better understanding of the concept of LDR and to assist in the further design and testing of LDR spectroscopy for the detection, localization and characterization of kissing bonds.

NH NMR shifts of new structurally characterized fac-[Re(CO)3(polyamine)]n+ complexes probed via outer-sphere hydrogen-bonding interactions to anions, including the paramagnetic [Re(IV)Br6]2- anion.

PubMed

Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2010-06-21

fac-[Re(I)(CO)(3)L](n) complexes serve as models for short-lived fac-[(99m)Tc(I)(CO)(3)L](n) imaging tracers (L = tridentate ligands forming two five-membered chelate rings defining the L face). Dangling groups on L, needed to achieve desirable biodistribution, complicate the NMR spectra, which are not readily understood. Using less complicated L, we found that NH groups (exo-NH) projecting toward the L face sometimes showed an upfield shift attributable to steric shielding of the exo-NH group from the solvent by the chelate rings. Our goal is to advance our ability to relate these spectral features to structure and solution properties. To investigate whether exo-NH groups in six-membered rings exhibit the same effect and whether the presence of dangling groups alters the effect, we prepared new fac-[Re(CO)(3)L](n+) complexes that allow direct comparisons of exo-NH shifts for six-membered versus five-membered chelate rings. New complexes were structurally characterized with the following L: dipn [N-3-(aminopropyl)-1,3-propanediamine], N'-Medipn (3,3'-diamino-N-methyldipropylamine), N,N-Me(2)dipn (N,N-dimethyldipropylenetriamine), aepn [N-2-(aminoethyl)-1,3-propanediamine], trpn [tris-(3-aminopropyl)amine], and tren [tris-(2-aminoethyl)amine]. In DMSO-d(6), the upfield exo-NH signals were exhibited by all complexes, indicating that the rings sterically shield the exo-NH groups from bulky solvent molecules. This interpretation was supported by exo-NH signal shift changes caused by added halide and [ReBr(6)](2-) anions, consistent with outer-sphere hydrogen-bond interactions between these anions and the exo-NH groups. For fac-[Re(CO)(3)(dipn)]PF(6) in acetonitrile-d(3), the exo-NH signal shifted further downfield in the series, Cl(-) > Br(-) > I(-), and the plateau in the shift change required a lower concentration for smaller anions. These results are consistent with steric shielding of the exo-NH groups by the chelate rings. Nevertheless, despite its size, the shape and charge of [ReBr(6)](2-) allowed the dianion to induce large upfield paramagnetic shifts of the exo-NH signal of fac-[Re(CO)(3)(dipn)]PF(6). This dianion shows promise as an outer-sphere hydrogen-bonding paramagnetic shift reagent.

Shallow halogen vacancies in halide optoelectronic materials

NASA Astrophysics Data System (ADS)

Shi, Hongliang; Du, Mao-Hua

2014-11-01

Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

A new interpretation of Serkowski's polarization law

NASA Astrophysics Data System (ADS)

Papoular, R.

2018-06-01

The basic tenets of the alternative interpretation to be presented here are that the spectral profiles of the star light polarization peaks observed in the visible and near IR are a result of the optical properties of silicate grains in the same spectral range, not of the grain size, provided it remains within the range of Rayleigh's approximation. The silicate properties are those obtained experimentally by Scott and Duley (1996) for the non-iron bearing amorphous forsterite and enstatite. The whole range of observed Serkowski polarization profiles can be simulated with mixtures made of forsterite plus an increasing fraction (0 to 0.5) of enstatite as the spectral peak shifts from 0.8 to 0.3 μm. Fits to individual observed polarization spectra are also demonstrated. The optical extinction of silicates in the vis/IR (the "transparency range") can be understood by analogy with the thoroughly studied amorphous hydrogenated carbons and amorphous silica. It is due to structural disorder (dangling bonds and coordination defects) and impurities, which give rise to electronic states in the forbidden gap of semi-conductors. Because they are partially localized, their extinction power is dramatically reduced and has been ignored or simply described by a low, flat plateau. As their number density depends on the environment, one expects variations in the ratio of optical extinction coefficients in the visible and mid-IR. It is also argued that the measured steep rise of extinction beyond 3 μm-1 into the UV is due to atomic transitions, and so cannot give rise to coherent molecular polarization, but only localized extinction.

SIEST-A-RT: a study of vacancy diffusion in crystalline silicon using a local-basis first-principle (SIESTA) activation technique (ART).

NASA Astrophysics Data System (ADS)

El Mellouhi, Fedwa; Mousseau, Normand; Ordejón, Pablo

2003-03-01

We report on a first-principle study of vacancy-induced self-diffusion in crystalline silicon. Our simulations are performed on supercells containing 63 and 215 atoms. We generate the diffusion paths using the activation-relaxation technique (ART) [1], which can sample efficiently the energy landscape of complex systems. The forces and energy are evaluated using SIESTA [2], a selfconsistent density functional method using standard norm-conserving pseudopotentials and a flexible numerical linear combination of atomic orbitals basis set. Combining these two methods allows us to identify diffusion paths that would not be reachable with this degree of accuracy, using other methods. After a full relaxation of the neutral vacancy, we proceed to search for local diffusion paths. We identify various mechanisms like the formation of the four fold coordinated defect, and the recombination of dangling bonds by WWW process. The diffusion of the vacancy proceeds by hops to first nearest neighbor with an energy barrier of 0.69 eV. This work is funded in part by NSERC and NATEQ. NM is a Cottrell Scholar of the Research Corporation. [1] G. T. Barkema and N. Mousseau, Event-based relaxation of continuous disordered systems, Phys. Rev. Lett. 77, 4358 (1996); N. Mousseau and G. T. Barkema, Traveling through potential energy landscapes of disordered materials: ART, Phys. Rev. E 57, 2419 (1998). [2] Density functional method for very large systems with LCAO basis sets D. Sánchez-Portal, P. Ordejón, E. Artacho and J. M. Soler, Int. J. Quant. Chem. 65, 453 (1997).

Synthesis of Lipid Based Polyols from 1-butene Metathesized Palm Oil for Use in Polyurethane Foam Applications

NASA Astrophysics Data System (ADS)

Sasidharan Pillai, Prasanth Kumar

This thesis explores the use of 1-butene cross metathesized palm oil (PMTAG) as a feedstock for preparation of polyols which can be used to prepare rigid and flexible polyurethane foams. PMTAG is advantageous over its precursor feedstock, palm oil, for synthesizing polyols, especially for the preparation of rigid foams, because of the reduction of dangling chain effects associated with the omega unsaturated fatty acids. 1-butene cross metathesis results in shortening of the unsaturated fatty acid moieties, with approximately half of the unsaturated fatty acids assuming terminal double bonds. It was shown that the associated terminal OH groups introduced through epoxidation and hydroxylation result in rigid foams with a compressive strength approximately 2.5 times higher than that of rigid foams from palm and soybean oil polyols. Up to 1.5 times improvement in the compressive strength value of the rigid foams from the PMTAG polyol was further obtained following dry and/or solvent assisted fractionation of PMTAG in order to reduce the dangling chain effects associated with the saturated components of the PMTAG. Flexible foams with excellent recovery was achieved from the polyols of PMTAG and the high olein fraction of PMTAG indicating that these bio-derived polyurethane foams may be suitable for flexible foam applications. PMTAG polyols with controlled OH values prepared via an optimized green solvent free synthetic strategy provided flexible foams with lower compressive strength and higher recovery; i.e., better flexible foam potential compared to the PMTAG derived foams with non-controlled OH values. Overall, this study has revealed that the dangling chain issues of vegetable oils can be addressed in part using appropriate chemical and physical modification techniques such as cross metathesis and fractionation, respectively. In fact, the rigidity and the compressive strength of the polyurethane foams were in very close agreement with the percentage of terminal hydroxyl and OH value of the polyol. The results obtained from the study can be used to convert PMTAG like materials into industrially valuable materials.

Hydrogenation effects on carrier transport in boron-doped ultrananocrystalline diamond/amorphous carbon films prepared by coaxial arc plasma deposition

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

Katamune, Yūki, E-mail: yuki-katamune@kyudai.jp; Takeichi, Satoshi; Ohmagari, Shinya

2015-11-15

Boron-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite (UNCD/a-C:H) films were deposited by coaxial arc plasma deposition with a boron-blended graphite target at a base pressure of <10{sup −3} Pa and at hydrogen pressures of ≤53.3 Pa. The hydrogenation effects on the electrical properties of the films were investigated in terms of chemical bonding. Hydrogen-scattering spectrometry showed that the maximum hydrogen content was 35 at. % for the film produced at 53.3-Pa hydrogen pressure. The Fourier-transform infrared spectra showed strong absorptions by sp{sup 3} C–H bonds, which were specific to the UNCD/a-C:H, and can be attributed to hydrogen atoms terminating the dangling bondsmore » at ultrananocrystalline diamond grain boundaries. Temperature-dependence of the electrical conductivity showed that the films changed from semimetallic to semiconducting with increasing hydrogen pressure, i.e., with enhanced hydrogenation, probably due to hydrogenation suppressing the formation of graphitic bonds, which are a source of carriers. Carrier transport in semiconducting hydrogenated films can be explained by a variable-range hopping model. The rectifying action of heterojunctions comprising the hydrogenated films and n-type Si substrates implies carrier transport in tunneling.« less

Bond strength evaluation in adhesive joints using NDE and DIC methods

NASA Astrophysics Data System (ADS)

Poudel, Anish

Adhesive bonding of graphite epoxy composite laminates to itself or traditional metal alloys in modern aerospace and aircraft structural applications offers an excellent opportunity to use the most efficient and intelligent combination of materials available thus providing an attractive package for efficient structural designs. However, one of the major issues of adhesive bonding is the occasional formation of interfacial defects such as kissing or weak bonds in the bondline interface. Also, there are shortcomings of existing non-destructive evaluation (NDE) methods to non-destructively detect/characterize these interfacial defects and reliably predicting the bond shear strength. As a result, adhesive bonding technology is still not solely implemented in primary structures of an aircraft. Therefore, there is a greater demand for a novel NDE tool that can meet the existing aerospace requirement for adhesive bondline characterization. This research implemented a novel Acoustography ultrasonic imaging and digital image correlation (DIC) technique to detect and characterize interfacial defects in the bondline and determine bond shear strength in adhesively bonded composite-metal joints. Adhesively bonded Carbon Fiber Reinforced Plastic (CFRP) laminate and 2024-T3 Aluminum single lap shear panels subjected to various implanted kissing/weak bond defects were the primary focus of this study. Kissing/weak bonds were prepared by controlled surface contamination in the composite bonding surface and also by improperly mixing the adhesive constituent. SEM analyses were also conducted to understand the surface morphology of substrates and their interaction with the contaminants. Morphological changes were observed in the microscopic scale and the chemical analysis confirmed the stability of the contaminant at or very close to the interface. In addition, it was also demonstrated that contaminants migrated during the curing of the adhesive from CFRP substrate which caused a decrease of bond shear strength in single lap shear test samples. Through-transmission ultrasonics (TTU) Acoustography at 3.8 MHz showed promising results on the detectability of bondline defects in adhesively bonded CFRP-Al lap shear test samples. A correlation between Acoustography ultrasonic attenuation and average bond shear strength in CFRP-Al lap shear panels demonstrated that differential attenuation increased with the reduction of the bond shear strength. Similarly, optical DIC tests were conducted to identify and quantify kissing bond defects in CFRP-Al single lap shear joints. DIC results demonstrated changes in the normal strain (epsilonyy) contour map of the contaminated specimens at relatively lower load levels (15% ~ 30% of failure loads). Kissing bond regions were characterized by negative strains, and these were attributed to high compressive bending strains and the localized disbonding taking placed at the bondline interface as a result of the load application. It was also observed that contaminated samples suffered from more compressive strains (epsilonyy) compared to the baseline sample along the loading direction and they suffered from less compressive strains (epsilonxx) compared to the baseline sample perpendicular to the loading direction. This demonstrated the adverse effect of the kissing bond on the adhesive joint integrity. This was a very significant finding for the reason that hybrid ultrasonic DIC is being developed as a faster, more efficient, and more reliable NDE technique for determining bond quality and predicting bond shear strength in adhesively bonded structures.

Improvements on the optical properties of Ge-Sb-Se chalcogenide glasses with iodine incorporation

NASA Astrophysics Data System (ADS)

Jiang, Chen; Wang, Xunsi; Zhu, Qingde; Nie, Qiuhua; Zhu, Minming; Zhang, Peiquan; Dai, Shixun; Shen, Xiang; Xu, Tiefeng; Cheng, Ci; Liao, Fangxing; Liu, Zijun; Zhang, Xianghua

2015-11-01

Decreasing glass network defects and improving optical transmittance are essential work for material researchers. We studied the function of halogen iodine (I) acting as a glass network modifier in Ge-Sb-Se-based chalcogenide glass system. A systematic series of Ge20Sb5Se75-xIx (x = 0, 5, 10, 15, 20 at.%) infrared (IR) chalcohalide glasses were investigated to decrease the weak absorption tail (WAT) and improve the mid-IR transparency. The mechanisms of the halogen I affecting the physical, thermal, and optical properties of Se-based chalcogenide glasses were reported. The structural evolutions of these glasses were also revealed by Raman spectroscopy and camera imaging. The progressive substitution of I for Se increased the optical bandgap. The WAT and scatting loss significantly decreased corresponding to the progressive decrease in structural defects caused by dangling bands and structure defects in the original Ge20Sb5Se75 glass. The achieved maximum IR transparency of Ge-Sb-Se-I glasses can reach up to 80% with an effective transmission window between 0.94 μm and 17 μm, whereas the absorption coefficient decreased to 0.029 cm-1 at 10.16 μm. Thus, these materials are promising candidates for developing low-loss IR fibers.

Chemical structural analysis of diamondlike carbon films: II. Raman analysis

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The chemical structure of diamondlike carbon (DLC) films, synthesized by photoemission-assisted glow discharge, has been analyzed by Raman spectroscopy. Raman analysis in conjunction with the sp2 cluster model clarified the film structure. The sp2 clusters in DLC films synthesized at low temperature preferred various aliphatic structures. Sufficient argon-ion assist allowed for formation of less strained DLC films containing large amounts of hydrogen. As the synthesis temperature was increased, thermal desorption of hydrogen left carbon dangling bonds with active unpaired electrons in the films, and the reactions that followed created strained films containing aromatic sp2 clusters. In parallel, the desorption of methane molecules from the growing surface by chemisorption of hydrogen radicals prevented the action of argon ions, promoting internal strain of the films. However, in synthesis at very high temperature, where sp2 clusters are sufficiently dominant, the strain was dissolved gradually. In contrast, the DLC films synthesized at low temperature were more stable than other films synthesized at the same temperature because of stable hydrogen-carbon bonds in the films.

Origins of Fermi-level pinning on GaN and InN polar and nonpolar surfaces

NASA Astrophysics Data System (ADS)

Segev, D.; Van de Walle, C. G.

2006-10-01

Using band structure and total energy methods, we study the atomic and electronic structures of the polar (+c and - c plane) and nonpolar (a and m plane) surfaces of GaN and InN. We identify two distinct microscopic origins for Fermi-level pinning on GaN and InN, depending on surface stoichiometry and surface polarity. At moderate Ga/N ratios unoccupied gallium dangling bonds pin the Fermi level on n-type GaN at 0.5 0.7 eV below the conduction-band minimum. Under highly Ga-rich conditions metallic Ga adlayers lead to Fermi-level pinning at 1.8 eV above the valence-band maximum. We also explain the source of the intrinsic electron accumulation that has been universally observed on polar InN surfaces. It is caused by In-In bonds leading to occupied surface states above the conduction-band minimum. We predict that such a charge accumulation will be absent on the nonpolar surfaces of InN, when prepared under specific conditions.

Molecular dynamics modeling of PPTA crystallite mechanical properties in the presence of defects

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

Mercer, Brian; Zywicz, Edward; Papadopoulos, Panayiotis

Here, the mechanical properties of PPTA crystallites, the fundamental building blocks of aramid polymer fibers such as Kevlar® and Twaron®, are studied here using molecular dynamics simulations. The ReaxFF interatomic potential is employed to study crystallite failure via covalent and hydrogen bond rupture in constant strain-rate tensile loading simulations. Emphasis is placed on analyzing how chain-end defects in the crystallite influence its mechanical response and fracture strength. Chain-end defects are found to affect the behavior of nearby chains in a region of the PPTA crystallite that is small relative to the typical crystallite size in manufactured aramid fibers. The centralmore » Csingle bondN bond along the backbone chain is identified as the weakest in the PPTA polymer chain backbone in dynamic strain-to-failure simulations of the crystallite. It is found that clustering of chain-ends leads to reduced crystallite strength and crystallite failure via hydrogen bond rupture and chain sliding, whereas randomly scattered defects impact the strength less and failure is by covalent bond rupture and chain scission. The axial crystallite modulus increases with increasing chain length and is independent of chain-end defect locations. On the basis of these findings, a theoretical model is proposed to predict the axial modulus as a function of chain length.« less

Molecular dynamics modeling of PPTA crystallite mechanical properties in the presence of defects

DOE PAGES

Mercer, Brian; Zywicz, Edward; Papadopoulos, Panayiotis

2017-03-11

Here, the mechanical properties of PPTA crystallites, the fundamental building blocks of aramid polymer fibers such as Kevlar® and Twaron®, are studied here using molecular dynamics simulations. The ReaxFF interatomic potential is employed to study crystallite failure via covalent and hydrogen bond rupture in constant strain-rate tensile loading simulations. Emphasis is placed on analyzing how chain-end defects in the crystallite influence its mechanical response and fracture strength. Chain-end defects are found to affect the behavior of nearby chains in a region of the PPTA crystallite that is small relative to the typical crystallite size in manufactured aramid fibers. The centralmore » Csingle bondN bond along the backbone chain is identified as the weakest in the PPTA polymer chain backbone in dynamic strain-to-failure simulations of the crystallite. It is found that clustering of chain-ends leads to reduced crystallite strength and crystallite failure via hydrogen bond rupture and chain sliding, whereas randomly scattered defects impact the strength less and failure is by covalent bond rupture and chain scission. The axial crystallite modulus increases with increasing chain length and is independent of chain-end defect locations. On the basis of these findings, a theoretical model is proposed to predict the axial modulus as a function of chain length.« less

Surface Passivation in Empirical Tight Binding

NASA Astrophysics Data System (ADS)

He, Yu; Tan, Yaohua; Jiang, Zhengping; Povolotskyi, Michael; Klimeck, Gerhard; Kubis, Tillmann

2016-03-01

Empirical Tight Binding (TB) methods are widely used in atomistic device simulations. Existing TB methods to passivate dangling bonds fall into two categories: 1) Method that explicitly includes passivation atoms is limited to passivation with atoms and small molecules only. 2) Method that implicitly incorporates passivation does not distinguish passivation atom types. This work introduces an implicit passivation method that is applicable to any passivation scenario with appropriate parameters. This method is applied to a Si quantum well and a Si ultra-thin body transistor oxidized with SiO2 in several oxidation configurations. Comparison with ab-initio results and experiments verifies the presented method. Oxidation configurations that severely hamper the transistor performance are identified. It is also shown that the commonly used implicit H atom passivation overestimates the transistor performance.

Fabrication of oxidation-resistant Ge colloidal nanoparticles by pulsed laser ablation in aqueous HCl

NASA Astrophysics Data System (ADS)

Hamanaka, Yasushi; Iwata, Masahiro; Katsuno, Junichi

2017-06-01

Spherical Ge nanoparticles with diameters of 20-80 nm were fabricated by laser ablation of a Ge single crystal in water and in aqueous HCl using sub-picosecond laser pulses (1040 nm, 700 fs, 100 kHz, and a pulse energy of 10 µJ). We found that the as-synthesized nanoparticles suffered rapid oxidization followed by dissolution when laser ablation was conducted in pure water. In contrast, oxidation of Ge nanoparticles produced in dilute HCl and stored intact was minimal, and colloidal dispersions of the Ge nanoparticles remained stable up to 7 days. It was elucidated that dangling bonds on the surfaces of the Ge nanoparticles were terminated by Cl, which inhibited oxidation, and that such hydrophilic surfaces might improve the dispersibility of nanoparticles in aqueous solvent.

Electronic Bandgap and Edge Reconstruction in Phosphorene Materials

DOE PAGES

Liang, Liangbo; Wang, Jun; Lin, Wenzhi; ...

2014-11-12

Single-layer black phosphorous (BP), or phosphorene, is a highly-anisotropic two-dimensional elemental material possessing promising semiconductor properties for flexible electronics. However, the direct bandgap of single-layer black phosphorus predicted theoretically has not been directly measured, and the properties of its edges have not been considered in detail. Here we report atomic scale electronic variation related to strain-induced anisotropic deformation of the puckered honeycomb structure of freshly cleaved black phosphorus using a highresolved scanning tunneling spectroscopy (STS) survey along the light (x) and heavy (y) effective mass directions. Through a combination of STS measurements and first-principles calculations, a model for edge reconstructionmore » is also determined. The reconstruction is shown to self-passivate any dangling bond by switching the oxidation state of phosphorous from +3 to +5.« less

Quantum transitions driven by one-bond defects in quantum Ising rings.

PubMed

Campostrini, Massimo; Pelissetto, Andrea; Vicari, Ettore

2015-04-01

We investigate quantum scaling phenomena driven by lower-dimensional defects in quantum Ising-like models. We consider quantum Ising rings in the presence of a bond defect. In the ordered phase, the system undergoes a quantum transition driven by the bond defect between a magnet phase, in which the gap decreases exponentially with increasing size, and a kink phase, in which the gap decreases instead with a power of the size. Close to the transition, the system shows a universal scaling behavior, which we characterize by computing, either analytically or numerically, scaling functions for the low-level energy differences and the two-point correlation function. We discuss the implications of these results for the nonequilibrium dynamics in the presence of a slowly varying parallel magnetic field h, when going across the first-order quantum transition at h=0.

CFRTP and stainless steel laser joining: Thermal defects analysis and joining parameters optimization

NASA Astrophysics Data System (ADS)

Jiao, Junke; Xu, Zifa; Wang, Qiang; Sheng, Liyuan; Zhang, Wenwu

2018-07-01

Experiments with different joining parameters were carried out on fiber laser welding system to explore the mechanism of CFRTP/stainless steel joining and the influence of the parameters on the joining quality. The thermal defect and the microstructure of the joint was tested by SEM, EDS. The joint strength and the thermal defect zone width was measured by the tensile tester and the laser confocal microscope, respectively. The influence of parameters such as the laser power, the joining speed and the clamper pressure on the stainless steel surface thermal defect and the joint strength was analyzed. The result showed that the thermal defect on the stainless steel surface would change metal's mechanical properties and reduce its service life. A chemical bonding was found between the CFRTP and the stainless steel besides the physical bonding and the mechanical bonding. The highest shear stress was obtained as the laser power, the joining speed and the clamper pressure is 280 W, 4 mm/s and 0.15 MPa, respectively.

Extended Tersoff potential for boron nitride: Energetics and elastic properties of pristine and defective h -BN

NASA Astrophysics Data System (ADS)

Los, J. H.; Kroes, J. M. H.; Albe, K.; Gordillo, R. M.; Katsnelson, M. I.; Fasolino, A.

2017-11-01

We present an extended Tersoff potential for boron nitride (BN-ExTeP) for application in large scale atomistic simulations. BN-ExTeP accurately describes the main low energy B, N, and BN structures and yields quantitatively correct trends in the bonding as a function of coordination. The proposed extension of the bond order, added to improve the dependence of bonding on the chemical environment, leads to an accurate description of point defects in hexagonal BN (h -BN) and cubic BN (c -BN). We have implemented this potential in the molecular dynamics LAMMPS code and used it to determine some basic properties of pristine 2D h -BN and the elastic properties of defective h -BN as a function of defect density at zero temperature. Our results show that there is a strong correlation between the size of the static corrugation induced by the defects and the weakening of the in-plane elastic moduli.

Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

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

Zhao, X. J.; Xue, X. L.; Guo, Z. X.

Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt N nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt N, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D 6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of Pt Nmore » clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt-57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d 96s 1) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. Our findings about Pt N clusters are also applicable to Ir N clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

HCl, KCl and KOH solvation resolved solute-solvent interactions and solution surface stress

NASA Astrophysics Data System (ADS)

Zhang, Xi; Xu, Yan; Zhou, Yong; Gong, Yinyan; Huang, Yongli; Sun, Chang Q.

2017-11-01

An incorporation of the hydrogen bond (O:Hsbnd O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent Hsbnd O bond phonon from 3200 to 3480 cm-1 in the hydration shells. The HO- in alkaline solution, however, shares not only the same Hsbnd O phonon redshift of compressed water from 3200 to < 3100 cm-1 but also the dangling bonds of H2O surface featured at 3610 cm-1. Salt and alkaline solvation enhances the solution surface stress by K+ and Cl- ionic polarization. The excessive H+ proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:Hsbnd O bonds of the solvent matrix is featured by: fH = 0 and fx ∝ 1-exp(-C/C0) (x = HO-, K+ and Cl-) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.

Nondestructive tests of regenerative chambers. [evaluating nondestructive methods of determining metal bond integrity

NASA Technical Reports Server (NTRS)

Malone, G. A.; Vecchies, L.; Wood, R.

1974-01-01

The capabilities and limitations of nondestructive evaluation methods were studied to detect and locate bond deficiencies in regeneratively cooled thrust chambers for rocket engines. Flat test panels and a cylinder were produced to simulate regeneratively cooled thrust chamber walls. Planned defects with various bond integrities were produced in the panels to evaluate the sensitivity, accuracy, and limitations of nondestructive methods to define and locate bond anomalies. Holography, acoustic emission, and ultrasonic scan were found to yield sufficient data to discern bond quality when used in combination and in selected sequences. Bonding techniques included electroforming and brazing. Materials of construction included electroformed nickel bonded to Nickel 200 and OFHC copper, electroformed copper bonded to OFHC copper, and 300 series stainless steel brazed to OFHC copper. Variations in outer wall strength, wall thickness, and defect size were evaluated for nondestructive test response.

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques

NASA Astrophysics Data System (ADS)

Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, Hsuan-Yu; Hsieh, Shang-Hsien; Limaye, Mukta V.; Chuang, Chen-Hao; Hsueh, Hung-Chung; Wang, Hsaiotsu; Chiou, Jau-Wern; Tsai, Hung-Ming; Pao, Chih-Wen; Chen, Chia-Hao; Lin, Hong-Ji; Lee, Jyh-Fu; Wu, Chun-Te; Wu, Jih-Jen; Pong, Way-Faung; Ohigashi, Takuji; Kosugi, Nobuhiro; Wang, Jian; Zhou, Jigang; Regier, Tom; Sham, Tsun-Kong

2014-07-01

Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.Efforts have been made to elucidate the origin of d0 magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO. Electronic supplementary information (ESI) available: Scanning photoelectron microscopy (SPEM) results of ZnO NCs and NWs. Computational details and calculated total and partial density of states (PDOS) of bulk wurtzite ZnO with oxygen anion vacancies (VO). See DOI: 10.1039/c4nr01961j

Effects of chemo-mechanical polishing on CdZnTe X-ray and gamma-ray detectors

DOE PAGES

Egarievwe, Stephen E.; Hossain, Anwar; Okwechime, Ifechukwude O.; ...

2015-06-23

Here, mechanically polishing cadmium zinc telluride (CdZnTe) wafers for x-ray and gamma-ray detectors often is inadequate in removing surface defects caused by cutting them from the ingots. Fabrication-induced defects, such as surface roughness, dangling bonds, and nonstoichiometric surfaces, often are reduced through polishing and etching the surface. In our earlier studies of mechanical polishing with alumina powder, etching with hydrogen bromide in hydrogen peroxide solution, and chemomechanical polishing with bromine–methanol–ethylene glycol solution, we found that the chemomechanical polishing process produced the least surface leakage current. In this research, we focused on using two chemicals to chemomechanically polish CdZnTe wafers aftermore » mechanical polishing, viz. bromine–methanol–ethylene glycol (BME) solution, and hydrogen bromide (HBr) in a hydrogen peroxide and ethylene–glycol solution. We used x-ray photoelectron spectroscopy (XPS), current–voltage (I–V) measurements, and Am-241 spectral response measurements to characterize and compare the effects of each solution. The results show that the HBr-based solution produced lower leakage current than the BME solution. Results from using the same chemomechanical polishing solution on two samples confirmed that the surface treatment affects the measured bulk current (a combination of bulk and surface currents). XPS results indicate that the tellurium oxide to tellurium peak ratios for the mechanical polishing process were reduced significantly by chemomechanical polishing using the BME solution (78.9% for Te 3d 5/2O 2 and 76.7% for Te 3d 3/2O 2) compared with the HBr-based solution (27.6% for Te 3d 5/2O 2 and 35.8% for Te 3d 3/2O 2). Spectral response measurements showed that the 59.5-keV peak of Am-241 remained under the same channel number for all three CdZnTe samples. While the BME-based solution gave a better performance of 7.15% full-width at half-maximum (FWHM) compared with 7.59% FWHM for the HBr-based solution, the latter showed a smaller variation in performance of 0.39% FWHM over 7 days compared with 0.69% for the BME-based solution.« less

Shallow halogen vacancies in halide optoelectronic materials

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

Shi, Hongliang; Du, Mao -Hua

2014-11-05

Halogen vacancies (V H) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep V H contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH 3NH 3PbI 3 and TlBr. Both CH 3NH 3PbI 3 and TlBr have been found to have shallow V H, in contrast to commonly seen deep V H in halides. In this paper, several halide optoelectronic materials, i.e., CH 3NH 3PbI 3, CH 3NH 3SnI 3 (photovoltaic materials), TlBr, and CsPbBrmore » 3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether V H is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns 2 ions both play important roles in creating shallow V H in halides such as CH 3NH 3PbI 3, CH 3NH 3SnI 3, and TlBr. The key to identifying halides with shallow V H is to find the right crystal structures and compounds that suppress cation orbital hybridization at V H, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at V H. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow V H as good electronic and optoelectronic materials.« less

Enhanced visible light photocatalytic activity in N-doped edge- and corner-truncated octahedral Cu2O

NASA Astrophysics Data System (ADS)

Zou, Mingming; Liu, Honghong; Feng, Lu; Thomas, Tiju; Yang, Minghui

2017-03-01

Edge- and corner-truncated octahedral Cu2O is successfully synthesized using an aqueous mixture of CuCl2, sodium dodecyl sulfate, NaOH, and NH2OH3·HCl. Cu2O1-xNx(150 °C, 30 min) samples are synthesized by nitridation of Cu2O using an ammonothermal process. Cu retains a formal valence state through and beyond the nitridation process. N concentration in this sample is 1.73 at%, out of which 1.08 at% is substitutional in nature. Photocatalytic activity of Cu2O1-xNx(150 °C, 30 min) sample is investigated and compared to that of pristine edge- and corner-truncated octahedral Cu2O. Results show that Cu2O1-xNx(150 °C, 30 min) sample with dominant {110} facets has a higher photocatalytic activity than the pristine Cu2O material. Higher surface energy and a greater density of the ;Cu; dangling bonds on {110} facets of edge- and corner-truncated octahedral Cu2O1-xNx is the plausible reason for the observed optimum catalytic activity. Furthermore defect states induced by nitridation results in improved visible light adsorption. And also the band edge states changes which brought about by N doping. This is an interesting result since it bypasses the usual challenge faced by pristine Cu2O which have band edge states between which transitions are normally forbidden. Selective radical quenching experiments suggest that photocatalytic activity of Cu2O1-xNx is due to formation of hydroxyl radicals in water, subsequent to photogeneration of charge carriers in the photocatalyst.

Adsorption of small inorganic molecules on a defective MoS2 monolayer.

PubMed

González, César; Biel, Blanca; Dappe, Yannick J

2017-04-05

We present a theoretical study of molecular adsorption on defects on a MoS 2 monolayer. Based on Density Functional Theory, our calculations confirm that small inorganic molecules, such as CO 2 , CO, H 2 O, NO, NO 2 , H 2 and N 2 , remain bonded to the pristine monolayer through weak van der Waals interactions, suggesting that the molecules may easily diffuse over the clean monolayer. On the other hand, the introduction of defects can lead to three different situations, depending on the defect and the molecule considered: physisorption, chemical (strong) bonding to the metallic defects, namely the Mo substitutional atoms on the S vacancies, and dissociation, that can take place spontaneously at 0 K in some specific cases or by the effect of thermal agitation in molecules such as CO 2 or NO 2 on the S vacancy. Our energetic and electronic analyses provide an explanation to such bonding possibilities, showing that in the low interacting situations, the molecules tend to adopt a planar configuration parallel to the monolayer, while a molecular rotation is favored in order to facilitate the bond formation on the reactive sites. Finally, the ab initio based Scanning Tunneling Microscopy (STM) simulations show the fingerprint of each molecule adsorbed on the most reactive site. This work opens the way to the possibility of tuning the catalytic properties of MoS 2 by controlling the creation of specific defects in the MoS 2 monolayer.

The cellular environment of cancerous human tissue. Interfacial and dangling water as a "hydration fingerprint".

PubMed

Abramczyk, Halina; Brozek-Pluska, Beata; Krzesniak, Marta; Kopec, Monika; Morawiec-Sztandera, Alina

2014-08-14

Despite a large number of publications, the role of water in the cellular environment of biological tissue has not been clarified. Characterizing the biological interface is a key challenge in understanding the interactions of water in the tissue. Although we often assume that the properties of the bulk water can be translated to the crowded biological environment, this approach must be considerably revised when considering the biological interface. To our knowledge, few studies have directly monitored the interactions and accumulation of water in the restricted environments of the biological tissue upon realistic crowding conditions. The present study focuses on a molecular picture of water molecules at the biological interface, or specifically, water molecules adjacent to the hydrophobic and hydrophilic surfaces of normal and cancerous tissues. We recorded and analyzed the IR and Raman spectra of the νs(OH) stretching modes of water at the biological interfaces of the human breast and neck tissues. The results revealed dramatic changes in the water content in the tissue and are potentially relevant to both the fundamental problems of interfacial water modeling and the molecular diagnostics of cancer as a 'hydration fingerprint'. Herein, we will discuss the origin of the vibrational substructures observed for the νs(OH) stretching modes of water, showing that the interfacial water interacting via H-bond with other water molecules and biomolecules at the biological surface and free OH vibration of the dangling water are sensitive indicators of the pathology between the normal (noncancerous) and cancerous tissue and cancer types. Copyright © 2014 Elsevier B.V. All rights reserved.

Formation of atomically ordered and chemically selective Si-O-Ti monolayer on Si0.5Ge0.5(110) for a MIS structure via H2O2(g) functionalization.

PubMed

Park, Sang Wook; Choi, Jong Youn; Siddiqui, Shariq; Sahu, Bhagawan; Galatage, Rohit; Yoshida, Naomi; Kachian, Jessica; Kummel, Andrew C

2017-02-07

Si 0.5 Ge 0.5 (110) surfaces were passivated and functionalized using atomic H, hydrogen peroxide (H 2 O 2 ), and either tetrakis(dimethylamino)titanium (TDMAT) or titanium tetrachloride (TiCl 4 ) and studied in situ with multiple spectroscopic techniques. To passivate the dangling bonds, atomic H and H 2 O 2 (g) were utilized and scanning tunneling spectroscopy (STS) demonstrated unpinning of the surface Fermi level. The H 2 O 2 (g) could also be used to functionalize the surface for metal atomic layer deposition. After subsequent TDMAT or TiCl 4 dosing followed by a post-deposition annealing, scanning tunneling microscopy demonstrated that a thermally stable and well-ordered monolayer of TiO x was deposited on Si 0.5 Ge 0.5 (110), and X-ray photoelectron spectroscopy verified that the interfaces only contained Si-O-Ti bonds and a complete absence of GeO x . STS measurements confirmed a TiO x monolayer without mid-gap and conduction band edge states, which should be an ideal ultrathin insulating layer in a metal-insulator-semiconductor structure. Regardless of the Ti precursors, the final Ti density and electronic structure were identical since the Ti bonding is limited by the high coordination of Ti to O.

Influence of surface passivation on the friction and wear behavior of ultrananocrystalline diamond and tetrahedral amorphous carbon thin films

NASA Astrophysics Data System (ADS)

Konicek, A. R.; Grierson, D. S.; Sumant, A. V.; Friedmann, T. A.; Sullivan, J. P.; Gilbert, P. U. P. A.; Sawyer, W. G.; Carpick, R. W.

2012-04-01

Highly sp3-bonded, nearly hydrogen-free carbon-based materials can exhibit extremely low friction and wear in the absence of any liquid lubricant, but this physical behavior is limited by the vapor environment. The effect of water vapor on friction and wear is examined as a function of applied normal force for two such materials in thin film form: one that is fully amorphous in structure (tetrahedral amorphous carbon, or ta-C) and one that is polycrystalline with <10 nm grains [ultrananocrystalline diamond (UNCD)]. Tribologically induced changes in the chemistry and carbon bond hybridization at the surface are correlated with the effect of the sliding environment and loading conditions through ex situ, spatially resolved near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. At sufficiently high relative humidity (RH) levels and/or sufficiently low loads, both films quickly achieve a low steady-state friction coefficient and subsequently exhibit low wear. For both films, the number of cycles necessary to reach the steady-state is progressively reduced for increasing RH levels. Worn regions formed at lower RH and higher loads have a higher concentration of chemisorbed oxygen than those formed at higher RH, with the oxygen singly bonded as hydroxyl groups (C-OH). While some carbon rehybridization from sp3 to disordered sp2 bonding is observed, no crystalline graphite formation is observed for either film. Rather, the primary solid-lubrication mechanism is the passivation of dangling bonds by OH and H from the dissociation of vapor-phase H2O. This vapor-phase lubrication mechanism is highly effective, producing friction coefficients as low as 0.078 for ta-C and 0.008 for UNCD, and wear rates requiring thousands of sliding passes to produce a few nanometers of wear.

Electrically detected crystal orientation dependent spin-Rabi beat oscillation of c-Si(111)/SiO2 interface states

NASA Astrophysics Data System (ADS)

Paik, Seoyoung; Lee, Sang-Yun; McCamey, Dane R.; Boehme, Christoph

2011-12-01

Electrically detected spin-Rabi beat oscillation of pairs of paramagnetic near interface states at the phosphorous doped (1016 cm-3) Si(111)/SiO2 interface is reported. Due to the g-factor anisotropy of the Pb center (a silicon surface dangling bond), one can tune intrapair Larmor frequency differences (Larmor separations) by orientation of the crystal with regard to an external magnetic field. Since Larmor separation governs the number of beating spin pairs, crystal orientation can control the beat current. This is used to identify spin states that are paired by mutual electronic transitions. The experiments confirm the presence of the previously reported 31P-Pb transition and provide direct experimental evidence of the previously hypothesized Pb-E' center (a near interface SiO2 bulk state) transition.

Radicals mediated magnetism in Ar plasma treated high-density polyethylene

NASA Astrophysics Data System (ADS)

Orendáč, M.; Čižmár, E.; Kažiková, V.; Orendáčová, A.; Řezníčková, A.; Kolská, Z.; Švorčík, V.

2018-05-01

Electron-spin resonance of high-density polyethylene treated by Ar plasma at 300 K was performed in X-band at temperatures from 2.1 K to 290 K. The observed spectra suggest presence of allyl radicals, whereas the central peak may be attributed to polyenyl radicals or dangled bonds. Pronounced narrowing of the resonance line observed above glassy temperature of polyethylene may be ascribed to thermally activated motional effect with the activation energy Ea /kB = 160 K. The absence of strong exchange interactions is suggested by negligible exchange narrowing found at 2.1 K. The suggestion is supported by the analysis of the temperature dependence of the intensity at low temperatures, which is explicable assuming the coexistence of non-interacting radicals and S = 1/2 dimers with a distribution of antiferromagnetic couplings varying from 2 K to nominally 25 K.

Growth model for arc-deposited fullerene-like CNx nanoparticles.

PubMed

Veisz, Bernadett; Radnóczi, György

2005-06-01

Multiwall CNx nanotubes, nanoonions, and amorphous nanoballs were formed by carbon DC arc evaporation in a nitrogen atmosphere. The samples were investigated by conventional and high-resolution transmission electron microscopy. We propose a fragment-by-fragment growth mechanism for the formation of the nanoparticles. Accordingly, particles and aggregates of particles form in the vacuum ambient by the collisions between atomic species and small fragments. This growth model is supported by the discontinuous inner shells and disordered surface layers composed from graphene fragments. Image simulations confirm the detectability of dangling and back-folding surface layers in the experimental images. Further, the simulated images also confirm that the growth of nanoonions starts from a single fullerene-like seed. The amorphous nanoballs form when ordering of the building blocks during growth is hindered by the cross-linking nitrogen bonds. Copyright (c) 2005 Wiley-Liss, Inc.

Optical properties of an indium doped CdSe nanocrystal: A density functional approach

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

Salini, K.; Mathew, Vincent, E-mail: vincent@cukerala.ac.in; Mathew, Thomas

2016-05-06

We have studied the electronic and optical properties of a CdSe nanocrystal doped with n-type impurity atom. First principle calculations of the CdSe nanocrystal based on the density functional theory (DFT), as implemented in the Vienna Ab Initio Simulation Package (VASP) was used in the calculations. We have introduced a single Indium impurity atom into CdSe nanocrystal with 1.3 nm diameter. Nanocrystal surface dangling bonds are passivated with hydrogen atom. The band-structure, density of states and absorption spectra of the doped and undopted nanocrystals were discussed. Inclusion of the n-type impurity atom introduces an additional electron in conduction band, and significantlymore » alters the electronic and optical properties of undoped CdSe nanocrystal. Indium doped CdSe nannocrystal have potential applications in optoelectronic devices.« less

Dynamic probe of ZnTe(110) surface by scanning tunneling microscopy

PubMed Central

Kanazawa, Ken; Yoshida, Shoji; Shigekawa, Hidemi; Kuroda, Shinji

2015-01-01

The reconstructed surface structure of the II–VI semiconductor ZnTe (110), which is a promising material in the research field of semiconductor spintronics, was studied by scanning tunneling microscopy/spectroscopy (STM/STS). First, the surface states formed by reconstruction by the charge transfer of dangling bond electrons from cationic Zn to anionic Te atoms, which are similar to those of IV and III–V semiconductors, were confirmed in real space. Secondly, oscillation in tunneling current between binary states, which is considered to reflect a conformational change in the topmost Zn–Te structure between the reconstructed and bulk-like ideal structures, was directly observed by STM. Third, using the technique of charge injection, a surface atomic structure was successfully fabricated, suggesting the possibility of atomic-scale manipulation of this widely applicable surface of ZnTe. PMID:27877752

High resolution structural characterisation of laser-induced defect clusters inside diamond

NASA Astrophysics Data System (ADS)

Salter, Patrick S.; Booth, Martin J.; Courvoisier, Arnaud; Moran, David A. J.; MacLaren, Donald A.

2017-08-01

Laser writing with ultrashort pulses provides a potential route for the manufacture of three-dimensional wires, waveguides, and defects within diamond. We present a transmission electron microscopy study of the intrinsic structure of the laser modifications and reveal a complex distribution of defects. Electron energy loss spectroscopy indicates that the majority of the irradiated region remains as sp3 bonded diamond. Electrically conductive paths are attributed to the formation of multiple nano-scale, sp2-bonded graphitic wires and a network of strain-relieving micro-cracks.

Effect of lattice defects on the electronic structures and floatability of pyrites

NASA Astrophysics Data System (ADS)

Xian, Yong-jun; Wen, Shu-ming; Chen, Xiu-ming; Deng, Jiu-shuai; Liu, Jian

2012-12-01

The electronic structures of three types of lattice defects in pyrites (i.e., As-substituted, Co-substituted, and intercrystalline Au pyrites) were calculated using the density functional theory (DFT). In addition, their band structures, density of states, and difference charge density were studied. The effect of the three types of lattice defects on the pyrite floatability was explored. The calculated results showed that the band-gaps of pyrites with Co-substitution and intercrystalline Au decreased significantly, which favors the oxidation of xanthate to dixanthogen and the adsorption of dixanthogen during pyrite flotation. The stability of the pyrites increased in the following order: As-substituted < perfect < Co-substituted < intercrystalline Au. Therefore, As-substituted pyrite is easier to be depressed by intensive oxidization compared to perfect pyrite in a strongly alkaline medium. However, Co-substituted and intercrystalline Au pyrites are more difficult to be depressed compared to perfect pyrite. The analysis of the Mulliken bond population and the electron density difference indicates that the covalence characteristic of the S-Fe bond is larger compared to the S-S bond in perfect pyrite. In addition, the presence of the three types of lattice defects in the pyrite bulk results in an increase in the covalence level of the S-Fe bond and a decrease in the covalence level of the S-S bond, which affect the natural floatability of the pyrites.

Effects of boron-nitride substrates on Stone-Wales defect formation in graphene: An ab initio molecular dynamics study

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

Jin, K.; Xiao, H. Y.; Zhang, Y.

2014-05-19

Ab initio molecular dynamics simulations are performed to investigate the effects of a boron nitride (BN) substrate on Stone-Wales (SW) defect formation and recovery in graphene. It is found that SW defects can be created by an off-plane recoil atom that interacts with the BN substrate. A mechanism with complete bond breakage for formation of SW defects in suspended graphene is also revealed for recoils at large displacement angles. In addition, further irradiation can result in recovery of the SW defects through a bond rotation mechanism in both graphene and graphene/BN, and the substrate has little effect on the recoverymore » process. This study indicates that the BN substrate enhances the irradiation resistance of graphene.« less

The 2√{3}×2√{3}R30 surface reconstruction of alkali/Si(1 1 1):B semiconducting surfaces

NASA Astrophysics Data System (ADS)

Tournier-Colletta, C.; Chaput, L.; Tejeda, A.; Cardenas, L. A.; Kierren, B.; Malterre, D.; Fagot-Revurat, Y.; Fèvre, P. Le; Bertran, F.; Taleb-Ibrahimi, A.

2013-02-01

The surface structure of alkali doped Si(1 1 1):B ultra-thin films has been studied by low-energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS) and scanning tunneling microscopy (STM). A comparative study of K/Si(1 1 1)-3 × 1 and K/Si(1 1 1):B-2√{3}×2√{3}R30 interfaces allowed us to determine the saturation coverage to be 0.5 monolayer in the later case. The 2√{3}-surface reconstruction is shown to be a common property of pure K, Rb, Cs materials and K0.4Rb0.6 alloys but progressively disappears if Rb is replaced by Ca. Taking into account the existence of two distinct boron sites in the ratio 1/3 as seen from B-1s core levels spectra, LAPW-DFT calculations have been carried out in order to optimize the atomic structure. As a result, alkali adatoms are shown to form trimers leading to a large modulation of the Sisbnd B bonds accompanied by an inhomogeneous doping of the dangling bonds in agreement with voltage dependent STM images.

Molecular Self-Assembly Driven by London Dispersion Forces

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

Li, Guo; Cooper, Valentino R; Cho, Jun-Hyung

2011-01-01

The nature and strength of intermolecular interactions are crucial to a variety of kinetic and dynamic processes at surfaces. Whereas strong chemisorption bonds are known to facilitate molecular binding, the importance of the weaker yet ubiquitous van der Waals (vdW) interactions remains elusive in most cases. Here we use first-principles calculations combined with kinetic Monte Carlo simulations to unambiguously demonstrate the vital role that vdW interactions play in molecular self-assembly, using styrene nanowire growth on silicon as a prototypical example. We find that, only when the London dispersion forces are included, accounting for the attractive parts of vdW interactions, canmore » the effective intermolecular interaction be reversed from being repulsive to attractive. Such attractive interactions, in turn, ensure the preferred growth of long wires under physically realistic conditions as observed experimentally. We further propose a cooperative scheme, invoking the application of an electric field and the selective creation of Si dangling bonds, to drastically improve the ordered arrangement of the molecular structures. The present study represents a significant step forward in the fundamental understanding and precise control of molecular self-assembly guided by London dispersion forces.« less

Magnetic and interface properties of the core-shell Fe3O4/Au nanocomposites

NASA Astrophysics Data System (ADS)

Baskakov, A. O.; Solov'eva, A. Yu.; Ioni, Yu. V.; Starchikov, S. S.; Lyubutin, I. S.; Khodos, I. I.; Avilov, A. S.; Gubin, S. P.

2017-11-01

Core-shell Fe3O4/Au nanostructures were obtained with an advanced method of two step synthesis and several complementary methodics were applied for investigation structural and magnetic properties of the samples. Along with X-ray diffraction and transmission electron microscopy, electron diffraction, optical, Raman and Mössbauer spectroscopy were used for nanoparticle characterization. It was established that the physical and structural properties Fe3O4/Au nanocomposites are specific of intrinsic properties of gold and magnetite. Mössbauer and Raman spectroscopy data indicated that magnetite was in a nonstoichiometric state with an excess of trivalent iron both in the initial Fe3O4 nanoparticles and in the Fe3O4/Au nanocomposites. As follows from the Mössbauer data, magnetic properties of iron ions in the internal area (in core) and in the surface layer of magnetite nanoparticles are different due to the rupture of exchange bonds at the particles surface. This leads to decrease in an effective magnetic moment at the surface. Gold atoms at the interface of the composites interact with dangling bonds of magnetite and stabilize the magnetic properties of the surface layers of magnetite.

Precursor-Surface Reactions in Plasma Deposition of Silicon Thin Films

NASA Astrophysics Data System (ADS)

Bakos, Tamas

2005-03-01

Device-quality hydrogenated amorphous silicon (a-Si:H) thin films are usually grown by plasma deposition under conditions where the SiH3 radical is the dominant deposition precursor. In this presentation, we report results of first-principles density functional theory calculations on the interactions of the SiH3 radical with the crystalline Si(100)-(2x1):H surface in conjunction with molecular-dynamics simulations of a-Si:H thin film growth by SiH3 radicals, which elucidate the pathways and energetics of surface reactions that govern important film properties. In particular, we show that an SiH3 radical can insert into strained surface Si-Si dimer bonds, abstract surface H through an Eley-Rideal mechanism, and passivate surface dangling bonds; these reactions follow exothermic and barrierless pathways that lead to a temperature-independent growth rate in agreement with experimental measurements. We also identify a thermally activated surface H abstraction process, in which the SiH3 radical diffuses through overcoordinated surface Si atoms until it encounters a favorable site for H abstraction; the diffusion and H-abstraction steps have commensurate activation barriers. This mechanism explains partly the reduction of the film H content at elevated substrate temperatures.

Low temperature growth of heavy boron-doped hydrogenated Ge epilayers and its application in Ge/Si photodetectors

NASA Astrophysics Data System (ADS)

Kuo, Wei-Cheng; Lee, Ming Jay; Wu, Mount-Learn; Lee, Chien-Chieh; Tsao, I.-Yu; Chang, Jenq-Yang

2017-04-01

In this study, heavily boron-doped hydrogenated Ge epilayers are grown on Si substrates at a low growth temperature (220 °C). The quality of the boron-doped epilayers is dependent on the hydrogen flow rate. The optical emission spectroscopic, X-ray diffraction and Hall measurement results demonstrate that better quality boron-doped Ge epilayers can be obtained at low hydrogen flow rates (0 sccm). This reduction in quality is due to an excess of hydrogen in the source gas, which breaks one of the Ge-Ge bonds on the Ge surface, leading to the formation of unnecessary dangling bonds. The structure of the boron doped Ge epilayers is analyzed by transmission electron microscopy and atomic force microscopy. In addition, the performance, based on the I-V characteristics, of Ge/Si photodetectors fabricated with boron doped Ge epilayers produced under different hydrogen flow rates was examined. The photodetectors with boron doped Ge epilayers produced with a low hydrogen flow rate (0 sccm) exhibited a higher responsivity of 0.144 A/W and a lower dark current of 5.33 × 10-7 A at a reverse bias of 1 V.

Nondestructive Evaluation Methods for the Ares I Common Bulkhead

NASA Technical Reports Server (NTRS)

Walker, James

2010-01-01

A large scale bonding demonstration test article was fabricated to prove out manufacturing techniques for the current design of the NASA Ares I Upper Stage common bulkhead. The common bulkhead serves as the single interface between the liquid hydrogen and liquid oxygen portions of the Upper Stage propellant tank. The bulkhead consists of spin-formed aluminum domes friction stir welded to Y-rings and bonded to a perforated phenolic honeycomb core. Nondestructive evaluation methods are being developed for assessing core integrity and the core-to-dome bond line of the common bulkhead. Detection of manufacturing defects such as delaminations between the core and face sheets as well as service life defects such as crushed or sheared core resulting from impact loading are all of interest. The focus of this work will be on the application of thermographic, shearographic, and phased array ultrasonic methods to the bonding demonstration article as well as various smaller test panels featuring design specific defect types and geometric features.

Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

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

Zhao, X. J.; Xue, X. L.; Jia, Yu

Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt{sub N} nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt{sub N}, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D{sub 6h} symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). However, the magic number of Pt{sub N}more » clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt{sub 57} motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d{sup 9}6s{sup 1}) of Pt, which result in a delicate balance between the enhanced Pt–Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. These findings about Pt{sub N} clusters are also applicable to Ir{sub N} clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. The findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures.

PubMed

Videla, Pablo E; Rossky, Peter J; Laria, D

2013-11-07

We use ring-polymer-molecular-dynamics (RPMD) techniques and the semi-empirical q-TIP4P/F water model to investigate the relationship between hydrogen bond connectivity and the characteristics of nuclear position fluctuations, including explicit incorporation of quantum effects, for the energetically low lying isomers of the prototype cluster [H2O]8 at T = 50 K and at 150 K. Our results reveal that tunneling and zero-point energy effects lead to sensible increments in the magnitudes of the fluctuations of intra and intermolecular distances. The degree of proton spatial delocalization is found to map logically with the hydrogen-bond connectivity pattern of the cluster. Dangling hydrogen bonds exhibit the largest extent of spatial delocalization and participate in shorter intramolecular O-H bonds. Combined effects from quantum and polarization fluctuations on the resulting individual dipole moments are also examined. From the dynamical side, we analyze the characteristics of the infrared absorption spectrum. The incorporation of nuclear quantum fluctuations promotes red shifts and sensible broadening relative to the classical profile, bringing the simulation results in much more satisfactory agreement with direct experimental information in the mid and high frequency range of the stretching band. While RPMD predictions overestimate the peak position of the low frequency shoulder, the overall agreement with that reported using an accurate, parameterized, many-body potential is reasonable, and far superior to that one obtains by implementing a partially adiabatic centroid molecular dynamics approach. Quantum effects on the collective dynamics, as reported by instantaneous normal modes, are also discussed.

Mechanical properties of highly defective graphene: from brittle rupture to ductile fracture.

PubMed

Xu, Lanqing; Wei, Ning; Zheng, Yongping

2013-12-20

Defects are generally believed to deteriorate the superlative performance of graphene-based devices but may also be useful when carefully engineered to tailor the local properties and achieve new functionalities. Central to most defect-associated applications is the defect coverage and arrangement. In this work, we investigate, by molecular dynamics simulations, the mechanical properties and fracture dynamics of graphene sheets with randomly distributed vacancies or Stone-Wales defects under tensile deformations over a wide defect coverage range. With defects presented, an sp-sp(2) bonding network and an sp-sp(2)-sp(3) bonding network are observed in vacancy-defected and Stone-Wales-defected graphene, respectively. The ultimate strength degrades gradually with increasing defect coverage and saturates in the high-ratio regime, whereas the fracture strain presents an unusual descending-saturating-improving trend. In the dense vacancy defect situation, the fracture becomes more plastic and super-ductility is observed. Further fracture dynamics analysis reveals that the crack trapping by sp-sp(2) and sp-sp(2)-sp(3) rings and the crack-tip blunting account for the ductile fracture, whereas geometric rearrangement on the entire sheet for vacancy defects and geometric rearrangement on the specific defect sites for Stone-Wales defects account for their distinctive rules of the evolution of the fracture strain.

Defects in a nonlinear pseudo one-dimensional solid

NASA Astrophysics Data System (ADS)

Blanchet, Graciela B.; Fincher, C. R., Jr.

1985-03-01

These infrared studies of acetanilide together with the existence of two equivalent structures for the hydrogen-bonded chain suggest the possibility of a topological defect state rather than a Davydov soliton as suggested previously. Acetanilide is an example of a class of one-dimensional materials where solitons are a consequence of a twofold degenerate structure and the nonlinear dynamics of the hydrogen-bonded network.

A Initio Theoretical Studies of Surfaces of Semiconductors

NASA Astrophysics Data System (ADS)

Wang, Jing

1993-01-01

The first semiconductor which we study with these techniques is the archetypal elemental semiconductor, silicon. We present the first extensive study of point defects on Si(100). We identify the principal defects and two primary mechanisms responsible for their dominance: the need to eliminate dangling bonds on the surface and the need to compensate the strain induced by topological effects. Furthermore, we present evidence that the presence of point defects on the Si(100) surface is not intrinsic to the ground state of the surface as a stress relieving mechanism but rather is due merely to thermal fluctuations. We address materials issues associated with the identification of the lowest energy surfaces of GaAs and the determination of the geometric structure of a GaAs crystallite growing freely in three dimensions. The fracture energies associated with (110), (100) and (111) interface planes are calculated and a Wulff construction indicates that an ideal stoichiometric GaAs crystal should be terminated with (110) surfaces. We investigate the more complex issues that arise on surfaces when aspects of these two semiconductors are mixed. We investigate the problem of growing GaAs on the Si(100) surface and demonstrate how and why the most fundamental properties of the resulting bulk GaAs material, such as its crystalline orientation, may depend sensitively on the interplay between growth conditions such as temperature and the properties of the Si surface. For stepped Si(100) -As, we show that the growth of As directly on top of the Si surface produces a metastable state, while the replacement of the original top Si layer leads to a lower energy configuration, with the rearrangement of the surface driven by the relaxation of stress by surface steps. Finally, we study delta -doping, where one attempts to grow a single layer of Si on a GaAs surface before continuing with the growth of bulk GaAs. We shall employ a slightly different modality of the ab initio approach. We shall use the predictive power of the ab initio approach to help guide experimental interpreation of otherwise enigmatic STM measurements. In particular, we will demonstrate by example that the predictive power of ab initio calculation allows one to harness the native chemical selectivity of the scanning tunneling electron microscope (STM) and produce an unambiguous and fully interpretable non-destructive chemical probe at the atomic level. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253 -1690.) (Abstract shortened by UMI.).

Influence of crystallography and bonding on the structure and migration of irrational interphase boundaries

NASA Astrophysics Data System (ADS)

Aaronson, H. I.

2006-03-01

Interphase boundary structure developed during precipitation from solid solution and during massive transformations is considered in diverse alloy systems in the presence of differences in stacking sequence across interphase boundaries. Linear misfit compensating defects, including misfit dislocations, structural disconnections, and misfit disconnections, are present over a wide range of crystallographie when both phases have metallic bonding. Misfit dislocations have also been observed when both phases have covalent bonding ( e.g., US: β US2 by Sole and van der Walt). These defects are also found when one phase is ionic and the other is metallic (Nb∶Al2O3 by Rühle et al.), albeit when the latter is formed by vapor deposition. However, when bonding is metallic in one phase but significantly covalent in the other, the structure of the interphase boundary appears to depend upon the strength of the covalent bonding relative to that in the metallically bonded phase. When this difference is large, growth can take place as if it were occurring at a free surface, resulting in orientation relationships that are irrational and conjugate habit planes that are ill matched ( e.g., ZrN: α Zr-N by Li et al. and Xe(solid):Al-Xe by Kishida and Yamaguchi). At lower levels of bonding directionality and strength, crystallography is again irrational, but now edge-to-edge-based low-energy structures can replace linear misfit compensating defects (γm:TiAl:αTi-Al by Reynolds et al.). In the perhaps still smaller difference case of Widmanstätten cementite precipitated from austenite, one orientation relationship yields plates with linear misfit compensating defects at their broad faces whereas another (presumably nucleated at different types of site) produces laths with poorly defined shapes and interfacial structures. Hence, Hume-Rothery-type bonding considerations can markedly affect interphase boundary structure and thus the mechanisms, kinetics, and morphology of growth.

Thermographic inspection of bond defects in Fiber Reinforced Polymer applied to masonry structures

NASA Astrophysics Data System (ADS)

Masini, N.; Aiello, M. A.; Capozzoli, L.; Vasanelli, E.

2012-04-01

Nowadays, externally bonded Fiber Reinforced Polymers (FRP) are extensively used for strengthening and repairing masonry and reinforced concrete existing structures; they have had a rapid spread in the area of rehabilitation for their many advantages over other conventional repair systems, such as lightweight, excellent corrosion and fatigue resistance, high strength, etc. FRP systems applied to masonry or concrete structures are typically installed using a wet-layup technique.The method is susceptible to cause flaws or defects in the bond between the FRP system and the substrate, which may reduce the effectiveness of the reinforcing systems and the correct transfer of load from the structure to the composite. Thus it is of primary importance to detect the presence of defects and to quantify their extension in order to eventually provide correct repair measurements. The IR thermography has been cited by the several guidelines as a good mean to qualitatively evaluate the presence of installation defects and to monitor the reinforcing system with time.The method is non-destructive and does not require contact with the composite or other means except air to detect the reinforcement. Some works in the literature have been published on this topic. Most of the researches aim at using the IR thermography technique to characterize quantitatively the defects in terms of depth, extension and type in order to have an experimental database on defect typology to evaluate the long term performances of the reinforcing system. Nevertheless, most of the works in the literature concerns with FRP applied to concrete structures without considering the case of masonry structures. In the present research artificial bond defects between FRP and the masonry substrate have been reproduced in laboratory and the IR multi temporal thermography technique has been used to detect them. Thermographic analysis has been carried out on two wall samples having limited dimensions (100 x 70 cm) both with and without plaster, reinforced with basalt and glass fiber strips for full height. Beneath FRP strips were simulated defects such as poor bonding or lack of adherence By statistical and algebraic operations, performed on thermographic multitemporal dataset, an attempt was made both to reduce the uncertainties of a typical IR active and passive test, but also to reconstruct exact geometrical shape of the simulated defects that characterize wall samples examined. Results are encouraging but more research is needed on this topic to establish a correct protocol to monitor the FRP performance with time and to quantitatively asses the presence and type of defect in the reinforcing system.

Adsorption and reactions of atmospheric constituents and pollutants on ice particles: an FTIR study

NASA Astrophysics Data System (ADS)

Rudakova, A. V.; Marinov, I. L.; Poretskiy, M. S.; Tsyganenko, A. A.

2009-04-01

Processes on icy particles attract much attention due to their importance for atmospheric science, ecology and astrophysics. In this work, adsorption and ecologically important reactions of some molecules on pure and mixed water icy films by means of FTIR spectroscopy have been investigated. The cell for spectral studies of adsorbed molecules at variable temperatures (55-370 K), described elsewhere1, enables one to run the spectra in the presence of gaseous adsorbate, and even to perform adsorption from the solution in some cryogenic solvents. For the studies of ice films, it was equipped with a device for water vapour sputtering from the heated capillaries and deposition onto the inner BaF2 or ZnSe windows of the cell, cooled by liquid nitrogen. Lower temperatures were obtained by pumping off evaporating nitrogen from the coolant volume. The estimated specific surface area of freshly deposited at 77 K water ice film was about 160 m2/g and decreases on raising the temperature together with the diminishing intensity of the bands of dangling OH (OD) groups at 3696 (2727) cm-1 until the latter disappear at 130 - 160 K when the changes of bulk absorption provide evidence for a phase transition from amorphous to polycrystalline ice. CO adsorption at 77 K results in two bands at 2153 and 2137 cm-1 assigned to molecules forming weak H-bond with the dangling hydroxyl groups and bound to unsaturated surface oxygen atoms, respectively2. The band of dangling hydroxyl groups moves to lower wavenumbers on adsorption of different molecules (hydrogen, nitrogen, methane, ozone, NO, ethane or chlorinated ethenes, etc.). The shift value depends on the nature of adsorbate. Besides this shift, spectra of adsorbed nitrogen and methane registered at 55 K reveal the adsorption intensity decrease at ~ 2650 cm-1 at the high-frequency slope of bulk adsorption, and increase at about 25 cm-1 below. We interpret this perturbation as a strengthening of H-bonds between surface water molecules, which act as adsorption sites either as a proton-donor or as a donor of the lone pair of electrons. Such adsorption-induced relaxation explains the dependence of physico-chemical properties of icy particles on the presence of atmospheric gases. Spectra HCN/D2O and ND3/D2O mixed icy films with low (1:10) dopant/water ratios do not manifest any changes in the acidic or basic properties of dangling hydroxyl groups or surface oxygen atoms, but reveal a difference in the proportion between the concentrations of these sites as compared with that for pure water ice. For high dopant concentrations (1:1), the dangling hydroxyls were not observed; the dominant adsorption sites for CO are likely to be the unsaturated oxygen atoms, while serious structural changes occur in the bulk of ices. Ecologically important reactions of atmospheric pollutants such as ozonolysis of ethene, chlorinated ethenes, hydrogen cyanide, and methyl bromide adsorbed on water ice film as well as the influence of UV radiation on this process have been studied in 77 - 200 K temperature range by FTIR spectroscopy. Ozone co-adsorption with ethene or C2H3Cl readily leads to ozonolysis reaction, which also starts for C2H2Cl2 isomers but only at temperatures elevated up to 120 - 150 K. Co-adsorption of O3 with HCN or CH3Br molecules in the dark does not lead to any noticeable spectral changes. Irradiation of HCN or CH3Br deposited on ice films in the presence of ozone leads to appearance of new bands revealing the formation of ozonolysis products. The same "synergetic effect" of simultaneous action of ozone and UV radiation at 77 K, was found for C2H2Cl2 isomers and C2Cl4, which are resistant against O3 even at higher temperatures. The obtained spectral dependence of photo-ozonolysis of C2Cl4 and HCN at 77 K shows that photoexcitation or photodissociation of ozone, evidently, accounts for the observed processes. The surface of ice particles, thus, plays the role of a condenser of atmospheric pollutants and acts as a micro- photoreactor in the atmospheric chemistry. Acknowledgments. The work was supported by INTAS (grant 03-51-5698) and RFBR (grants 06-03-32836 and 06-05-64646). 1. Otero Areán С., Manoilova O.V., Tsyganenko A.A., Turnes Palomino G., Peñarroya Mentruit M., Geobaldo F., Garrone E. Eur. J. Inorg. Chem., 2001, No 7, 1739. 2. Rudakova A.V., Sekushin V.N., Marinov I.L., Tsyganenko A.A. Langmuir, 25 (2009) 000.

Experimental and theoretical study on Raman spectra of magnesium fluoride clusters and solids.

PubMed

Neelamraju, S; Bach, A; Schön, J C; Fischer, D; Jansen, M

2012-11-21

In this study, the Raman and IR spectra of a large number of isomers of MgF(2) clusters and of possible bulk polymorphs of MgF(2) are calculated and compared with experimental data observed using a low-temperature atom beam deposition. The bulk polymorphs were taken from earlier work, while the cluster modifications for the neutral (MgF(2))(n) (n = 1-10) clusters and charged clusters (up to the trimer anion and cation, (Mg(3)F(7))(-) and (Mg(3)F(5))(+), respectively) are determined in the present work by global energy landscape explorations using simulated annealing. These theoretical calculations are complemented by an experimental study on both the vapor phase and the deposited films of MgF(2), which are generated in a low-temperature atom beam deposition setup for the synthesis of MgF(2) bulk phases. The MgF(2) vapor and film are characterized via Raman spectroscopy of the MgF(2) gas phase species embedded in an Ar-matrix and of the MgF(2)-films deposited onto a cooled substrate, respectively. We find that, in the vapor phase, there are monomers and dimers and charged species to be present in our experimental setup. Furthermore, the results suggest that in the amorphous bulk MgF(2), rutile-like domains are present and MgF(2) clusters similar to those in the matrix. Finally, peaks at about 800 cm(-1), which are in the same range as the A(g) modes of clusters with dangling fluorine atoms connected to three-coordinated Mg atoms, indicate that such dangling bonds are also present in amorphous MgF(2).

Surface Roughness of Various Diamond-Like Carbon Films

NASA Astrophysics Data System (ADS)

Liu, Dongping; Liu, Yanhong; Chen, Baoxiang

2006-11-01

Atomic force microscopy is used to estimate and compare the surface morphology of hydrogenated and hydrogen-free diamond-like carbon (DLC) films. The films were prepared by using DC magnetron sputtering of a graphite target, pulsed cathodic carbon arcs, electron cyclotron resonance (ECR), plasma source ion implantation and dielectric barrier discharge (DBD). The difference in the surface structure is presented for each method of deposition. The influences of various discharge parameters on the film surface properties are discussed based upon the experimental results. The coalescence process via the diffusion of adsorbed carbon species is responsible for the formation of hydrogen-free DLC films with rough surfaces. The films with surface roughness at an atomic level can be deposited by energetic ion impacts in a highly ionized carbon plasma. The dangling bonds created by atomic hydrogen lead to the uniform growth of hydrocarbon species at the a-C:H film surfaces of the ECR or DBD plasmas.

Effects of reducing temperatures on the hydrogen storage capacity of double-walled carbon nanotubes with Pd loading.

PubMed

Sheng, Qu; Wu, Huimin; Wexler, David; Liu, Huakun

2014-06-01

The effects of different temperatures on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) with palladium loading have been investigated. When we use different temperatures, the particle sizes and specific surface areas of the samples are different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the amount of hydrogen storage capacity was determined (by AMC Gas Reactor Controller) to be 1.70, 1.85, 2.00, and 1.93 wt% for pristine DWCNTS and for 2%Pd/DWCNTs-300 degrees C, 2%Pd/DWCNTs-400 degrees C, and 2%Pd/DWCNTs-500 degrees C, respectively. We found that the hydrogen storage capacity can be enhanced by loading with 2% Pd nanoparticles and selecting a suitable temperature. Furthermore, the sorption can be attributed to the chemical reaction between atomic hydrogen and the dangling bonds of the DWCNTs.

Spin-polarized electron emitter: Mn-doped GaN nanotubes and their arrays

NASA Astrophysics Data System (ADS)

Hao, Shaogang; Zhou, Gang; Wu, Jian; Duan, Wenhui; Gu, Bing-Lin

2004-03-01

The influences from the doping magnetic atom, Mn, on the geometry, electronic properties, and spin-polarization characteristics are demonstrated for open armchair gallium nitrogen (GaN) nanotubes and arrays by use of the first-principles calculations. The interaction between dangling bonds of Ga (Mn) and N atoms at the open-end promotes the self-close of the tube mouth and formation of a more stable open semicone top. Primarily owing to hybridization of Mn 3d and N 2p orbitals, one Mn atom introduces several impurity energy levels into the original energy gap, and the calculated magnetic moment is 4μB. The electron spin polarizations in the field emission are theoretically evaluated. We suggest that armchair open GaN nanotube arrays doped with a finite number of magnetic atoms may have application potential as the electron source of spintronic devices in the future.

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics.

PubMed

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution.

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics

PubMed Central

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution. PMID:25962096

Atomic and electronic structure of the CdTe(111)B–(2√3 × 4) orthogonal surface

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

Bekenev, V. L., E-mail: bekenev@ipms.kiev.ua; Zubkova, S. M.

2017-01-15

The atomic and electronic structure of four variants of Te-terminated CdTe(111)B–(2√3 × 4) orthogonal polar surface (ideal, relaxed, reconstructed, and reconstructed with subsequent relaxation) are calculated ab initio for the first time. The surface is modeled by a film composed of 12 atomic layers with a vacuum gap of ~16 Å in the layered superlattice approximation. To close Cd dangling bonds on the opposite side of the film, 24 fictitious hydrogen atoms with a charge of 1.5 electrons each are added. Ab initio calculations are performed using the Quantum Espresso program based on density functional theory. It is demonstrated thatmore » relaxation leads to splitting of the four upper layers. The band energy structures and total and layer-by-layer densities of electronic states for the four surface variants are calculated and analyzed.« less

Si(111) strained layers on Ge(111): Evidence for c (2 ×4 ) domains

NASA Astrophysics Data System (ADS)

Zhachuk, R.; Coutinho, J.; Dolbak, A.; Cherepanov, V.; Voigtländer, B.

2017-08-01

The tensile-strained Si (111 ) layers grown on top of Ge (111 ) substrates are studied by combining scanning tunneling microscopy, low-energy electron diffraction, and first-principles calculations. It is shown that the layers exhibit c (2 ×4 ) domains, which are separated by domain walls along <1 ¯10 > directions. A model structure for the c (2 ×4 ) domains is proposed, which shows low formation energy and good agreement with the experimental data. The results of our calculations suggest that Ge atoms are likely to replace Si atoms with dangling bonds on the surface (rest-atoms and adatoms), thus significantly lowering the surface energy and inducing the formation of domain walls. The experiments and calculations demonstrate that when surface strain changes from compressive to tensile, the (111) reconstruction converts from dimer-adatom-stacking fault-based to adatom-based structures.

Effects of chemical states of carbon on deuterium retention in carbon-containing materials

NASA Astrophysics Data System (ADS)

Oyaidzu, Makoto; Kimura, Hiromi; Nakahata, Toshihiko; Nishikawa, Yusuke; Tokitani, Masayuki; Oya, Yasuhisa; Iwakiri, Hirotomo; Yoshida, Naoaki; Okuno, Kenji

2007-08-01

Deuterium retention behavior in highly oriented pyrolytic graphite (HOPG), poly-crystalline diamond, poly-crystalline SiC, sintered WC, and converted B 4C were investigated to reveal tritium behavior in re-deposition and co-deposition layers. Such layers would contain carbon, when the first wall and/or divertor were made of graphite or carbon-containing materials. Furthermore, the employment of other materials such as tungsten, and first wall conditioning such as boronization would complicate the layers. No different deuterium trapping sites due to carbon from those in HOPG were found in all the samples, where two deuterium trapping processes were observed: hot atom chemical trapping of energetic deuterium by a dangling bond of carbon and thermochemical trapping of thermalized deuterium in a constituent atom vacancy surrounded by carbons. Additionally, the latter reaction could be easily counteracted by or competed with the other deuterium trapping reactions by constituent atoms.

Transition-metal impurities in semiconductors and heterojunction band lineups

NASA Astrophysics Data System (ADS)

Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

1988-10-01

The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

Two-probe STM experiments at the atomic level.

PubMed

Kolmer, Marek; Olszowski, Piotr; Zuzak, Rafal; Godlewski, Szymon; Joachim, Christian; Szymonski, Marek

2017-11-08

Direct characterization of planar atomic or molecular scale devices and circuits on a supporting surface by multi-probe measurements requires unprecedented stability of single atom contacts and manipulation of scanning probes over large, nanometer scale area with atomic precision. In this work, we describe the full methodology behind atomically defined two-probe scanning tunneling microscopy (STM) experiments performed on a model system: dangling bond dimer wire supported on a hydrogenated germanium (0 0 1) surface. We show that 70 nm long atomic wire can be simultaneously approached by two independent STM scanners with exact probe to probe distance reaching down to 30 nm. This allows direct wire characterization by two-probe I-V characteristics at distances below 50 nm. Our technical results presented in this work open a new area for multi-probe research, which can be now performed with precision so far accessible only by single-probe scanning probe microscopy (SPM) experiments.

Analytical study of nano-scale logical operations

NASA Astrophysics Data System (ADS)

Patra, Moumita; Maiti, Santanu K.

2018-07-01

A complete analytical prescription is given to perform three basic (OR, AND, NOT) and two universal (NAND, NOR) logic gates at nano-scale level using simple tailor made geometries. Two different geometries, ring-like and chain-like, are taken into account where in each case the bridging conductor is coupled to a local atomic site through a dangling bond whose site energy can be controlled by means of external gate electrode. The main idea is that when injecting electron energy matches with site energy of local atomic site transmission probability drops exactly to zero, whereas the junction exhibits finite transmission for other energies. Utilizing this prescription we perform logical operations, and, we strongly believe that the proposed results can be verified in laboratory. Finally, we numerically compute two-terminal transmission probability considering general models and the numerical results match exactly well with our analytical findings.

Van der Waals Interactions of Organic Molecules on Semiconductor and Metal Surfaces: a Comparative Study

NASA Astrophysics Data System (ADS)

Li, Guo; Cooper, Valentino; Cho, Jun-Hyung; Tamblyn, Isaac; Du, Shixuan; Neaton, Jeffrey; Gao, Hong-Jun; Zhang, Zhenyu

2012-02-01

We present a comparative investigation of vdW interactions of the organic molecules on semiconductor and metal surfaces using the DFT method implemented with vdW-DF. For styrene/H-Si(100), the vdW interactions reverse the effective intermolecular interaction from repulsive to attractive, ensuring preferred growth of long wires as observed experimentally. We further propose that an external E field and the selective creation of Si dangling bonds can drastically improve the ordered arrangement of the molecular nanowires [1]. For BDA/Au(111), the vdW interactions not only dramatically enhances the adsorption energies, but also significantly changes the molecular configurations. In the azobenzene/Ag(111) system, vdW-DF produces superior predictions for the adsorption energy than those obtained with other vdW corrected DFT approaches, providing evidence for the applicability of the vdW-DF method [2].

Selenium-assisted controlled growth of graphene-Bi2Se3 nanoplates hybrid Dirac materials by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Sun, Zhencui; Man, Baoyuan; Yang, Cheng; Liu, Mei; Jiang, Shouzhen; Zhang, Chao; Zhang, Jiaxin; Liu, Fuyan; Xu, Yuanyuan

2016-03-01

Se seed layers were used to synthesize the high-quality graphene-Bi2Se3 nanoplates hybrid Dirac materials via chemical vapor deposition (CVD) method. The morphology, crystallization and structural properties of the hybrid Dirac materials were characterized by SEM, EDS, Raman, XRD, AFM and HRTEM. The measurement results verify that the Se seed layer on the graphene surface can effectively saturate the surface dangling bonds of the graphene, which not only impel the uniform Bi2Se3 nanoplates growing along the horizontal direction but also can supply enough Se atoms to fill the Se vacancies. We also demonstrate the Se seed layer can effectively avoid the interaction of Bi2Se3 and the graphene. Further experiments testify the different Se seed layer on the graphene surface can be used to control the density of the Bi2Se3 nanoplates.

Hybrid chalcogenide nanoparticles: 2D-WS2 nanocrystals inside nested WS2 fullerenes.

PubMed

Hoshyargar, Faegheh; Corrales, Tomas P; Branscheid, Robert; Kolb, Ute; Kappl, Michael; Panthöfer, Martin; Tremel, Wolfgang

2013-10-28

The MOCVD assisted formation of nested WS2 inorganic fullerenes (IF-WS2) was performed by enhancing surface diffusion with iodine, and fullerene growth was monitored by taking TEM snapshots of intermediate products. The internal structure of the core-shell nanoparticles was studied using scanning electron microscopy (SEM) after cross-cutting with a focused ion beam (FIB). Lamellar reaction intermediates were found occluded in the fullerene particles. In contrast to carbon fullerenes, layered metal chalcogenides prefer the formation of planar, plate-like structures where the dangling bonds at the edges are stabilized by excess S atoms. The effects of the reaction and annealing temperatures on the composition and morphology of the final product were investigated, and the strength of the WS2 shell was measured by intermittent contact-mode AFM. The encapsulated lamellar structures inside the hollow spheres may lead to enhanced tribological activities.

Infrared spectral marker bands characterizing a transient water wire inside a hydrophobic membrane protein.

PubMed

Wolf, Steffen; Freier, Erik; Cui, Qiang; Gerwert, Klaus

2014-12-14

Proton conduction along protein-bound "water wires" is an essential feature in membrane proteins. Here, we analyze in detail a transient water wire, which conducts protons via a hydrophobic barrier within a membrane protein to create a proton gradient. It is formed only for a millisecond out of three water molecules distributed at inactive positions in a polar environment in the ground state. The movement into a hydrophobic environment causes characteristic shifts of the water bands reflecting their different chemical properties. These band shifts are identified by time-resolved Fourier Transform Infrared difference spectroscopy and analyzed by biomolecular Quantum Mechanical/Molecular Mechanical simulations. A non-hydrogen bonded ("dangling") O-H stretching vibration band and a broad continuum absorbance caused by a combined vibration along the water wire are identified as characteristic marker bands of such water wires in a hydrophobic environment. The results provide a basic understanding of water wires in hydrophobic environments.

Dependence of electrical and time stress in organic field effect transistor with low temperature forming gas treated Al2O3 gate dielectrics.

PubMed

Lee, Sunwoo; Chung, Keum Jee; Park, In-Sung; Ahn, Jinho

2009-12-01

We report the characteristics of the organic field effect transistor (OFET) after electrical and time stress. Aluminum oxide (Al2O3) was used as a gate dielectric layer. The surface of the gate oxide layer was treated with hydrogen (H2) and nitrogen (N2) mixed gas to minimize the dangling bond at the interface layer of gate oxide. According to the two stress parameters of electrical and time stress, threshold voltage shift was observed. In particular, the mobility and subthreshold swing of OFET were significantly decreased due to hole carrier localization and degradation of the channel layer between gate oxide and pentacene by electrical stress. Electrical stress is a more critical factor in the degradation of mobility than time stress caused by H2O and O2 in the air.

Band-Edge Exciton Fine Structure and Recombination Dynamics in InP/ZnS Colloidal Nanocrystals.

PubMed

Biadala, Louis; Siebers, Benjamin; Beyazit, Yasin; Tessier, Mickaël D; Dupont, Dorian; Hens, Zeger; Yakovlev, Dmitri R; Bayer, Manfred

2016-03-22

We report on a temperature-, time-, and spectrally resolved study of the photoluminescence of type-I InP/ZnS colloidal nanocrystals with varying core size. By studying the exciton recombination dynamics we assess the exciton fine structure in these systems. In addition to the typical bright-dark doublet, the photoluminescence stems from an upper bright state in spite of its large energy splitting (∼100 meV). This striking observation results from dramatically lengthened thermalization processes among the fine structure levels and points to optical-phonon bottleneck effects in InP/ZnS nanocrystals. Furthermore, our data show that the radiative recombination of the dark exciton scales linearly with the bright-dark energy splitting for CdSe and InP nanocrystals. This finding strongly suggests a universal dangling bonds-assisted recombination of the dark exciton in colloidal nanostructures.

Molecular Monolayers for Electrical Passivation and Functionalization of Silicon-Based Solar Energy Devices.

PubMed

Veerbeek, Janneke; Firet, Nienke J; Vijselaar, Wouter; Elbersen, Rick; Gardeniers, Han; Huskens, Jurriaan

2017-01-11

Silicon-based solar fuel devices require passivation for optimal performance yet at the same time need functionalization with (photo)catalysts for efficient solar fuel production. Here, we use molecular monolayers to enable electrical passivation and simultaneous functionalization of silicon-based solar cells. Organic monolayers were coupled to silicon surfaces by hydrosilylation in order to avoid an insulating silicon oxide layer at the surface. Monolayers of 1-tetradecyne were shown to passivate silicon micropillar-based solar cells with radial junctions, by which the efficiency increased from 8.7% to 9.9% for n + /p junctions and from 7.8% to 8.8% for p + /n junctions. This electrical passivation of the surface, most likely by removal of dangling bonds, is reflected in a higher shunt resistance in the J-V measurements. Monolayers of 1,8-nonadiyne were still reactive for click chemistry with a model catalyst, thus enabling simultaneous passivation and future catalyst coupling.

Facile fabrication and electrical investigations of nanostructured p-Si/n-TiO2 hetero-junction diode

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

2018-05-01

In this work, we have fabricated the nanostructured p-Si/n-TiO2 hetero-junction diode by using a facile spin-coating method. The XRD analysis suggests the presence of well crystalline anatase TiO2 film on Si with small grain size (˜16 nm). We have drawn the band alignment using Anderson model to understand the electrical transport across the junction. The current-voltage (J-V) characteristics analysis reveals the good rectification ratio (103 at ± 3 V) and slightly higher ideality factor (4.7) of our device. The interface states are responsible for the large ideality factor as Si/TiO2 form a dissimilar interface and possess a large number of dangling bonds. The study reveals the promises to be used Si/TiO2 diode as an alternative to the traditional p-n homo-junction diode, which typically require high budget.

Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes.

PubMed

Kroupa, Daniel M; Vörös, Márton; Brawand, Nicholas P; Bronstein, Noah; McNichols, Brett W; Castaneda, Chloe V; Nozik, Arthur J; Sellinger, Alan; Galli, Giulia; Beard, Matthew C

2018-06-08

We studied the optical absorption enhancement in colloidal suspensions of PbS quantum dots (QD) upon ligand exchange from oleate to a series of cinnamate ligands. By combining experiments and ab initio simulations, we elucidate physical parameters that govern the optical absorption enhancement. We find that, within the cinnamate/PbS QD system, the optical absorption enhancement scales linearly with the electronic gap of the ligand, indicating that the ligand/QD coupling occurs equally efficient between the QD and ligand HOMO and their respective LUMO levels. Disruption of the conjugation that connects the aromatic ring and its substituents to the QD core causes a reduction of the electronic coupling. Our results further support the notion that the ligand/QD complex should be considered as a distinct chemical system with emergent behavior rather than a QD core with ligands whose sole purpose is to passivate surface dangling bonds and prevent agglomeration.

A novel image enhancement algorithm based on stationary wavelet transform for infrared thermography to the de-bonding defect in solid rocket motors

NASA Astrophysics Data System (ADS)

Liu, Tao; Zhang, Wei; Yan, Shaoze

2015-10-01

In this paper, a multi-scale image enhancement algorithm based on low-passing filtering and nonlinear transformation is proposed for infrared testing image of the de-bonding defect in solid propellant rocket motors. Infrared testing images with high-level noise and low contrast are foundations for identifying defects and calculating the defects size. In order to improve quality of the infrared image, according to distribution properties of the detection image, within framework of stationary wavelet transform, the approximation coefficients at suitable decomposition level is processed by index low-passing filtering by using Fourier transform, after that, the nonlinear transformation is applied to further process the figure to improve the picture contrast. To verify validity of the algorithm, the image enhancement algorithm is applied to infrared testing pictures of two specimens with de-bonding defect. Therein, one specimen is made of a type of high-strength steel, and the other is a type of carbon fiber composite. As the result shown, in the images processed by the image enhancement algorithm presented in the paper, most of noises are eliminated, and contrast between defect areas and normal area is improved greatly; in addition, by using the binary picture of the processed figure, the continuous defect edges can be extracted, all of which show the validity of the algorithm. The paper provides a well-performing image enhancement algorithm for the infrared thermography.

Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

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

Lumpkin, Gregory R.; Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234; Pruneda, Miguel

2007-04-15

The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis ofmore » the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.« less

Transformation between divacancy defects induced by an energy pulse in graphene.

PubMed

Xia, Jun; Liu, XiaoYi; Zhou, Wei; Wang, FengChao; Wu, HengAn

2016-07-08

The mutual transformations among the four typical divacancy defects induced by a high-energy pulse were studied via molecular dynamics simulation. Our study revealed all six possible mutual transformations and found that defects transformed by absorbing energy to overcome the energy barrier with bonding, debonding, and bond rotations. The reversibility of defect transformations was also investigated by potential energy analysis. The energy difference was found to greatly influence the transformation reversibility. The direct transformation path was irreversible if the energy difference was too large. We also studied the correlation between the transformation probability and the input energy. It was found that the transformation probability had a local maxima at an optimal input energy. The introduction of defects and their structural evolutions are important for tailoring the exceptional properties and thereby performances of graphene-based devices, such as nanoporous membranes for the filtration and desalination of water.

Friction pull plug welding: chamfered heat sink pull plug design

NASA Technical Reports Server (NTRS)

Coletta, Edmond R. (Inventor); Cantrell, Mark A. (Inventor)

2005-01-01

The average strength of a pull plug weld is increased and weak bonding eliminated by providing a dual included angle at the top one third of the pull plug. Plugs using the included angle of the present invention had consistent high strength, no weak bonds and were substantially defect free. The dual angle of the pull plug body increases the heat and pressure of the weld in the region of the top one third of the plug. This allows the plug to form a tight high quality solid state bond. The dual angle was found to be successful in elimination of defects on both small and large plugs.

The structural and electronic properties of cleaved silicon (111) surfaces following adsorption of silver

NASA Astrophysics Data System (ADS)

Le Lay, G.; Chauvet, A.; Manneville, M.; Kern, R.

Silver overlayers for coverages ranging from zero to several monolayers are evaporated on vacuum-cleaved (111) silicon surfaces and carefully examined using low-energy electron diffraction (diffraction patterns and I(v) curves), and Auger electron spectroscopy (condensation/desorption curves), with the aim of establishing a closer correlation between the adsorption process, the different superlattices observed (i.e. 7 × 7-R(±19°1), 3 × 3-R(30° ), 3 × 1 and 6 × 1), the growth mechanism of the deposit on the one hand and the electronic properties of the system recently probed using photoemission yield spectroscopy on the other hand. These new results basically confirm the direct relations we had previously shown between the growth mode as monitored with electron diffraction LEED, RHEED, TED and Auger spectroscopy, and the electronic structures as investigated by low energy electron spectroscopy, but permit a deeper insight into the adsorption process at low coverage. At room temperature on the 2 × 1 cleavage structure where the silver-silicon interaction is weak, the adsorbed phase is completed at about 6/7 of a monolayer (θ ≃ 6/7) and a local arrangement of vacancies in the adlayer yields the 7 superstructure, while little effect on the silicon dangling bonds is noticed, but when silver two-dimensional islands (θ > 6/7) growing in a quasi layer fashion have covered the substrate surface. At higher temperatures three-dimensional growth of crystallites occurs after completion of the 3 phase whose saturation coverage increases with condensation temperatures, maxima ranging from θ ˜ 0.7 to θ ˜ 1.0 ( T ˜ 500°C) for different cleaves. This Si(111) 3-Ag surface exhibits again the same dangling bond peak as a clean 2 × 1 Si surface, despite the fact that the interaction between Ag and Si is now rather strong, as is confirmed by desorption experiments ( T ˜ 600°C). We thus critically discuss the geometrical models of this 3 phase previously devised and tentatively propose a new one which accounts better for these recent results, along with models of the 3 × 1 and 6 × 1 structures observed in the course of the desorption process.

Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study

NASA Astrophysics Data System (ADS)

Sinthika, S.; Kumar, E. Mathan; Surya, V. J.; Kawazoe, Y.; Park, Noejung; Iyakutti, K.; Thapa, Ranjit

2015-12-01

Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level.

Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study

PubMed Central

Sinthika, S.; Kumar, E. Mathan; Surya, V. J.; Kawazoe, Y.; Park, Noejung; Iyakutti, K.; Thapa, Ranjit

2015-01-01

Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir–Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level. PMID:26626147

Activation of CO and CO2 on homonuclear boron bonds of fullerene-like BN cages: first principles study.

PubMed

Sinthika, S; Kumar, E Mathan; Surya, V J; Kawazoe, Y; Park, Noejung; Iyakutti, K; Thapa, Ranjit

2015-12-02

Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level.

Ultrasonic guided wave monitoring of composite wing skin-to-spar bonded joints in aerospace structures

NASA Astrophysics Data System (ADS)

Matt, Howard; Bartoli, Ivan; Lanza di Scalea, Francesco

2005-10-01

The monitoring of adhesively bonded joints by ultrasonic guided waves is the general topic of this paper. Specifically, composite-to-composite joints representative of the wing skin-to-spar bonds of unmanned aerial vehicles (UAVs) are examined. This research is the first step towards the development of an on-board structural health monitoring system for UAV wings based on integrated ultrasonic sensors. The study investigates two different lay-ups for the wing skin and two different types of bond defects, namely poorly cured adhesive and disbonded interfaces. The assessment of bond state is based on monitoring the strength of transmission through the joints of selected guided modes. The wave propagation problem is studied numerically by a semi-analytical finite element method that accounts for viscoelastic damping, and experimentally by ultrasonic testing that uses small PZT disks preferably exciting and detecting the single-plate s0 mode. Both the models and the experiments confirm that the ultrasonic energy transmission through the joint is highly dependent on the bond conditions, with defected bonds resulting in increased transmission strength. Large sensitivity to the bond conditions is found at mode coupling points, as a result of the large interlayer energy transfer.

A guided-wave system for monitoring the wing skin-to-spar bond in unmanned aerial vehicles

NASA Astrophysics Data System (ADS)

Matt, Howard; Bartoli, Ivan; Lanza di Scalea, Francesco; Marzani, Alessandro; Coccia, Stefano; Oliver, Joseph; Kosmatka, John; Rizzo, Piervincenzo; Restivo, Gaetano

2005-05-01

Unmanned Aerial Vehicles (UAVs) are being increasingly used in military as well as civil applications. A critical part of the structure is the adhesive bond between the wing skin and the supporting spar. If not detected early, bond defects originating during manufacturing or in service flight can lead to inefficient flight performance and eventual global failure. This paper will present results from a bond inspection system based on attached piezoelectric disks probing the skin-to-spar bondline with ultrasonic guided waves in the hundreds of kilohertz range. The test components were CFRP composite panels of two different fiber layups bonded to a CFRP composite tube using epoxy adhesive. Three types of bond conditions were simulated, namely regions of poor cohesive strength, regions with localized disbonds and well bonded regions. The root mean square and variance of the received time-domain signals and their discrete wavelet decompositions were computed for the dominant modes propagating through the various bond regions in two different inspection configurations. Semi-analytical finite element analysis of the bonded multilayer joint was also carried out to identify and predict the sensitivity of the predominant carrier modes to the different bond defects. Emphasis of this research is based upon designing a built-in system for monitoring the structural integrity of bonded joints in UAVs and other aerospace structures.

Hydrogen desorption from hydrogen fluoride and remote hydrogen plasma cleaned silicon carbide (0001) surfaces

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

King, Sean W., E-mail: sean.king@intel.com; Tanaka, Satoru; Davis, Robert F.

2015-09-15

Due to the extreme chemical inertness of silicon carbide (SiC), in-situ thermal desorption is commonly utilized as a means to remove surface contamination prior to initiating critical semiconductor processing steps such as epitaxy, gate dielectric formation, and contact metallization. In-situ thermal desorption and silicon sublimation has also recently become a popular method for epitaxial growth of mono and few layer graphene. Accordingly, numerous thermal desorption experiments of various processed silicon carbide surfaces have been performed, but have ignored the presence of hydrogen, which is ubiquitous throughout semiconductor processing. In this regard, the authors have performed a combined temperature programmed desorptionmore » (TPD) and x-ray photoelectron spectroscopy (XPS) investigation of the desorption of molecular hydrogen (H{sub 2}) and various other oxygen, carbon, and fluorine related species from ex-situ aqueous hydrogen fluoride (HF) and in-situ remote hydrogen plasma cleaned 6H-SiC (0001) surfaces. Using XPS, the authors observed that temperatures on the order of 700–1000 °C are needed to fully desorb C-H, C-O and Si-O species from these surfaces. However, using TPD, the authors observed H{sub 2} desorption at both lower temperatures (200–550 °C) as well as higher temperatures (>700 °C). The low temperature H{sub 2} desorption was deconvoluted into multiple desorption states that, based on similarities to H{sub 2} desorption from Si (111), were attributed to silicon mono, di, and trihydride surface species as well as hydrogen trapped by subsurface defects, steps, or dopants. The higher temperature H{sub 2} desorption was similarly attributed to H{sub 2} evolved from surface O-H groups at ∼750 °C as well as the liberation of H{sub 2} during Si-O desorption at temperatures >800 °C. These results indicate that while ex-situ aqueous HF processed 6H-SiC (0001) surfaces annealed at <700 °C remain terminated by some surface C–O and Si–O bonding, they may still exhibit significant chemical reactivity due to the creation of surface dangling bonds resulting from H{sub 2} desorption from previously undetected silicon hydride and surface hydroxide species.« less

Turning things downside up: Adsorbate induced water flipping on Pt(111)

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

Kimmel, Gregory A.; Zubkov, Tykhon; Smith, R. Scott

2014-11-14

We have examined the adsorption of the weakly bound species N2, O2, CO and Kr on the water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O2 have little effect on the structure and vibrational spectrum of the “ ” water monolayermore » while adsorption of both N2, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “ ” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.« less

Modelling of ‘sub-atomic’ contrast resulting from back-bonding on Si(111)-7×7

PubMed Central

Jarvis, Samuel P; Rashid, Mohammad A

2016-01-01

Summary It has recently been shown that ‘sub-atomic’ contrast can be observed during NC-AFM imaging of the Si(111)-7×7 substrate with a passivated tip, resulting in triangular shaped atoms [Sweetman et al. Nano Lett. 2014, 14, 2265]. The symmetry of the features, and the well-established nature of the dangling bond structure of the silicon adatom means that in this instance the contrast cannot arise from the orbital structure of the atoms, and it was suggested by simple symmetry arguments that the contrast could only arise from the backbonding symmetry of the surface adatoms. However, no modelling of the system has been performed in order to understand the precise origin of the contrast. In this paper we provide a detailed explanation for ‘sub-atomic’ contrast observed on Si(111)-7×7 using a simple model based on Lennard-Jones potentials, coupled with a flexible tip, as proposed by Hapala et al. [Phys. Rev. B 2014, 90, 085421] in the context of interpreting sub-molecular contrast. Our results show a striking similarity to experimental results, and demonstrate how ‘sub-atomic’ contrast can arise from a flexible tip exploring an asymmetric potential created due to the positioning of the surrounding surface atoms. PMID:27547610

Theoretical investigations on the structures and properties of CL-20/TNT cocrystal and its defective models by molecular dynamics simulation.

PubMed

Hang, Gui-Yun; Yu, Wen-Li; Wang, Tao; Wang, Jin-Tao

2018-06-09

"Perfect" and defective models of CL-20/TNT cocrystal explosive were established. Molecular dynamics methods were introduced to determine the structures and predict the comprehensive performances, including stabilities, sensitivity, energy density and mechanical properties, of the different models. The influences of crystal defects on the properties of these explosives were investigated and evaluated. The results show that, compared with the "perfect" model, the rigidity and toughness of defective models are decreased, while the ductility, tenacity and plastic properties are enhanced. The binding energies, interaction energy of the trigger bond, and the cohesive energy density of defective crystals declined, thus implying that stabilities are weakened, the explosive molecule is activated, trigger bond strength is diminished and safety is worsened. Detonation performance showed that, owing to the influence of crystal defects, the density is lessened, detonation pressure and detonation velocity are also declined, i.e., the power of defective explosive is decreased. In a word, the crystal defects may have a favorable effect on the mechanical properties, but have a disadvantageous influence on sensitivity, stability and energy density of CL-20/TNT cocrystal explosive. The results could provide theoretical guidance and practical instructions to estimate the properties of defective crystal models.

Friction pull plug welding: top hat plug design

NASA Technical Reports Server (NTRS)

Coletta, Edmond R. (Inventor); Cantrell, Mark A. (Inventor)

2001-01-01

Friction Pull Plug Welding is a solid state repair process for defects up to one inch in length, only requiring single sided tooling, or outside skin line (OSL), for preferred usage on flight hardware. The most prevalent defect associated with Friction Pull Plug Welding (FPPW) was a top side or inside skin line (ISL) lack of bonding. Bonding was not achieved at this location due to the reduction in both frictional heat and welding pressure between the plug and plate at the end of the weld. Thus, in order to eliminate the weld defects and increase the plug strength at the plug `top` a small `hat` section is added to the pull plug for added frictional heating and pressure.

Friction pull plug welding: top hat plug design

NASA Technical Reports Server (NTRS)

Coletta, Edmond R. (Inventor); Cantrell, Mark A. (Inventor)

2002-01-01

Friction Pull Plug Welding is a solid state repair process for defects up to one inch in length, only requiring single sided tooling, or outside skin line (OSL), for preferred usage on flight hardware. The most prevalent defect associated with Friction Pull Plug Welding (FPPW) was a top side or inside skin line (ISL) lack of bonding. Bonding was not achieved at this location due to the reduction in both frictional heat and welding pressure between the plug and plate at the end of the weld. Thus, in order to eliminate the weld defects and increase the plug strength at the plug `top` a small `hat` section is added to the pull plug for added frictional heating and pressure.

The Optoelectronic Properties of Nanoparticles from First Principles Calculations

NASA Astrophysics Data System (ADS)

Brawand, Nicholas Peter

The tunable optoelectronic properties of nanoparticles through the modification of their size, shape, and surface chemistry, make them promising platforms for numerous applications, including electronic and solar conversion devices. However, the rational design and optimization of nanostructured materials remain open challenges, e.g. due to difficulties in controlling and reproducing synthetic processes and in precise atomic-scale characterization. Hence, the need for accurate theoretical predictions, which can complement and help interpret experiments and provide insight into the underlying physical properties of nanostructured materials. This dissertation focuses on the development and application of first principles calculations to predict the optoelectronic properties of nanoparticles. Novel methods based on density functional theory are developed, implemented, and applied to predict both optical and charge transport properties. In particular, the generalization of dielectric dependent hybrid functionals to finite systems is introduced and shown to yield highly accurate electronic structure properties of molecules and nanoparticles, including photoemission and absorption properties. In addition, an implementation of constrained density functional theory is discussed, for the calculation of hopping transport in nanoparticle systems. The implementation was verified against literature results and compared against other methods used to compute transport properties, showing that some methods used in the literature give unphysical results for thermally disordered systems. Furthermore, the constrained density functional theory implementation was coupled to the self-consistent image charge method, making it possible to include image charge effects self-consistently when predicting charge transport properties of nanoparticles near interfaces. The methods developed in this dissertation were then applied to study the optoelectronic and transport properties of specific systems, in particular, silicon and lead chalcogenide nanoparticles. In the case of Si, blinking in oxidized Si nanoparticles was addressed. Si dangling bonds at the surface were found to introduce defect states which, depending on their charge and local stress conditions, may give rise to ON and OFF states responsible for exponential blinking statistics. We also investigated, engineering of band edge positions of nanoparticles through post-synthetic surface chemistry modification, with a focus on lead chalcogenides. In collaboration with experiment, we demonstrated how band edge positions of lead sulfide nanoparticles can be tuned by over 2.0 eV. We established a clear relationship between ligand dipole moments and nanoparticle band edge shifts which can be used to engineer nanoparticles for optoelectronic applications. Calculations of transport properties focused on charge transfer in silicon and lead chalcogenide nanoparticles. Si nanoparticles with deep defects and shallow impurities were investigated, showing that shallow defects may be more detrimental to charge transport than previously assumed. In the case of lead chalcogenide nanoparticles, hydrogen was found to form complexes with defects which can be used to remove potentially detrimental charge traps in nanoparticle solids. The methods and results presented in this dissertation are expected to help guide engineering of nanoparticles for future device applications.

Nondestructive test of regenerative chambers

NASA Technical Reports Server (NTRS)

Malone, G. A.; Stauffis, R.; Wood, R.

1972-01-01

Flat panels simulating internally cooled regenerative thrust chamber walls were fabricated by electroforming, brazing and diffusion bonding to evaluate the feasibility of nondestructive evaluation techniques to detect bonds of various strength integrities. Ultrasonics, holography, and acoustic emission were investigated and found to yield useful and informative data regarding the presence of bond defects in these structures.

Bond-equilibrium theory of liquid Se-Te alloys. II. Effect of singly attached ring molecules

NASA Astrophysics Data System (ADS)

Cutler, Melvin; Bez, Wolfgang G.

1981-06-01

A statistical-mechanical theory for bond equilibrium of chain polymers containing threefold (3F) and onefold (1F) bond defects is extended to include the effects of free ring molecules and ring molecules attached to chains by a single 3F atom. Positively charged singly attached rings are shown to play a key role in bond equilibrium in liquid Sex Te1-x by permitting the formation of ion pairs in which both constituents are effectively chain terminators, thus decreasing the average polymer size. The theory is applied to explain the behavior of the paramagnetic susceptibility, χp, and electronic transport as affected by the Fermi energy EF. It is found that the increase in χp with the concentration of Te is primarily the result of the smaller energy for breaking Te bonds. In addition, attached rings play an important role in determining the effect of temperature on χp. At x<~0.5, the concentrations of both free and attached rings becomes small at high T because of the high concentration of bond defects.

The detection and quantification of the defects in adhesive bonded joints of the piezoelectric sensors by infrared thermographic nondestructive testing

NASA Astrophysics Data System (ADS)

Vinod, P. N.; Joseph, Sherin; John, Reji

2017-04-01

In this paper, efficacy of pulsed thermography technique has been explored for the first time for the detection and quantification of the subsurface defects present in the rubber-encapsulated piezoelectric sensors. Initial experiments were performed on adhesively bonded joints of the rubber/Al or rubber/PZT control samples to find out an optimum acquisition time for the 3-mm rubber encapsulants. Thermographic measurements were performed in the reflection mode and acquired thermal images were analysed and processed images were described in terms of the phase images. The defective regions are identified as delamination of the adhesive joints at the interface of rubber and PZT stacks, and presence of porosity in the encapsulation in the inspected hydrophone. The defect depths of the observed anomalies were calculated empirically from the plots of the peak time of thermal contrast (tmax) maximum and thermal contrast maximum (Cmax) for a particular defect. The estimated defect depths of the prominent porosity observed in the PZT hydrophone are found nearly 1 mm from the surface.

Strengthening of defected beam-column joints using CFRP.

PubMed

Mahmoud, Mohamed H; Afefy, Hamdy M; Kassem, Nesreen M; Fawzy, Tarek M

2014-01-01

This paper presents an experimental study for the structural performance of reinforced concrete (RC) exterior beam-column joints rehabilitated using carbon-fiber-reinforced polymer (CFRP). The present experimental program consists of testing 10 half-scale specimens divided into three groups covering three possible defects in addition to an adequately detailed control specimen. The considered defects include the absence of the transverse reinforcement within the joint core, insufficient bond length for the beam main reinforcement and inadequate spliced implanted column on the joint. Three different strengthening schemes were used to rehabilitate the defected beam-column joints including externally bonded CFRP strips and sheets in addition to near surface mounted (NSM) CFRP strips. The failure criteria including ultimate capacity, mode of failure, initial stiffness, ductility and the developed ultimate strain in the reinforcing steel and CFRP were considered and compared for each group for the control and the CFRP-strengthened specimens. The test results showed that the proposed CFRP strengthening configurations represented the best choice for strengthening the first two defects from the viewpoint of the studied failure criteria. On the other hand, the results of the third group showed that strengthening the joint using NSM strip technique enabled the specimen to outperform the structural performance of the control specimen while strengthening the joints using externally bonded CFRP strips and sheets failed to restore the strengthened joints capacity.

Micro-Raman study on the softening and stiffening of phonons in rutile titanium dioxide film: Competing effects of structural defects, crystallite size, and lattice strain

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

Gautam, Subodh K.; Singh, Fouran, E-mail: fouran@gmail.com; Sulania, I.

2014-04-14

Softening and stiffening of phonons in rutile titanium dioxide films are investigated by in situ micro-Raman studies during energetic ion irradiation. The in situ study minimized other possible mechanisms of phonon dynamics. Initial softening and broadening of Raman shift are attributed to the phonon confinement by structural defects and loss of stoichiometry. The stiffening of A{sub 1g} mode is ascribed to large distortion of TiO{sub 6} octahedra under the influence of lattice strain in the (110) plane, which gives rise to lengthening of equatorial Ti-O bond and shortening of apical Ti-O bond. The shortening of apical Ti-O bond induces stiffeningmore » of A{sub 1g} mode in the framework of the bond-order-length-strength correlation mechanism.« less

Influence of charged defects on the interfacial bonding strength of tantalum- and silver-doped nanograined TiO2.

PubMed

Azadmanjiri, Jalal; Wang, James; Berndt, Christopher C; Kapoor, Ajay; Zhu, De Ming; Ang, Andrew S M; Srivastava, Vijay K

2017-05-17

A nano-grained layer including line defects was formed on the surface of a Ti alloy (Ti alloy , Ti-6Al-4V ELI). Then, the micro- and nano-grained Ti alloy with the formation of TiO 2 on its top surface was coated with a bioactive Ta layer with or without incorporating an antibacterial agent of Ag that was manufactured by magnetron sputtering. Subsequently, the influence of the charged defects (the defects that can be electrically charged on the surface) on the interfacial bonding strength and hardness of the surface system was studied via an electronic model. Thereby, material systems of (i) Ta coated micro-grained titanium alloy (Ta/MGTi alloy ), (ii) Ta coated nano-grained titanium alloy (Ta/NGTi alloy ), (iii) TaAg coated micro-grained titanium alloy (TaAg/MGTi alloy ) and (iv) TaAg coated nano-grained titanium alloy (TaAg/NGTi alloy ) were formed. X-ray photoelectron spectroscopy was used to probe the electronic structure of the micro- and nano-grained Ti alloy , and so-formed heterostructures. The thin film/substrate interfaces exhibited different satellite peak intensities. The satellite peak intensity may be related to the interfacial bonding strength and hardness of the surface system. The interfacial layer of TaAg/NGTi alloy exhibited the highest satellite intensity and maximum hardness value. The increased bonding strength and hardness in the TaAg/NGTi alloy arises due to the negative core charge of the dislocations and neighbor space charge accumulation, as well as electron accumulation in the created semiconductor phases of larger band gap at the interfacial layer. These two factors generate interfacial polarization and enhance the satellite intensity. Consequently, the interfacial bonding strength and hardness of the surface system are improved by the formation of mixed covalent-ionic bonding structures around the dislocation core area and the interfacial layer. The bonding strength relationship by in situ XPS on the metal/TiO 2 interfacial layer may be examined with other noble metals and applied in diverse fields.

Effect of Buckling Modes on the Fatigue Life and Damage Tolerance of Stiffened Structures

NASA Technical Reports Server (NTRS)

Davila, Carlos G.; Bisagni, Chiara; Rose, Cheryl A.

2015-01-01

The postbuckling response and the collapse of composite specimens with a co-cured hat stringer are investigated experimentally and numerically. These specimens are designed to evaluate the postbuckling response and the effect of an embedded defect on the collapse load and the mode of failure. Tests performed using controlled conditions and detailed instrumentation demonstrate that the damage tolerance, fatigue life, and collapse loads are closely tied with the mode of the postbuckling deformation, which can be different between two nominally identical specimens. Modes that tend to open skin/stringer defects are the most damaging to the structure. However, skin/stringer bond defects can also propagate under shearing modes. In the proposed paper, the effects of initial shape imperfections on the postbuckling modes and the interaction between different postbuckling deformations and the propagation of skin/stringer bond defects under quasi-static or fatigue loads will be examined.

Synergistic damage effects of vacuum ultraviolet photons and O2 in SiCOH ultra-low-k dielectric films

NASA Astrophysics Data System (ADS)

Lee, J.; Graves, D. B.

2010-10-01

Damage incurred during plasma processing, leading to increases in dielectric constant k, is a persistent problem with porous ultra-low-k dielectric films, such as SiCOH. Although most of the proposed mechanisms of plasma-induced damage focus on the role of ion bombardment and radical attack, we show that plasma-generated vacuum ultraviolet (VUV) photons can play a role in creating damage leading to increases in the dielectric constant of this material. Using a vacuum beam apparatus with a calibrated VUV lamp, we show that 147 nm VUV photons impacting SiCOH results in post-exposure adsorption and reaction with water vapour from the atmosphere to form silanol bonds, thereby raising the dielectric constant. Furthermore, the level of damage increases synergistically under simultaneous exposure to VUV photons and O2. The vacuum beam photon fluences are representative of typical plasma processes, as measured in a separate plasma tool. Fourier-transform infrared (FTIR) spectroscopy (ex situ) and mass spectrometry (in situ) imply that O2 reacts with methyl radicals formed from scissioned Si-C bonds to create CO2 and H2O, the latter combining with Si dangling bonds to generate more SiOH groups than with photon exposure alone. In addition, sample near-surface diffusivity, manipulated through ion bombardment and sample heating, can be seen to affect this process. These results demonstrate that VUV photo-generated surface reactions can be potent contributors to ultra-low-k dielectric SiCOH film plasma-induced damage, and suggest that they could play analogous roles in other plasma-surface interactions.

High-Resolution Electron Energy Loss Studies of Oxygen, Hydrogen, Nitrogen, Nitric Oxide, and Nitrous Oxide Adsorption on Germanium Surfaces.

NASA Astrophysics Data System (ADS)

Entringer, Anthony G.

The first high resolution electron energy loss spectroscopy (HREELS) studies of the oxidation and nitridation of germanium surfaces are reported. Both single crystal Ge(111) and disordered surfaces were studied. Surfaces were exposed to H, O_2, NO, N _2O, and N, after cleaning in ultra-high vacuum. The Ge surfaces were found to be non-reactive to molecular hydrogen (H_2) at room temperature. Exposure to atomic hydrogen (H) resulted hydrogen adsorption as demonstrated by the presence of Ge-H vibrational modes. The HREEL spectrum of the native oxide of Ge characteristic of nu -GeO_2 was obtained by heating the oxide to 200^circC. Three peaks were observed at 33, 62, and 106 meV for molecular oxygen (O_2) adsorbed on clean Ge(111) at room temperature. These peaks are indicative of dissociative bonding and a dominant Ge-O-Ge bridge structure. Subsequent hydrogen exposure resulted in a shift of the Ge-H stretch from its isolated value of 247 meV to 267 meV, indicative of a dominant +3 oxidation state. A high density of dangling bonds and defects and deeper oxygen penetration at the amorphous Ge surface result in a dilute bridge structure with a predominant +1 oxidation state for similar exposures. Molecules of N_2O decompose at the surfaces to desorbed N_2 molecules and chemisorbed oxygen atoms. In contrast, both oxygen and nitrogen are detected at the surfaces following exposure to NO molecules. Both NO and N_2O appear to dissociate and bond at the top surface layer. Molecular nitrogen (N_2) does not react with the Ge surfaces, however, a precursor Ge nitride is observed at room temperature following exposure to nitrogen atoms and ions. Removal of oxygen by heating of the NO-exposed surface to 550^circC enabled the identification of the Ge-N vibrational modes. These modes show a structure similar to that of germanium nitride. This spectrum is also identical to that of the N-exposed surface heated to 550^circC. Surface phonon modes of the narrow-gap semiconducting compounds Mg _2Sn, Mg_2Ge and Mg _2Si were detected at 29, 32, and 40 meV, respectively. The native oxide of all three show a dominant Mg-O mode at 80 meV. Probable Sn-O, Ge-O, and Si-O modes are also identified. Complete removal of the oxide layer was accomplished only on the Mg_2 Si surface but resulted in no noticeable change in the energy of the surface phonon. Results are compared to the known bulk optical properties of these compounds.

Remote monitoring of bond line defects between a composite panel and a stiffener using distributed piezoelectric sensors

NASA Astrophysics Data System (ADS)

Yu, Xudong; Fan, Zheng; Puliyakote, Sreedhar; Castaings, Michel

2018-03-01

Structural health monitoring (SHM) using ultrasonic guided waves has proven to be attractive for the identification of damage in composite plate-like structures, due to its realization of both significant propagation distances and reasonable sensitivity to defects. However, topographical features such as bends, lap joints, and bonded stiffeners are often encountered in these structures, and they are susceptible to various types of defects as a consequence of stress concentration and cyclic loading during the service life. Therefore, the health condition of such features has to be assessed effectively to ensure the safe operation of the entire structure. This paper proposes a novel feature guided wave (FGW) based SHM strategy, in which proper FGWs are exploited as a screening tool to rapidly interrogate the representative stiffener-adhesive bond-composite skin assembly. An array of sensors permanently attached to the vicinity of the feature is used to capture scattered waves from the localized damage occurring in the bond line. This technique is combined with an imaging approach, and the damage reconstruction is achieved by the synthetic focusing algorithm using these scattered signals. The proposed SHM scheme is implemented in both the 3D finite element simulation and the experiment, and the results are in good agreement, demonstrating the feasibility of such SHM strategy.

Investigation of a Photoelectrochemical Passivated ZnO-Based Glucose Biosensor

PubMed Central

Lee, Ching-Ting; Chiu, Ying-Shuo; Ho, Shu-Ching; Lee, Yao-Jung

2011-01-01

A vapor cooling condensation system was used to deposit high quality intrinsic ZnO thin films and intrinsic ZnO nanorods as the sensing membrane of extended-gate field-effect-transistor (EGFET) glucose biosensors. The sensing sensitivity of the resulting glucose biosensors operated in the linear range was 13.4 μA mM−1 cm−2. To improve the sensing sensitivity of the ZnO-based glucose biosensors, the photoelectrochemical method was utilized to passivate the sidewall surfaces of the ZnO nanorods. The sensing sensitivity of the ZnO-based glucose biosensors with passivated ZnO nanorods was significantly improved to 20.33 μA mM−1 cm−2 under the same measurement conditions. The experimental results verified that the sensing sensitivity improvement was the result of the mitigation of the Fermi level pinning effect caused by the dangling bonds and the surface states induced on the sidewall surface of the ZnO nanorods. PMID:22163867

CW and pulsed electrically detected magnetic resonance spectroscopy at 263 GHz/12 T on operating amorphous silicon solar cells

NASA Astrophysics Data System (ADS)

Akhtar, W.; Schnegg, A.; Veber, S.; Meier, C.; Fehr, M.; Lips, K.

2015-08-01

Here we describe a new high frequency/high field continuous wave and pulsed electrically detected magnetic resonance (CW EDMR and pEDMR) setup, operating at 263 GHz and resonance fields between 0 and 12 T. Spin dependent transport in illuminated hydrogenated amorphous silicon p-i-n solar cells at 5 K and 90 K was studied by in operando 263 GHz CW and pEDMR alongside complementary X-band CW EDMR. Benefiting from the superior resolution at 263 GHz, we were able to better resolve EDMR signals originating from spin dependent hopping and recombination processes. 5 K EDMR spectra were found to be dominated by conduction and valence band tail states involved in spin dependent hopping, with additional contributions from triplet exciton states. 90 K EDMR spectra could be assigned to spin pair recombination involving conduction band tail states and dangling bonds as the dominating spin dependent transport process, with additional contributions from valence band tail and triplet exciton states.

Au Colloids Formed by Ion Implantation in Muscovite Mica Studied by Vibrational and Electronic Spectroscopes and Atomic Force Microscopy

NASA Technical Reports Server (NTRS)

Tung, Y. S.; Henderson, D. O.; Mu, R.; Ueda, A.; Collins, W. E.; White, C. W.; Zuhr, R. A.; Zhu, Jane G.

1997-01-01

Au was implanted into the (001) surface of Muscovite mica at an energy of 1.1 MeV and at doses of 1, 3, 6, and 10 x 10(exp 16) ions/cu cm. Optical spectra of the as-implanted samples revealed a peak at 2.28 eV (545 nm) which is attributed to the surface plasmon absorption of Au colloids. The infrared reflectance measurements show a decreasing reflectivity with increasing ion dose in the Si-O stretching region (900-1200 /cm). A new peak observed at 967 /cm increases with the ion dose and is assigned to an Si-O dangling bond. Atomic force microscopy images of freshly cleaved samples implanted with 6 and 10 x 10(exp 16) ions/sq cm indicated metal colloids with diameters between 0.9- 1.5 nm. AFM images of the annealed samples showed irregularly shaped structures with a topology that results from the fusion of smaller colloids.

DNA Origami-Graphene Hybrid Nanopore for DNA Detection.

PubMed

Barati Farimani, Amir; Dibaeinia, Payam; Aluru, Narayana R

2017-01-11

DNA origami nanostructures can be used to functionalize solid-state nanopores for single molecule studies. In this study, we characterized a nanopore in a DNA origami-graphene heterostructure for DNA detection. The DNA origami nanopore is functionalized with a specific nucleotide type at the edge of the pore. Using extensive molecular dynamics (MD) simulations, we computed and analyzed the ionic conductivity of nanopores in heterostructures carpeted with one or two layers of DNA origami on graphene. We demonstrate that a nanopore in DNA origami-graphene gives rise to distinguishable dwell times for the four DNA base types, whereas for a nanopore in bare graphene, the dwell time is almost the same for all types of bases. The specific interactions (hydrogen bonds) between DNA origami and the translocating DNA strand yield different residence times and ionic currents. We also conclude that the speed of DNA translocation decreases due to the friction between the dangling bases at the pore mouth and the sequencing DNA strands.

Use of low energy hydrogen ion implants in high efficiency crystalline silicon solar cells

NASA Technical Reports Server (NTRS)

Fonash, S. J.; Singh, R.

1985-01-01

This program is a study of the use of low energy hydrogen ion implantation for high efficiency crystalline silicon solar cells. The first quarterly report focuses on two tasks of this program: (1) an examination of the effects of low energy hydrogen implants on surface recombination speed; and (2) an examination of the effects of hydrogen on silicon regrowth and diffusion in silicon. The first part of the project focussed on the measurement of surface properties of hydrogen implanted silicon. Low energy hydrogen ions when bombarded on the silicon surface will create structural damage at the surface, deactivate dopants and introduce recombination centers. At the same time the electrically active centers such as dangling bonds will be passivated by these hydrogen ions. Thus hydrogen is expected to alter properties such as the surface recombination velocity, dopant profiles on the emitter, etc. In this report the surface recombination velocity of a hydrogen emplanted emitter was measured.

Role of humidity in reducing the friction of graphene layers on textured surfaces

NASA Astrophysics Data System (ADS)

Li, Zheng-yang; Yang, Wen-jing; Wu, Yan-ping; Wu, Song-bo; Cai, Zhen-bing

2017-05-01

A multiple-layer graphene was prepared on steel surface to reduce friction and wear. A graphene-containing ethanol solution was dripped on the steel surface, and several layers of graphene flakes were deposited on the surface after ethanol evaporated. Tribological performance of graphene-contained surface (GCS) was induced by reciprocating ball against plate contact in different RH (0% (dry nitrogen), 30%, 60%, and 90%). Morphology and wear scar were analyzed by OM, 2D profile, SEM, Raman spectroscopy, and XPS. Results show that GCS can substantially reduce the wear and coefficient of friction (COF) in 60% relative humidity (RH). Low COF occurs due to graphene layer providing a small shear stress on the friction interface. Meanwhile, conditions of high RH and textured surface could make the low COF persist for a longer time. High moisture content can stabilize and protect the graphene C-network from damage due to water dissociative chemisorption with carbon dangling bonds, and the textured surface was attributed to release graphene layer stored in the dimple.

Two-dimensional electronic transport and surface electron accumulation in MoS2.

PubMed

Siao, M D; Shen, W C; Chen, R S; Chang, Z W; Shih, M C; Chiu, Y P; Cheng, C-M

2018-04-12

Because the surface-to-volume ratio of quasi-two-dimensional materials is extremely high, understanding their surface characteristics is crucial for practically controlling their intrinsic properties and fabricating p-type and n-type layered semiconductors. Van der Waals crystals are expected to have an inert surface because of the absence of dangling bonds. However, here we show that the surface of high-quality synthesized molybdenum disulfide (MoS 2 ) is a major n-doping source. The surface electron concentration of MoS 2 is nearly four orders of magnitude higher than that of its inner bulk. Substantial thickness-dependent conductivity in MoS 2 nanoflakes was observed. The transfer length method suggested the current transport in MoS 2 following a two-dimensional behavior rather than the conventional three-dimensional mode. Scanning tunneling microscopy and angle-resolved photoemission spectroscopy measurements confirmed the presence of surface electron accumulation in this layered material. Notably, the in situ-cleaved surface exhibited a nearly intrinsic state without electron accumulation.

Quantum Degeneracy in Atomic Point Contacts Revealed by Chemical Force and Conductance

NASA Astrophysics Data System (ADS)

Sugimoto, Yoshiaki; Ondráček, Martin; Abe, Masayuki; Pou, Pablo; Morita, Seizo; Perez, Ruben; Flores, Fernando; Jelínek, Pavel

2013-09-01

Quantum degeneracy is an important concept in quantum mechanics with large implications to many processes in condensed matter. Here, we show the consequences of electron energy level degeneracy on the conductance and the chemical force between two bodies at the atomic scale. We propose a novel way in which a scanning probe microscope can detect the presence of degenerate states in atomic-sized contacts even at room temperature. The tunneling conductance G and chemical binding force F between two bodies both tend to decay exponentially with distance in a certain distance range, usually maintaining direct proportionality G∝F. However, we show that a square relation G∝F2 arises as a consequence of quantum degeneracy between the interacting frontier states of the scanning tip and a surface atom. We demonstrate this phenomenon on the Si(111)-(7×7) surface reconstruction where the Si adatom possesses a strongly localized dangling-bond state at the Fermi level.

Self-Assembled Si(111) Surface States: 2D Dirac Material for THz Plasmonics.

PubMed

Wang, Z F; Liu, Feng

2015-07-10

Graphene, the first discovered 2D Dirac material, has had a profound impact on science and technology. In the last decade, we have witnessed huge advances in graphene related fundamental and applied research. Here, based on first-principles calculations, we propose a new 2D Dirac band on the Si(111) surface with 1/3 monolayer halogen coverage. The sp(3) dangling bonds form a honeycomb superstructure on the Si(111) surface that results in an anisotropic Dirac band with a group velocity (∼10(6)  m/s) comparable to that in graphene. Most remarkably, the Si-based surface Dirac band can be used to excite a tunable THz plasmon through electron-hole doping. Our results demonstrate a new way to design Dirac states on a traditional semiconductor surface, so as to make them directly compatible with Si technology. We envision this new type of Dirac material to be generalized to other semiconductor surfaces with broad applications.

Self-Assembled Si(111) Surface States: 2D Dirac Material for THz Plasmonics

NASA Astrophysics Data System (ADS)

Wang, Z. F.; Liu, Feng

2015-07-01

Graphene, the first discovered 2D Dirac material, has had a profound impact on science and technology. In the last decade, we have witnessed huge advances in graphene related fundamental and applied research. Here, based on first-principles calculations, we propose a new 2D Dirac band on the Si(111) surface with 1 /3 monolayer halogen coverage. The s p3 dangling bonds form a honeycomb superstructure on the Si(111) surface that results in an anisotropic Dirac band with a group velocity (˜106 m /s ) comparable to that in graphene. Most remarkably, the Si-based surface Dirac band can be used to excite a tunable THz plasmon through electron-hole doping. Our results demonstrate a new way to design Dirac states on a traditional semiconductor surface, so as to make them directly compatible with Si technology. We envision this new type of Dirac material to be generalized to other semiconductor surfaces with broad applications.

Tuning a Schottky barrier of epitaxial graphene/4H-SiC (0001) by hydrogen intercalation

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

Dharmaraj, P.; Justin Jesuraj, P.; Jeganathan, K., E-mail: kjeganathan@yahoo.com

We report the electron transport properties of epitaxial graphene (EG) grown on 4H-SiC (0001) by low energy electron-beam irradiation. As-grown EG (AEG) on SiC interface exhibits rectifying current-voltage characteristics with a low Schottky barrier (SB) of 0.55 ± 0.05 eV and high reverse current leakage. The SB of AEG/SiC junction is extremely impeded by the Fermi level pinning (FLP) above the Dirac point due to charged states at the interface. Nevertheless, a gentle hydrogen intercalation at 900 °C enables the alleviation of both FLP and carrier scattering owing to the saturation of dangling bonds as evidenced by the enhancement of SB (0.75 ± 0.05 eV) and highmore » electron mobility well excess of 6000 cm{sup 2} V{sup −1} s{sup −1}.« less

Impurity gettering in silicon using cavities formed by helium implantation and annealing

DOEpatents

Myers, Jr., Samuel M.; Bishop, Dawn M.; Follstaedt, David M.

1998-01-01

Impurity gettering in silicon wafers is achieved by a new process consisting of helium ion implantation followed by annealing. This treatment creates cavities whose internal surfaces are highly chemically reactive due to the presence of numerous silicon dangling bonds. For two representative transition-metal impurities, copper and nickel, the binding energies at cavities were demonstrated to be larger than the binding energies in precipitates of metal silicide, which constitutes the basis of most current impurity gettering. As a result the residual concentration of such impurities after cavity gettering is smaller by several orders of magnitude than after precipitation gettering. Additionally, cavity gettering is effective regardless of the starting impurity concentration in the wafer, whereas precipitation gettering ceases when the impurity concentration reaches a characteristic solubility determined by the equilibrium phase diagram of the silicon-metal system. The strong cavity gettering was shown to induce dissolution of metal-silicide particles from the opposite side of a wafer.

Impurity gettering in silicon using cavities formed by helium implantation and annealing

DOEpatents

Myers, S.M. Jr.; Bishop, D.M.; Follstaedt, D.M.

1998-11-24

Impurity gettering in silicon wafers is achieved by a new process consisting of helium ion implantation followed by annealing. This treatment creates cavities whose internal surfaces are highly chemically reactive due to the presence of numerous silicon dangling bonds. For two representative transition-metal impurities, copper and nickel, the binding energies at cavities were demonstrated to be larger than the binding energies in precipitates of metal silicide, which constitutes the basis of most current impurity gettering. As a result the residual concentration of such impurities after cavity gettering is smaller by several orders of magnitude than after precipitation gettering. Additionally, cavity gettering is effective regardless of the starting impurity concentration in the wafer, whereas precipitation gettering ceases when the impurity concentration reaches a characteristic solubility determined by the equilibrium phase diagram of the silicon-metal system. The strong cavity gettering was shown to induce dissolution of metal-silicide particles from the opposite side of a wafer. 4 figs.

WSe2 nanoribbons: new high-performance thermoelectric materials.

PubMed

Chen, Kai-Xuan; Luo, Zhi-Yong; Mo, Dong-Chuan; Lyu, Shu-Shen

2016-06-28

In this work, for the first time, we systematically investigate the ballistic transport properties of WSe2 nanoribbons using first-principles methods. Armchair nanoribbons with narrow ribbon width are mostly semiconductive but the zigzag nanoribbons are metallic. Surprisingly, an enhancement in thermoelectric performance is discovered moving from monolayers to nanoribbons, especially armchair ones. The maximum room-temperature thermoelectric figure of merit of 2.2 for an armchair nanoribbon is discovered. This may be contributed to by the effects of the disordered edges, owing to the existence of dangling bonds at the ribbon edge. H-passivation has turned out to be an effective way to stabilize the edge atoms, which enhances the thermodynamic stability of the nanoribbons. In addition, after H-passivation, all of the armchair nanoribbons exhibit semiconductive properties with similar band gaps (∼1.3 eV). Our work provides instructional theoretical evidence for the application of armchair WSe2 nanoribbons as promising thermoelectric materials. The enhancement mechanism of the disordered edge effect can also encourage further exploration to achieve outstanding thermoelectric materials.

Control of the kerf size and microstructure in Inconel 738 superalloy by femtosecond laser beam cutting

NASA Astrophysics Data System (ADS)

Wei, J.; Ye, Y.; Sun, Z.; Liu, L.; Zou, G.

2016-05-01

Femtosecond laser beam cutting is becoming widely used to meet demands for increasing accuracy in micro-machining. In this paper, the effects of processing parameters in femtosecond laser beam cutting on the kerf size and microstructure in Inconel 738 have been investigated. The defocus, pulse width and scanning speed were selected to study the controllability of the cutting process. Adjusting and matching the processing parameters was a basic enhancement method to acquire well defined kerf size and the high-quality ablation of microstructures, which has contributed to the intensity clamping effect. The morphology and chemical compositions of these microstructures on the cut surface have been characterized by a scanning electron microscopy equipped with an energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Additionally, the material removal mechanism and oxidation mechanism on the Inconel 738 cut surface have also been discussed on the basis of the femtosecond laser induced normal vaporization or phase explosion, and trapping effect of the dangling bonds.

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

NASA Astrophysics Data System (ADS)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

Injectible candidate sealants for fetal membrane repair: Bonding and toxicity in vitro

PubMed Central

Bilic, Grozdana; Brubaker, Carrie; Messersmith, Phillip B.; Mallik, Ajit S.; Quinn, Thomas M.; Haller, Claudia; Done, Elisa; Gucciardo, Leonardo; Zeisberger, Steffen M.; Zimmermann, Roland; Deprest, Jan; Zisch, Andreas H.

2010-01-01

Objective This study was undertaken to test injectible surgical sealants that are biocompatible with fetal membranes, eventually for closure of iatrogenic membrane defects. Study Design Dermabond, Histoacryl, Tissucol fibrin glue, and three types of in situ forming poly(ethylene glycol)-based polymer hydrogels were tested for acute toxicity upon direct contact with fetal membranes for 24h. For determination of elution toxicity, extracts of sealants were incubated on amnion cell cultures for 72h. Bonding and toxicity was assessed through morphological and/or biochemical analysis. Results Extracts of all adhesives were non-toxic for cultured cells. However, only Tissucol and one type of poly(ethylene glycol)-based hydrogel, mussel-mimetic tissue adhesive, showed efficient, non-disruptive, non-toxic bonding to fetal membranes. Mussel-mimetic tissue adhesive applied over membrane defects created with a 3.5 mm trocar accomplished leak-proof closure that withstood membrane stretch in an in vitro model. Conclusion A synthetic hydrogel-type tissue adhesive emerged as potential sealing modality for iatrogenic membrane defects that merits further evaluation in vivo. PMID:20096254

A randomized controlled clinical trial of a HEMA-free all-in-one adhesive in non-carious cervical lesions at 1 year.

PubMed

Van Landuyt, K L; Peumans, M; Fieuws, S; De Munck, J; Cardoso, M V; Ermis, R B; Lambrechts, P; Van Meerbeek, B

2008-10-01

One-step self-etch adhesives are the most recent generation of adhesives introduced onto the market. The objective of this randomized controlled clinical trial was to test the hypothesis that a one-step self-etch adhesive performs equally well as a conventional three-step etch&rinse adhesive (gold standard). Fifty-two patients had 267 non-carious cervical lesions restored with Gradia Direct Anterior (GC). These composite restorations were bonded either with the 'all-in-one' adhesive G-Bond (GC) or with the three-step etch&rinse adhesive Optibond FL (Kerr). The restorations were evaluated after 6 and 12 months clinical service regarding their retention, marginal integrity and discoloration, caries occurrence, preservation of tooth vitality and post-operative sensitivity. Retention loss, severe marginal defects and/or discoloration that needed intervention (repair or replacement) and the occurrence of caries were considered as clinical failures. A logistic regression analysis with generalized estimating equations was used to account for the clustered data (multiple restorations per patient). The recall rate at 1 year was 98%. The statistical analysis revealed a relatively low patient factor, indicating that supplementary information could be obtained from the additional restorations placed per patient. The retention rate for G-Bond was 98.5% compared to 99.3% for Optibond FL, due to the retention loss of two and one restorations, respectively. There were no significant differences between the two adhesives regarding the evaluated parameters except for the presence of small enamel marginal defects with G-Bond. After 12 months, the simplified one-step G-Bond and the three-step Optibond FL were clinically equally successful, even though both adhesives were characterized by progressive degradation of marginal adaptation, and G-Bond exhibited more small enamel marginal defects.

Suppression of interfacial voids formation during silane (SiH4)-based silicon oxide bonding with a thin silicon nitride capping layer

NASA Astrophysics Data System (ADS)

Lee, Kwang Hong; Bao, Shuyu; Wang, Yue; Fitzgerald, Eugene A.; Seng Tan, Chuan

2018-01-01

The material properties and bonding behavior of silane-based silicon oxide layers deposited by plasma-enhanced chemical vapor deposition were investigated. Fourier transform infrared spectroscopy was employed to determine the chemical composition of the silicon oxide films. The incorporation of hydroxyl (-OH) groups and moisture absorption demonstrates a strong correlation with the storage duration for both as-deposited and annealed silicon oxide films. It is observed that moisture absorption is prevalent in the silane-based silicon oxide film due to its porous nature. The incorporation of -OH groups and moisture absorption in the silicon oxide films increase with the storage time (even in clean-room environments) for both as-deposited and annealed silicon oxide films. Due to silanol condensation and silicon oxidation reactions that take place at the bonding interface and in the bulk silicon, hydrogen (a byproduct of these reactions) is released and diffused towards the bonding interface. The trapped hydrogen forms voids over time. Additionally, the absorbed moisture could evaporate during the post-bond annealing of the bonded wafer pair. As a consequence, defects, such as voids, form at the bonding interface. To address the problem, a thin silicon nitride capping film was deposited on the silicon oxide layer before bonding to serve as a diffusion barrier to prevent moisture absorption and incorporation of -OH groups from the ambient. This process results in defect-free bonded wafers.

Nanocarbon: Defect Architectures and Properties

NASA Astrophysics Data System (ADS)

Vuong, Amanda

The allotropes of carbon make its solid phases amongst the most diverse of any element. It can occur naturally as graphite and diamond, which have very different properties that make them suitable for a wide range of technological and commercial purposes. Recent developments in synthetic carbon include Highly Oriented Pyrolytic Graphite (HOPG) and nano-carbons, such as fullerenes, nanotubes and graphene. The main industrial application of bulk graphite is as an electrode material in steel production, but in purified nuclear graphite form, it is also used as a moderator in Advanced Gas-cooled Reactors across the United Kingdom. Both graphene and graphite are damaged over time when subjected to bombardment by electrons, neutrons or ions, and these have a wide range of effects on their physical and electrical properties, depending on the radiation flux and temperature. This research focuses on intrinsic defects in graphene and dimensional change in nuclear graphite. The method used here is computational chemistry, which complements physical experiments. Techniques used comprise of density functional theory (DFT) and molecular dynamics (MD), which are discussed in chapter 2 and chapter 3, respectively. The succeeding chapters describe the results of simulations performed to model defects in graphene and graphite. Chapter 4 presents the results of ab initio DFT calculations performed to investigate vacancy complexes that are formed in AA stacked bilayer graphene. In AB stacking, carbon atoms surrounding the lattice vacancies can form interlayer structures with sp2 bonding that are lower in energy compared to in-plane reconstructions. From the investigation of AA stacking, sp2 interlayer bonding of adjacent multivacancy defects in registry creates a type of stable sp2 bonded wormhole between the layers. Also, a new class of mezzanine structure characterised by sp3 interlayer bonding, resembling a prismatic vacancy loop has also been identified. The mezzanine, which is a V6 hexavacancy variant, where six sp3 carbon atoms sit midway between two carbon layers and bond to both, is substantially more stable than any other vacancy aggregate in AA stacked layers. Chapter 5 presents the results of ab initio DFT calculations performed to investigate the wormhole and mezzanine defect that were identified in chapter 4 and the ramp defect discovered by Trevethan et al.. DFT calculations were performed on these defects in twisted bilayer graphene. From the investigation of vacancy complexes in twisted bilayer graphene, it is found that vacancy complexes are unstable in the twisted region and are more favourable in formation energy when the stacking arrangement is close to AA or AB stacking. It has also been discovered that the ramp defect is more stable in the twisted bilayer graphene compared to the mezzanine defect. Chapter 6 presents the results of ab initio DFT calculations performed to investigate a form of extending defect, prismatic edge dislocation. Suarez-Martinez et al.'s research suggest the armchair core is disconnected from any other layer, whilst the zigzag core is connected. In the investigation here, the curvature of the mezzanine defect allows it to swing between the armchair, zigzag and Klein in the AA stacking. For the AB stacking configuration, the armchair and zigzag core are connected from any other layer. Chapter 7 present results of MD simulations using the adaptive intermolecular reactive empirical bond order (AIREBO) potential to investigate the dimensional change of graphite due to the formation of vacancies present in a single crystal. It has been identified that there is an expansion along the c-axis, whilst a contraction along the a- and b- axes due to the coalescence of vacancy forming in-plane and between the layers. The results here are in good agreement with experimental studies of low temperature irradiation. The final chapter gives conclusions to this work.

Turning things downside up: Adsorbate induced water flipping on Pt(111)

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

Kimmel, Greg A., E-mail: gregory.kimmel@pnnl.gov, E-mail: bruce.kay@pnnl.gov; Zubkov, Tykhon; Smith, R. Scott

2014-11-14

We have examined the adsorption of the weakly bound species N{sub 2}, O{sub 2}, CO, and Kr on the (√(37)×√(37))R25.3{sup ∘} water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy, and temperature programmed desorption. In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O{sub 2} have little effect on the structure and vibrational spectrum of the “√(37)”more » water monolayer while adsorption of both N{sub 2}, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “√(37)” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.« less

Role of Surface Chemistry in Grain Adhesion and Dissipation during Collisions of Silica Nanograins

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

Quadery, Abrar H.; Tucker, William C.; Dove, Adrienne R.

2017-08-01

The accretion of dust grains to form larger objects, including planetesimals, is a central problem in planetary science. It is generally thought that weak van der Waals interactions play a role in accretion at small scales where gravitational attraction is negligible. However, it is likely that in many instances, chemical reactions also play an important role, and the particular chemical environment on the surface could determine the outcomes of dust grain collisions. Using atomic-scale simulations of collisional aggregation of nanometer-sized silica (SiO{sub 2}) grains, we demonstrate that surface hydroxylation can act to weaken adhesive forces and reduce the ability ofmore » mineral grains to dissipate kinetic energy during collisions. The results suggest that surface passivation of dangling bonds, which generally is quite complete in an Earth environment, should tend to render mineral grains less likely to adhere during collisions. It is shown that during collisions, interactions scale with interparticle distance in a manner consistent with the formation of strong chemical bonds. Finally, it is demonstrated that in the case of collisions of nanometer-scale grains with no angular momentum, adhesion can occur even for relative velocities of several kilometers per second. These results have significant implications for early planet formation processes, potentially expanding the range of collision velocities over which larger dust grains can form.« less

Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure

NASA Astrophysics Data System (ADS)

Liu, Xiaoyu; Xu, Jingping; Liu, Lu; Cheng, Zhixiang; Huang, Yong; Gong, Jingkang

2017-08-01

The effects of different NH3-plasma treatment procedures on interfacial and electrical properties of Ge MOS capacitors with stacked gate dielectric of HfTiON/TaON were investigated. The NH3-plasma treatment was performed at different steps during fabrication of the stacked gate dielectric, i.e. before or after interlayer (TaON) deposition, or after deposition of high-k dielectric (HfTiON). It was found that the excellent interface quality with an interface-state density of 4.79 × 1011 eV-1 cm-2 and low gate leakage current (3.43 × 10-5 A/cm2 at {V}{{g}}=1 {{V}}) could be achieved for the sample with NH3-plasma treatment directly on the Ge surface before TaON deposition. The involved mechanisms are attributed to the fact that the NH3-plasma can directly react with the Ge surface to form more Ge-N bonds, i.e. more GeO x Ny, which effectively blocks the inter-diffusion of elements and suppresses the formation of unstable GeO x interfacial layer, and also passivates oxygen vacancies and dangling bonds near/at the interface due to more N incorporation and decomposed H atoms from the NH3-plasma. Project supported by the National Natural Science Foundation of China (Nos. 61176100, 61274112).

Supramolecular self-assembly on the B-Si(111)-(√3x√3) R30° surface: From single molecules to multicomponent networks

NASA Astrophysics Data System (ADS)

Makoudi, Younes; Jeannoutot, Judicaël; Palmino, Frank; Chérioux, Frédéric; Copie, Guillaume; Krzeminski, Christophe; Cleri, Fabrizio; Grandidier, Bruno

2017-09-01

Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces.

Intramolecular proton transfer boosts water oxidation catalyzed by a Ru complex

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

Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, J.

We introduce a new family of complexes with the general formula [Ru n(tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda 2– being [2,2':6',2"-terpyridine]-6,6"-dicarboxylate, including complex [Ru IV(OH)(tda-κ-N 3O)(py) 2] +, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), includingmore » solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s –1 at pH 7.0 and 50,000 s –1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.« less

Intramolecular proton transfer boosts water oxidation catalyzed by a Ru complex

DOE PAGES

Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, J.; ...

2015-07-30

We introduce a new family of complexes with the general formula [Ru n(tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda 2– being [2,2':6',2"-terpyridine]-6,6"-dicarboxylate, including complex [Ru IV(OH)(tda-κ-N 3O)(py) 2] +, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), includingmore » solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s –1 at pH 7.0 and 50,000 s –1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.« less

Theoretical evidence for unexpected O-rich phases at corners of MgO surfaces

NASA Astrophysics Data System (ADS)

Bhattacharya, Saswata; Berger, Daniel; Reuter, Karsten; Ghiringhelli, Luca M.; Levchenko, Sergey V.

2017-12-01

Realistic oxide materials are often semiconductors, in particular at elevated temperatures, and their surfaces contain undercoordinated atoms at structural defects such as steps and corners. Using hybrid density-functional theory and ab initio atomistic thermodynamics, we investigate the interplay of bond-making, bond-breaking, and charge-carrier trapping at the corner defects at the (100) surface of a p -doped MgO in thermodynamic equilibrium with an O2 atmosphere. We show that by manipulating the coordination of surface atoms, one can drastically change and even reverse the order of stability of reduced versus oxidized surface sites.

Applied algorithm in the liner inspection of solid rocket motors

NASA Astrophysics Data System (ADS)

Hoffmann, Luiz Felipe Simões; Bizarria, Francisco Carlos Parquet; Bizarria, José Walter Parquet

2018-03-01

In rocket motors, the bonding between the solid propellant and thermal insulation is accomplished by a thin adhesive layer, known as liner. The liner application method involves a complex sequence of tasks, which includes in its final stage, the surface integrity inspection. Nowadays in Brazil, an expert carries out a thorough visual inspection to detect defects on the liner surface that may compromise the propellant interface bonding. Therefore, this paper proposes an algorithm that uses the photometric stereo technique and the K-nearest neighbor (KNN) classifier to assist the expert in the surface inspection. Photometric stereo allows the surface information recovery of the test images, while the KNN method enables image pixels classification into two classes: non-defect and defect. Tests performed on a computer vision based prototype validate the algorithm. The positive results suggest that the algorithm is feasible and when implemented in a real scenario, will be able to help the expert in detecting defective areas on the liner surface.

Acoustic Monitoring of Adhesive Bond Curing in Wood Laminates.

NASA Astrophysics Data System (ADS)

Biernacki, Jacek Marek

Challenges in manufacturing of wood products, such as glulam, include difficulty in controlling bonding variables and assessing bond quality. This dissertation investigates an ultrasonic method as a means of monitoring of curing and assessing bond quality in wood laminates. The effect of curing on ultrasonic transmission was studied using specimens of clear Douglas-fir, 100 x 200 x 600 mm, with the adhesive bond in the center of the specimen. Monitoring was performed simultaneously at normal and angular (5 ^circ nominal) incidence to the bond plane. Acoustic measurements were supplemented with destructive cure monitoring, standard bond strength measurement, monitoring of bulk viscosity curing, gel time measurement, and microscopic (SEM) examination. Angular incidence gave greater sensitivity to bond quality and curing status than did normal incidence. Analysis of wave propagation showed that displacement for transmission at a small angle (on the order of 5^circ ) was nearly parallel to the bond, which seems to explain greater sensitivity of angular incidence. Experimental results showed that this method was effective in detection of curing phases, such as spread, penetration, and hardening, defective bonds, and the effect of clamping pressure. An "unloading effect", measured as a relative transmission reduction after the clamping load was released, was sensitive to defective bonds, including uncured (kissing), underspread, and uneven spread bonds. Thick bonds (0.5 and 1.0 mm) caused the greatest increase in transmission, since waves at start of curing were highly attenuated. In angular transmission, thick-bond curing curves showed a characteristic inflection, which may be used to identify thick bonds and measure the curing rate. The results of this dissertation could be utilized to develop commercial systems in glulam manufacturing, which could evaluate: (a) phase of and completion of curing (b) bond quality (c) optimum clamping pressure. Similar systems could also be developed to monitor lumber and panel products curing at high temperature, such as LVL (laminated veneer lumber), OSB (oriented strandboard) and particleboard.

Coordination modes of multidentate ligands in fac-[Re(CO)(3)(polyaminocarboxylate)] analogues of (99m)Tc radiopharmaceuticals. dependence on aqueous solution reaction conditions.

PubMed

Lipowska, Malgorzata; He, Haiyang; Xu, Xiaolong; Taylor, Andrew T; Marzilli, Patricia A; Marzilli, Luigi G

2010-04-05

We study Re analogues of (99m)Tc renal agents to interpret previous results at the (99m)Tc tracer level. The relative propensities of amine donors versus carboxylate oxygen donors of four L = polyaminocarboxylate ligands to coordinate in fac-[Re(I)(CO)(3)L](n) complexes were assessed by examining the reaction of fac-[Re(I)(CO)(3)(H(2)O)(3)](+) under conditions differing in acidity and temperature. All four L [N,N-bis-(2-aminoethyl)glycine (DTGH), N,N-ethylenediaminediacetic acid, diethylenetriamine-N-malonic acid, and diethylenetriamine-N-acetic acid] can coordinate as tridentate ligands while creating a dangling chain terminated in a carboxyl group. Dangling carboxyl groups facilitate renal clearance in fac-[(99m)Tc(I)(CO)(3)L](n) agents. Under neutral conditions, the four ligands each gave two fac-[Re(I)(CO)(3)L](n) products with HPLC traces correlating well with known traces of the fac-[(99m)Tc(I)(CO)(3)L](n) mixtures. Such mixtures are common in renal agents because the needed dangling carboxyl group can compete for a coordination site. However, the HPLC separations needed to assess the biodistribution of a single tracer are impractical in a clinical setting. One goal in investigating this Re chemistry is to identify conditions for avoiding this problem of mixtures in preparations of fac-[(99m)Tc(I)(CO)(3)L](n) renal tracers. After separation and isolation of the fac-[Re(I)(CO)(3)L](n) products, NMR analysis of all products and single crystal X-ray crystallographic analysis of both DTGH products, as well as one product each from the other L, allowed us to establish coordination mode unambiguously. The product favored in acidic conditions has a dangling amine chain and more bound oxygen. The product favored in basic conditions has a dangling carboxyl chain and more bound nitrogen. At the elevated temperatures used for simulating tracer preparation, equilibration was facile (ca. 1 h or less), allowing selective formation of one product by utilizing acidic or basic conditions. The results of this fundamental study offer protocols and guidance useful for the design and preparation of fac-[(99m)Tc(I)(CO)(3)L](n) agents consisting of a single tracer.

Role of Defects on Regioselectivity of Nano Pristine Graphene.

PubMed

Kudur Jayaprakash, Gururaj; Casillas, Norberto; Astudillo-Sánchez, Pablo D; Flores-Moreno, Roberto

2016-11-17

Here analytical Fukui functions based on density functional theory are applied to investigate the redox reactivity of pristine and defected graphene lattices. A carbon H-terminated graphene structure (with 96 carbon atoms) and a graphene defected surface with Stone-Wales rearrangement and double vacancy defects are used as models. Pristine sp 2 -hybridized, hexagonal arranged carbon atoms exhibit a symmetric reactivity. In contrast, common carbon atoms at reconstructed polygons in Stone-Wales and double vacancy graphene display large reactivity variations. The improved reactivity and the regioselectivity at defected graphene is correlated to structural changes that caused carbon-carbon bond length variations at defected zones.

System-size convergence of point defect properties: The case of the silicon vacancy

NASA Astrophysics Data System (ADS)

Corsetti, Fabiano; Mostofi, Arash A.

2011-07-01

We present a comprehensive study of the vacancy in bulk silicon in all its charge states from 2+ to 2-, using a supercell approach within plane-wave density-functional theory, and systematically quantify the various contributions to the well-known finite size errors associated with calculating formation energies and stable charge state transition levels of isolated defects with periodic boundary conditions. Furthermore, we find that transition levels converge faster with respect to supercell size when only the Γ-point is sampled in the Brillouin zone, as opposed to a dense k-point sampling. This arises from the fact that defect level at the Γ-point quickly converges to a fixed value which correctly describes the bonding at the defect center. Our calculated transition levels with 1000-atom supercells and Γ-point only sampling are in good agreement with available experimental results. We also demonstrate two simple and accurate approaches for calculating the valence band offsets that are required for computing formation energies of charged defects, one based on a potential averaging scheme and the other using maximally-localized Wannier functions (MLWFs). Finally, we show that MLWFs provide a clear description of the nature of the electronic bonding at the defect center that verifies the canonical Watkins model.

Hydrophilic Graphene Preparation from Gallic Acid Modified Graphene Oxide in Magnesium Self-Propagating High Temperature Synthesis Process

NASA Astrophysics Data System (ADS)

Cao, Lei; Li, Zhenhuan; Su, Kunmei; Cheng, Bowen

2016-10-01

Hydrophilic graphene sheets were synthesized from a mixture of magnesium and gallic acid (GA) modified graphene oxide (GO) in a self-propagating high-temperature synthesis (SHS) process, and hydrophilic graphene sheets displayed the higher C/O ratio (16.36), outstanding conductivity (~88900 S/m) and excellent water-solubility. GO sheets were connected together by GA, and GA was captured to darn GO structure defects through the formation of hydrogen bonds and ester bonds. In SHS process, the most oxygen ions of GO reacted with magnesium to prevent the escape of carbon dioxide and carbon monoxide to from the structure defects associated with vacancies, and GA could take place the high-temperature carbonization, during which a large-area graphene sheets formed with a part of the structure defects being repaired. When only GO was reduced by magnesium in SHS process, and the reduced GO (rGO) exhibited the smaller sheets, the lower C/O ratio (15.26), the weaker conductivity (4200 S/m) and the poor water-solubility because rGO inevitably left behind carbon vacancies and topological defects. Therefore, the larger sheet, less edge defects and free structure defects associated with vacancies play a key role for graphene sheets good dispersion in water.

Subsurface defect detection in first layer of pavement structure and reinforced civil engineering structure by FRP bonding using active infrared thermography

NASA Astrophysics Data System (ADS)

Dumoulin, Jean; Ibos, Laurent

2010-05-01

In many countries road network ages while road traffic and maintenance costs increase. Nowadays, thousand and thousand kilometers of roads are each year submitted to surface distress survey. They generally lean on pavement surface imaging measurement techniques, mainly in the visible spectrum, coupled with visual inspection or image processing detection of emergent distresses. Nevertheless, optimisation of maintenance works and costs requires an early detection of defects within the pavement structure when they still are hidden from surface. Accordingly, alternative measurement techniques for pavement monitoring are currently under investigation (seismic methods, step frequency radar). On the other hand, strengthening or retrofitting of reinforced concrete structures by externally bonded Fiber Reinforced Polymer (FRP) systems is now a commonly accepted and widespread technique. However, the use of bonding techniques always implies following rigorous installing procedures. To ensure the durability and long-term performance of the FRP reinforcements, conformance checking through an in situ auscultation of the bonded FRP systems is then highly suitable. The quality-control program should involve a set of adequate inspections and tests. Visual inspection and acoustic sounding (hammer tap) are commonly used to detect delaminations (disbonds) but are unable to provide sufficient information about the depth (in case of multilayered composite) and width of debonded areas. Consequently, rapid and efficient inspection methods are also required. Among the non destructive methods under study, active infrared thermography was investigated both for pavement and civil engineering structures through experiments in laboratory and numerical simulations, because of its ability to be also used on field. Pulse Thermography (PT), Pulse Phase Thermography (PPT) and Principal Component Thermography (PCT) approaches have been tested onto pavement samples and CFRP bonding on concrete samples in laboratory. In parallel numerical simulations have been used to generate a set of time sequence of thermal maps for simulated samples with and without subsurface defect. Using this set of experimental and simulated data different approaches (thermal contrast, FFT analysis, polynomial interpolation, singular value decomposition…) for defect location have been studied and compared. Defect depth retrieval was also studied on such data using different thermal model coupled to a direct or an inverse approach. Trials were conducted both with an uncooled and cooled infrared camera with different measurement performances. Results obtained will be discussed and analysed in the paper we plan to present. Finally, combining numerical simulations and experiments allows us discussing on the sensitivity influence of the infrared camera used to detect subsurface defects.

Room-temperature bonding of epitaxial layer to carbon-cluster ion-implanted silicon wafers for CMOS image sensors

NASA Astrophysics Data System (ADS)

Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari

2018-06-01

We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.

Investigation on the diffusion bonding of tungsten and EUROFER97

NASA Astrophysics Data System (ADS)

Basuki, Widodo Widjaja; Aktaa, Jarir

2011-10-01

Due to its advantages, tungsten is selected as armor and structural material for use in future fusion power plants. To apply tungsten as structural material, a joint to EUROFER97 is foreseen in current divertor design for which the diffusion bonding is considered in this work. The joining must have acceptable strength and ductility without significant change in microstructures. So far, numerous diffusion bonding experiments without and with post bonding heat treatment (PBHT) are performed at 1050 °C for various bonding duration. For the bonding processes without PBHT, the bonding seams obtained are defect free and have a very high tensile strength. However they are brittle due to a thin layer of FeW intermetallic phase and metal carbides. For the bonding processes with PBHT, the bonding specimens fail at the bonding seam.

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

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

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A.

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties ofmore » these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.« less

Atomic configurations in AP-MOVPE grown lattice-mismatched InGaAsN films unravelled by X-ray photoelectron spectroscopy combined with bulk and surface characterization techniques

NASA Astrophysics Data System (ADS)

López-Escalante, M. C.; Ściana, B.; Dawidowski, W.; Bielak, K.; Gabás, M.

2018-03-01

This work presents the results of X-ray photoelectron spectroscopy studies on the bonding N configuration in InGaAsN epilayers grown by atmospheric pressure metal organic vapour phase epitaxy. Growth temperature has been tuned in order to obtain both, relaxed and strained layers. The studies were concentrated on analysing the influence of the growth temperature, post growth thermal annealing process and surface quality on the formation of Ga-N and In-N bonds as well as N-related defects. The contamination of InGaAsN films by growth precursor residues and oxides has also been addressed. The growth temperature stands out as a decisive factor boosting In-N bonds formation, while the thermal annealing seems to affect the N-related defects density in the layers.

Atomic Origins of the Self-Healing Function in Cement-Polymer Composites.

PubMed

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A; Childers, M Ian; Fernandez, Carlos; Koech, Phillip K; Bennett, Wendy D; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2018-01-24

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.

A Statistics-Based Cracking Criterion of Resin-Bonded Silica Sand for Casting Process Simulation

NASA Astrophysics Data System (ADS)

Wang, Huimin; Lu, Yan; Ripplinger, Keith; Detwiler, Duane; Luo, Alan A.

2017-02-01

Cracking of sand molds/cores can result in many casting defects such as veining. A robust cracking criterion is needed in casting process simulation for predicting/controlling such defects. A cracking probability map, relating to fracture stress and effective volume, was proposed for resin-bonded silica sand based on Weibull statistics. Three-point bending test results of sand samples were used to generate the cracking map and set up a safety line for cracking criterion. Tensile test results confirmed the accuracy of the safety line for cracking prediction. A laboratory casting experiment was designed and carried out to predict cracking of a cup mold during aluminum casting. The stress-strain behavior and the effective volume of the cup molds were calculated using a finite element analysis code ProCAST®. Furthermore, an energy dispersive spectroscopy fractographic examination of the sand samples confirmed the binder cracking in resin-bonded silica sand.

The hybrid lattice of K(x)Fe(2-y)Se2: where superconductivity and magnetism coexist.

PubMed

Louca, Despina; Park, Keeseong; Li, Bing; Neuefeind, Joerg; Yan, Jiaqiang

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of K(x)Fe(2-y)Se2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, with the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize.

Connecting defects and amorphization in UiO-66 and MIL-140 metal–organic frameworks: a combined experimental and computational study.

PubMed

Bennett, Thomas D; Todorova, Tanya K; Baxter, Emma F; Reid, David G; Gervais, Christel; Bueken, Bart; Van de Voorde, B; De Vos, Dirk; Keen, David A; Mellot-Draznieks, Caroline

2016-01-21

The mechanism and products of the structural collapse of the metal–organic frameworks (MOFs) UiO-66, MIL-140B and MIL-140C upon ball-milling are investigated through solid state 13C NMR and pair distribution function (PDF) studies, finding amorphization to proceed by the breaking of a fraction of metal–ligand bonding in each case. The amorphous products contain inorganic–organic bonding motifs reminiscent of the crystalline phases. Whilst the inorganic Zr6O4(OH)4 clusters of UiO-66 remain intact upon structural collapse, the ZrO backbone of the MIL-140 frameworks undergoes substantial distortion. Density functional theory calculations have been performed to investigate defective models of MIL-140B and show, through comparison of calculated and experimental 13C NMR spectra, that amorphization and defects in the materials are linked.

HgCdTe Surface and Defect Study Program.

DTIC Science & Technology

1985-07-01

a! Td . - a,+ - , are the bonding and antibonding one electron energy states "- "𔃾 owing only to covalent and ionic interactions, . = T . . (U6 II .1...Group Meeting. Boulder CO. 1983; T. W. Jamet atid B. Fandvacncyforatin eerg) t inreae popotioal o a Ziack. 4bd . low inverse power of the average bond

Cy3 and Cy5 dyes attached to oligonucleotide terminus stabilize DNA duplexes: predictive thermodynamic model.

PubMed

Moreira, Bernardo G; You, Yong; Owczarzy, Richard

2015-03-01

Cyanine dyes are important chemical modifications of oligonucleotides exhibiting intensive and stable fluorescence at visible light wavelengths. When Cy3 or Cy5 dye is attached to 5' end of a DNA duplex, the dye stacks on the terminal base pair and stabilizes the duplex. Using optical melting experiments, we have determined thermodynamic parameters that can predict the effects of the dyes on duplex stability quantitatively (ΔG°, Tm). Both Cy dyes enhance duplex formation by 1.2 kcal/mol on average, however, this Gibbs energy contribution is sequence-dependent. If the Cy5 is attached to a pyrimidine nucleotide of pyrimidine-purine base pair, the stabilization is larger compared to the attachment to a purine nucleotide. This is likely due to increased stacking interactions of the dye to the purine of the complementary strand. Dangling (unpaired) nucleotides at duplex terminus are also known to enhance duplex stability. Stabilization originated from the Cy dyes is significantly larger than the stabilization due to the presence of dangling nucleotides. If both the dangling base and Cy3 are present, their thermodynamic contributions are approximately additive. New thermodynamic parameters improve predictions of duplex folding, which will help design oligonucleotide sequences for biophysical, biological, engineering, and nanotechnology applications. Copyright © 2015. Published by Elsevier B.V.

Guided wave phased array sensor tuning for improved defect detection and characterization

NASA Astrophysics Data System (ADS)

Philtron, Jason H.; Rose, Joseph L.

2014-03-01

Ultrasonic guided waves are finding increased use in a variety of Nondestructive Evaluation and Structural Health Monitoring applications due to their efficiency in defect detection using a sensor at a single location to inspect a large area of a structure and an ability to inspect hidden and coated areas for example. With a thorough understanding of guided wave mechanics, researchers can predict which guided wave modes will have a high probability of success in a particular nondestructive evaluation application. For example, in a sample problem presented here to access bond integrity, researchers may choose to use a guided wave mode which has high in-plane displacement, stress, or other feature at the interface. However, since material properties used for modeling work may not be precise for the development of dispersion curves, in many cases guided wave mode and frequency selection should be adjusted for increased inspection efficiency in the field. In this work, a phased array comb transducer is used to sweep over phase velocity - frequency space to tune mode excitation for improved defect characterization performance. A thin polycarbonate layer bonded to a thick metal plate is considered with a contaminated surface prior to bonding. Physicallybased features are used to correlate wave signals with defect detection. Features assessed include arrival time and the frequency of maximum amplitude. A pseudo C-scan plot is presented which can be used to simplify data analysis. Excellent results are obtained.

Effect of a New Surface Treatment Solution on the Bond Strength of Composite to Enamel

DTIC Science & Technology

2016-06-01

enamel ( Erickson et al., 2005). More significantly, clinical studies have shown significantly less marginal defects and staining with selective...using phosphoric acid. Erickson et al., (2009) also found improved bond strengths with a selective-etch step and attributed this to the degree of...cut enamel and dentin. Oper Dent 2005;30(1):39-49. Erickson RL, Barkmeier WW, Kimmes NS. Bond strength of self-etch adhesives to pre-etched

Applying a nonlinear, pitch-catch, ultrasonic technique for the detection of kissing bonds in friction stir welds.

PubMed

Delrue, Steven; Tabatabaeipour, Morteza; Hettler, Jan; Van Den Abeele, Koen

2016-05-01

Friction stir welding (FSW) is a promising technology for the joining of aluminum alloys and other metallic admixtures that are hard to weld by conventional fusion welding. Although FSW generally provides better fatigue properties than traditional fusion welding methods, fatigue properties are still significantly lower than for the base material. Apart from voids, kissing bonds for instance, in the form of closed cracks propagating along the interface of the stirred and heat affected zone, are inherent features of the weld and can be considered as one of the main causes of a reduced fatigue life of FSW in comparison to the base material. The main problem with kissing bond defects in FSW, is that they currently are very difficult to detect using existing NDT methods. Besides, in most cases, the defects are not directly accessible from the exposed surface. Therefore, new techniques capable of detecting small kissing bond flaws need to be introduced. In the present paper, a novel and practical approach is introduced based on a nonlinear, single-sided, ultrasonic technique. The proposed inspection technique uses two single element transducers, with the first transducer transmitting an ultrasonic signal that focuses the ultrasonic waves at the bottom side of the sample where cracks are most likely to occur. The large amount of energy at the focus activates the kissing bond, resulting in the generation of nonlinear features in the wave propagation. These nonlinear features are then captured by the second transducer operating in pitch-catch mode, and are analyzed, using pulse inversion, to reveal the presence of a defect. The performance of the proposed nonlinear, pitch-catch technique, is first illustrated using a numerical study of an aluminum sample containing simple, vertically oriented, incipient cracks. Later, the proposed technique is also applied experimentally on a real-life friction stir welded butt joint containing a kissing bond flaw. Copyright © 2016 Elsevier B.V. All rights reserved.

Study of spin-dependent transitions and spin coherence at the (111) oriented phosphorous doped crystalline silicon to silicon dioxide interface using pulsed electrically detected magnetic resonance

NASA Astrophysics Data System (ADS)

Paik, Seoyoung

A study of spin-dependent electronic transitions at the (111) oriented phosphorous doped crystalline silicon (c-Si) to silicon dioxide (SiO 2) interface is presented for [31P] = 1015 cm-3 and [31P] = 1016 cm -3 and a temperature range between T ≈ 5K and T ≈ 15K. Using pulsed electrically detected magnetic resonance (pEDMR), spin-dependent transitions involving 31P donor states and two different interface states are observed, namely (i) Pb centers which can be identified by their characteristic anisotropy and (ii) the E' center which is attributed to defects of the near interface SiO 2 bulk. Correlation measurements of the dynamics of spin-dependent recombination confirm that previously proposed transitions between 31P and the interface defects take place. The influence of these near interface transitions on the 31P donor spin coherence time T 2 as well as the donor spin-lattice relaxation time T 1 is then investigated by comparison of spin Hahn echo decay measurements obtained from conventional bulk sensitive pulsed electron paramagnetic resonance and surface sensitive pEDMR measurements, as well as surface sensitive electrically detected inversion recovery experiments. The measurements reveal that the T2 times of both interface states and 31P donor electrons spins in proximity of them are consistently shorter than the T1 times, and both T2 and T1 times of the near interface donors are reduced by several orders of magnitude from those in the bulk, at T ≤ 13 K. The T 2 times of the 31P donor electrons are in agreement with the prediction by De Sousa that they are limited by interface defect-induced field noise. To further investigate the dynamic properties of spin-dependent near interface processes, electrical detection of spin beat oscillation between resonantly induced spin-Rabi nutation is conducted at the phosphorous doped (1016cm-3) Si(111)/SiO2 interface. Predictions of Rabi beat oscillations based on several different spin-pair models are compared with measured Rabi beat nutation data. Due to the g-factor anisotropy of the Pb center (a silicon surface dangling bond), one can tune intra-pair Larmor frequency differences (Larmor separations) by orientation of the crystal with regard to an external magnetic field. Since Larmor separation governs the number of beating spin-pairs, crystal orientation can control the beat current. This is used to identify spin states that are paired by mutual electronic transitions. Based on the agreement between hypothesis and data, the experiments confirm the presence of the previously observed 31P-P b transition and the previously hypothesized P b to near interface SiO2 bulk state (E' center) transition.

Effect of Nd: YAG laser irradiation on surface properties and bond strength of zirconia ceramics.

PubMed

Liu, Li; Liu, Suogang; Song, Xiaomeng; Zhu, Qingping; Zhang, Wei

2015-02-01

This study investigated the effect of neodymium-doped yttrium aluminum garnet (Nd: YAG) laser irradiation on surface properties and bond strength of zirconia ceramics. Specimens of zirconia ceramic pieces were divided into 11 groups according to surface treatments as follows: one control group (no treatment), one air abrasion group, and nine laser groups (Nd: YAG irradiation). The laser groups were divided by applying with different output power (1, 2, or 3 W) and irradiation time (30, 60, or 90 s). Following surface treatments, the morphological characteristics of ceramic pieces was observed, and the surface roughness was measured. All specimens were bonded to resin cement. After, stored in water for 24 h and additionally aged by thermocycling, the shear bond strength was measured. Dunnett's t test and one-way ANOVA were performed as the statistical analyses for the surface roughness and the shear bond strength, respectively, with α = .05. Rougher surface of the ceramics could be obtained by laser irradiation with higher output power (2 and 3 W). However, cracks and defects were also found on material surface. The shear bond strength of laser groups was not obviously increased, and it was significantly lower than that of air abrasion group. No significant differences of the shear bond strength were found among laser groups treated with different output power or irradiation time. Nd: YAG laser irradiation cannot improve the surface properties of zirconia ceramics and cannot increase the bond strength of the ceramics. Enhancing irradiation power and extending irradiation time cannot induce higher bond strength of the ceramics and may cause material defect.

Direct writing on graphene 'paper' by manipulating electrons as 'invisible ink'.

PubMed

Zhang, Wei; Zhang, Qiang; Zhao, Meng-Qiang; Kuhn, Luise Theil

2013-07-12

The combination of self-assembly (bottom up) and nano-imprint lithography (top down) is an efficient and effective way to record information at the nanoscale by writing. The use of an electron beam for writing is quite a promising strategy; however, the 'paper' on which to save the information is not yet fully realized. Herein, graphene was selected as the thinnest paper for recording information at the nanoscale. In a transmission electron microscope, in situ high precision writing and drawing were achieved on graphene nanosheets by manipulating electrons with a 1 nm probe (probe current ~2 × 10(-9) A m(-2)) in scanning transmission electron microscopy (STEM) mode. Under electron probe irradiation, the carbon atom tends to displace within a crystalline specimen, and dangling bonds are formed from the original sp(2) bonding after local carbon atoms have been kicked off. The absorbed random foreign amorphous carbon assembles along the line of the scanning direction induced by secondary electrons and is immobilized near the edge. With the ultralow secondary electron yield of the graphene, additional foreign atoms determining the accuracy of the pattern have been greatly reduced near the targeting region. Therefore, the electron probe in STEM mode serves as invisible ink for nanoscale writing and drawing. These results not only shed new light on the application of graphene by the interaction of different forms of carbon, but also illuminate the interaction of different carbon forms through electron beams.

Cleavage strongly influences whether soluble HIV-1 envelope glycoprotein trimers adopt a native-like conformation

PubMed Central

Ringe, Rajesh P.; Sanders, Rogier W.; Yasmeen, Anila; Kim, Helen J.; Lee, Jeong Hyun; Cupo, Albert; Korzun, Jacob; Derking, Ronald; van Montfort, Thijs; Julien, Jean-Philippe; Wilson, Ian A.; Klasse, Per Johan; Ward, Andrew B.; Moore, John P.

2013-01-01

We compare the antigenicity and conformation of soluble, cleaved vs. uncleaved envelope glycoprotein (Env gp)140 trimers from the subtype A HIV type 1 (HIV-1) strain BG505. The impact of gp120–gp41 cleavage on trimer structure, in the presence or absence of trimer-stabilizing modifications (i.e., a gp120–gp41 disulfide bond and an I559P gp41 change, together designated SOSIP), was assessed. Without SOSIP changes, cleaved trimers disintegrate into their gp120 and gp41-ectodomain (gp41ECTO) components; when only the disulfide bond is present, they dissociate into gp140 monomers. Uncleaved gp140s remain trimeric whether SOSIP substitutions are present or not. However, negative-stain electron microscopy reveals that only cleaved trimers form homogeneous structures resembling native Env spikes on virus particles. In contrast, uncleaved trimers are highly heterogeneous, adopting a variety of irregular shapes, many of which appear to be gp120 subunits dangling from a central core that is presumably a trimeric form of gp41ECTO. Antigenicity studies with neutralizing and nonneutralizing antibodies are consistent with the EM images; cleaved, SOSIP-stabilized trimers express quaternary structure-dependent epitopes, whereas uncleaved trimers expose nonneutralizing gp120 and gp41ECTO epitopes that are occluded on cleaved trimers. These findings have adverse implications for using soluble, uncleaved trimers for structural studies, and the rationale for testing uncleaved trimers as vaccine candidates also needs to be reevaluated. PMID:24145402

Nondestructive evaluation of defects in carbon fiber reinforced polymer (CFRP) composites

NASA Astrophysics Data System (ADS)

Ngo, Andrew C. Y.; Goh, Henry K. H.; Lin, Karen K.; Liew, W. H.

2017-04-01

Carbon fiber reinforced polymer (CFRP) composites are increasingly used in aerospace applications due to its superior mechanical properties and reduced weight. Adhesive bonding is commonly used to join the composite parts since it is capable of joining incompatible or dissimilar components. However, insufficient adhesive or contamination in the adhesive bonds might occur and pose as threats to the integrity of the plane during service. It is thus important to look for suitable nondestructive testing (NDT) techniques to detect and characterize the sub-surface defects within the CFRP composites. Some of the common NDT techniques include ultrasonic techniques and thermography. In this work, we report the use of the abovementioned techniques for improved interpretation of the results.

Two-Dimensional Si-Nanodisk Array Fabricated Using Bio-Nano-Process and Neutral Beam Etching for Realistic Quantum Effect Devices

NASA Astrophysics Data System (ADS)

Huang, Chi-Hsien; Igarashi, Makoto; Woné, Michel; Uraoka, Yukiharu; Fuyuki, Takashi; Takeguchi, Masaki; Yamashita, Ichiro; Samukawa, Seiji

2009-04-01

A high-density, large-area, and uniform two-dimensional (2D) Si-nanodisk array was successfully fabricated using the bio-nano-process, advanced etching techniques, including a treatment using nitrogen trifluoride and hydrogen radical (NF3 treatment) and a damage-free chlorine neutral beam (NB). By using the surface oxide formed by neutral beam oxidation (NBO) for the preparation of a 2D nanometer-sized iron core array as an etching mask, a well-ordered 2D Si-nanodisk array was obtained owing to the dangling bonds of the surface oxide. By changing the NF3 treatment time without changing the quantum effect of each nanodisk, we could control the gap between adjacent nanodisks. A device with two electrodes was fabricated to investigate the electron transport in a 2D Si-nanodisk array. Current fluctuation and time-dependent currents were clearly observed owing to the charging-discharging of the nanodisks adjacent to the current percolation path. The new structure may have great potential for future novel quantum effect devices.

Distributions of Thermal-Annealing Activation Energies for Light-Induced Spins in Fast and Slow Processes in a-Si1-xNx:H Alloys

NASA Astrophysics Data System (ADS)

Zhang, Jinyan; Kumeda, Minoru; Shimizu, Tatsuo

1995-10-01

We report on the thermal annealing of light-induced neutral dangling bonds (DB's) created by strong band-gap illumination at 77 K and room temperature (RT) in amorphous silicon-nitrogen alloys ( a-Si1- xN x:H). We find that the light-induced DB's are annealed out with distinct distributions of annealing activation energies (E A's). The distribution for the light-induced DB's created in the fast process (FDB's) and the one for those created in the slow process (SDB's) are separated unambiguously: E A for FDB's is in the range from 0 to 0.7 eV, in which two separated peaks (centered at about 0.09 and 0.4 eV) are embodied, and E A for SDB's is in the range from 0.6 to 1.4 eV, centered at about 1 eV, in a-Si0.5N0.5:H. Moreover, the results demonstrate that the distributions of E A for FDB's and SDB's depend on illumination temperature and illumination time.

Ta2O5 Polycrystalline Silicon Capacitors with CF4 Plasma Treatment

NASA Astrophysics Data System (ADS)

Kao, Chyuan-Haur; Chen, Hsiang

2012-04-01

In this research, the effects of CF4 plasma treatment with post annealing on the electrical characteristics and material properties of Ta2O5 dielectrics were determined. The dielectric performance characteristics of samples under different treatment conditions were measured using equivalent oxide thickness (EOT), current density-electric field (J-E) characteristics, gate voltage shift versus time, and Weibull plots. In addition, X-ray diffraction (XRD) analysis provided insight into the changes in crystalline structure, atomic force microscopy (AFM) measurements visualized the surface roughness, and secondary ion mass spectroscopy (SIMS) revealed the distribution of fluorine ions inside the dielectric samples. Findings indicate that dielectric performance can be significantly improved by CF4 plasma treatment for 1 min with post annealing at 800 °C. The improvements in electrical characteristics were caused by the appropriate incorporation of the fluorine atoms and the removal of the dangling bonds and traps. The Ta2O5 dielectric incorporated with appropriate CF4 plasma and annealing treatments shows great promise for future generation of nonvolatile memory applications.

Interface passivation and trap reduction via hydrogen fluoride for molybdenum disulfide on silicon oxide back-gate transistors

NASA Astrophysics Data System (ADS)

Hu, Yaoqiao; San Yip, Pak; Tang, Chak Wah; Lau, Kei May; Li, Qiang

2018-04-01

Layered semiconductor molybdenum disulfide (MoS2) has recently emerged as a promising material for flexible electronic and optoelectronic devices because of its finite bandgap and high degree of gate control. Here, we report a hydrogen fluoride (HF) passivation technique for improving the carrier mobility and interface quality of chemical vapor deposited monolayer MoS2 on a SiO2/Si substrate. After passivation, the fabricated MoS2 back-gate transistors demonstrate a more than double improvement in average electron mobility, a reduced gate hysteresis gap of 3 V, and a low interface trapped charge density of ˜5.8 × 1011 cm-2. The improvements are attributed to the satisfied interface dangling bonds, thus a reduction of interface trap states and trapped charges. Surface x-ray photoelectron spectroscopy analysis and first-principles simulation were performed to verify the HF passivation effect. The results here highlight the necessity of a MoS2/dielectric passivation strategy and provides a viable route for enhancing the performance of MoS2 nano-electronic devices.

Confined high-pressure chemical deposition of hydrogenated amorphous silicon.

PubMed

Baril, Neil F; He, Rongrui; Day, Todd D; Sparks, Justin R; Keshavarzi, Banafsheh; Krishnamurthi, Mahesh; Borhan, Ali; Gopalan, Venkatraman; Peacock, Anna C; Healy, Noel; Sazio, Pier J A; Badding, John V

2012-01-11

Hydrogenated amorphous silicon (a-Si:H) is one of the most technologically important semiconductors. The challenge in producing it from SiH(4) precursor is to overcome a significant kinetic barrier to decomposition at a low enough temperature to allow for hydrogen incorporation into a deposited film. The use of high precursor concentrations is one possible means to increase reaction rates at low enough temperatures, but in conventional reactors such an approach produces large numbers of homogeneously nucleated particles in the gas phase, rather than the desired heterogeneous deposition on a surface. We report that deposition in confined micro-/nanoreactors overcomes this difficulty, allowing for the use of silane concentrations many orders of magnitude higher than conventionally employed while still realizing well-developed films. a-Si:H micro-/nanowires can be deposited in this way in extreme aspect ratio, small-diameter optical fiber capillary templates. The semiconductor materials deposited have ~0.5 atom% hydrogen with passivated dangling bonds and good electronic properties. They should be suitable for a wide range of photonic and electronic applications such as nonlinear optical fibers and solar cells. © 2011 American Chemical Society

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

ROS evaluation for a series of CNTs and their derivatives using an ESR method with DMPO.

PubMed

Tsuruoka, S; Takeuchi, K; Koyama, K; Noguchi, T; Endo, M; Tristan, F; Terrones, M; Matsumoto, H; Saito, N; Usui, Y; Porter, D W; Castranova, V

Carbon nanotubes (CNTs) are important materials in advanced industries. It is a concern that pulmonary exposure to CNTs may induce carcinogenic responses. It has been recently reported that CNTs scavenge ROS though non-carbon fibers generate ROS. A comprehensive evaluation of ROS scavenging using various kinds of CNTs has not been demonstrated well. The present work specifically investigates ROS scavenging capabilities with a series of CNTs and their derivatives that were physically treated, and with the number of commercially available CNTs. CNT concentrations were controlled at 0.2 through 0.6 wt%. The ROS scavenging rate was measured by ESR with DMPO. Interestingly, the ROS scavenging rate was not only influenced by physical treatments, but was also dependent on individual manufacturing methods. Ratio of CNTs to DMPO/ hydrogen peroxide is a key parameter to obtain appropriate ROS quenching results for comparison of CNTs. The present results suggest that dangling bonds are not a sole factor for scavenging, and electron transfer on the CNT surface is not clearly determined to be the sole mechanism to explain ROS scavenging.

Probing topological Fermi-Arcs and bulk boundary correspondence in the Weyl semimetal TaAs

NASA Astrophysics Data System (ADS)

Batabyal, Rajib; Morali, Noam; Avraham, Nurit; Sun, Yan; Schmidt, Marcus; Felser, Claudia; Stern, Ady; Yan, Binghai; Beidenkopf, Haim

The relation between surface Fermi-arcs and bulk Weyl cones in a Weyl semimetal, uniquely allows to study the notion of bulk to surface correspondence. We visualize these topological Fermi arc states on the surface of the Weyl semi-metal tantalum arsenide using scanning tunneling spectroscopy. Its surface hosts 12 Fermi arcs amongst several other surface bands of non-topological origin. We detect the possible scattering processes of surface bands in which Fermi arcs are involved including intra- and inter arc scatterings and arc-trivial scatterings. Each of the measured scattering processes entails additional information on the unique nature of Fermi arcs in tantalum arsenide: their contour, their energy-momentum dispersion and its relation with the bulk Weyl nodes. We further identify a sharp distinction between the wave function's spatial distribution of topological versus trivial bands. The non-topological surface bands, which are derived from the arsenic dangling bonds, are tightly bound to the arsenic termination layer. In contrast, the Fermi-arc bands reside on the deeper tantalum layer, penetrating into the bulk, which is predominantly derived from tantalum orbitals.

The quest for inorganic fullerenes

NASA Astrophysics Data System (ADS)

Pietsch, Susanne; Dollinger, Andreas; Strobel, Christoph H.; Park, Eun Ji; Ganteför, Gerd; Seo, Hyun Ook; Kim, Young Dok; Idrobo, Juan-Carlos; Pennycook, Stephen J.

2015-10-01

Experimental results of the search for inorganic fullerenes are presented. MonSm- and WnSm- clusters are generated with a pulsed arc cluster ion source equipped with an annealing stage. This is known to enhance fullerene formation in the case of carbon. Analogous to carbon, the mass spectra of the metal chalcogenide clusters produced in this way exhibit a bimodal structure. The species in the first maximum at low mass are known to be platelets. Here, the structure of the species in the second maximum is studied by anion photoelectron spectroscopy, scanning transmission electron microscopy, and scanning tunneling microcopy. All experimental results indicate a two-dimensional structure of these species and disagree with a three-dimensional fullerene-like geometry. A possible explanation for this preference of two-dimensional structures is the ability of a two-element material to saturate the dangling bonds at the edges of a platelet by excess atoms of one element. A platelet consisting of a single element only cannot do this. Accordingly, graphite and boron might be the only materials forming nano-spheres because they are the only single element materials assuming two-dimensional structures.

Structure analysis of Si(111)-7 × 7 reconstructed surface by transmission electron diffraction

NASA Astrophysics Data System (ADS)

Takayanagi, Kunio; Tanishiro, Yasumasa; Takahashi, Shigeki; Takahashi, Masaetsu

1985-12-01

The atomic structure of the 7 × 7 reconstructed Si(111) surface has been analysed by ultra-high vacuum (UHV) transmission electron diffraction (TED). A possible projected structure of the surface is deduced from the intensity distribution in TED patterns of normal electron incidence and from Patterson and Fourier syntheses of the intensities. A new three-dimensional structure model, the DAS model, is proposed: The model consists of 12 adatoms arranged locally in the 2 × 2 structure, a stacking fault layer and a layer with a vacancy at the corner and 9 dimers on the sides of each of the two triangular subcells of the 7 × 7 unit cell. The silicon layers in one subcell are stacked with the normal sequence, CcAaB + adatoms, while those in the other subcell are stacked with a faulted sequence, CcAa/C + adatoms. The model has only 19 dangling bonds, the smallest number among models so far proposed. Previously proposed models are tested quantitatively by the TED intensity. Advantages and limits of the TED analysis are discussed.

Rate equation analysis of hydrogen uptake on Si (100) surfaces

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

Inanaga, S.; Rahman, F.; Khanom, F.

2005-09-15

We have studied the uptake process of H on Si (100) surfaces by means of rate equation analysis. Flowers' quasiequilibrium model for adsorption and desorption of H [M. C. Flowers, N. B. H. Jonathan, A. Morris, and S. Wright, Surf. Sci. 396, 227 (1998)] is extended so that in addition to the H abstraction (ABS) and {beta}{sub 2}-channel thermal desorption (TD) the proposed rate equation further includes the adsorption-induced desorption (AID) and {beta}{sub 1}-TD. The validity of the model is tested by the experiments of ABS and AID rates in the reaction system H+D/Si (100). Consequently, we find it canmore » well reproduce the experimental results, validating the proposed model. We find the AID rate curve as a function of surface temperature T{sub s} exhibits a clear anti-correlation with the bulk dangling bond density versus T{sub s} curve reported in the plasma-enhanced chemical vapor deposition (CVD) for amorphous Si films. The significance of the H chemistry in plasma-enhanced CVD is discussed.« less

Effect of the Microstructure on Diffusion Bonded AA5083, AA6082 and AA7075 Aluminium Alloys

NASA Astrophysics Data System (ADS)

Venugopal, S.; Mahendran, G.

2018-05-01

Rolled plates of aluminium alloys AA5083, AA6082 and AA7075 of 5 mm thickness are joined by diffusion bonding at varied parameters. The microstructure evolution of AA5083, AA6082 and AA7075 aluminium alloys is characterized by Transmission Electron Microscopy (TEM). Metallurgical investigations and mechanical tests are also performed to correlate the results of the TEM investigations with the mechanical properties of the produced diffusion bonded joints. It is observed that the bonding and shear strength of the alloys increase with the increase in bonding temperature, due to the diffusion of micro-constituents in the interface. High temperature enhances the uniform distribution of secondary phase particles and reduces pore formation/defects in the bonded joints.

Method for vacuum fusion bonding

DOEpatents

Ackler, Harold D.; Swierkowski, Stefan P.; Tarte, Lisa A.; Hicks, Randall K.

2001-01-01

An improved vacuum fusion bonding structure and process for aligned bonding of large area glass plates, patterned with microchannels and access holes and slots, for elevated glass fusion temperatures. Vacuum pumpout of all components is through the bottom platform which yields an untouched, defect free top surface which greatly improves optical access through this smooth surface. Also, a completely non-adherent interlayer, such as graphite, with alignment and location features is located between the main steel platform and the glass plate pair, which makes large improvements in quality, yield, and ease of use, and enables aligned bonding of very large glass structures.

Fusion bonding and alignment fixture

DOEpatents

Ackler, Harold D.; Swierkowski, Stefan P.; Tarte, Lisa A.; Hicks, Randall K.

2000-01-01

An improved vacuum fusion bonding structure and process for aligned bonding of large area glass plates, patterned with microchannels and access holes and slots, for elevated glass fusion temperatures. Vacuum pumpout of all the components is through the bottom platform which yields an untouched, defect free top surface which greatly improves optical access through this smooth surface. Also, a completely non-adherent interlayer, such as graphite, with alignment and location features is located between the main steel platform and the glass plate pair, which makes large improvements in quality, yield, and ease of use, and enables aligned bonding of very large glass structures.

Ultrafast exciton migration in an HJ-aggregate: Potential surfaces and quantum dynamics

NASA Astrophysics Data System (ADS)

Binder, Robert; Polkehn, Matthias; Ma, Tianji; Burghardt, Irene

2017-01-01

Quantum dynamical and electronic structure calculations are combined to investigate the mechanism of exciton migration in an oligothiophene HJ aggregate, i.e., a combination of oligomer chains (J-type aggregates) and stacked aggregates of such chains (H-type aggregates). To this end, a Frenkel exciton model is parametrized by a recently introduced procedure [Binder et al., J. Chem. Phys. 141, 014101 (2014)] which uses oligomer excited-state calculations to perform an exact, point-wise mapping of coupled potential energy surfaces to an effective Frenkel model. Based upon this parametrization, the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method is employed to investigate ultrafast dynamics of exciton transfer in a small, asymmetric HJ aggregate model composed of 30 sites and 30 active modes. For a partially delocalized initial condition, it is shown that a torsional defect confines the trapped initial exciton, and planarization induces an ultrafast resonant transition between an HJ-aggregated segment and a covalently bound "dangling chain" end. This model is a minimal realization of experimentally investigated mixed systems exhibiting ultrafast exciton transfer between aggregated, highly planarized chains and neighboring disordered segments.

Polymerization and Structure of Bio-Based Plastics: A Computer Simulation

NASA Astrophysics Data System (ADS)

Khot, Shrikant N.; Wool, Richard P.

2001-03-01

We recently examined several hundred chemical pathways to convert chemically functionalized plant oil triglycerides, monoglycerides and reactive diluents into high performance plastics with a broad range of properties (US Patent No. 6,121,398). The resulting polymers had linear, branched, light- and highly-crosslinked chain architectures and could be used as pressure sensitive adhesives, elastomers and high performance rigid thermoset composite resins. To optimize the molecular design and minimize the number of chemical trials in this system with excess degrees of freedom, we developed a computer simulation of the free radical polymerization process. The triglyceride structure, degree of chemical substitution, mole fractions, fatty acid distribution function, and reaction kinetic parameters were used as initial inputs on a 3d lattice simulation. The evolution of the network fractal structure was computed and used to measure crosslink density, dangling ends, degree of reaction and defects in the lattice. The molecular connectivity was used to determine strength via a vector percolation model of fracture. The simulation permitted the optimal design of new bio-based materials with respect to monomer selection, cure reaction conditions and desired properties. Supported by the National Science Foundation

Corrosion Behavior of an Abradable Seal Coating System

NASA Astrophysics Data System (ADS)

Zhang, Feng; Xu, Cunguan; Lan, Hao; Huang, Chuanbing; Zhou, Yang; Du, Lingzhong; Zhang, Weigang

2014-08-01

A novel NiTi/BN composite abradable coating and two traditional Ni/C and Ni/BN coatings were manufactured with NiAl as the bond layer using thermal spray technology and their corrosion behaviors were investigated. In salt spray corrosion testing of the Ni/BN coating, defective sites of the metal matrix were corroded preferentially. Simulated occlusion experiments and electrochemical tests indicated that migration of ions resulted in pH decrease and Cl- enrichment in defects, and a more aggressive electrolyte led to a decrease of the corrosion potential of the metal inside defects but an increase of the corrosion current density, representing an autocatalytic corrosion process. Moreover, galvanic corrosion between the top and bond coatings of the abradable system was studied via the electrochemical technique. The results showed that, for the NiTi/BN, Ni/BN, and Ni/graphite coatings with a NiAl bond coating, current flow was generated between the anode and cathode. The NiTi/BN coating acted as the cathode due to its passivation, while the Ni/BN and Ni/graphite coatings acted as the anode because of their lower corrosion potential compared with the NiAl coating. The anode suffered serious corrosion damage due to galvanic corrosion, while the cathode corroded only slightly.

A Dynamic Pathway for Stone-Wales Bond Rotation on Carbon Nanotubes through Diamond-Like Bonds

NASA Technical Reports Server (NTRS)

Wei, Chen-Yu; Srivastava, Deepak; Cho, Kyeong-Jae; Menon, Madhu

2003-01-01

A new lower energy barrier with a two-step pathway of Stone-Wales (SW) ,ond rotation on carbon nanotubes (CNTs) is found through molecular dynamics (MD) simulations of CNTs under tension. The first step involves going over to a stable sp3-like metastable configuration with half rotated and partially tilted C-C bond. The second step involves going over to the fully rotated C-C bond with the formation of a SW defect in the nanotube. The energy barrier for this two-step dynamic pathway is significantly lower than the previously known static barrier for in-plane rotation of the C-C bond on a tensile strained (> 4%) CNT.

Tuning thermal conduction via extended defects in graphene

NASA Astrophysics Data System (ADS)

Huang, Huaqing; Xu, Yong; Zou, Xiaolong; Wu, Jian; Duan, Wenhui

2013-05-01

Designing materials for desired thermal conduction can be achieved via extended defects. We theoretically demonstrate the concept by investigating thermal transport in graphene nanoribbons (GNRs) with the extended line defects observed by recent experiments. Our nonequilibrium Green's function study excluding phonon-phonon interactions finds that thermal conductance can be tuned over wide ranges (more than 50% at room temperature), by controlling the orientation and the bond configuration of the embedded extended defect. Further transmission analysis reveals that the thermal-conduction tuning is attributed to two fundamentally different mechanisms, via modifying the phonon dispersion and/or tailoring the strength of defect scattering. The finding, applicable to other materials, provides useful guidance for designing materials with desired thermal conduction.

Scale-free crystallization of two-dimensional complex plasmas: Domain analysis using Minkowski tensors

NASA Astrophysics Data System (ADS)

Böbel, A.; Knapek, C. A.; Räth, C.

2018-05-01

Experiments of the recrystallization processes in two-dimensional complex plasmas are analyzed to rigorously test a recently developed scale-free phase transition theory. The "fractal-domain-structure" (FDS) theory is based on the kinetic theory of Frenkel. It assumes the formation of homogeneous domains, separated by defect lines, during crystallization and a fractal relationship between domain area and boundary length. For the defect number fraction and system energy a scale-free power-law relation is predicted. The long-range scaling behavior of the bond-order correlation function shows clearly that the complex plasma phase transitions are not of the Kosterlitz, Thouless, Halperin, Nelson, and Young type. Previous preliminary results obtained by counting the number of dislocations and applying a bond-order metric for structural analysis are reproduced. These findings are supplemented by extending the use of the bond-order metric to measure the defect number fraction and furthermore applying state-of-the-art analysis methods, allowing a systematic testing of the FDS theory with unprecedented scrutiny: A morphological analysis of lattice structure is performed via Minkowski tensor methods. Minkowski tensors form a complete family of additive, motion covariant and continuous morphological measures that are sensitive to nonlinear properties. The FDS theory is rigorously confirmed and predictions of the theory are reproduced extremely well. The predicted scale-free power-law relation between defect fraction number and system energy is verified for one more order of magnitude at high energies compared to the inherently discontinuous bond-order metric. It is found that the fractal relation between crystalline domain area and circumference is independent of the experiment, the particular Minkowski tensor method, and the particular choice of parameters. Thus, the fractal relationship seems to be inherent to two-dimensional phase transitions in complex plasmas. Minkowski tensor analysis turns out to be a powerful tool for investigations of crystallization processes. It is capable of revealing nonlinear local topological properties, however, still provides easily interpretable results founded on a solid mathematical framework.

Silicon carbon(001) gas-source molecular beam epitaxy from methyl silane and silicon hydride: The effects of carbon incorporation and surface segregation on growth kinetics

NASA Astrophysics Data System (ADS)

Foo, Yong-Lim

Si1-yCy alloys were grown on Si(001) by gas-source molecular-beam epitaxy (GS-MBE) from Si2H6/CH3 SiH3 mixtures as a function of C concentration y (0 to 2.6 at %) and deposition temperature Ts (500--600°C). High-resolution x-ray diffraction reciprocal lattice maps show that all layers are in tension and fully coherent with their substrates. Film growth rates R decrease with both y and Ts, and the rate of decrease in R as a function of y increases rapidly with Ts. In-situ isotopically-tagged D2 temperature-programmed desorption (TPD) measurements reveal that C segregates to the second-layer during steady-state Si1-y Cy(001) growth. This, in turn, results in charge-transfer from Si surface dangling bonds to second-layer C atoms, which have a higher electronegativity than Si. From the TPD results, we obtain the coverage θ Si*(y, Ts) of Si* surface sites with C backbonds as well as H2 desorption energies Ed from both Si and Si* surface sites. This leads to an increase in the H2 desorption rate, and hence should yield higher film deposition rates, with increasing y and/or Ts during Si1-yCy(001) growth. The effect, however, is more than offset by the decrease in Si2H 6 reactive sticking probabilities at Si* surface sites. Film growth rates R(Ts, JSi2H6,J CH3SiH3 ) calculated using a simple transition-state kinetic model, together with measured kinetic parameters, were found to be in good agreement with the experimental data. At higher growth temperature (725 and 750°C), superlattice structures consisting of alternating Si-rich and C-rich sublayers form spontaneously during the gas-source molecular beam epitaxial growth of Si1-y Cy layers from constant Si2H6 and CH 3SiH3 precursor fluxes. The formation of a self-organized superstructure is due to a complex interaction among competing surface reactions. During growth of the initial Si-rich sublayer, C strongly segregates to the second layer resulting in charge transfer from surface Si atom dangling bonds of to C backbonds. This, in turn, decreases the Si2H6 sticking probability and, hence, the sublayer deposition rate. This continues until a critical C coverage is reached allowing the nucleation and growth of a C-rich sublayer until the excess C is depleted. At this point, the self-organized bilayer process repeats itself.

Influence of vacancy defect on surface feature and adsorption of Cs on GaN(0001) surface.

PubMed

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at B(Ga) site on N vacancy defect surface. The E(ads) of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable.

Influence of Vacancy Defect on Surface Feature and Adsorption of Cs on GaN(0001) Surface

PubMed Central

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at BGa site on N vacancy defect surface. The E ads of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable. PMID:25126599

NQR Line Broadening Due to Crystal Lattice Imperfections and Its Relationship to Shock Sensitivity

NASA Astrophysics Data System (ADS)

Caulder, S. M.; Buess, M. L.; Garroway, A. N.; Miller, P. J.

2004-07-01

The hydrodynamic hot spot model is used to explain the difference between shock sensitive and shock insensitive explosives. Among the major factors that influence the shock sensitivity of energetic compounds are the quality and particle size of the energetic crystals used to formulate the cast plastic bonded explosive. As do all energetic compounds, RDX and HMX exhibit internal crystal defects the magnitude and type of which depend on the manufacturing process used to synthesize and re-crystallize the energetic compound. Nuclear Quadrupole Resonance (NQR) spectroscopy was used to determine the crystal quality of RDX, HMX and CL-20 obtained from various manufacturers. The NQR experimental results are discussed. Cast plastic bonded explosives were made using the RDX and HMX obtained from the various manufacturers and subsequently subjected to the NOL large-scale gap test (LSGT). The results of the LSGT are discussed and correlated with the NQR results. A relationship between the crystal defect density and shock initiation pressure of the plastic bonded explosive is developed and discussed.

Effect of Rotational Speed on Microstructure and Mechanical Properties of Refill Friction Stir Spot Welded 2024 Al Alloy

NASA Astrophysics Data System (ADS)

Li, Zhengwei; Gao, Shuangsheng; Ji, Shude; Yue, Yumei; Chai, Peng

2016-04-01

Refill friction stir spot welding (RFSSW) was successfully used to weld alclad 2024 aluminum alloy with different thicknesses. Effects of tool rotational speed on the weld formation, microstructure, and mechanical properties of the RFSSW welds were mainly discussed. Results show that keyhole is successfully refilled and welding defects such as flash, annular groove, and material adhesion can be observed. A bright contrast bonding ligament is found embedded in the weld and it is thicker in the center. Defects of hook, void, lack of mixing, and incomplete refilling can be found at the thermo-mechanically affected zone/stir zone (TMAZ/SZ) interface, which can be attributed to weak metallurgical bonding effect. With increasing the tool rotational speed, thickness of the bonding ligament decreases, grains in the SZ coarsen, hardness of the SZ decreases, and lap shear load of the welds decreases. When changing the rotating speed, impact strength shows rather complicated variation trend.

The hybrid lattice of KxFe2−ySe2: where superconductivity and magnetism coexist

PubMed Central

Louca, Despina; Park, Keeseong; Li, Bing; Neuefeind, Joerg; Yan, Jiaqiang

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of KxFe2−ySe2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, with the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize. PMID:23782976

The hybrid lattice of K xFe 2-ySe 2: where superconductivity and magnetism coexist

DOE PAGES

Yang, Junjie; Duan, Chunruo; Huang, Qing; ...

2013-01-01

Much remains unknown of the microscopic origin of superconductivity in atomically disordered systems of amorphous alloys or in crystals riddled with defects. A manifestation of this conundrum is envisaged in the highly defective superconductor of K xFe 2-ySe 2. How can superconductivity survive under such crude conditions that call for strong electron localization? Here, we show that the Fe sublattice is locally distorted and accommodates two kinds of Fe valence environments giving rise to a bimodal bond-distribution, with short and long Fe bonds. The bimodal bonds are present even as the system becomes superconducting in the presence of antiferromagnetism, withmore » the weight continuously shifting from the short to the long with increasing K content. Such a hybrid state is most likely found in cuprates as well while our results point to the importance of the local atomic symmetry by which exchange interactions between local moments materialize.« less

Plasma combined self-assembled monolayer pretreatment on electroplated-Cu surface for low temperature Cu-Sn bonding in 3D integration

NASA Astrophysics Data System (ADS)

Wang, Junqiang; Wang, Qian; Wu, Zijian; Tan, Lin; Cai, Jian; Wang, Dejun

2017-05-01

A novel pretreatment of plasma combined self-assembled monolayer (PcSAM) was proposed to improve surface properties of electroplated Cu for low temperature Cu-Sn bonding in 3D integration. Measurement results revealed that self-assemble monolayer (SAM) would be easier absorbed on plasma-activated Cu surface and protect the clean surface from re-oxidation when storage. The absorbed SAM layer could be removed by thermal desorption during bonding process. With optimal PcSAM pretreatment, oxygen content of the Cu surface was reduced to as low as 1.39%. The followed Cu-Sn bonding was realized at low temperature of 200 °C. Finally, bonding interface exhibited a defect-free interconnection, and bonding strength has reached as high as 68.7 MPa.

Observation of interface defects in thermally oxidized SiC using positron annihilation

NASA Astrophysics Data System (ADS)

Dekker, James; Saarinen, Kimmo; Ólafsson, Halldór; Sveinbjörnsson, Einar Ö.

2003-03-01

Positron annihilation has been applied to study thermally oxidized 4H- and 6H-SiC. The SiC/SiO2 interface is found to contain a high density of open-volume defects. The positron trapping at the interface defects correlates with the charge of the interface determined by capacitance-voltage experiments. For oxides grown on n-SiC substrates, the positron annihilation characteristics at these defects are nearly indistinguishable from those of a silicon/oxide interface, with no discernable contribution from C-related bonds or carbon clusters. These results indicate that those defects at the SiC/oxide interface, which are visible to positrons, are similar to those at the Si/oxide interface. The positron annihilation characteristics suggest that these defects are vacancies surrounded by oxygen atoms.

Electrical properties of amorphous and epitaxial Si-rich silicide films composed of W-atom-encapsulated Si clusters

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

Okada, Naoya, E-mail: okada-naoya@aist.go.jp; Nanoelectronics Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8562; Institute of Applied Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573

We investigated the electrical properties and derived the energy band structures of amorphous Si-rich W silicide (a-WSi{sub n}) films and approximately 1-nm-thick crystalline WSi{sub n} epitaxial films (e-WSi{sub n}) on Si (100) substrates with composition n = 8–10, both composed of Si{sub n} clusters each of which encapsulates a W atom (WSi{sub n} clusters). The effect of annealing in the temperature range of 300–500 °C was also investigated. The Hall measurements at room temperature revealed that a-WSi{sub n} is a nearly intrinsic semiconductor, whereas e-WSi{sub n} is an n-type semiconductor with electron mobility of ∼8 cm{sup 2}/V s and high sheet electron density ofmore » ∼7 × 10{sup 12 }cm{sup −2}. According to the temperature dependence of the electrical properties, a-WSi{sub n} has a mobility gap of ∼0.1 eV and mid gap states in the region of 10{sup 19 }cm{sup −3} eV{sup −1} in an optical gap of ∼0.6 eV with considerable band tail states; e-WSi{sub n} has a donor level of ∼0.1 eV with sheet density in the region of 10{sup 12 }cm{sup −2} in a band gap of ∼0.3 eV. These semiconducting band structures are primarily attributed to the open band-gap properties of the constituting WSi{sub n} cluster. In a-WSi{sub n}, the random network of the clusters generates the band tail states, and the formation of Si dangling bonds results in the generation of mid gap states; in e-WSi{sub n}, the original cluster structure is highly distorted to accommodate the Si lattice, resulting in the formation of intrinsic defects responsible for the donor level.« less

Intrinsic microstructure of Si/GaAs heterointerfaces fabricated by surface-activated bonding at room temperature

NASA Astrophysics Data System (ADS)

Ohno, Yutaka; Yoshida, Hideto; Takeda, Seiji; Liang, Jianbo; Shigekawa, Naoteru

2018-02-01

The intrinsic microstructure of Si/GaAs heterointerfaces fabricated by surface-activated bonding at room temperature is examined by plane-view transmission electron microscopy (TEM) and cross-sectional scanning TEM using damage-free TEM specimens prepared only by mechanochemical etching. The bonded heterointerfaces include an As-deficient crystalline GaAs layer with a thickness of less than 1 nm and an amorphous Si layer with a thickness of approximately 3 nm, introduced by the irradiation of an Ar atom beam for surface activation before bonding. It is speculated that the interface resistance mainly originates from the As-deficient defects in the former layer.

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4.

PubMed

Wright, Robert J; Zhang, Wei; Yang, Xinzheng; Fasulo, Meg; Tilley, T Don

2012-01-07

Proposed electrocatalytic proton reduction intermediates of hydrogenase mimics were synthesized, observed, and studied computationally. A new mechanism for H(2) generation appears to involve Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3), the dianions {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)Fe(CO)(2)](2-) (3(2-)), the bridging hydride {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)(μ-H)Fe(CO)(2)]}(-), 3H(-)(bridging), and the terminal hydride 3H(-)(term-stag), {[1,2-S(2)C(6)H(4)][HFe(CO)(3)Fe(CO)(3)]}(-), as intermediates. The dimeric sodium derivative of 3(2-), {[Na(2)(THF)(OEt(2))(3)][3(2-)]}(2) (4) was isolated from reaction of Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3) with excess sodium and was characterized by X-ray crystallography. It possesses a bridging CO and an unsymmetrically bridging dithiolate ligand. Complex 4 reacts with 4 equiv. of triflic or benzoic acid (2 equiv. per Fe center) to generate H(2) and 3 in 75% and 60% yields, respectively. Reaction of 4 with 2 equiv. of benzoic acid generated two hydrides in a 1.7 : 1 ratio (by (1)H NMR spectroscopy). Chemical shift calculations on geometry optimized structures of possible hydride isomers strongly suggest that the main product, 3H(-)(bridging), possesses a bridging hydride ligand, while the minor product is a terminal hydride, 3H(-)(term-stag). Computational studies support a catalytic proton reduction mechanism involving a two-electron reduction of 3 that severs an Fe-S bond to generate a dangling thiolate and an electron rich Fe center. The latter iron center is the initial site of protonation, and this event is followed by protonation at the dangling thiolate to give the thiol thiolate [Fe(2)H(CO)(6)(1,2-SHSC(6)H(4))]. This species then undergoes an intramolecular acid-base reaction to form a dihydrogen complex that loses H(2) and regenerates 3.

Native characterization of nucleic acid motif thermodynamics via non-covalent catalysis

PubMed Central

Wang, Chunyan; Bae, Jin H.; Zhang, David Yu

2016-01-01

DNA hybridization thermodynamics is critical for accurate design of oligonucleotides for biotechnology and nanotechnology applications, but parameters currently in use are inaccurately extrapolated based on limited quantitative understanding of thermal behaviours. Here, we present a method to measure the ΔG° of DNA motifs at temperatures and buffer conditions of interest, with significantly better accuracy (6- to 14-fold lower s.e.) than prior methods. The equilibrium constant of a reaction with thermodynamics closely approximating that of a desired motif is numerically calculated from directly observed reactant and product equilibrium concentrations; a DNA catalyst is designed to accelerate equilibration. We measured the ΔG° of terminal fluorophores, single-nucleotide dangles and multinucleotide dangles, in temperatures ranging from 10 to 45 °C. PMID:26782977

Performance and economics of the PV hybrid power system at Dangling Rope Marina, Utah

NASA Astrophysics Data System (ADS)

Rosenthal, Andrew L.

1999-03-01

The National Park Service has operated a large photovoltaic (PV) hybrid power system at the Dangling Rope Marina since August 1996. Performance and economic analyses for this system based on its first year of operation have been published elsewhere [1,2]. Now, as the system enters its third year of operation, recent changes to the site electrical load and impending additions to the PV array raise new interest in this site as the subject of analysis and evaluation. In 1998, energy conservation measures reduced the site electrical load by 10-12%. At the same time, funding has been allocated to expand the PV array by 40% in 1999. This paper analyzes the effects that these changes will have on the site's fuel use and 20-year life cycle cost.

Silicone nasal prosthesis retained by an intranasal stent: a clinical report.

PubMed

Goveas, Reiyal; Puttipisitchet, Ongart; Shrestha, Binit; Thaworanunta, Sita; Srithavaj, M L Theerathavaj

2012-08-01

Nasal defects after tumor excision can leave a patient functionally and esthetically impaired. Loss of nasal septal cartilage support causes the soft tissue to collapse or undergo stenosis, further compounding the problem. Intranasal stents can be used to maintain the patency of such nasal defects. This clinical report describes the use of an acrylic resin nasal stent bonded to a silicone nasal prosthesis to rehabilitate a patient with a nasal defect. Copyright © 2012 The Editorial Council of the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

Facile synthesis of novel two- and three-dimensional coordination polymers containing dialkyltin phosphonate-based tri/tetra-nuclear clusters with appended sulfonate groups.

PubMed

Shankar, Ravi; Jain, Archana; Singh, Atul Pratap; Kociok-Köhn, Gabriele; Molloy, Kieran C

2009-04-20

The coordination-driven self-assemblies of mixed-ligand dialkyltin derivatives, [(Et(2)Sn)(4) (O(2)P(OH)Me)(2)(O(3)PMe)(2)(OSO(2)Et)(2) x 2 H(2)O](n) 1, [(Et(2)Sn)(3)(O(3)PMe)(2)(OSO(2)Me)(2) x CHCl(3)](n) 2, and [(Me(2)Sn)(3)(O(3)PBu(t))(2)(OSO(2)Me)(2) x 2 CHCl(3)](n) 3 have been achieved by reacting the tin precursors, [R(2)Sn(OR(1))(OSO(2)R(1))](n) (R = Et, R(1) = Et (1a), Me (2a); R = Me, R(1) = Me (3a)) with an equimolar amount of methylphosphonic/t-butylphosphonic acid under mild conditions (rt, 8 h, CH(2)Cl(2)). These have been characterized by IR and multinuclear ((1)H, (13)C, (31)P, and (119)Sn) NMR spectroscopy as well as single crystal X-ray diffraction. The asymmetric unit of 1 is composed of a tetranuclear, Sn(4)(mu(2)-PO(2))(2)(mu(3)-PO(3))(2) core bearing an appended ethanesulfonate group on each terminal tin (Sn2) atom and two P(OH)...O hydrogen bonded water molecules. The ladder-like structural motif thus formed is extended into one-dimensional polymeric chains by virtue of bridging bidentate mode of the sulfonate groups. These chains are linked by O-H...O(S) hydrogen bonds involving H(2)O molecules and oxygen atoms of the sulfonate groups. The asymmetric units of 2 and 3 are composed of trinuclear tin clusters with a Sn(3)(mu(3)-PO(3))(2) core and two dangling methanesulfonate groups which are covalently bonded to the tin centers. The construction of three-dimensional self-assemblies is effected by variable bonding modes (mu(2), mu(3) in 2; mu(2) in 3) of the methanesulfonate groups. Both the structural motifs possess five- and six-coordinated tin atoms and form rectangular channels which are occupied by CHCl(3) molecules.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond

NASA Astrophysics Data System (ADS)

Olivier, E. J.; Neethling, J. H.; Kroon, R. E.; Naidoo, S. R.; Allen, C. S.; Sawada, H.; van Aken, P. A.; Kirkland, A. I.

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

PubMed

Olivier, E J; Neethling, J H; Kroon, R E; Naidoo, S R; Allen, C S; Sawada, H; van Aken, P A; Kirkland, A I

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.

An innovative approach for investigating the ceramic bracket-enamel interface - optical coherence tomography and confocal microscopy

NASA Astrophysics Data System (ADS)

Romînu, Roxana Otilia; Sinescu, Cosmin; Romînu, Mihai; Negrutiu, Meda; Laissue, Philippe; Mihali, Sorin; Cuc, Lavinia; Hughes, Michael; Bradu, Adrian; Podoleanu, Adrian

2008-09-01

Bonding has become a routine procedure in several dental specialties - from prosthodontics to conservative dentistry and even orthodontics. In many of these fields it is important to be able to investigate the bonded interfaces to assess their quality. All currently employed investigative methods are invasive, meaning that samples are destroyed in the testing procedure and cannot be used again. We have investigated the interface between human enamel and bonded ceramic brackets non-invasively, introducing a combination of new investigative methods - optical coherence tomography (OCT) and confocal microscopy (CM). Brackets were conventionally bonded on conditioned buccal surfaces of teeth The bonding was assessed using these methods. Three dimensional reconstructions of the detected material defects were developed using manual and semi-automatic segmentation. The results clearly prove that OCT and CM are useful in orthodontic bonding investigations.

Structure and Properties of fac-[Re(I)(CO)3(NTA)](2-) (NTA(3-) = Trianion of Nitrilotriacetic Acid) and fac-[Re(I)(CO)3(L)](n-) Analogues Useful for Assessing the Excellent Renal Clearance of the fac-[(99m)Tc(I)(CO)3(NTA)](2-) Diagnostic Renal Agent.

PubMed

Klenc, Jeffrey; Lipowska, Malgorzata; Abhayawardhana, Pramuditha L; Taylor, Andrew T; Marzilli, Luigi G

2015-07-06

We previously identified two new agents based on the [(99m)Tc(V)O](3+) core with renal clearances in human volunteers 30% higher than that of the widely used clinical tracer (99m)Tc-MAG3 (MAG3(5-) = penta-anion of mercaptoacetyltriglycine). However, renal agents with even higher clearances are needed. More recently, we changed our focus from the [(99m)Tc(V)O](3+) core to the discovery of superior tracers based on the fac-[(99m)Tc(I)(CO)3](+) core. Compared to (99m)Tc-MAG3, fac-[(99m)Tc(I)(CO)3(NTA)](2-) (NTA(3-) = trianion of nitrilotriacetic acid) holds great promise by virtue of its efficient renal clearance via tubular secretion and the absence of hepatobiliary elimination, even in patients with severely reduced renal function. We report here NMR, molecular (X-ray) structure, and solution data on fac-[Re(I)(CO)3(NTA)](2-) with a -CH2CO2(-) dangling monoanionic chain and on two fac-[Re(I)(CO)3(L)](-) analogues with either a -CH2CONH2 or a -CH2CH2OH dangling neutral chain. In these three fac-[Re(I)(CO)3(L)](n-) complexes, the fac-[Re(I)(CO)3(N(CH2CO2)2)](-) moiety is structurally similar and has similar electronic properties (as assessed by NMR data). In reported and ongoing studies, the two fac-[(99m)Tc(I)(CO)3(L)](-) analogues with these neutral dangling chains were found to have pharmacokinetic properties very similar to those of fac-[(99m)Tc(I)(CO)3(NTA)](2-). Therefore, we reach the unexpected conclusion that in fac-[(99m)Tc(I)(CO)3(L)](n-) agents, renal clearance is affected much more than anticipated by features of the core plus the chelate rings (the [(99m)Tc(I)(CO)3(N(CH2CO2)2)](-) moiety) than by the presence of a negatively charged dangling carboxylate chain.

Effects of different production technologies on mechanical and metallurgical properties of precious metal denture alloys

NASA Astrophysics Data System (ADS)

Ferro, Paolo; Battaglia, Eleonora; Capuzzi, Stefano; Berto, Filippo

2017-12-01

Precious metal alloys can be supplied in traditional plate form or innovative drop form with high degree of purity. The aim of the present work is to evaluate the influence of precious metal alloy form on metallurgical and mechanical properties of the final dental products with particular reference to metal-ceramic bond strength and casting defects. A widely used alloy for denture was selected; its nominal composition was close to 55 wt% Pd - 34 wt% Ag - 6 wt% In - 3 wt% Sn. Specimens were produced starting from the alloy in both plate and drop forms. A specific test method was developed to obtain results that could be representative of the real conditions of use. In order to achieve further information about the adhesion behaviour and resistance, the fracture surfaces of the samples were observed using `Scanning Electron Microscopy (SEM)'. Moreover, material defects caused by the moulding process were studied. The form of the alloy before casting does not significantly influence the shear bond strength between the metal and the ceramic material (p-value=0,976); however, according to SEM images, products from drop form alloy show less solidification defects compared to products obtained with plate form alloy. This was attributed to the absence of polluting additives used in the production of drop form alloy. This study shows that the use of precious metal denture alloys supplied in drop form does not affect the metal-ceramic bond strength compared to alloys supplied in the traditional plate form. However, compared to the plate form, the drop form is found free of solidification defects, less expensive to produce and characterized by minor environmental impacts.

Anatase (101)-like Structural Model Revealed for Metastable Rutile TiO2(011) Surface.

PubMed

Xu, Meiling; Shao, Sen; Gao, Bo; Lv, Jian; Li, Quan; Wang, Yanchao; Wang, Hui; Zhang, Lijun; Ma, Yanming

2017-03-08

Titanium dioxide has been widely used as an efficient transition metal oxide photocatalyst. However, its photocatalytic activity is limited to the ultraviolet spectrum range due to the large bandgap beyond 3 eV. Efforts to reduce the bandgap to achieve a broader spectrum range of light absorption have been successfully attempted via the experimental synthesis of dopant-free metastable surface structures of rutile-type TiO 2 (011) 2 × 1. This new surface phase possesses a reduced bandgap of ∼2.1 eV, showing great potential for an excellent photocatalyst covering a wide range of visible light. There is a need to establish the atomistic structure of this metastable surface to understand the physical cause for the bandgap reduction and to improve the future design of photocatalysts. Here, we report computational investigations in an effort to unravel this surface structure via swarm structure-searching simulations. The established structure adopts the anatase (101)-like structure model, where the topmost 2-fold O atoms form a quasi-hexagonal surface pattern and bond with the unsaturated 5-fold and 4-fold Ti atoms in the next layer. The predicted anatase (101)-like surface model can naturally explain the experimental observation of the STM images, the electronic bandgap, and the oxidation state of Ti 4+ . Dangling bonds on the anatase (101)-like surface are abundant making it a superior photocatalyst. First-principles molecular dynamics simulations have supported the high photocatalytic activity by showing that water and formic acid molecules dissociate spontaneously on the anatase (101)-like surface.

Interactions of Polyethylenimines with Zwitterionic and Anionic Lipid Membranes.

PubMed

Kwolek, Urszula; Jamróz, Dorota; Janiczek, Małgorzata; Nowakowska, Maria; Wydro, Paweł; Kepczynski, Mariusz

2016-05-17

Interactions between polyethylenimines (PEIs) and phospholipid membranes are of fundamental importance for various biophysical applications of these polymers such as gene delivery. Despite investigations into the nature of these interactions, their molecular basis remains poorly understood. In this article, we combined experimental methods and atomistic molecular dynamics (MD) simulations to obtain comprehensive insight into the effect of linear and branched PEIs on zwitterionic and anionic bilayers used as simple models of mammalian cellular membranes. Our results show that PEIs adsorb only partially on the surface of zwitterionic membranes by forming hydrogen bonds to the lipid headgroups, whereas a large part of the polymer chains dangles freely in the aqueous phase. In contrast, PEIs readily adhere to and insert into the anionic membrane. The attraction of the polymer chains to the membrane is due to electrostatic interactions as well as hydrogen bonding between the amine groups of PEI and the phosphate groups of lipids. These interactions were found to induce a substantial reorganization of the bilayer in the polymer vicinity due to the reorientation of lipid molecules. The lipid headgroups were pulled toward the center of the membrane, which can facilitate transmembrane translocations of anionic lipids. Furthermore, the PEI-lipid interactions affect the stability of liposomal dispersions, but we did not see any evidence of disruption of the vesicular structures into small fragments at polymer concentrations typically used in gene therapy. Our results provide a detailed molecular-level description of the lipid organization in the membrane in the presence of polycations that can be useful in understanding their mechanisms of in vitro and in vivo cytotoxicity.

N-MOSFETs Formed on Solid Phase Epitaxially Grown GeSn Film with Passivation by Oxygen Plasma Featuring High Mobility.

PubMed

Fang, Yung-Chin; Chen, Kuen-Yi; Hsieh, Ching-Heng; Su, Chang-Chia; Wu, Yung-Hsien

2015-12-09

Solid phase epitaxially grown GeSn was employed as the platform to assess the eligibility of direct O2 plasma treatment on GeSn surface for passivation of GeSn N-MOSFETs. It has been confirmed that O2 plasma treatment forms a GeSnO(x) film on the surface and the GeSnO(x) topped by in situ Al2O3 constitutes the gate stack of GeSn MOS devices. The capability of the surface passivation was evidenced by the low interface trap density (D(it)) of 1.62 × 10(11) cm(-2) eV(-1), which is primarily due to the formation of Ge-O and Sn-O bonds at the surface by high density/reactivity oxygen radicals that effectively suppress dangling bonds and decrease gap states. The good D(it) not only makes tiny frequency dispersion in the characterization of GeSn MOS capacitors, but results in GeSn N-MOSFETs with outstanding peak electron mobility as high as 518 cm(2)/(V s) which outperforms other devices reported in the literature due to reduced undesirable carrier scattering. In addition, the GeSn N-MOSFETs also exhibit promising characteristics in terms of acceptable subthreshold swing of 156 mV/dec and relatively large I(ON)/I(OFF) ratio more than 4 orders. Moreover, the robust reliability in terms small V(t) variation against high field stress attests the feasibility of using the O2 plasma-treated passivation to advanced GeSn technology.

Nanotwin Detection and Domain Polarity Determination via Optical Second Harmonic Generation Polarimetry.

PubMed

Ren, Ming-Liang; Agarwal, Rahul; Nukala, Pavan; Liu, Wenjing; Agarwal, Ritesh

2016-07-13

We demonstrate that optical second harmonic generation (SHG) can be utilized to determine the exact nature of nanotwins in noncentrosymmetric crystals, which is challenging to resolve via conventional transmission electron or scanned probe microscopies. Using single-crystalline nanotwinned CdTe nanobelts and nanowires as a model system, we show that SHG polarimetry can distinguish between upright (Cd-Te bonds) and inverted (Cd-Cd or Te-Te bonds) twin boundaries in the system. Inverted twin boundaries are generally not reported in nanowires due to the lack of techniques and complexity associated with the study of the nature of such defects. Precise characterization of the nature of defects in nanocrystals is required for deeper understanding of their growth and physical properties to enable their application in future devices.

Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation.

PubMed

Cortecchia, Daniele; Neutzner, Stefanie; Srimath Kandada, Ajay Ram; Mosconi, Edoardo; Meggiolaro, Daniele; De Angelis, Filippo; Soci, Cesare; Petrozza, Annamaria

2017-01-11

Only a selected group of two-dimensional (2D) lead-halide perovskites shows a peculiar broad-band photoluminescence. Here we show that the structural distortions of the perovskite lattice can determine the defectivity of the material by modulating the defect formation energies. By selecting and comparing two archetype systems, namely, (NBT) 2 PbI 4 and (EDBE)PbI 4 perovskites (NBT = n-butylammonium and EDBE = 2,2-(ethylenedioxy)bis(ethylammonium)), we find that only the latter, subject to larger deformation of the Pb-X bond length and X-Pb-X bond angles, sees the formation of V F color centers whose radiative decay ultimately leads to broadened PL. These findings highlight the importance of structural engineering to control the optoelectronic properties of this class of soft materials.

Density-functional theory molecular dynamics simulations of a-HfO2/Ge(100)(2 × 1) and a-ZrO2/Ge(100)(2 × 1) interface passivation.

PubMed

Chagarov, E A; Porter, L; Kummel, A C

2016-02-28

The structural properties of a-HfO2/Ge(2 × 1)-(001) and a-ZrO2/Ge(2 × 1)-(001) interfaces were investigated with and without a GeOx interface interlayer using density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic a-HfO2 and a-ZrO2 samples were generated using a hybrid classical-DFT MD "melt-and-quench" approach and tested against experimental properties. The oxide/Ge stacks were annealed at 700 K, cooled to 0 K, and relaxed providing the system with enough freedom to form realistic interfaces. For each high-K/Ge stack type, two systems with single and double interfaces were investigated. All stacks were free of midgap states; however, stacks with a GeO(x) interlayer had band-edge states which decreased the band gaps by 0%-30%. These band-edge states were mainly produced by under-coordinated Ge atoms in GeO(x) layer or its vicinity due to deformation, intermixing, and bond-breaking. The DFT-MD simulations show that electronically passive interfaces can be formed either directly between high-K dielectrics and Ge or with a monolayer of GeO2 if the processing does not create or properly passivate under-coordinated Ge atoms and Ge's with significantly distorted bonding angles. Comparison to the charge states of the interfacial atoms from DFT to experimental x-ray photoelectron spectroscopy results shows that while most studies of gate oxide on Ge(001) have a GeO(x) interfacial layer, it is possible to form an oxide/Ge interface without a GeO(x) interfacial layer. Comparison to experiments is consistent with the dangling bonds in the suboxide being responsible for midgap state formation.

Energetics of a Li Atom adsorbed on B/N doped graphene with monovacancy

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

Rani, Babita, E-mail: babitabaghla15@gmail.com; Department of Physics, Punjabi University, Patiala 147002; Jindal, V.K.

We use density functional theory (DFT) to study the adsorption properties and diffusion of Li atom across B/N-pyridinic graphene. Regardless of the dopant type, B atoms of B-pyridinic graphene lose electron density. On the other hand, N atoms (p-type dopants) have tendency to gain electron density in N-pyridinic graphene. Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene are responsible for stronger binding of Li with the substrates as compared to pristine graphene. The binding energy of Li with B/N-pyridinic graphene exceeds the cohesive energy of bulk Li, making it energetically unfavourable for Li to form clusters on these substrates.more » Li atom gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals while Li on B-pyridinic prefers the ionic bonding. Also, significant distortion of N-pyridinic graphene upon Li adsorption is a consequence of the change in bonding mechanism between Li atom and the substrate. Our results show that bonding character and hence binding energies between Li and graphene can be tuned with the help of B/N doping of monovacancy defects. Further, the sites for most stable adsorption are different for the two types of doped and defective graphene, leading to greater Li uptake capacity of B-pyridinic graphene near the defect. In addition, B-pyridinic graphene offering lower diffusion barrier, ensures better Li kinetics. Thus, B-pyridinic graphene presents itself as a better anode material for LIBs as compared to N-pyridinic graphene. - Graphical abstract: Adsorption and diffusion of Li atom across the B/N doped monovacancy graphene is studied using ab-initio DFT calculations. Our results show that bonding mechanism and binding of Li with graphene can be tuned with the help of N/B doping of defects. Also, B-pyridinic graphene presents itself as a better anode material for lithium ion batteries as compared to N-pyridinic graphene. Display Omitted - Highlights: • Density functional theory (DFT) calculations are employed to study the effect of B/N doping of monovacancy graphene on the adsorption and diffusion of Li atom across the sheet using VASP. • Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene (p-type semiconductors) as compared to pristine graphene lead to stronger binding of Li. It also exceeds the cohesive energy of bulk Li. Thus, uniform distribution of Li atoms is possible on both substrates. • Li gets adsorbed stably at centre of defect in N-pyridinic graphene. B-pyridinic graphene has stable adsorption of Li at hollow site of hexagon, neighboring the defect, having only one boron atom. It leads to maximum Li uptake capacity of B-pyridinic graphene. • Li gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals. This change in bonding mechanism causes significant distortion of the substrate. On the other hand, Li on B-pyridinic graphene shows ionic bonding character. • B-pyridinic graphene offers lower energy barrier for Li to diffuse across the substrate in comparison to N-pyridinic graphene. Thus, B-pyridinic graphene presents itself as a better anode material for lithium ion batteries due to optimal Li adsorption and better diffusion kinetics.« less

[Free latissimus dorsi flap transfer for reconstruction of soft tissue defects of the lower extremity].

PubMed

Knobloch, K; Herold, C; Vogt, P M

2012-04-01

Sustainable and durable soft tissue coverage at the lower extremity following trauma, tumor resections, sequelae of radiation therapy or osteomyelitis using free latissimus dorsi muscle transfer is provided by a free latissimus dorsi muscle flap. Soft tissue defects at the lower extremity following trauma, tumor resections, and sequelae of radiation therapy or osteomyelitis. Thoracotomy with incision of the latissimus dorsi muscle; a relative contraindication in wheelchair drivers as well as in overhead athletes due to potential diminished strength and shoulder proprioception following latissimus dorsi muscle transplantation. Under general anesthesia the patient is positioned laterally, and a substantial and meticulous debridement of the defect is performed, as is the identification and preparation of the target vessel, which is preferentially the posterior tibial artery at the calf, or more proximally the popliteal or femoral artery from the medial side as well as concomitant veins/the great saphenous vein. A tailored latissimus dorsi musculocutaneous flap is harvested with subsequent microsurgical anastomosis to the target vessel with preferential end-to-side anastomosis of the artery and end-to-end anastomosis of one or two veins. A 24-h intermediate care unit, clinical flap monitoring for at least 5-7 days, dangling of the flap using an elastic bandage for an initial 3  times  5 min starting on POD 7, compression stockings for at least 6 months subsequently. From 2001-2007 75 free latissimus dorsi flaps were performed (53 ± 17 years) for soft tissue coverage at the lower extremity. In 58% the target vessel was the posterior tibial artery, in 11% the femoral artery, in 8% the anterior tibial artery and in 8% the popliteal artery. In 15% an arteriovenous (AV) loop was applied. Overall free flap survival was 95%. We encountered four total flap losses, exclusively in complex reconstructions with AV-loop situations.

Optimized ultra-thin manganin alloy passivated fine-pitch damascene compatible bump-less Cu-Cu bonding at sub 200 °C for three-dimensional Integration applications

NASA Astrophysics Data System (ADS)

Panigrahi, Asisa Kumar; Hemanth Kumar, C.; Bonam, Satish; Ghosh, Tamal; Rama Krishna Vanjari, Siva; Govind Singh, Shiv

2018-02-01

Enhanced Cu diffusion, Cu surface passivation, and smooth surface at the bonding interface are the key essentials for high quality Cu-Cu bonding. Previously, we have demonstrated optimized 3 nm thin Manganin metal-alloy passivation from oxidation and also helps to reduce the surface roughness to about 0.8 nm which substantially led to high quality Cu-Cu bonding. In this paper, we demonstrated an ultra fine-pitch (<25 µm) Cu-Cu bonding using an optimized Manganin metal-alloy passivation. This engineered surface passivation approach led to high quality bonding at sub 200 °C temperature and 0.4 MPa. Very low specific contact resistance of 1.4 × 10-7 Ω cm2 and the defect free bonded interface is clear indication of high quality bonding for future multilayer integrations. Furthermore, electrical characterization of the bonded structure was performed under various robust conditions as per International Technology Roadmap for Semiconductors (ITRS Roadmap) in order to satisfy the stability of the bonded structure.

Buffer-eliminated, charge-neutral epitaxial graphene on oxidized 4H-SiC (0001) surface

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

Sirikumara, Hansika I., E-mail: hansi.sirikumara@siu.edu; Jayasekera, Thushari, E-mail: thushari@siu.edu

Buffer-eliminated, charge-neutral epitaxial graphene (EG) is important to enhance its potential in device applications. Using the first principles Density Functional Theory calculations, we investigated the effect of oxidation on the electronic and structural properties of EG on 4H-SiC (0001) surface. Our investigation reveals that the buffer layer decouples from the substrate in the presence of both silicate and silicon oxy-nitride at the interface, and the resultant monolayer EG is charge-neutral in both cases. The interface at 4H-SiC/silicate/EG is characterized by surface dangling electrons, which opens up another route for further engineering EG on 4H-SiC. Dangling electron-free 4H-SiC/silicon oxy-nitride/EG is idealmore » for achieving charge-neutral EG.« less

Effect of vacancies on the mechanical properties of phosphorene nanotubes.

PubMed

Sorkin, V; Zhang, Y W

2018-06-08

Using density functional tight-binding method, we studied the mechanical properties, deformation and failure of armchair (AC) and zigzag (ZZ) phosphorene nanotubes (PNTs) with monovacancies and divacancies subjected to uniaxial tensile strain. We found that divacancies in AC PNTs and monovacancies in ZZ PNTs possess the lowest vacancy formation energy, which decreases with the tube diameter in AC PNTs and increases in ZZ PNTs. The Young's modulus is reduced, while the radial and thickness Poisson's ratios are increased by hosted vacancies. In defective AC PNTs, deformation involves fracture of the intra-pucker bonds and formation of the new inter-pucker bonds at a critical strain, and the most stretched bonds around the vacancy rupture first, triggering a sequence of the structural transformations terminated by the ultimate failure. The critical strain of AC PNTs is reduced significantly by hosted vacancies, whereas their effect on the critical stress is relatively weaker. Defective ZZ PNTs fail in a brittle-like manner once the most stretched bonds around a vacancy rupture, and vacancies are able to significantly reduce the failure strain but only moderately reduce the failure stress of ZZ PNTs. The understandings revealed here on the mechanical properties and the deformation and failure mechanisms of PNTs provide useful guidelines for their design and fabrication as building blocks in nanodevices.

Effect of vacancies on the mechanical properties of phosphorene nanotubes

NASA Astrophysics Data System (ADS)

Sorkin, V.; Zhang, Y. W.

2018-06-01

Using density functional tight-binding method, we studied the mechanical properties, deformation and failure of armchair (AC) and zigzag (ZZ) phosphorene nanotubes (PNTs) with monovacancies and divacancies subjected to uniaxial tensile strain. We found that divacancies in AC PNTs and monovacancies in ZZ PNTs possess the lowest vacancy formation energy, which decreases with the tube diameter in AC PNTs and increases in ZZ PNTs. The Young’s modulus is reduced, while the radial and thickness Poisson’s ratios are increased by hosted vacancies. In defective AC PNTs, deformation involves fracture of the intra-pucker bonds and formation of the new inter-pucker bonds at a critical strain, and the most stretched bonds around the vacancy rupture first, triggering a sequence of the structural transformations terminated by the ultimate failure. The critical strain of AC PNTs is reduced significantly by hosted vacancies, whereas their effect on the critical stress is relatively weaker. Defective ZZ PNTs fail in a brittle-like manner once the most stretched bonds around a vacancy rupture, and vacancies are able to significantly reduce the failure strain but only moderately reduce the failure stress of ZZ PNTs. The understandings revealed here on the mechanical properties and the deformation and failure mechanisms of PNTs provide useful guidelines for their design and fabrication as building blocks in nanodevices.

Periodic density functional theory study of ethylene hydrogenation over Co3O4 (1 1 1) surface: The critical role of oxygen vacancies

NASA Astrophysics Data System (ADS)

Lu, Jinhui; Song, JiaJia; Niu, Hongling; Pan, Lun; Zhang, Xiangwen; Wang, Li; Zou, Ji-Jun

2016-05-01

Recently, metal oxides are attracting increasing interests as hydrogenation catalyst. Herein we studied the hydrogenation of ethylene on perfect and oxygen defective Co3O4 (1 1 1) using periodic density functional theory. The energetics and pathways of ethylene hydrogenation to ethane were determined. We have demonstrated that (i) H2 dissociation on Co3O4 is a complicated two-step process through a heterolytic cleavage, followed by the migration of H atom and finally yields the homolytic product on both perfect and oxygen defective Co3O4 (1 1 1) surfaces easily. (ii) After introducing the surface oxygen vacancy, the stepwise hydrogenation of ethylene by atomic hydrogen is much easier than that on perfect surface due to the weaker bond strength of OH group. The strength of Osbnd H bond is a crucial factor for the hydrogenation reaction which involves the breakage of Osbnd H bond. The formation of oxygen vacancy increases the electronic charges at the adjacent surface O, which reduces its capability of further gaining electrons from adsorbed atomic hydrogen and then weakens the strength of Osbnd H bond. These results emphasize the importance of the oxygen vacancies for hydrogenation on metal oxides.

Supramolecular Polymers with Multiple Types of Binding Motifs: From Fundamental Studies to Multifunctional Materials

DTIC Science & Technology

2015-07-10

studies metallo and hydrogen bonded supramolecular polymers that exhibit defect healing characteristics and multi- 1. REPORT DATE (DD-MM-YYYY) 4...supramolecular polymers that exhibit defect healing characteristics and multi-responsive actuators. It also report on a new class of supramolecular glasses. (a...2014; San Francisco, CA, USA Talks D. Balkenende “Optically responsive supramolecular glasses” Swiss Soft Days, 02.10.14, Lausanne

Maternal bond with cardiosurgically treated infant. Qualitative analysis of mothers' narratives.

PubMed

Sikora, Karolina; Janusz, Bernadetta

2014-01-01

The aim of this work is to describe the experience of being a mother by women who together with their children stay on the ward after cardiac surgical correction of congenital heart defects. The research material consisted of the narratives of mothers whose children were born with a heart defect and surgically treated. Four women aged 21-30 years were participants of this study. The age of the subjects' children ranged from 5 weeks to 1 year and three months. The heart defects with which the children were born were hypoplastic left heart syndrome (HLHS ) or atrioventricular canal defect. The research was carried out using the narrative interview. Qualitative analysis was carried out according to the rules of thematic analysis. The results of the research confirm that cardiac treatment can have a significant impact on maternal care patterns and the mother-infant bonding process. Intermittent contact with an infant can lead to loss of control over what happens to the child and the loss of a sense of competence to care for him. Medical staff face the challenge of supporting the parents of hospitalized children in the process of building relationships with a sick infant. The actions of doctors and nurses to enable parents to care for a baby can help foster their sense of competence and responsibility.

Adsorption of metal atoms at a buckled graphene grain boundary using model potentials

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

Helgee, Edit E.; Isacsson, Andreas

Two model potentials have been evaluated with regard to their ability to model adsorption of single metal atoms on a buckled graphene grain boundary. One of the potentials is a Lennard-Jones potential parametrized for gold and carbon, while the other is a bond-order potential parametrized for the interaction between carbon and platinum. Metals are expected to adsorb more strongly to grain boundaries than to pristine graphene due to their enhanced adsorption at point defects resembling those that constitute the grain boundary. Of the two potentials considered here, only the bond-order potential reproduces this behavior and predicts the energy of themore » adsorbate to be about 0.8 eV lower at the grain boundary than on pristine graphene. The Lennard-Jones potential predicts no significant difference in energy between adsorbates at the boundary and on pristine graphene. These results indicate that the Lennard-Jones potential is not suitable for studies of metal adsorption on defects in graphene, and that bond-order potentials are preferable.« less

Disorder and defects are not intrinsic to boron carbide

NASA Astrophysics Data System (ADS)

Mondal, Swastik; Bykova, Elena; Dey, Somnath; Ali, Sk Imran; Dubrovinskaia, Natalia; Dubrovinsky, Leonid; Parakhonskiy, Gleb; van Smaalen, Sander

2016-01-01

A unique combination of useful properties in boron-carbide, such as extreme hardness, excellent fracture toughness, a low density, a high melting point, thermoelectricity, semi-conducting behavior, catalytic activity and a remarkably good chemical stability, makes it an ideal material for a wide range of technological applications. Explaining these properties in terms of chemical bonding has remained a major challenge in boron chemistry. Here we report the synthesis of fully ordered, stoichiometric boron-carbide B13C2 by high-pressure-high-temperature techniques. Our experimental electron-density study using high-resolution single-crystal synchrotron X-ray diffraction data conclusively demonstrates that disorder and defects are not intrinsic to boron carbide, contrary to what was hitherto supposed. A detailed analysis of the electron density distribution reveals charge transfer between structural units in B13C2 and a new type of electron-deficient bond with formally unpaired electrons on the C-B-C group in B13C2. Unprecedented bonding features contribute to the fundamental chemistry and materials science of boron compounds that is of great interest for understanding structure-property relationships and development of novel functional materials.

The mechanism of proton conduction in phosphoric acid

NASA Astrophysics Data System (ADS)

Vilčiauskas, Linas; Tuckerman, Mark E.; Bester, Gabriel; Paddison, Stephen J.; Kreuer, Klaus-Dieter

2012-06-01

Neat liquid phosphoric acid (H3PO4) has the highest intrinsic proton conductivity of any known substance and is a useful model for understanding proton transport in other phosphate-based systems in biology and clean energy technologies. Here, we present an ab initio molecular dynamics study that reveals, for the first time, the microscopic mechanism of this high proton conductivity. Anomalously fast proton transport in hydrogen-bonded systems involves a structural diffusion mechanism in which intramolecular proton transfer is driven by specific hydrogen bond rearrangements in the surrounding environment. Aqueous media transport excess charge defects through local hydrogen bond rearrangements that drive individual proton transfer reactions. In contrast, strong, polarizable hydrogen bonds in phosphoric acid produce coupled proton motion and a pronounced protic dielectric response of the medium, leading to the formation of extended, polarized hydrogen-bonded chains. The interplay between these chains and a frustrated hydrogen-bond network gives rise to the high proton conductivity.

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

NASA Astrophysics Data System (ADS)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

Direct heteroarylation polymerization: guidelines for defect-free conjugated polymers.

PubMed

Bura, Thomas; Beaupré, Serge; Légaré, Marc-André; Quinn, Jesse; Rochette, Etienne; Blaskovits, J Terence; Fontaine, Frédéric-Georges; Pron, Agnieszka; Li, Yuning; Leclerc, Mario

2017-05-01

Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C-H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation ( E a ) of the adjacent C-H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP.

Passivating the sulfur vacancy in monolayer MoS2

NASA Astrophysics Data System (ADS)

Lu, Haichang; Kummel, Andrew; Robertson, John

2018-06-01

Various methods to passivate the sulfur vacancy in 2D MoS2 are modeled using density functional theory (DFT) to understand the passivation mechanism at an atomic scale. First, the organic super acid, bis(trifluoromethane)sulfonimide (TFSI) is a strong protonating agent, and it is experimentally found to greatly increase the photoluminescence efficiency. DFT simulations find that the effectiveness of passivation depends critically on the charge state and number of hydrogens donated by TFSI since this determines the symmetry of the defect complex. A symmetrical complex is formed by three hydrogen atoms bonding to the defect in a -1 charge state, and this gives no bandgap states and a Fermi level in the midgap. However, a charge state of +1 gives a lower symmetry complex with one state in the gap. One or two hydrogens also give complexes with gap states. Second, passivation by O2 can provide partial passivation by forming a bridge bond across the S vacancy, but it leaves a defect state in the lower bandgap. On the other hand, substitutional additions do not shift the vacancy states out of the gap.

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

Effects of different preparation procedures during tooth whitening on enamel bonding.

PubMed

Wilson, Dustin; Xu, Changqi; Hong, Liang; Wang, Yong

2009-04-01

The objective of this study was to assess effects of some clinically related preparation procedures during tooth whitening on enamel bonding properties. Sixty-two extracted human teeth were cleaned and divided into four groups. Forty-two of the teeth were left with their natural surface intact while 20 teeth were polished to form a flat surface. Half of the tooth served as the experimental side and received one of the two whitening products: Opalescence (10% carbamide peroxide) and Crest Whitestrips (6.5% hydrogen peroxide), for 2 weeks. Post-bleaching intervals included: 1 day, 1 week, and 2 weeks. On these days, tooth (10 mm x 1.5 mm x 1.5 mm) sections were evaluated using Raman spectroscopy, scanning electron microscopy and tensile bond strength tests. T-test, ANOVA test, and mixed model regression analysis were used to assess the differences. No significant difference existed between natural surface and polished surface teeth for all groups at both Day One and Week Two (P > 0.05). On Day One, both treated groups had significant lower bond strength than the control group (P = 0.002). After 2 weeks, no significant difference existed between any group (P = 0.381). SEM indicated that resin-enamel interfaces in bleached enamel exhibited more defects in granular formations when compared to the control. Raman results indicated a lower degree of polymerization (DP) of adhesive at the interface for treated teeth surfaces. In summary, pre-bleaching surface treatments such as polish or non-polish, had no effect on bond strength. Bleaching significantly decreased bond strength initially, but after 2 weeks, bleaching had no significant effect on bond strength. Storage time had significant effect on Opalescence treated enamel, but not on control and Whitestrip treated enamel. The decrease of bond strength may be related to interfacial defects and low DP due to oxygen release after bleaching.

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

Akatsu, T.; Bourdelle, K.K.; Richtarch, C.

Extended defects formed after hydrogen implantation into Si and Ge (100) substrates and subsequent thermal anneals were investigated by transmission electron microscopy. The majority of the extended defects formed in both materials were platelet-like structures lying on {l_brace}100{r_brace} and {l_brace}111{r_brace} planes. We found {l_brace}100{r_brace} platelets not only parallel but also perpendicular to the surface. In Ge wafers, high density of {l_brace}311{r_brace} defects and nanobubbles with the average size of 2 nm were observed. The difference between two materials can be attributed to the weaker strength of Ge-H bond.

Slow positron beam study of hydrogen ion implanted ZnO thin films

NASA Astrophysics Data System (ADS)

Hu, Yi; Xue, Xudong; Wu, Yichu

2014-08-01

The effects of hydrogen related defect on the microstructure and optical property of ZnO thin films were investigated by slow positron beam, in combination with x-ray diffraction, infrared and photoluminescence spectroscopy. The defects were introduced by 90 keV proton irradiation with doses of 1×1015 and 1×1016 ions cm-2. Zn vacancy and OH bonding (VZn+OH) defect complex were identified in hydrogen implanted ZnO film by positron annihilation and infrared spectroscopy. The formation of these complexes led to lattice disorder in hydrogen implanted ZnO film and suppressed the luminescence process.

Large-scale quantum transport calculations for electronic devices with over ten thousand atoms

NASA Astrophysics Data System (ADS)

Lu, Wenchang; Lu, Yan; Xiao, Zhongcan; Hodak, Miro; Briggs, Emil; Bernholc, Jerry

The non-equilibrium Green's function method (NEGF) has been implemented in our massively parallel DFT software, the real space multigrid (RMG) code suite. Our implementation employs multi-level parallelization strategies and fully utilizes both multi-core CPUs and GPU accelerators. Since the cost of the calculations increases dramatically with the number of orbitals, an optimal basis set is crucial for including a large number of atoms in the ``active device'' part of the simulations. In our implementation, the localized orbitals are separately optimized for each principal layer of the device region, in order to obtain an accurate and optimal basis set. As a large example, we calculated the transmission characteristics of a Si nanowire p-n junction. The nanowire is along (110) direction in order to minimize the number dangling bonds that are saturated by H atoms. Its diameter is 3 nm. The length of 24 nm is necessary because of the long-range screening length in Si. Our calculations clearly show the I-V characteristics of a diode, i.e., the current increases exponentially with forward bias and is near zero with backward bias. Other examples will also be presented, including three-terminal transistors and large sensor structures.

Lithium effect on the electronic properties of porous silicon for energy storage applications: a DFT study.

PubMed

González, I; Sosa, A N; Trejo, A; Calvino, M; Miranda, A; Cruz-Irisson, M

2018-05-23

Theoretical studies on the effect of Li on the electronic properties of porous silicon are still scarce; these studies could help us in the development of Li-ion batteries of this material which overcomes some limitations that bulk silicon has. In this work, the effect of interstitial and surface Li on the electronic properties of porous Si is studied using the first-principles density functional theory approach and the generalised gradient approximation. The pores are modeled by removing columns of atoms of an otherwise perfect Si crystal, dangling bonds of all surfaces are passivated with H atoms, and then Li is inserted on interstitial positions on the pore wall and compared with the replacement of H atoms with Li. The results show that the interstitial Li creates effects similar to n-type doping where the Fermi level is shifted towards the conduction band with band crossings of the said level thus acquiring metallic characteristics. The surface Li introduces trap-like states in the electronic band structures which increase as the number of Li atom increases with a tendency to become metallic. These results could be important for the application of porous Si nanostructures in Li-ion batteries technology.

Ultralow 1/f Noise in a Heterostructure of Superconducting Epitaxial Cobalt Disilicide Thin Film on Silicon.

PubMed

Chiu, Shao-Pin; Yeh, Sheng-Shiuan; Chiou, Chien-Jyun; Chou, Yi-Chia; Lin, Juhn-Jong; Tsuei, Chang-Chyi

2017-01-24

High-precision resistance noise measurements indicate that the epitaxial CoSi 2 /Si heterostructures at 150 and 2 K (slightly above its superconducting transition temperature T c of 1.54 K) exhibit an unusually low 1/f noise level in the frequency range of 0.008-0.2 Hz. This corresponds to an upper limit of Hooge constant γ ≤ 3 × 10 -6 , about 100 times lower than that of single-crystalline aluminum films on SiO 2 capped Si substrates. Supported by high-resolution cross-sectional transmission electron microscopy studies, our analysis reveals that the 1/f noise is dominated by excess interfacial Si atoms and their dimer reconstruction induced fluctuators. Unbonded orbitals (i.e., dangling bonds) on excess Si atoms are intrinsically rare at the epitaxial CoSi 2 /Si(100) interface, giving limited trapping-detrapping centers for localized charges. With its excellent normal-state properties, CoSi 2 has been used in silicon-based integrated circuits for decades. The intrinsically low noise properties discovered in this work could be utilized for developing quiet qubits and scalable superconducting circuits for future quantum computing.

Structure refinement of the δ1p phase in the Fe-Zn system by single-crystal X-ray diffraction combined with scanning transmission electron microscopy.

PubMed

Okamoto, Norihiko L; Tanaka, Katsushi; Yasuhara, Akira; Inui, Haruyuki

2014-04-01

The structure of the δ1p phase in the iron-zinc system has been refined by single-crystal synchrotron X-ray diffraction combined with scanning transmission electron microscopy. The large hexagonal unit cell of the δ1p phase with the space group of P63/mmc comprises more or less regular (normal) Zn12 icosahedra, disordered Zn12 icosahedra, Zn16 icosioctahedra and dangling Zn atoms that do not constitute any polyhedra. The unit cell contains 52 Fe and 504 Zn atoms so that the compound is expressed with the chemical formula of Fe13Zn126. All Fe atoms exclusively occupy the centre of normal and disordered icosahedra. Iron-centred normal icosahedra are linked to one another by face- and vertex-sharing forming two types of basal slabs, which are bridged with each other by face-sharing with icosioctahedra, whereas disordered icosahedra with positional disorder at their vertex sites are isolated from other polyhedra. The bonding features in the δ1p phase are discussed in comparison with those in the Γ and ζ phases in the iron-zinc system.

High-aspect ratio micro- and nanostructures enabled by photo-electrochemical etching for sensing and energy harvesting applications

NASA Astrophysics Data System (ADS)

Alhalaili, Badriyah; Dryden, Daniel M.; Vidu, Ruxandra; Ghandiparsi, Soroush; Cansizoglu, Hilal; Gao, Yang; Saif Islam, M.

2018-03-01

Photo-electrochemical (PEC) etching can produce high-aspect ratio features, such as pillars and holes, with high anisotropy and selectivity, while avoiding the surface and sidewall damage caused by traditional deep reactive ion etching (DRIE) or inductively coupled plasma (ICP) RIE. Plasma-based techniques lead to the formation of dangling bonds, surface traps, carrier leakage paths, and recombination centers. In pursuit of effective PEC etching, we demonstrate an optical system using long wavelength (λ = 975 nm) infra-red (IR) illumination from a high-power laser (1-10 W) to control the PEC etching process in n-type silicon. The silicon wafer surface was patterned with notches through a lithography process and KOH etching. Then, PEC etching was introduced by illuminating the backside of the silicon wafer to enhance depth, resulting in high-aspect ratio structures. The effect of the PEC etching process was optimized by varying light intensities and electrolyte concentrations. This work was focused on determining and optimizing this PEC etching technique on silicon, with the goal of expanding the method to a variety of materials including GaN and SiC that are used in designing optoelectronic and electronic devices, sensors and energy harvesting devices.

Edge-induced Schottky barrier modulation at metal contacts to exfoliated molybdenum disulfide flakes

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

Nouchi, Ryo, E-mail: r-nouchi@21c.osakafu-u.ac.jp

2016-08-14

Ultrathin two-dimensional semiconductors obtained from layered transition-metal dichalcogenides such as molybdenum disulfide (MoS{sub 2}) are promising for ultimately scaled transistors beyond Si. Although the shortening of the semiconductor channel is widely studied, the narrowing of the channel, which should also be important for scaling down the transistor, has been examined to a lesser degree thus far. In this study, the impact of narrowing on mechanically exfoliated MoS{sub 2} flakes was investigated according to the channel-width-dependent Schottky barrier heights at Cr/Au contacts. Narrower channels were found to possess a higher Schottky barrier height, which is ascribed to the edge-induced band bendingmore » in MoS{sub 2}. The higher barrier heights degrade the transistor performance as a higher electrode-contact resistance. Theoretical analyses based on Poisson's equation showed that the edge-induced effect can be alleviated by a high dopant impurity concentration, but this strategy should be limited to channel widths of roughly 0.7 μm because of the impurity-induced charge-carrier mobility degradation. Therefore, proper termination of the dangling bonds at the edges should be necessary for aggressive scaling with layered semiconductors.« less

Photoconductivity of ultra-thin Ge(GeSn) layers grown in Si by low-temperature molecular beam epitaxy

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

Talochkin, A. B., E-mail: tal@isp.nsc.ru; Novosibirsk State University, Novosibirsk 630090; Chistokhin, I. B.

2016-04-07

Photoconductivity (PC) spectra of Si/Ge(GeSn)/Si structures with the ultra-thin (1.0–2.3 nm) Ge and GeSn alloy layers grown by the low-temperature (T = 100 °C) molecular beam epitaxy are studied. Photoresponse in the range of 1.2–0.4 eV related to light absorption in the buried Ge(GeSn) layer is observed. It is shown that in case of lateral PC, a simple diffusion model can be used to determine the absorption coefficient of this layer α ∼ 10{sup 5 }cm{sup −1}. This value is 100 times larger than that of a single Ge quantum dot layer and is reached significantly above the band gap of most bulk semiconductors. The observedmore » absorption is caused by optical transitions between electron and hole states localized at the interfaces. The anomalous high value of α can be explained by the unusual state of Ge(GeSn) layer with high concentration of dangling bonds, the optical properties of which have been predicted theoretically by Knief and von Niessen (Phys. Rev. B 59, 12940 (1999)).« less

Te Monolayer-Driven Spontaneous van der Waals Epitaxy of Two-dimensional Pnictogen Chalcogenide Film on Sapphire.

PubMed

Hwang, Jae-Yeol; Kim, Young-Min; Lee, Kyu Hyoung; Ohta, Hiromichi; Kim, Sung Wng

2017-10-11

Demands on high-quality layer structured two-dimensional (2D) thin films such as pnictogen chalcogenides and transition metal dichalcogenides are growing due to the findings of exotic physical properties and potentials for device applications. However, the difficulties in controlling epitaxial growth and the unclear understanding of van der Waals epitaxy (vdWE) for a 2D chalcogenide film on a three-dimensional (3D) substrate have been major obstacles for the further advances of 2D materials. Here, we exploit the spontaneous vdWE of a high-quality 2D chalcogenide (Bi 0.5 Sb 1.5 Te 3 ) film by the chalcogen-driven surface reconstruction of a conventional 3D sapphire substrate. It is verified that the in situ formation of a pseudomorphic Te atomic monolayer on the surface of sapphire, which results in a dangling bond-free surface, allows the spontaneous vdWE of 2D chalcogenide film. Since this route uses the natural surface reconstruction of sapphire with chalcogen under vacuum condition, it can be scalable and easily utilized for the developments of various 2D chalcogenide vdWE films through conventional thin-film fabrication technologies.

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

Tong, H.; Yu, N. N.; Yang, Z.

Opposite to the almost persistent p-type conductivity of the crystalline chalcogenides along the GeTe-Sb{sub 2}Te{sub 3} tie line, n-type Hall mobility is observed in crystalline GeTe/Sb{sub 2}Te{sub 3} superlattice-like material (SLL) with a short period length. We suggest that this unusual carrier characteristic originates from the structural disorder introduced by the lattice strain and dangling bonds at the SLL interfaces, which makes the crystalline SLLs behave like the amorphous chalcogenides. Detailed structural disorder in crystalline SLL has been studied by Raman scattering, X-ray photoelectron spectroscopy, as well as Variable-energy positron annihilation spectroscopy measurements. First-principles calculations results show that this structuralmore » disorder gives rise to three-site junctions that dominate the charge transport as the period length decreases and result in the anomalously signed Hall effect in the crystalline SLL. Our findings indicate a similar tetrahedral structure in the amorphous and crystalline states of SLLs, which can significantly reduce the entropy difference. Due to the reduced entropy loss and increased resistivity of crystalline phase introduced by disorder, it is not surprising that the SLLs exhibit extremely lower RESET current and power consumption.« less

Alkylation of a bioinspired high spin Ni(II)N{sub 3}S{sub 2} complex with bifunctional reagents

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

Chohan, B. S., E-mail: bsc12@psu.edu

2013-12-15

Crystal structures of two S-alkylated complexes generated from the reaction of iodoacetamide and iodoethanol with an air and moisture sensitive high spin Ni(II) pentacoordinate triaminodithiolate complex, 1 are determined by X-ray structure analysis. Crystals of complex 2, [NiC{sub 16}H{sub 31}N{sub 5}O{sub 2}S{sub 2}]I{sub 2}, are triclinic, sp. gr. P-bar1 , Z = 2. Crystals of complex 3, [NiC{sub 16}H{sub 28}N{sub 3}O{sub 2}S{sub 2}]I{sub 2}, are monoclinic, sp. gr. P2{sub 1}/c, Z = 4. Structures of complexes 2 and 3 are very similar: one of the S-acetamide (2) or S-ethanol (3) groups coordinates to the Ni center through the oxygen atom formingmore » N{sub 3}S{sub 2}O hexacoordination; the other group remains unbound to the Ni and left dangling. Crystal packing shows that complexes 2 and 3 interact with the iodide counterions, and that only complex 2 interact with neighboring molecules; some of these close intermolecular contacts include H-bonding interactions.« less

The quest for inorganic fullerenes

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

Pietsch, Susanne; Dollinger, Andreas; Strobel, Christoph H.

2015-10-02

Experimental results of the search for inorganic fullerenes are presented. Mo nS m - and W nS m - clusters are generated with a pulsed arc cluster ion source equipped with an annealing stage. This is known to enhance fullerene formation in the case of carbon. Analogous to carbon, the mass spectra of the metal chalcogenide clusters produced in this way exhibit a bimodal structure. Moreover, the species in the first maximum at low mass are known to be platelets. The structure of the species in the second maximum is studied by anion photoelectron spectroscopy, scanning transmission electron microscopy,more » and scanning tunneling microcopy. All experimental results indicate a two-dimensional structure of these species and disagree with a three-dimensional fullerene-like geometry. A possible explanation for this preference of two-dimensional structures is the ability of a two-element material to saturate the dangling bonds at the edges of a platelet by excess atoms of one element. A platelet consisting of a single element only cannot do this. Likewise, graphite and boron might be the only materials forming nano-spheres because they are the only single element materials assuming two-dimensional structures.« less

The quest for inorganic fullerenes

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

Pietsch, Susanne; Dollinger, Andreas; Strobel, Christoph H.

2015-10-07

Experimental results of the search for inorganic fullerenes are presented. Mo{sub n}S{sub m}{sup −} and W{sub n}S{sub m}{sup −} clusters are generated with a pulsed arc cluster ion source equipped with an annealing stage. This is known to enhance fullerene formation in the case of carbon. Analogous to carbon, the mass spectra of the metal chalcogenide clusters produced in this way exhibit a bimodal structure. The species in the first maximum at low mass are known to be platelets. Here, the structure of the species in the second maximum is studied by anion photoelectron spectroscopy, scanning transmission electron microscopy, andmore » scanning tunneling microcopy. All experimental results indicate a two-dimensional structure of these species and disagree with a three-dimensional fullerene-like geometry. A possible explanation for this preference of two-dimensional structures is the ability of a two-element material to saturate the dangling bonds at the edges of a platelet by excess atoms of one element. A platelet consisting of a single element only cannot do this. Accordingly, graphite and boron might be the only materials forming nano-spheres because they are the only single element materials assuming two-dimensional structures.« less

An enhanced surface passivation effect in InGaN/GaN disk-in-nanowire light emitting diodes for mitigating Shockley-Read-Hall recombination.

PubMed

Zhao, Chao; Ng, Tien Khee; Prabaswara, Aditya; Conroy, Michele; Jahangir, Shafat; Frost, Thomas; O'Connell, John; Holmes, Justin D; Parbrook, Peter J; Bhattacharya, Pallab; Ooi, Boon S

2015-10-28

We present a detailed study of the effects of dangling bond passivation and the comparison of different sulfide passivation processes on the properties of InGaN/GaN quantum-disk (Qdisk)-in-nanowire based light emitting diodes (NW-LEDs). Our results demonstrated the first organic sulfide passivation process for nitride nanowires (NWs). The results from Raman spectroscopy, photoluminescence (PL) measurements, and X-ray photoelectron spectroscopy (XPS) showed that octadecylthiol (ODT) effectively passivated the surface states, and altered the surface dynamic charge, and thereby recovered the band-edge emission. The effectiveness of the process with passivation duration was also studied. Moreover, we also compared the electro-optical performance of NW-LEDs emitting at green wavelength before and after ODT passivation. We have shown that the Shockley-Read-Hall (SRH) non-radiative recombination of NW-LEDs can be greatly reduced after passivation by ODT, which led to a much faster increasing trend of quantum efficiency and higher peak efficiency. Our results highlighted the possibility of employing this technique to further design and produce high performance NW-LEDs and NW-lasers.

2D layered insulator hexagonal boron nitride enabled surface passivation in dye sensitized solar cells.

PubMed

Shanmugam, Mariyappan; Jacobs-Gedrim, Robin; Durcan, Chris; Yu, Bin

2013-11-21

A two-dimensional layered insulator, hexagonal boron nitride (h-BN), is demonstrated as a new class of surface passivation materials in dye-sensitized solar cells (DSSCs) to reduce interfacial carrier recombination. We observe ~57% enhancement in the photo-conversion efficiency of the DSSC utilizing h-BN coated semiconductor TiO2 as compared with the device without surface passivation. The h-BN coated TiO2 is characterized by Raman spectroscopy to confirm the presence of highly crystalline, mixed monolayer/few-layer h-BN nanoflakes on the surface of TiO2. The passivation helps to minimize electron-hole recombination at the TiO2/dye/electrolyte interfaces. The DSSC with h-BN passivation exhibits significantly lower dark saturation current in the low forward bias region and higher saturation in the high forward bias region, respectively, suggesting that the interface quality is largely improved without impeding carrier transport at the material interface. The experimental results reveal that the emerging 2D layered insulator could be used for effective surface passivation in solar cell applications attributed to desirable material features such as high crystallinity and self-terminated/dangling-bond-free atomic planes as compared with high-k thin-film dielectrics.

Characterization of bond line discontinuities in a high-Mn TWIP steel pipe welded by HF-ERW

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

Park, Gitae; Kim, Bongyoon; Kang, Yongjoon

In this work, the microstructure and defects in a high-frequency electrical resistance welded (HF-ERW) pipe of high-Mn twinning-induced plasticity (TWIP) steel were characterized. The microstructure of the base metal and the bond line were examined using both optical microscopy and scanning electron microscopy. The features of the bond line were similar to those of conventional steel. Simultaneously, the circumferential ductility was evaluated via a flaring test. It was concluded that the deterioration of the circumferential ductility in a high-Mn TWIP steel pipe was caused by irregular shaped oxide defects and a penetrator that had been formed during welding. Specifically, themore » penetrator, which is composed of MnO and Mn{sub 2}SiO{sub 4}, was found to be the most influential on the circumferential ductility of the welded pipe. The penetrator was analyzed using both an electron probe micro analyzer and transmission electron microscopy, and the formation sequence of the penetrator was evaluated. - Highlights: •This study focused on applying the HF-ERW process to the seam welding of expandable pipe using TWIP steels. •For improvement of the circumferential ductility, deterioration factors were characterized. •Penetrator which would mainly deteriorate the circumferential ductility consisted of round MnO and Mn{sub 2}SiO{sub 4}. •Metallurgical evidence of existing theory regarding the mechanism of defect formation during the HF-ERW was characterized.« less

Evaluation of injectable strontium-containing borate bioactive glass cement with enhanced osteogenic capacity in a critical-sized rabbit femoral condyle defect model.

PubMed

Zhang, Yadong; Cui, Xu; Zhao, Shichang; Wang, Hui; Rahaman, Mohamed N; Liu, Zhongtang; Huang, Wenhai; Zhang, Changqing

2015-02-04

The development of a new generation of injectable bone cements that are bioactive and have enhanced osteogenic capacity for rapid osseointegration is receiving considerable interest. In this study, a novel injectable cement (designated Sr-BBG) composed of strontium-doped borate bioactive glass particles and a chitosan-based bonding phase was prepared and evaluated in vitro and in vivo. The bioactive glass provided the benefits of bioactivity, conversion to hydroxyapatite, and the ability to stimulate osteogenesis, while the chitosan provided a cohesive biocompatible and biodegradable bonding phase. The Sr-BBG cement showed the ability to set in situ (initial setting time = 11.6 ± 1.2 min) and a compressive strength of 19 ± 1 MPa. The Sr-BBG cement enhanced the proliferation and osteogenic differentiation of human bone marrow-derived mesenchymal stem cells in vitro when compared to a similar cement (BBG) composed of chitosan-bonded borate bioactive glass particles without Sr. Microcomputed tomography and histology of critical-sized rabbit femoral condyle defects implanted with the cements showed the osteogenic capacity of the Sr-BBG cement. New bone was observed at different distances from the Sr-BBG implants within eight weeks. The bone-implant contact index was significantly higher for the Sr-BBG implant than it was for the BBG implant. Together, the results indicate that this Sr-BBG cement is a promising implant for healing irregularly shaped bone defects using minimally invasive surgery.

DFT simulation on H2 adsorption over Ni-decorated defective h-BN nanosheets

NASA Astrophysics Data System (ADS)

Zhou, Xuan; Chu, Wei; Zhou, Yanan; Sun, Wenjing; Xue, Ying

2018-05-01

Nickel doped defective h-BN nanosheets and their potential application on hydrogen storage were explored by density functional theory (DFT) calculation. Three types of defective h-BN (SW defect, VB and VN substrates) were modeled. In comparison with the SW defect, the B or N vacancy can improve the interaction between Ni atom and h-BN nanosheet strikingly. Furthermore, the Ni-doped SW defect sheet shows chemisorption on H2 molecules, and the Hsbnd H bond is partially dissociated. While on the VB sheet, Ni adatom interacts with H2 in the range of physisorption. However, the Ni-functionalized VN sheet exhibits a desirable adsorption on H2, and the corresponding energy varies from -0.40 to -0.51 eV, which is favorable for H2 adsorption and release at ambient conditions. As a result, the VN substrate is expected to a desirable support for H2 storage. Our work provides an insight into H2 storage on Ni-functionalized defective h-BN monolayer.

Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

DOE PAGES

Liu, Yuanyue; Xiao, Hai; Goddard, William A.

2016-04-21

Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX 2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gapmore » states. Here, we show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX 2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.« less

Evaluation of nondestructive testing techniques for the space shuttle nonmetallic thermal protection system

NASA Technical Reports Server (NTRS)

Tiede, D. A.

1972-01-01

A program was conducted to evaluate nondestructive analysis techniques for the detection of defects in rigidized surface insulation (a candidate material for the Space Shuttle thermal protection system). Uncoated, coated, and coated and bonded samples with internal defects (voids, cracks, delaminations, density variations, and moisture content), coating defects (holes, cracks, thickness variations, and loss of adhesion), and bondline defects (voids and unbonds) were inspected by X-ray radiography, acoustic, microwave, high-frequency ultrasonic, beta backscatter, thermal, holographic, and visual techniques. The detectability of each type of defect was determined for each technique (when applicable). A possible relationship between microwave reflection measurements (or X-ray-radiography density measurements) and the tensile strength was established. A possible approach for in-process inspection using a combination of X-ray radiography, acoustic, microwave, and holographic techniques was recommended.

Synthesis of photochromic nanoparticles and determination of the mechanism of photochromism

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

Inoue, Shuhei, E-mail: shu18@hiroshima-u.ac.jp; Matsumura, Yukihiko; Kawamoto, Takahiro

2016-05-15

Photochromic nanoparticles of zinc-silicon oxide were synthesized using plasma enhanced chemical vapor deposition. These particles turned black upon irradiating with ultraviolet light. We investigated this phenomenon using density functional theory calculations. Silicon inclusions create trap levels and oxygen defects that reduce the ionization potential of ZnO. This forms a quantum potential between ZnO and zinc-silicon oxide, and the excited electron is stable. Because oxygen defects also increase the bond overlap population between the zinc atoms in a ZnO crystal, they introduce further defects and help in the formation of quantum potentials. Growth of a perfect crystal of ZnO prevents themore » formation of oxygen defects, which is not desirable for photochromism.« less

Method for the growth of large low-defect single crystals

NASA Technical Reports Server (NTRS)

Powell, J. Anthony (Inventor); Neudeck, Philip G. (Inventor); Trunek, Andrew J. (Inventor); Spry, David J. (Inventor)

2008-01-01

A method and the benefits resulting from the product thereof are disclosed for the growth of large, low-defect single-crystals of tetrahedrally-bonded crystal materials. The process utilizes a uniquely designed crystal shape whereby the direction of rapid growth is parallel to a preferred crystal direction. By establishing several regions of growth, a large single crystal that is largely defect-free can be grown at high growth rates. This process is particularly suitable for producing products for wide-bandgap semiconductors, such as SiC, GaN, AlN, and diamond. Large low-defect single crystals of these semiconductors enable greatly enhanced performance and reliability for applications involving high power, high voltage, and/or high temperature operating conditions.

Role of topographical defects in organic film growth of 4,4' -biphenyldicarboxylic acid on graphene: A low-energy electron microscopy study

NASA Astrophysics Data System (ADS)

Khokhar, Fawad S.; van Gastel, Raoul; Poelsema, Bene

2010-11-01

We have used low-energy electron microscopy (LEEM) to study the formation of self-assembled molecular networks on graphene sheets. 4,4' -biphenyldicarboxylic acid (BDA) molecular networks were grown using organic molecular beam epitaxy. LEEM images provide direct insight in the growth dynamics and show that defects in the graphene play a crucial role in the final morphology of the molecular film that forms. BDA is demonstrated to form hydrogen bond-stabilized chains on graphene. Dark-field LEEM images reveal that the same defects that determine the morphology of the film, also direct the orientation of the domains, highlighting the importance of understanding the role of defects in epitaxial processes on graphene.

Wide-range simulation of elastoplastic wave fronts and failure of solids under high-speed loading

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

Saveleva, Natalia, E-mail: saveleva@icmm.ru; Bayandin, Yuriy, E-mail: buv@icmm.ru; Naimark, Oleg, E-mail: naimark@icmm.ru

2015-10-27

The aim of this paper is numerical study of deformation processes and failure of vanadium under shock-wave loading. According developed statistical theory of solid with mesoscopic defects the constitutive equations were proposed in terms of two structural variables characterizing behavior of defects ensembles: defect density tensor and structural scaling parameter. On the basis of wide-range constitutive equations the mathematical model of deformation behavior and failure of vanadium was developed taking into account the bond relaxation mechanisms, multistage of fracture and nonlinearity kinetic of defects. Results of numerical simulation allow the description of the major effects of shock wave propagation (elasticmore » precursor decay, grow of spall strength under grow strain rate)« less

Ambient Carbon Dioxide Capture Using Boron-Rich Porous Boron Nitride: A Theoretical Study.

PubMed

Li, Lanlan; Liu, Yan; Yang, Xiaojing; Yu, Xiaofei; Fang, Yi; Li, Qiaoling; Jin, Peng; Tang, Chengchun

2017-05-10

The development of highly efficient sorbent materials for CO 2 capture under ambient conditions is of great importance for reducing the impact of CO 2 on the environment and climate change. In this account, strong CO 2 adsorption on a boron antisite (B N ) in boron-rich porous boron nitrides (p-BN) was developed and studied. The results indicated that the material achieved larger adsorption energies of 2.09 eV (201.66 kJ/mol, PBE-D). The electronic structure calculations suggested that the introduction of B N in p-BN induced defect electronic states in the energy gap region, which strongly impacted the adsorption properties of the material. The bonding between the B N defect and the CO 2 molecule was clarified, and it was found that the electron donation first occurred from CO 2 to the B N double-acceptor state then, followed by electron back-donation from B N to CO 2 accompanied by the formation of a B N -C bond. The thermodynamic properties indicated that the adsorption of CO 2 on the B N defect to form anionic CO 2 δ- species was spontaneous at temperatures below 350 K. Both the large adsorption energies and the thermodynamic properties ensured that p-BN with a B N defect could effectively capture CO 2 under ambient conditions. Finally, to evaluate the energetic stability, the defect formation energies were estimated. The formation energy of the B N defects was found to strongly depend on the chemical environment, and the selection of different reactants (B or N sources) would achieve the goal of reducing the formation energy. These findings provided a useful guidance for the design and fabrication of a porous BN sorbent for CO 2 capture.

Kinetics of interior loop formation in semiflexible chains.

PubMed

Hyeon, Changbong; Thirumalai, D

2006-03-14

Loop formation between monomers in the interior of semiflexible chains describes elementary events in biomolecular folding and DNA bending. We calculate analytically the interior distance distribution function for semiflexible chains using a mean field approach. Using the potential of mean force derived from the distance distribution function we present a simple expression for the kinetics of interior looping by adopting Kramers theory. For the parameters, that are appropriate for DNA, the theoretical predictions in comparison with the case are in excellent agreement with explicit Brownian dynamics simulations of wormlike chain (WLC) model. The interior looping times (tauIC) can be greatly altered in the cases when the stiffness of the loop differs from that of the dangling ends. If the dangling end is stiffer than the loop then tauIC increases for the case of the WLC with uniform persistence length. In contrast, attachment of flexible dangling ends enhances rate of interior loop formation. The theory also shows that if the monomers are charged and interact via screened Coulomb potential then both the cyclization (tauc) and interior looping (tauIC) times greatly increase at low ionic concentration. Because both tauc and tauIC are determined essentially by the effective persistence length [lp(R)] we computed lp(R) by varying the range of the repulsive interaction between the monomers. For short range interactions lp(R) nearly coincides with the bare persistence length which is determined largely by the backbone chain connectivity. This finding rationalizes the efficacy of describing a number of experimental observations (response of biopolymers to force and cyclization kinetics) in biomolecules using WLC model with an effective persistence length.

Understanding and Calibrating Density-Functional-Theory Calculations Describing the Energy and Spectroscopy of Defect Sites in Hexagonal Boron Nitride.

PubMed

Reimers, Jeffrey R; Sajid, A; Kobayashi, Rika; Ford, Michael J

2018-03-13

Defect states in 2-D materials present many possible uses but both experimental and computational characterization of their spectroscopic properties is difficult. We provide and compare results from 13 DFT and ab initio computational methods for up to 25 excited states of a paradigm system, the V N C B defect in hexagonal boron nitride (h-BN). Studied include: (i) potentially catastrophic effects for computational methods arising from the multireference nature of the closed-shell and open-shell states of the defect, which intrinsically involves broken chemical bonds, (ii) differing results from DFT and time-dependent DFT (TDDFT) calculations, (iii) comparison of cluster models to periodic-slab models of the defect, (iv) the starkly differing effects of nuclear relaxation on the various electronic states that control the widths of photoabsorption and photoemission spectra as broken bonds try to heal, (v) the effect of zero-point energy and entropy on free-energy differences, (vi) defect-localized and conduction/valence-band transition natures, and (vii) strategies needed to ensure that the lowest-energy state of a defect can be computationally identified. Averaged state-energy differences of 0.3 eV are found between CCSD(T) and MRCI energies, with thermal effects on free energies sometimes also being of this order. However, DFT-based methods can perform very poorly. Simple generalized-gradient functionals like PBE fail at the most basic level and should never be applied to defect states. Hybrid functionals like HSE06 work very well for excitations within the triplet manifold of the defect, with an accuracy equivalent to or perhaps exceeding the accuracy of the ab initio methods used. However, HSE06 underestimates triplet-state energies by on average of 0.7 eV compared to closed-shell singlet states, while open-shell singlet states are predicted to be too low in energy by 1.0 eV. This leads to misassignment of the ground state of the V N C B defect. Long-range corrected functionals like CAM-B3LYP are shown to work much better and to represent the current entry level for DFT calculations on defects. As significant differences between cluster and periodic-slab models are also found, the widespread implementation of such functionals in periodic codes is in urgent need.

Cost-effective method of manufacturing a 3D MEMS optical switch

NASA Astrophysics Data System (ADS)

Carr, Emily; Zhang, Ping; Keebaugh, Doug; Chau, Kelvin

2009-02-01

growth of data and video transport networks. All-optical switching eliminates the need for optical-electrical conversion offering the ability to switch optical signals transparently: independent of data rates, formats and wavelength. It also provides network operators much needed automation capabilities to create, monitor and protect optical light paths. To further accelerate the market penetration, it is necessary to identify a path to reduce the manufacturing cost significantly as well as enhance the overall system performance, uniformity and reliability. Currently, most MEMS optical switches are assembled through die level flip-chip bonding with either epoxies or solder bumps. This is due to the alignment accuracy requirements of the switch assembly, defect matching of individual die, and cost of the individual components. In this paper, a wafer level assembly approach is reported based on silicon fusion bonding which aims to reduce the packaging time, defect count and cost through volume production. This approach is successfully demonstrated by the integration of two 6-inch wafers: a mirror array wafer and a "snap-guard" wafer, which provides a mechanical structure on top of the micromirror to prevent electrostatic snap-down. The direct silicon-to-silicon bond eliminates the CTEmismatch and stress issues caused by non-silicon bonding agents. Results from a completed integrated switch assembly will be presented, which demonstrates the reliability and uniformity of some key parameters of this MEMS optical switch.

Hybrid FSWeld-bonded joint fatigue behaviour

NASA Astrophysics Data System (ADS)

Lertora, Enrico; Mandolfino, Chiara; Gambaro, Carla; Pizzorni, Marco

2018-05-01

Aluminium alloys, widely used in aeronautics, are increasingly involved in the automotive industry due to the good relationship between mechanical strength and specific weight. The lightening of the structures is the first objective, which allows the decreasing in the weight in motion. The use of aluminium alloys has also seen the introduction of the Friction Stir Welding (FSW) technique for the production of structural overlapping joints. FSW allows us to weld overlap joints free from defects, but with the presence of a structural notch further aggravated by the presence of a "hook" defect near the edge of the weld. Furthermore, FSW presents a weld penetration area connected to the tool geometry and penetration. The experimental activity will be focused on the combination of two different joining techniques, which can synergistically improve the final joint resistance. In particular, the welding and bonding process most commonly known as weld-bonding is defined as a hybrid process, as it combines two different junction processes. In this paper we analyse FSWelded AA6082 aluminium alloy overlapped joint with the aim of quantitatively evaluating the improvement provided by the presence of an epoxy adhesive between the plates. After optimising the weld-bonding process, the mechanical behaviour of welded joints will be analysed by static and dynamic tests. The presence of the adhesive should limit the negative effect of the structural notch inevitable in a FSW overlapped joint.

Control of Defects in Aluminum Gallium Nitride ((Al)GaN) Films on Grown Aluminum Nitride (AlN) Substrates

DTIC Science & Technology

2013-02-01

Nord, J.; Albe, K.; Erhart, P.; Nordlund, K. Modelling of Compound Semiconductors: Analytical Bond-order Potential for Gallium , Nitrogen and Gallium ...Control of Defects in Aluminum Gallium Nitride ((Al)GaN) Films on Grown Aluminum Nitride (AlN) Substrates by Iskander G. Batyrev, Chi-Chin Wu...Aluminum Gallium Nitride ((Al)GaN) Films on Grown Aluminum Nitride (AlN) Substrates Iskander G. Batyrev and N. Scott Weingarten Weapons and

Some material structural properties of SOI substrates produced by SDB technology

NASA Astrophysics Data System (ADS)

Hui, Li; Guo-Liang, Sun; Juan, Zhan; Qin-Yi, Tong

1987-10-01

SOI substrates have been produced by silicon direct bonding (SDB) technology. Thermal oxides ranging in thickness from native oxide to 1 μm or even more, on either or both wafers have been bonded successfully. The fracture strength of the SOI layer is 130-200 kg/cm 2 which is similar to the value of intrinsic bulk silicon. Dislocations have been shown to be concentrated on the backsides of the substrate and no additional defects have been developed within 80 μm of the Si-SiO 2 bonding area. Mobility and minority carrier lifetime similar to that of the original bulk silicon have been obtained after annealing.

Three-dimensional finite element analysis of the application of attachment for obturator framework in unilateral maxillary defect.

PubMed

Sun, J; Jiao, T; Tie, Y; Wang, D-M

2008-09-01

The aim of this study was to evaluate the stress on the abutment teeth and framework ina unilateral maxillary defect which was restored by an obturator retained by resin-bonded extra coronal attachment. A three-dimensional finite element model of the human unilateral maxillary defect was constructed. Traditional obturator framework with four casting circumferential clasp was established (model 1). A continuous lingual guide plane of 0.5 mm thickness on all of the remaining teeth, with Mini-SG/F attachment on the mesial surface of the central incisor was also established (model 2). The modelling and analytical processes were performed using the ANSYS technologies. Stress was transmitted to the anterior part of the palate, with stress values being lower on the anterior teeth compared with the posteriors. The highest stress value of model 1 and model 2 was 13.1 Mpa, 19.9 Mpa respectively. Stress concentrations were found at the junction of the attachment to the lingual guide plane and the anterior part of the lingual plane. The results of this study suggest that the application of a resin-bonded extra coronal attachment for obturator retention is in accordance with the design principles for the restorative treatment of maxillary defects.The design of the attachment framework needs to be further investigated. Benefit can be gained by splinting the abutment teeth.

Investigation of hydrogen interaction with defects in zirconia

NASA Astrophysics Data System (ADS)

Melikhova, O.; Kuriplach, J.; Čížek, J.; Procházka, I.; Brauer, G.; Anwand, W.

2010-04-01

Defect studies of a ZrO2 + 9 mol. % Y2O3 single crystal were performed in this work using a high resolution positron lifetime spectroscopy combined with slow positron implantation spectroscopy. In order to elucidate the nature of positron trapping sites observed experimentally, the structural relaxations of several types of vacancy-like defects in zirconia were performed and positron characteristics for them were calculated. Relaxed atomic configurations of studied defects were obtained by means of ab initio pseudopotential method within the supercell approach. Theoretical calculations indicated that neither oxygen vacancies nor their neutral complexes with substitute yttrium atoms are capable of positron trapping. On the other hand, zirconium vacancies are deep positron traps and are most probably responsible for the saturated positron trapping observed in yttria stabilized zirconia single crystals. However, the calculated positron lifetime for zirconium vacancy is apparently longer than the experimental value corresponding to a single-component spectrum measured for the cubic ZrO2 + 9 mol. % Y2O3 single crystal. It was demonstrated that this effect can be explained by hydrogen trapped in zirconium vacancies. On the basis of structure relaxations, we found that zirconium vacancy - hydrogen complexes represent deep positron traps with the calculated lifetime close to the experimental one. In zirconium vacancy - hydrogen complexes the hydrogen atom forms an O-H bond with one of the nearest neighbour oxygen atoms. The calculated bond length is close to 1 Å.

Adhesion characterization and defect sizing of sandwich honeycomb composites.

PubMed

Ndiaye, Elhadji Barra; Maréchal, Pierre; Duflo, Hugues

2015-09-01

Defects may appear in composite structures during their life cycle. A 10MHz 128 elements phased array transducer was investigated to characterize join bonds and defects in sandwich honeycomb composite structures. An adequate focal law throughout the composite skin gives the ultrasonic dispersive properties of the composite skin and glue layer behind. The resulting B-scan cartographies allow characterizing locally the honeycomb adhesion. Experimental measurements are compared in good agreement with the Debye Series Method (DSM). In the processed C-scan image, flaws are detectable and measurable, localized both in the scanning plane and in the thickness of the composite skin. Copyright © 2015 Elsevier B.V. All rights reserved.

OCT for early quality evaluation of tooth-composite bond in clinical trials.

PubMed

Haak, Rainer; Schmidt, Patrick; Park, Kyung-Jin; Häfer, Matthias; Krause, Felix; Ziebolz, Dirk; Schneider, Hartmut

2018-06-19

To evaluate early quality of composite restorations with a universal adhesive in different application modes clinically and with optical coherence tomography (OCT). 22 patients with four non-carious cervical lesions each received composite restorations (Filtek Supreme TM XTE, 3 M). The universal adhesive Scotchbond Universal TM (SBU, 3 M) was applied with three etching protocols: self-etch (SE), selective-enamel-etch (SEE) and etch-and-rinse (ER). The etch-and-rinse adhesive OptiBond TM FL (OFL, Kerr) served as a control. Restorations were imaged by OCT (Thorlabs) directly after application (t 0 ). After 14 days (t 1 ) and 6 month (t 2 ) OCT imaging (interfacial adhesive defects) was repeated combined with clinical assessment (FDI criteria). Groups were compared by Friedman-/Wilcoxon- and McNemar-Test. No differences were seen clinically between groups (p i ≥ 0.500). OCT assessment revealed more adhesive defects at the enamel interface with SBU/SE at t 0- t 2 compared to all groups (p i ≤ 0.016). OFL showed more defects than SBU/ER (t 1 : p = 0.01; t 2 : p = 0.083). At dentin/cementum interface OFL exhibited more adhesive defects than SBU with all conditioning modes (t 0 , t 1 , p i ≤ 0.003) and at t 2 to SBU/SE and SBU/ER (p < 0.001). Since t 1 defects with SBU were detected more frequently in the SE and SEE modes compared to ER (p i ≤ 0.037). In contrast to SBU defects increased with OFL up to t 2 (p i ≤ 0.007). In contrast to clinical evaluation, OCT revealed subtle adhesive defects directly after application that might interfere with clinical success. It was demonstrated that ER doesn't decrease initial adhesion of SBU to dentin. Copyright © 2018. Published by Elsevier Ltd.

Control of CFRP strengthening applied to civil structures by IR thermography

NASA Astrophysics Data System (ADS)

Grinzato, E.; Trentin, R.; Bison, P. G.; Marinetti, S.

2007-04-01

NdT methods are highly promoted by an increasing demand of checking the effectiveness of strengthening and repair intervention on structural components, both in buildings and bridges. IR thermography exhibits excellent performances, particularly when innovative materials as CFRP (Carbon Fiber Reinforced Polymer) are used. Non destructive control by the use of thermographic analysis is used to detect adhesion defects or imperfections, which can lead the component to become brittle and collapsing unexpectedly. This paper shows as the geometrical evaluation of delaminated areas is carried out. Laboratory tests both on reduced or full scale are illustrated in order to set up and validate the proposed procedure. An experimental study on samples bonded with FRP and containing defects appropriately applied at the interface, will be presented. A series of beams (10 m long) have been tested under bending loads and strengthened conditions, by placing a pre-impregnated thin carbon (CFRP) laminate at the intrados. Different reinforcement configurations have been adopted in the beams (ordinary steel reinforcement and with addition of pre-stressed strands), using mechanical devices for the anchorage of the supplementary pre-tension of the strips. At local level, the simulation of possible lack of bonding during loading or intrinsic defects and imperfections has been contextually analysed on specifically dimensioned specimens. Different algorithms have been applied at the evaluation stage in order to estimate the defect size and location. Particularly, the extension of the delamination is estimate with a simple and robust algorithm. In facts, standards set the limit for acceptable defects, both in terms of number and size.

Strain compatibility tests for sprayed foam cryogenic insulation

NASA Technical Reports Server (NTRS)

Hill, W. L.; Kimberlin, D. O.

1970-01-01

Mechanical stress applied to foam-coated aluminum alloy specimens maintained at cryogenic temperature simulates actual use conditions of the foam insulation. The testing reveals defects in the polyurethane foam or in the foam to metal bond.

High Cycle Fatigue Properties Of Electron Beam Melted TI-6AL-4V Samples Without And With Integrated Defects ("Effects Of Defects")

NASA Astrophysics Data System (ADS)

Brandl, Erhard; Greitemeier, Daniel; Maier, Hans Jurgen; Syassen, Freerk

2012-07-01

The understanding of additive manufactured material properties is still at an early stage and mostly not profound. Nowadays, there is only little experience in predicting the effect of defects (e.g. porosity, unmelted spots, insufficient bonding between the layers) on the fatigue behaviour. In this paper, some of these questions are adressed. An electron beam melting process is used to manufacture Ti-6Al-4V high cycle fatigue samples without and with intentionally integrated defects inside of the samples. The samples were annealed or hot isostatically pressed. The defects were analysed by non- destructive methods before and by light/electron microscopy after the tests. In order to predict the high cycle fatigue properties, the crack propagation properties of the material (da/dN - ΔK curve) were tested and AFGROW simulation was used.

Comparative study on predicting Young's modulus of graphene sheets using nano-scale continuum mechanics approach

NASA Astrophysics Data System (ADS)

Rafiee, Roham; Eskandariyun, Amirali

2017-06-01

In this research, nano-scale continuum modeling is employed to predict Young's modulus of graphene sheet. The lattice nano-structure of a graphene sheet is replaced with a discrete space-frame structure simulating carbon-carbon bonds with either beam or spring elements. A comparative study is carried out to check the influence of employed elements on estimated Young's moduli of graphene sheets in both horizontal and vertical directions. A detailed analysis is also conducted to investigate the influence of graphene sheet sizes on its Young's modulus and corresponding aspect ratios that unwelcomed end effects disappear on the results are extracted. At the final stage, defected graphene sheets suffering from vacancy defects are investigated through a stochastic analysis taking into account both number of defects and their locations as random parameters. The reduction level in the Young's moduli of defected graphene sheets compared with non-defected ones is analyzed and reported.

Modification of the G-phonon mode of graphene by nitrogen doping

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

Lukashev, Pavel V., E-mail: pavel.lukashev@uni.edu; Hurley, Noah; Zhao, Liuyan

2016-01-25

The effect of nitrogen doping on the phonon spectra of graphene is analyzed. In particular, we employ first-principles calculations and scanning Raman analysis to investigate the dependence of phonon frequencies in graphene on the concentration of nitrogen dopants. We demonstrate that the G phonon frequency shows oscillatory behavior as a function of nitrogen concentration. We analyze different mechanisms which could potentially be responsible for this behavior, such as Friedel charge oscillations around the localized nitrogen impurity atom, the bond length change between nitrogen impurity and its nearest neighbor carbon atoms, and the long-range interactions of the nitrogen point defects. Wemore » show that the bond length change and the long range interaction of point defects are possible mechanisms responsible for the oscillatory behavior of the G frequency as a function of nitrogen concentration. At the same time, Friedel charge oscillations are unlikely to contribute to this behavior.« less

Low-temperature formation of Ga-oxide/GaN interface with remote oxygen plasma and its interface properties

NASA Astrophysics Data System (ADS)

Yamamoto, Taishi; Taoka, Noriyuki; Ohta, Akio; Truyen, Nguyen Xuan; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Makihara, Katsunori; Shimizu, Mitsuaki; Miyazaki, Seiichi

2018-06-01

The Ga-oxide/GaN structures formed by remote oxygen plasma (ROP) exposure at various temperatures (T s) and times have been systematically investigated. X-ray photoelectron spectroscopy clarified the formation of Ga2O3 layers with close-to-stoichiometric composition and a slight N incorporation of ∼6 at. %. Also, we found that a high T s increases the intensity of a signal related to the N–O bond, which is located near the Ga-oxide/GaN interfaces. Total photoelectron yield spectroscopy (PYS) also revealed that the ROP exposure at T s of 300 °C produces fewer filled defect states in the bandgap of GaN than at 500 °C. This difference in the filled defect states could be attributable to the amount of N–O bonds at the interface.

Superhydrophobic nanostructured Kapton® surfaces fabricated through Ar + O2 plasma treatment: Effects of different environments on wetting behaviour

NASA Astrophysics Data System (ADS)

Barshilia, Harish C.; Ananth, A.; Gupta, Nitant; Anandan, C.

2013-03-01

Kapton® [poly (4,4'-oxy diphenylene pyromellitimide)] polyimides have widespread usage in semiconductor devices, solar arrays, protective coatings and space applications, due to their excellent chemical and physical properties. In addition to their inherent properties, imparting superhydrophobicity on these surfaces will be an added advantage. Present work describes the usage of Ar + O2 plasma treatment for the preparation of superhydrophobic Kapton® surfaces. Immediately after the plasma treatment, the surfaces showed superhydrophilicity as a result of high energy dangling bonds and polar group concentration. But the samples kept in low vacuum for 48 h exhibited superhydrophobicity with high water contact angles (>150°). It is found that the post plasma treatment process, called ageing, especially in low vacuum plays an important role in delivering superhydrophobic property to Kapton®. Field emission scanning electron microscopy and atomic force microscopy were used to probe the physical changes in the surface of the Kapton®. The surfaces showed formation of nano-feathers and nano-tussock microstructures with variation in surface roughness against plasma treatment time. A thorough chemical investigation was performed using Fourier transform infrared spectroscopy and micro-Raman spectroscopy, which revealed changes in the surface of the Ar + O2 plasma treated Kapton®. Surface chemical species of Kapton® were confirmed again by X-ray photoelectron spectroscopy spectra for untreated surfaces whereas Ar + O2 plasma treated samples showed the de-bonding and re-organization of structural elements. Creation of surface roughness plays a dominant role in the contribution of superhydrophobicity to Kapton® apart from the surface modifications due to Ar + O2 plasma treatment and ageing in low vacuum.

Hydrogen loss and its improved retention in hydrogen plasma treated a-SiNx:H films: ERDA study with 100 MeV Ag7+ ions

NASA Astrophysics Data System (ADS)

Bommali, R. K.; Ghosh, S.; Khan, S. A.; Srivastava, P.

2018-05-01

Hydrogen loss from a-SiNx:H films under irradiation with 100 MeV Ag7+ ions using elastic recoil detection analysis (ERDA) experiment is reported. The results are explained under the basic assumptions of the molecular recombination model. The ERDA hydrogen concentration profiles are composed of two distinct hydrogen desorption processes, limited by rapid molecular diffusion in the initial stages of irradiation, and as the fluence progresses a slow process limited by diffusion of atomic hydrogen takes over. Which of the aforesaid processes dominates, is determined by the continuously evolving Hydrogen concentration within the films. The first process dominates when the H content is high, and as the H concentration falls below a certain threshold (Hcritical) the irradiation generated H radicals have to diffuse through larger distances before recombining to form H2, thereby significantly bringing down the hydrogen evolution rate. The ERDA measurements were also carried out for films treated with low temperature (300 °C) hydrogen plasma annealing (HPA). The HPA treated films show a clear increase in Hcritical value, thus indicating an improved diffusion of atomic hydrogen, resulting from healing of weak bonds and passivation of dangling bonds. Further, upon HPA films show a significantly higher H concentration relative to the as-deposited films, at advanced fluences. These results indicate the potential of HPA towards improved H retention in a-SiNx:H films. The study distinguishes clearly the presence of two diffusion processes in a-SiNx:H whose diffusion rates differ by an order of magnitude, with atomic hydrogen not being able to diffuse further beyond ∼ 1 nm from the point of its creation.

Hydrogen release at metal-oxide interfaces: A first principle study of hydrogenated Al/SiO2 interfaces

NASA Astrophysics Data System (ADS)

Huang, Jianqiu; Tea, Eric; Li, Guanchen; Hin, Celine

2017-06-01

The Anode Hydrogen Release (AHR) mechanism at interfaces is responsible for the generation of defects, that traps charge carriers and can induce dielectric breakdown in Metal-Oxide-Semiconductor Field Effect Transistors. The AHR has been extensively studied at Si/SiO2 interfaces but its characteristics at metal-silica interfaces remain unclear. In this study, we performed Density Functional Theory (DFT) calculations to study the hydrogen release mechanism at the typical Al/SiO2 metal-oxide interface. We found that interstitial hydrogen atoms can break interfacial Alsbnd Si bonds, passivating a Si sp3 orbital. Interstitial hydrogen atoms can also break interfacial Alsbnd O bonds, or be adsorbed at the interface on aluminum, forming stable Alsbnd Hsbnd Al bridges. We showed that hydrogenated Osbnd H, Sisbnd H and Alsbnd H bonds at the Al/SiO2 interfaces are polarized. The resulting bond dipole weakens the Osbnd H and Sisbnd H bonds, but strengthens the Alsbnd H bond under the application of a positive bias at the metal gate. Our calculations indicate that Alsbnd H bonds and Osbnd H bonds are more important than Sisbnd H bonds for the hydrogen release process.

A Novel Fabrication Method of Bi₂Te₃-Based Thermoelectric Modules by Indium Electroplating and Thermocompression Bonding.

PubMed

Yoon, Jongchan; Bae, Sung Hwa; Sohn, Ho-Sang; Son, Injoon; Kim, Kyung Tae; Ju, Young-Wan

2018-09-01

In this study, we devised a method to bond thermoelectric elements directly to copper electrodes by plating indium with a relatively low melting point. A coating of indium, ~30 μm in thickness, was fabricated by electroplating the surface of a Bi2Te3-based thermoelectric element with a nickel diffusion barrier layer. They were then subjected to direct thermocompression bonding at 453 K on a hotplate for 10 min at a pressure of 1.1 kPa. Scanning electron microscopy images confirmed that a uniform bond was formed at the copper electrode/thermoelectric element interface, and the melted/solidified indium layer was defect free. Thus, the proposed novel method of fabricating a thermoelectric module by electroplating indium on the surface of the thermoelectric element and directly bonding with the copper electrode can be used to obtain a uniformly bonded interface even at a relatively low temperature without the use of solder pastes.

Chromophores in phenylenevinylene-based conjugated polymers: role of conformational kinks and chemical defects.

PubMed

Hennebicq, Emmanuelle; Deleener, Caroline; Brédas, Jean-Luc; Scholes, Gregory D; Beljonne, David

2006-08-07

The influence of chemical defects and conformational kinks on the nature of the lowest electronic excitations in phenylenevinylene-based polymers is assessed at the semiempirical quantum-chemical level. The amount of excited-state localization and the amplitude of through-space (Coulomb-like) versus through-bond (charge-transfer-like) interactions have been quantified by comparing the results provided by excitonic and supermolecular models. While excitation delocalization among conjugated segments delineated by the defects occurs in the acceptor configuration, self-confinement on individual chromophores follows from geometric relaxation in the excited-state donor configuration. The extent of excited-state localization is found to be sensitive to both the nature of the defect and the length of the conjugated chains. Implications for resonant energy transfer along conjugated polymer chains are discussed.

Efficiency droop in GaN LEDs at high injection levels: Role of hydrogen

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

Bochkareva, N. I.; Sheremet, I. A.; Shreter, Yu. G., E-mail: y.shreter@mail.ioffe.ru

2016-10-15

Point defects in GaN and, in particular, their manifestation in the photoluminescence, optical absorption, and recombination current in light-emitting diodes with InGaN/GaN quantum wells are analyzed. The results of this analysis demonstrate that the wide tail of defect states in the band gap of GaN facilitates the trap-assisted tunneling of thermally activated carriers into the quantum well, but simultaneously leads to a decrease in the nonradiative-recombination lifetime and to an efficiency droop as the quasi-Fermi levels intersect the defect states with increasing forward bias. The results reveal the dominant role of hydrogen in the recombination activity of defects with danglingmore » bonds and in the efficiency of GaN-based devices.« less

Self-Diffusion in Amorphous Silicon by Local Bond Rearrangements

NASA Astrophysics Data System (ADS)

Kirschbaum, J.; Teuber, T.; Donner, A.; Radek, M.; Bougeard, D.; Böttger, R.; Hansen, J. Lundsgaard; Larsen, A. Nylandsted; Posselt, M.; Bracht, H.

2018-06-01

Experiments on self-diffusion in amorphous silicon (Si) were performed at temperatures between 460 to 600 ° C . The amorphous structure was prepared by Si ion implantation of single crystalline Si isotope multilayers epitaxially grown on a silicon-on-insulator wafer. The Si isotope profiles before and after annealing were determined by means of secondary ion mass spectrometry. Isothermal diffusion experiments reveal that structural relaxation does not cause any significant intermixing of the isotope interfaces whereas self-diffusion is significant before the structure recrystallizes. The temperature dependence of self-diffusion is described by an Arrhenius law with an activation enthalpy Q =(2.70 ±0.11 ) eV and preexponential factor D0=(5.5-3.7+11.1)×10-2 cm2 s-1 . Remarkably, Q equals the activation enthalpy of hydrogen diffusion in amorphous Si, the migration of bond defects determining boron diffusion, and the activation enthalpy of solid phase epitaxial recrystallization reported in the literature. This close agreement provides strong evidence that self-diffusion is mediated by local bond rearrangements rather than by the migration of extended defects as suggested by Strauß et al. (Phys. Rev. Lett. 116, 025901 (2016), 10.1103/PhysRevLett.116.025901).

A charge-optimized many-body potential for the U-UO2-O2 system

NASA Astrophysics Data System (ADS)

Li, Yangzhong; Liang, Tao; Sinnott, Susan B.; Phillpot, Simon R.

2013-12-01

Building on previous charge-optimized many-body (COMB) potentials for metallic α-U and gaseous O2, we have developed a new potential for UO2, which also allows the simulation of U-UO2-O2 systems. The UO2 lattice parameter, elastic constants and formation energies of stoichiometric and non-stoichiometric intrinsic defects are well reproduced. Moreover, this is the first rigid-ion potential that produces the correct deviation of the Cauchy relation, as well as the first classical interatomic potential that is able to determine the defect energies of non-stoichiometric intrinsic point defects in UO2 with an appropriate reference state. The oxygen molecule interstitial in the α-U structure is shown to decompose, with some U-O bonds approaching the natural bond length of perfect UO2. Finally, we demonstrate the capability of this COMB potential to simulate a complex system by performing a simulation of the α-U + O2 → UO2 phase transformation. We also identify a possible mechanism for uranium oxidation and the orientation of the resulting fluorite UO2 structure relative to the coordinate system of orthorhombic α-U.

Multiscale simulations of defect dipole-enhanced electromechanical coupling at dilute defect concentrations

NASA Astrophysics Data System (ADS)

Liu, Shi; Cohen, R. E.

2017-08-01

The role of defects in solids of mixed ionic-covalent bonds such as ferroelectric oxides is complex. Current understanding of defects on ferroelectric properties at the single-defect level remains mostly at the empirical level, and the detailed atomistic mechanisms for many defect-mediated polarization-switching processes have not been convincingly revealed quantum mechanically. We simulate the polarization-electric field (P-E) and strain-electric field (ɛ-E) hysteresis loops for BaTiO3 in the presence of generic defect dipoles with large-scale molecular dynamics and provide a detailed atomistic picture of the defect dipole-enhanced electromechanical coupling. We develop a general first-principles-based atomistic model, enabling a quantitative understanding of the relationship between macroscopic ferroelectric properties and dipolar impurities of different orientations, concentrations, and dipole moments. We find that the collective orientation of dipolar defects relative to the external field is the key microscopic structure feature that strongly affects materials hardening/softening and electromechanical coupling. We show that a small concentration (≈0.1 at. %) of defect dipoles dramatically improves electromechanical responses. This offers the opportunity to improve the performance of inexpensive polycrystalline ferroelectric ceramics through defect dipole engineering for a range of applications including piezoelectric sensors, actuators, and transducers.

Design of defect spins in piezoelectric aluminum nitride for solid-state hybrid quantum technologies

DOE PAGES

Seo, Hosung; Govoni, Marco; Galli, Giulia

2016-02-15

Spin defects in wide-band gap semiconductors are promising systems for the realization of quantum bits, or qubits, in solid-state environments. To date, defect qubits have only been realized in materials with strong covalent bonds. Here, we introduce a strain-driven scheme to rationally design defect spins in functional ionic crystals, which may operate as potential qubits. In particular, using a combination of state-of-the-art ab-initio calculations based on hybrid density functional and many-body perturbation theory, we predicted that the negatively charged nitrogen vacancy center in piezoelectric aluminum nitride exhibits spin-triplet ground states under realistic uni- and bi-axial strain conditions; such states maymore » be harnessed for the realization of qubits. As a result, the strain-driven strategy adopted here can be readily extended to a wide range of point defects in other wide-band gap semiconductors, paving the way to controlling the spin properties of defects in ionic systems for potential spintronic technologies.« less

Qualitative properties of roasting defect beans and development of its classification methods by hyperspectral imaging technology.

PubMed

Cho, Jeong-Seok; Bae, Hyung-Jin; Cho, Byoung-Kwan; Moon, Kwang-Deog

2017-04-01

Qualitative properties of roasting defect coffee beans and their classification methods were studied using hyperspectral imaging (HSI). The roasting defect beans were divided into 5 groups: medium roasting (Cont), under developed (RD-1), over roasting (RD-2), interior under developed (RD-3), and interior scorching (RD-4). The following qualitative properties were assayed: browning index (BI), moisture content (MC), chlorogenic acid (CA), trigonelline (TG), and caffeine (CF) content. Their HSI spectra (1000-1700nm) were also analysed to develop the classification methods of roasting defect beans. RD-2 showed the highest BI and the lowest MC, CA, and TG content. The accuracy of classification model of partial least-squares discriminant was 86.2%. The most powerful wavelength to classify the defective beans was approximately 1420nm (related to OH bond). The HSI reflectance values at 1420nm showed similar tendency with MC, enabling the use of this technology to classify the roasting defect beans. Copyright © 2016. Published by Elsevier Ltd.

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

Liu, Yuanyue; Xiao, Hai; Goddard, William A.

Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX 2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gapmore » states. Here, we show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX 2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.« less

The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Liu, Zhixue; Ling, Lixia; Wang, Baojun

2015-10-01

The perfect and defective surfaces of anatase TiO2 including (1 0 1) and (0 0 1) surfaces have been chosen to probe into the effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and initial dissociation step. Here, the results are obtained by density functional theory (DFT) calculation together with the periodic slab model. Our results show that the surface structure of anatase TiO2 can obviously affect the behavior of ethanol adsorption and the catalytic activity of its initial dissociation step; firstly, on the perfect and defective surfaces of anatase (1 0 1), ethanol dominantly exists in the form of molecule adsorption; however, ethanol is the dissociative adsorption on the hydroxylated anatase (0 0 1), and the coexistences of molecular and dissociation adsorption modes on the perfect anatase (0 0 1). On the other hand, the initial dissociation step of ethanol with molecule adsorption prefers to begin with its O-H bond cleavage leading to CH3CH2O and H species rather than the cleavage of its α-C-H, β-C-H, C-C and C-O bonds, namely, the preferable O-H bond cleavage for the initial dissociation step of ethanol is independent of the surface structure of anatase TiO2; however, the corresponding catalytic activity of ethanol initial dissociation step with the O-H bond cleavage on different anatase TiO2 surfaces is in the following order: hydroxylated (0 0 1) > perfect (0 0 1) > defective (1 0 1) > perfect (1 0 1), suggesting that the catalytic activity for the initial dissociation step of ethanol is sensitive to the surface structure of anatase TiO2, and the hydroxylated (0 0 1) is the most favorable surface. Among these surfaces, the most favorable product for the initial dissociation step of ethanol is CH3CH2O species.

The Effect of Two Soft Drinks on Bracket Bond Strength and on Intact and Sealed Enamel: An In Vitro Study.

PubMed

Pasha, Azam; Sindhu, D; Nayak, Rabindra S; Mamatha, J; Chaitra, K R; Vishwakarma, Swati

2015-01-01

This study was conducted to evaluate the effect of two soft drinks, Coca-Cola and Mirinda orange on bracket bond strength, on adhesive remnant on teeth after debonding the bracket, and to observe by means of scanning electron microscope (SEM) the effect of these drinks on intact and sealed enamel. 120 non-carious maxillary premolar teeth already extracted for Orthodontic purposes were taken and divided into three groups, i.e., Coca-Cola drink, Mirinda orange, and control (artificial saliva) group. Brackets were bonded using conventional methods. Teeth were kept in soft drinks for 15 days, for 15 min, 3 times a day, separated by intervals of 2 h. At other times, they were kept in artificial saliva. The samples, thus obtained were evaluated for shear bond strength using the universal testing machine and subsequently subjected for adhesive remnant index (ARI) scores. SEM study on all the three groups was done for evaluating enamel surface of the intact and sealed enamel. The lowest mean resistance to shearing forces was shown by Mirinda orange group (5.30 ± 2.74 Mpa) followed by Coca-Cola group (6.24 ± 1.59 Mpa) and highest resistance to shearing forces by control group (7.33 ± 1.72 Mpa). The ARI scores revealed a cohesive failure in control samples and an adhesive failure in Mirinda and cola samples. SEM results showed areas of defect due to erosion caused by acidic soft drinks on intact and sealed enamel surface. Mirinda group showed the lowest resistance to shearing forces, followed by Coca-Cola group and with the highest resistance to shearing forces by the control group. There were significant differences between the control group and the study groups. Areas of defects, which were caused by erosion related to acidic soft drinks on the enamel surface around the adhesive, were seen. Areas of defects caused by Coca-Cola were more extensive when compared to Mirinda orange drink.