Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Lee, J.-S.; Stanford, J. A.; Grant, W. K.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Swanberg, E. L.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L. J.; Shah, K.

2013-09-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. Samples of as polished TlBr were treated separately with 2%Br:MeOH, 10%HF, 10%HCl and 96%SOCl2 solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry. Results suggest anion substitution at the surface with subsequent shallow heterojunction formation. Surface chemistry and valence band electronic structure were further correlated with the goal of optimizing the long-term stability and radiation response.

Secondary Electron Emission Spectroscopy of Diamond Surfaces

NASA Technical Reports Server (NTRS)

Krainsky, Isay L.; Asnin, Vladimir M.; Petukhov, Andre G.

1999-01-01

This report presents the results of the secondary electron emission spectroscopy study of hydrogenated diamond surfaces for single crystals and chemical vapor-deposited polycrystalline films. One-electron calculations of Auger spectra of diamond surfaces having various hydrogen coverages are presented, the major features of the experimental spectra are explained, and a theoretical model for Auger spectra of hydrogenated diamond surfaces is proposed. An energy shift and a change in the line shape of the carbon core-valence-valence (KVV) Auger spectra were observed for diamond surfaces after exposure to an electron beam or by annealing at temperatures higher than 950 C. This change is related to the redistribution of the valence-band local density of states caused by hydrogen desorption from the surface. A strong negative electron affinity (NEA) effect, which appeared as a large, narrow peak in the low-energy portion of the spectrum of the secondary electron energy distribution, was also observed on the diamond surfaces. A fine structure in this peak, which was found for the first time, reflected the energy structure of the bottom of the conduction band. Further, the breakup of the bulk excitons at the surface during secondary electron emission was attributed to one of the features of this structure. The study demonstrated that the NEA type depends on the extent of hydrogen coverage of the diamond surface, changing from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surface.

First principle study of structural, electronic and fermi surface properties of aluminum praseodymium

NASA Astrophysics Data System (ADS)

Shugani, Mani; Aynyas, Mahendra; Sanyal, S. P.

2018-05-01

We present a structural, Electronic and Fermi surface properties of Aluminum Praseodymium (AlPr) using First-principles density functional calculation by using full potential linearized augmented plane wave (FP-LAPW) method within generalized gradient approximation (GGA). The ground state properties along with electronic and Fermi surface properties are studied. It is found that AlPr is metallic and the bonding between Al and Pr is covalent.

Structure of electroexplosive TiC-Ni composite coatings on steel after electron-beam treatment

NASA Astrophysics Data System (ADS)

Romanov, D. A.; Goncharova, E. N.; Budovskikh, E. A.; Gromov, V. E.; Ivanov, Yu. F.; Teresov, A. D.; Kazimirov, S. A.

2016-11-01

The phase and elemental compositions of the surface layer in Hardox 450 steel after electroexplosive spraying of a TiC-Ni composite coating and subsequent irradiation by a submillisecond high-energy electron beam are studied by the methods of modern physical metallurgy. The electron-beam treatment conditions that result in the formation of dense surface layers having high luster and a submicrocrystalline structure based on titanium carbide and nickel are found. It is shown that electron-beam treatment of an electroexplosive coating performed under melting conditions leads to the formation of a homogeneous (in structure and concentration) surface layer.

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

Nelson, A. J.; Voss, L. F.; Beck, P. R.

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-04-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl2, Br:MeOH, and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p, and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

The physics and chemistry of graphene-on-surfaces.

PubMed

Zhao, Guoke; Li, Xinming; Huang, Meirong; Zhen, Zhen; Zhong, Yujia; Chen, Qiao; Zhao, Xuanliang; He, Yijia; Hu, Ruirui; Yang, Tingting; Zhang, Rujing; Li, Changli; Kong, Jing; Xu, Jian-Bin; Ruoff, Rodney S; Zhu, Hongwei

2017-07-31

Graphene has demonstrated great potential in next-generation electronics due to its unique two-dimensional structure and properties including a zero-gap band structure, high electron mobility, and high electrical and thermal conductivity. The integration of atom-thick graphene into a device always involves its interaction with a supporting substrate by van der Waals forces and other intermolecular forces or even covalent bonding, and this is critical to its real applications. Graphene films on different surfaces are expected to exhibit significant differences in their properties, which lead to changes in their morphology, electronic structure, surface chemistry/physics, and surface/interface states. Therefore, a thorough understanding of the surface/interface properties is of great importance. In this review, we describe the major "graphene-on-surface" structures and examine the roles of their properties and related phenomena in governing the overall performance for specific applications including optoelectronics, surface catalysis, anti-friction and superlubricity, and coatings and composites. Finally, perspectives on the opportunities and challenges of graphene-on-surface systems are discussed.

Surface determination through atomically resolved secondary-electron imaging

PubMed Central

Ciston, J.; Brown, H. G.; D'Alfonso, A. J.; Koirala, P.; Ophus, C.; Lin, Y.; Suzuki, Y.; Inada, H.; Zhu, Y.; Allen, L. J.; Marks, L. D.

2015-01-01

Unique determination of the atomic structure of technologically relevant surfaces is often limited by both a need for homogeneous crystals and ambiguity of registration between the surface and bulk. Atomically resolved secondary-electron imaging is extremely sensitive to this registration and is compatible with faceted nanomaterials, but has not been previously utilized for surface structure determination. Here we report a detailed experimental atomic-resolution secondary-electron microscopy analysis of the c(6 × 2) reconstruction on strontium titanate (001) coupled with careful simulation of secondary-electron images, density functional theory calculations and surface monolayer-sensitive aberration-corrected plan-view high-resolution transmission electron microscopy. Our work reveals several unexpected findings, including an amended registry of the surface on the bulk and strontium atoms with unusual seven-fold coordination within a typically high surface coverage of square pyramidal TiO5 units. Dielectric screening is found to play a critical role in attenuating secondary-electron generation processes from valence orbitals. PMID:26082275

Surface determination through atomically resolved secondary-electron imaging

DOE PAGES

Ciston, J.; Brown, H. G.; D’Alfonso, A. J.; ...

2015-06-17

We report that unique determination of the atomic structure of technologically relevant surfaces is often limited by both a need for homogeneous crystals and ambiguity of registration between the surface and bulk. Atomically resolved secondary-electron imaging is extremely sensitive to this registration and is compatible with faceted nanomaterials, but has not been previously utilized for surface structure determination. Here we show a detailed experimental atomic-resolution secondary-electron microscopy analysis of the c(6 x 2) reconstruction on strontium titanate (001) coupled with careful simulation of secondary-electron images, density functional theory calculations and surface monolayer-sensitive aberration-corrected plan-view high-resolution transmission electron microscopy. Our workmore » reveals several unexpected findings, including an amended registry of the surface on the bulk and strontium atoms with unusual seven-fold coordination within a typically high surface coverage of square pyramidal TiO 5 units. Lastly, dielectric screening is found to play a critical role in attenuating secondary-electron generation processes from valence orbitals.« less

Bulk and surface electronic structures of MgO

NASA Astrophysics Data System (ADS)

Schönberger, U.; Aryasetiawan, F.

1995-09-01

The bulk electronic structure of MgO is calculated from first principles including correlation effects within the GW approximation. The band gap, the position of the 2s O band, and the valence band width are in good agreement with experiment. From the quasiparticle band structure, optical transitions corresponding to the main optical absorption peaks are identified. The energy-loss spectrum is also calculated and compared with experiment. The surface electronic structure of MgO(100) is calculated self-consistently within the local-density approximation. It is found that states observed in a recent photoemission experiment outside the bulk allowed states are close to surface states.

Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis

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

Ong, Phuong-Vu; Johnson, Lewis E.; Hosono, Hideo

Structure, thermodynamic stability, and electronic properties of CaH 2 surfaces in (001),(110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (~5.2 eV) is in agree-ment with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ~2.7 eV. Surface VH aremore » predicted to aggregate into dimers and form electron-rich centers (e -)Ca 2+(e -) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH 2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.« less

The gradient structure of the NiTi surface layers subjected to tantalum ion beam alloying

NASA Astrophysics Data System (ADS)

Girsova, S. L.; Poletika, T. M.; Meisner, L. L.; Schmidt, E. Yu

2017-05-01

The NiTi shape memory alloy has been modified by ion implantation with Ta to improve the surface and biological properties. The elemental and phase composition and structure of the surface and near-surface layers of NiTi specimens after the Ta ion implantation with the fluency D = 3 × 1017 cm-2 and D = 6 × 1017 cm-2 are examined. The methods of Auger electron spectroscopy (AES), transmission electron microscopy (TEM), and electron dispersion analysis (EDS) are used. It is found that a nonuniform distribution of elements along the depth of the surface layer after the ion implantation of NiTi specimens, regardless of the regime, is accompanied by the formation of a number of sublayer structures.

Novel microstructural growth in the surface of Inconel 625 by the addition of SiC under electron beam melting

NASA Astrophysics Data System (ADS)

Ahmad, M.; Ali, G.; Ahmed, Ejaz; Haq, M. A.; Akhter, J. I.

2011-06-01

Electron beam melting is being used to modify the microstructure of the surfaces of materials due to its ability to cause localized melting and supercooling of the melt. This article presents an experimental study on the surface modification of Ni-based superalloy (Inconel 625) reinforced with SiC ceramic particles under electron beam melting. Scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction techniques have been applied to characterize the resulted microstructure. The results revealed growth of novel structures like wire, rod, tubular, pyramid, bamboo and tweezers type morphologies in the modified surface. In addition to that fibrous like structure was also observed. Formation of thin carbon sheet has been found at the regions of decomposed SiC. Electron beam modified surface of Inconel 625 alloy has been hardened twice as compared to the as-received samples. Surface hardening effect may be attributed to both the formation of the novel structures as well as the introduction of Si and C atom in the lattice of Inconel 625 alloy.

Oxides Surfaces and Novel Electronic Properties

NASA Astrophysics Data System (ADS)

Koirala, Pratik

The scope of this thesis extends to the study of surface structures and electronic properties in a number of complex oxides. The c(6x2) surface reconstruction on SrTiO3 (001) was solved using a combination of plan view transmission electron microscopy imaging, atomic resolution secondary electron imaging, and density functional theory calculations. This work provided fundamental insights on the effects of dielectric screening in secondary electron generation. A thorough analysis on the limitation and functionality of transmission plan view imaging showed that the kinematical approximations used in the separation of top and bottom surfaces is only valid in thin samples (˜5 nm or less for SrTiO3). The presence of an inversion center in the surface structure also made separation of the top and bottom surfaces more robust. Surface studies of two other oxides, KTaO3 and NdGaO3, provided understanding on the mechanism of surface heterogeneity and segregation. In the case of KTaO3, selective ion sputtering and the loss of K resulted in large stoichiometric variations at the surface. Annealing of such samples led to the formation of a potassium deficient tetragonal phase (K 6Ta10.8O30) on the surface. A similar phenomenon was also observed in NdGaO3. Exploratory surface studies of the rare earth scandates (ReScO3 , Re = Gd, Tb, Dy) led to the observation of large flexoelectric bending inside an electron microscope. Thin rods of these scandates bent by up to 90 degree under a focused electron beam; the bending was fully reversible. Ex-situ measurements of flexoelectric coe cient performed by an- other graduate student, Christopher Mizzi, confirmed that the scandates have a large flexocoupling voltage (˜42 V). Electronic structure of the lanthanide scandates was studied using temperature depen- dent X-ray photoelectron spectroscopy and hybrid density functional theory calculations. The amount of charging under X-ray illumination was greatly reduced with increasing temperature owing to the presence of oxygen vacancies and surface band gap reduction. These results also indicated that the 4f-electrons are active components of the valence band electronic structure. We believe that the lanthanide scandates are a rich playground of material properties and have potential for applications in electronic and nano-mechanical devices.

Gold-film coating assisted femtosecond laser fabrication of large-area, uniform periodic surface structures.

PubMed

Feng, Pin; Jiang, Lan; Li, Xin; Rong, Wenlong; Zhang, Kaihu; Cao, Qiang

2015-02-20

A simple, repeatable approach is proposed to fabricate large-area, uniform periodic surface structures by a femtosecond laser. 20 nm gold films are coated on semiconductor surfaces on which large-area, uniform structures are fabricated. In the case study of silicon, cross-links and broken structures of laser induced periodic surface structures (LIPSSs) are significantly reduced on Au-coated silicon. The good consistency between the scanning lines facilitates the formation of large-area, uniform LIPSSs. The diffusion of hot electrons in the Au films increases the interfacial carrier densities, which significantly enhances interfacial electron-phonon coupling. High and uniform electron density suppresses the influence of defects on the silicon and further makes the coupling field more uniform and thus reduces the impact of laser energy fluctuations, which homogenizes and stabilizes large-area LIPSSs.

Electronic Structure of Ytterbium-Doped Strontium Fluoroapatite: Photoemission and Photoabsorption Investigation

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

Nelson, Art J.; Van Buuren, Tony W.; Bostedt, C

X-ray photoemission and x-ray photoabsorption were used to study the composition and the electronic structure of ytterbium-doped strontium fluoroapatite (Yb:S-FAP). High resolution photoemission measurements on the valence band electronic structure and Sr 3d, P 2p and 2s, Yb 4d and 4p, F 1s and O 1s core lines were used to evaluate the surface and near surface chemistry of this fluoroapatite. Element specific density of unoccupied electronic states in Yb:S-FAP were probed by x-ray absorption spectroscopy (XAS) at the Yb 4d (N4,5-edge), Sr 3d (M4,5-edge), P 2p (L2,3-edge), F 1s and O 1s (K-edges) absorption edges. These results provide themore » first measurements of the electronic structure and surface chemistry of this material.« less

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Evolution of magnetism of Cr nanoclusters on a Au(111) surface

NASA Astrophysics Data System (ADS)

Gotsis, Harry; Kioussis, Nicholas; Papaconstantopoulos, Dimitri

2004-03-01

Advances in low-temperature scanning tunneling microscopy under ultrahigh vacuum have provided new opportunities for investigating the magnetic structures of nanoclusters adsorbed on surfaces. Recent STM studies of Cr trimers on the Au(111) surface suggest a switching between two distinct electronic states. We have carried out ab initio electronic structure calculations to investigate the structural, electronic and magnetic properties of isolated Cr atoms, Cr dimers and trimers in different geometry. We will present results for the evolution of magnetic behavior including noncollinear magnetism and provide insight in the connection between magnetism and geometry.

Preface: Special Topic Section on Advanced Electronic Structure Methods for Solids and Surfaces.

PubMed

Michaelides, Angelos; Martinez, Todd J; Alavi, Ali; Kresse, Georg; Manby, Frederick R

2015-09-14

This Special Topic section on Advanced Electronic Structure Methods for Solids and Surfaces contains a collection of research papers that showcase recent advances in the high accuracy prediction of materials and surface properties. It provides a timely snapshot of a growing field that is of broad importance to chemistry, physics, and materials science.

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

NASA Astrophysics Data System (ADS)

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

1989-02-01

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

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

Ivanov, Yuri, E-mail: yufi55@mail.ru; National Research Tomsk State University, 36 Lenina Str., Tomsk, 634050; National Research Tomsk Polytechnic University, 30 Lenina Str., Tomsk, 634050

The present work is devoted to numerical simulation of temperature fields and the analysis of structural and strength properties of the samples surface layer of boron carbide ceramics treated by the high-current pulsed electron-beam of the submillisecond duration. The samples made of sintered boron carbide ceramics are used in these investigations. The problem of calculating the temperature field is reduced to solving the thermal conductivity equation. The electron beam density ranges between 8…30 J/cm{sup 2}, while the pulse durations are 100…200 μs in numerical modelling. The results of modelling the temperature field allowed ascertaining the threshold parameters of the electronmore » beam, such as energy density and pulse duration. The electron beam irradiation is accompanied by the structural modification of the surface layer of boron carbide ceramics either in the single-phase (liquid or solid) or two-phase (solid-liquid) states. The sample surface of boron carbide ceramics is treated under the two-phase state (solid-liquid) conditions of the structural modification. The surface layer is modified by the high-current pulsed electron-beam produced by SOLO installation at the Institute of High Current Electronics of the Siberian Branch of the Russian Academy of Sciences, Tomsk, Russia. The elemental composition and the defect structure of the modified surface layer are analyzed by the optical instrument, scanning electron and transmission electron microscopes. Mechanical properties of the modified layer are determined measuring its hardness and crack resistance. Research results show that the melting and subsequent rapid solidification of the surface layer lead to such phenomena as fragmentation due to a crack network, grain size reduction, formation of the sub-grained structure due to mechanical twinning, and increase of hardness and crack resistance.« less

Atomically precise lateral modulation of a two-dimensional electron liquid in anatase TiO 2 thin films

DOE PAGES

Wang, Zhiming; Zhong, Z.; Walker, S. McKeown; ...

2017-03-10

Engineering the electronic band structure of two-dimensional electron liquids (2DELs) confined at the surface or interface of transition metal oxides is key to unlocking their full potential. Here we describe a new approach to tailoring the electronic structure of an oxide surface 2DEL demonstrating the lateral modulation of electronic states with atomic scale precision on an unprecedented length scale comparable to the Fermi wavelength. To this end, we use pulsed laser deposition to grow anatase TiO 2 films terminated by a (1 x 4) in-plane surface reconstruction. Employing photo-stimulated chemical surface doping we induce 2DELs with tunable carrier densities thatmore » are confined within a few TiO 2 layers below the surface. Subsequent in situ angle resolved photoemission experiments demonstrate that the (1 x 4) surface reconstruction provides a periodic lateral perturbation of the electron liquid. Furthermore, this causes strong backfolding of the electronic bands, opening of unidirectional gaps and a saddle point singularity in the density of states near the chemical potential.« less

Theoretical and experimental investigations of superconductivity. Amorphous semiconductors, superconductivity and magnetism

NASA Technical Reports Server (NTRS)

Cohen, M. H.

1973-01-01

The research activities from 1 March 1963 to 28 February 1973 are summarized. Major lectures are listed along with publications on superconductivity, superfluidity, electronic structures and Fermi surfaces of metals, optical spectra of solids, electronic structure of insulators and semiconductors, theory of magnetic metals, physics of surfaces, structures of metals, and molecular physics.

Theoretical Study of tip apex electronic structure in Scanning Tunneling Microscope

NASA Astrophysics Data System (ADS)

Choi, Heesung; Huang, Min; Randall, John; Cho, Kyeongjae

2011-03-01

Scanning Tunneling Microscope (STM) has been widely used to explore diverse surface properties with an atomic resolution, and STM tip has played a critical role in controlling surface structures. However, detailed information of atomic and electronic structure of STM tip and the fundamental understanding of STM images are still incomplete. Therefore, it is important to develop a comprehensive understanding of the electronic structure of STM tip. We have studied the atomic and electronic structures of STM tip with various transition metals (TMs) by DFT method. The d-electrons of TM tip apex atoms show different orbital states near the Fermi level. We will present comprehensive data of STM tips from our DFT calculation. Verified quantification of the tip electronic structures will lead to fundamental understanding of STM tip structure-property relationship. This work is supported by the DARPA TBN Program and the Texas ETF. DARPA Tip Based Nanofabrication Program and the Emerging Technology Fund of the State of Texas.

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.

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

WC/Co composite surface structure and nano graphite precipitate induced by high current pulsed electron beam irradiation

NASA Astrophysics Data System (ADS)

Hao, S. Z.; Zhang, Y.; Xu, Y.; Gey, N.; Grosdidier, T.; Dong, C.

2013-11-01

High current pulsed electron beam (HCPEB) irradiation was conducted on a WC-6% Co hard alloy with accelerating voltage of 27 kV and pulse duration of 2.5 μs. The surface phase structure was examined by using glancing-angle X-ray diffraction (GAXRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM) methods. The surface tribological properties were measured. It was found that after 20 pulses of HCPEB irradiation, the surface structure of WC/Co hard alloy was modified dramatically and composed of a mixture of nano-grained WC1-x, Co3W9C4, Co3W3C phases and graphite precipitate domains ˜50 nm. The friction coefficient of modified surface decreased to ˜0.38 from 0.6 of the initial state, and the wear rate reduced from 8.4 × 10-5 mm3/min to 6.3 × 10-6 mm3/min, showing a significant self-lubricating effect.

Studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2012-02-01

The study of oxidation of single crystal metal surfaces is important in understanding the corrosive and catalytic processes associated with thin film metal oxides. The structures formed on oxidized transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which result from the diffusion of oxygen into subsurface regions. In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. The results of calculations of positron binding energy, positron work function, and annihilation characteristics of surface trapped positrons with relevant core electrons as function of oxygen coverage are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES).

Effect of electronic structure of the diamond surface on the strength of the diamond-metal interface

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1981-01-01

A diamond surface undergoes a transformation in its electronic structure by a vacuum anneal at approximately 900 C. The polished surface has no electronic states in the band gap, whereas the annealed surface has both occupied and unoccupied states in the and gap and exhibits some electrical conductivity. The effect of this transformation on the strength of the diamond metal interface was investigated by measuring the static friction force of an atomically clean meta sphere on a diamond flat in ultrahigh vacuum. It was found that low friction (weak bonding) is associated with the diamond surface devoid of gap states whereas high friction (strong bonding) is associated with the diamond surface with gap states. Exposure of the annealed surface to excited hydrogen also leads to weak bonding. The interfacial bond is discussed in terms of interaction of the metal conduction band electrons with the band gap states on the diamond surface. Effects of surface electrical conductivity on the interfacial bond are also be considered.

Modification of Structure and Tribological Properties of the Surface Layer of Metal-Ceramic Composite under Electron Irradiation in the Plasmas of Inert Gases

NASA Astrophysics Data System (ADS)

Ovcharenko, V. E.; Ivanov, K. V.; Mohovikov, A. A.; Yu, B.; Xu, Yu; Zhong, L.

2018-01-01

Metal-ceramic composites are the main materials for high-load parts in tribomechanical systems. Modern approaches to extend the operation life of tribomechanical systems are based on increasing the strength and tribological properties of the surface layer having 100 to 200 microns in depth. The essential improvement of the properties occurs when high dispersed structure is formed in the surface layer using high-energy processing. As a result of the dispersed structure formation the more uniform distribution of elastic stresses takes place under mechanical or thermal action, the energy of stress concentrators emergence significantly increases and the probability of internal defects formation reduces. The promising method to form the dispersed structure in the surface layer is pulse electron irradiation in the plasmas of inert gases combining electron irradiation and ion bombardment in one process. The present work reports upon the effect of pulse electron irradiation in plasmas of different inert gases with different atomic mass and ionization energy on the structure and tribological properties of the surface layer of TiC/(Ni-Cr) metal-ceramic composite with the volume ratio of the component being 50:50. It is experimentally shown that high-dispersed heterophase structure with a fraction of nanosized particles is formed during the irradiation. Electron microscopy study reveals that refining of the initial coarse TiC particles occurs via their dissolution in the molten metal binder followed by the precipitation of secondary fine particles in the interparticle layers of the binder. The depth of modified layer and the fraction of nanosized particles increase when the atomic number of the plasma gas increases and ionization energy decreases. The wear resistance of metal-ceramic composite improves in accordance to the formation of nanocrystalline structure in the surface layer.

Modeling of reduced effective secondary electron emission yield from a velvet surface

DOE PAGES

Swanson, Charles; Kaganovich, Igor D.

2016-12-05

Complex structures on a material surface can significantly reduce total secondary electron emission from that surface. A velvet is a surface that consists of an array of vertically standing whiskers. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at the bottom of the structure and on the sides of the velvet whiskers. We performed numerical simulations and developed an approximate analytical model that calculates the net secondary electron emission yield from a velvet surface as a function of the velvet whisker length and packing density, and the angle of incidence of primary electrons. We foundmore » that to suppress secondary electrons, the following condition on dimensionless parameters must be met: (π/2) DΑ tan θ >> 1, where theta is the angle of incidence of the primary electron from the normal, D is the fraction of surface area taken up by the velvet whisker bases, and A is the aspect ratio, A = h/r, the ratio of height to radius of the velvet whiskers. We find that velvets available today can reduce the secondary electron yield by 90% from the value of a flat surface. As a result, the values of optimal velvet whisker packing density that maximally suppresses the secondary electron emission yield are determined as a function of velvet aspect ratio and the electron angle of incidence.« less

Surface modification of Ti alloy by electro-explosive alloying and electron-beam treatment

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

Gromov, Victor, E-mail: gromov@physics.sibsiu.ru; Kobzareva, Tatiana, E-mail: kobzarevatanya@mail.ru; Budovskikh, Evgeniy, E-mail: budovskih-ea@physics.sibsiu.ru

2016-01-15

By methods of modern physical metallurgy the analysis of structure phase states of titanium alloy VT6 is carried out after electric explosion alloying with boron carbide and subsequent irradiation by pulsed electron beam. The formation of an electro-explosive alloying zone of a thickness up to 50 µm, having a gradient structure, characterized by decrease in the concentration of carbon and boron with increasing distance to the treatable surface has been revealed. Subsequent electron-beam treatment of alloying zone leads to smoothing of the alloying area surface and is accompanied by the multilayer structure formation at the depth of 30 µm withmore » alternating layers with different alloying degrees having the structure of submicro - and nanoscale level.« less

Effect of ammonia and methane adsorption on the electronic structure of undoped and Fe-doped 2D silica: a first-principles calculation

NASA Astrophysics Data System (ADS)

Chibisov, A. N.; Chibisova, M. A.

2018-05-01

Two-dimensional silicon oxide (2D SiO2) is a unique surface phase with interesting optical, structural and electronic properties. In this study, important novel results on the effect of Fe on the structural and electronic properties of 2D SiO2 during adsorption of CH4 and NH3 molecules are presented. Density functional theory calculations are used to investigate the interaction of CH4 and NH3 molecules with silica. The electronic structure and molecules adsorption energy are studied in detail for undoped and Fe-doped surfaces. The results show that adsorption of CH4 and NH3 molecules on the surface decreases the spin polarization of Fe/SiO2. The results are relevant to understanding the adsorption physics of 2D SiO2 for practical usage in modern nanoelectronic sensors for nanotechnology and optoelectronics.

Electron affinity of cubic boron nitride terminated with vanadium oxide

NASA Astrophysics Data System (ADS)

Yang, Yu; Sun, Tianyin; Shammas, Joseph; Kaur, Manpuneet; Hao, Mei; Nemanich, Robert J.

2015-10-01

A thermally stable negative electron affinity (NEA) for a cubic boron nitride (c-BN) surface with vanadium-oxide-termination is achieved, and its electronic structure was analyzed with in-situ photoelectron spectroscopy. The c-BN films were prepared by electron cyclotron resonance plasma-enhanced chemical vapor deposition employing BF3 and N2 as precursors. Vanadium layers of ˜0.1 and 0.5 nm thickness were deposited on the c-BN surface in an electron beam deposition system. Oxidation of the metal layer was achieved by an oxygen plasma treatment. After 650 °C thermal annealing, the vanadium oxide on the c-BN surface was determined to be VO2, and the surfaces were found to be thermally stable, exhibiting an NEA. In comparison, the oxygen-terminated c-BN surface, where B2O3 was detected, showed a positive electron affinity of ˜1.2 eV. The B2O3 evidently acts as a negatively charged layer introducing a surface dipole directed into the c-BN. Through the interaction of VO2 with the B2O3 layer, a B-O-V layer structure would contribute a dipole between the O and V layers with the positive side facing vacuum. The lower enthalpy of formation for B2O3 is favorable for the formation of the B-O-V layer structure, which provides a thermally stable surface dipole and an NEA surface.

Transmission electron diffraction determination of the Ge(001)-(2 × 1) surface structure

NASA Astrophysics Data System (ADS)

Collazo-Davila, C.; Grozea, D.; Landree, E.; Marks, L. D.

1997-04-01

The lateral displacements in the Ge(001)-(2 × 1) surface reconstruction have been determined using transmission electron diffraction (TED). The best-fit model includes displacements extending six layers into the bulk. The atomic positions found agree with X-ray studies to within a few hundredths of an ångström. With the positions determined so precisely, it is suggested that the Ge(001)-(2 × 1) surface can now serve as a standard for comparison with theoretical surface structure calculations. The results from the currently available theoretical studies on the surface are compared with the experimentally determined structure.

Multi-walled carbon nanotube structural instability with/without metal nanoparticles under electron beam irradiation

NASA Astrophysics Data System (ADS)

Khan, Imran; Huang, Shengli; Wu, Chenxu

2017-12-01

The structural transformation of multi-walled carbon nanotubes (MWCNT) under electron beam (e-beam) irradiation at room temperature is studied, with respect to a novel passivation effect due to gold nanoparticles (Au NPs). MWCNT structural evolution induced by energetic e-beam irradiation leads to faster shrinkage, as revealed via in situ transmission electron microscopy, while MWCNT surface modification with Au NPs (Au-MWCNT) slows down the shrinkage by impeding the structural evolution process for a prolonged time under the same irradiation conditions. The new relationship between MWCNT and Au-MWCNT shrinking radii and irradiation time illustrates that the MWCNT shrinkage rate is faster than either theoretical predictions or the same process in Au-MWCNTs. As compared with the outer surface energy (positive curvature), the inner surface energy (negative curvature) of the MWCNT contributes more to the athermal evaporation of tube wall atoms, leading to structural instability and shrinkage under e-beam irradiation. Conversely, Au NPs possess only outer surface energy (positive curvature) compared with the MWCNT. Their presence on MWCNT surfaces retards the dynamics of MWCNT structural evolution by slowing down the evaporation process of carbon atoms, thus restricting Au-MWCNT shrinkage. Au NP interaction and growth evolves athermally on MWCNT surfaces, exhibits increase in their size, and indicates the association of this mechanism with the coalescence induced by e-beam activated electronic excitations. Despite their growth, Au NPs show extreme structural stability, and remain crystalline under prolonged irradiation. It is proposed that the surface energy of MWCNTs and Au NPs, together with e-beam activated soft modes or lattice instability effects, predominantly govern all the above varieties of structural evolution.

Surface sensitization mechanism on negative electron affinity p-GaN nanowires

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Feng, Shu; Lu, Feifei

2018-03-01

The surface sensitization is the key to prepare negative electron affinity photocathode. The thesis emphasizes on the study of surface sensitization mechanism of p-type doping GaN nanowires utilizing first principles based on density function theory. The adsorption energy, work function, dipole moment, geometry structure, electronic structure and optical properties of Mg-doped GaN nanowires surfaces with various coverages of Cs atoms are investigated. The GaN nanowire with Mg doped in core position is taken as the sensitization base. At the initial stage of sensitization, the best adsorption site for Cs atom on GaN nanowire surface is BN, the bridge site of two adjacent N atoms. Surface sensitization generates a p-type internal surface with an n-type surface state, introducing a band bending region which can help reduce surface barrier and work function. With increasing Cs coverage, work functions decrease monotonously and the "Cs-kill" phenomenon disappears. For Cs coverage of 0.75 ML and 1 ML, the corresponding sensitization systems reach negative electron affinity state. Through surface sensitization, the absorption curves are red shifted and the absorption coefficient is cut down. All theoretical calculations can guide the design of negative electron affinity Mg doped GaN nanowires photocathode.

Ultrastructure Processing and Environmental Stability of Advanced Structural and Electronic Materials.

DTIC Science & Technology

1983-03-01

network dissolution, electron beam simulated desorption, electron signal decay, oxidation, oxide layer , growth kinetics, silicon carbide, assivation...surface layers on silicate glasses are reviewed. A type IIIB glass surface is proposed. The mechanisms of hydrothermal attack of two phase lithia...method to make reliable lifetime predictions. Use of electron beam techniques is essential for understanding surface layers formed on glasses (Section III

Interfacial Coupling and Electronic Structure of Two-Dimensional Silicon Grown on the Ag(111) Surface at High Temperature.

PubMed

Feng, Jiagui; Wagner, Sean R; Zhang, Pengpeng

2015-06-18

Freestanding silicene, a monolayer of Si arranged in a honeycomb structure, has been predicted to give rise to massless Dirac fermions, akin to graphene. However, Si structures grown on a supporting substrate can show properties that strongly deviate from the freestanding case. Here, combining scanning tunneling microscopy/spectroscopy and differential conductance mapping, we show that the electrical properties of the (√3 x √3) phase of few-layer Si grown on Ag(111) strongly depend on film thickness, where the electron phase coherence length decreases and the free-electron-like surface state gradually diminishes when approaching the interface. These features are presumably attributable to the inelastic inter-band electron-electron scattering originating from the overlap between the surface state, interface state and the bulk state of the substrate. We further demonstrate that the intrinsic electronic structure of the as grown (√3 x √3) phase is identical to that of the (√3 x √3)R30° reconstructed Ag on Si(111), both of which exhibit the parabolic energy-momentum dispersion relation with comparable electron effective masses. These findings highlight the essential role of interfacial coupling on the properties of two-dimensional Si structures grown on supporting substrates, which should be thoroughly scrutinized in pursuit of silicene.

Control of two-dimensional electronic states at anatase Ti O2(001 ) surface by K adsorption

NASA Astrophysics Data System (ADS)

Yukawa, R.; Minohara, M.; Shiga, D.; Kitamura, M.; Mitsuhashi, T.; Kobayashi, M.; Horiba, K.; Kumigashira, H.

2018-04-01

The nature of the intriguing metallic electronic structures appearing at the surface of anatase titanium dioxide (a-Ti O2 ) remains to be elucidated, mainly owing to the difficulty of controlling the depth distribution of the oxygen vacancies generated by photoirradiation. In this study, K atoms were adsorbed onto the (001) surface of a-Ti O2 to dope electrons into the a-Ti O2 and to confine the electrons in the surface region. The success of the electron doping and its controllability were confirmed by performing in situ angle-resolved photoemission spectroscopy as well as core-level measurements. Clear subband structures were observed in the surface metallic states, indicating the creation of quasi-two-dimensional electron liquid (q2DEL) states in a controllable fashion. With increasing electron doping (K adsorption), the q2DEL states exhibited crossover from polaronic liquid states with multiple phonon-loss structures originating from the long-range Fröhlich interaction to "weakly correlated metallic" states. In the q2DEL states in the weakly correlated metallic region, a kink due to short-range electron-phonon coupling was clearly observed at about 80 ±10 meV . The characteristic energy is smaller than that previously observed for the metallic states of a-Ti O2 with three-dimensional nature (˜110 meV ) . These results suggest that the dominant electron-phonon coupling is modulated by anisotropic carrier screening in the q2DEL states.

Vibrational Properties of Hydrogen-Bonded Systems Using the Multireference Generalization to the "On-the-Fly" Electronic Structure within Quantum Wavepacket ab Initio Molecular Dynamics (QWAIMD).

PubMed

Li, Junjie; Li, Xiaohu; Iyengar, Srinivasan S

2014-06-10

We discuss a multiconfigurational treatment of the "on-the-fly" electronic structure within the quantum wavepacket ab initio molecular dynamics (QWAIMD) method for coupled treatment of quantum nuclear effects with electronic structural effects. Here, multiple single-particle electronic density matrices are simultaneously propagated with a quantum nuclear wavepacket and other classical nuclear degrees of freedom. The multiple density matrices are coupled through a nonorthogonal configuration interaction (NOCI) procedure to construct the instantaneous potential surface. An adaptive-mesh-guided set of basis functions composed of Gaussian primitives are used to simplify the electronic structure calculations. Specifically, with the replacement of the atom-centered basis functions positioned on the centers of the quantum-mechanically treated nuclei by a mesh-guided band of basis functions, the two-electron integrals used to compute the electronic structure potential surface become independent of the quantum nuclear variable and hence reusable along the entire Cartesian grid representing the quantum nuclear coordinates. This reduces the computational complexity involved in obtaining a potential surface and facilitates the interpretation of the individual density matrices as representative diabatic states. The parametric nuclear position dependence of the diabatic states is evaluated at the initial time-step using a Shannon-entropy-based sampling function that depends on an approximation to the quantum nuclear wavepacket and the potential surface. This development is meant as a precursor to an on-the-fly fully multireference electronic structure procedure embedded, on-the-fly, within a quantum nuclear dynamics formalism. We benchmark the current development by computing structural, dynamic, and spectroscopic features for a series of bihalide hydrogen-bonded systems: FHF(-), ClHCl(-), BrHBr(-), and BrHCl(-). We find that the donor-acceptor structural features are in good agreement with experiments. Spectroscopic features are computed using a unified velocity/flux autocorrelation function and include vibrational fundamentals and combination bands. These agree well with experiments and other theories.

Stacking the Deck: Leveraging Surface Interactions to Tune Interfacial Electronic Structure

NASA Astrophysics Data System (ADS)

Maughan, Bret; Eads, Calley; Zahl, Percy; Sutter, Peter; Monti, Oliver

We present results from a series of experiments aimed at understanding and controlling molecular interactions in phthalocyanine (Pc) thin-films on Cu(110) to tailor the interfacial electronic structure. Using low-temperature scanning tunneling microscopy (LT-STM), we identify interactions that drive surface-molecule coupling, molecular self-assembly and thin-film order. We provide evidence that interactions with native Cu adatoms play a pivotal role in self-assembly of Pc systems, along with anisotropic nanoribbon growth dynamics, supported by an agent-based kinetic Monte Carlo (AB-KMC) simulation. We show further that self-assembled nanoribbon length can be controlled using surface diffusion barriers and that ordered 2D thin-film growth is promoted by diminishing surface-molecule interactions that otherwise dominate native Cu(110) interfaces. Altogether, this detailed structural understanding allows us to interpret interfacial electronic structure and dynamics, uncovered through ultraviolet (UPS) and two-photon photoemission (2PPE) spectroscopy experiments, in molecular configuration-specific detail. In all, our understanding of interfacial processes guides strategic modifications to both surface and molecule to harness interfacial interactions and thereby modify the collective electronic structure of the interface. NSF No. CHE-1213243 and No. CHE-1565497, Arizona TRIF, DOE/BNL Cntrct No. DE-SC0012704, and DOE No. DE-SC0016343.

Theoretical study of the noble metals on semiconductor surfaces and Ti-base shape memory alloys

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

Ding, Yungui

1994-07-27

The electronic and structural properties of the (√3 x√3) R30° Ag/Si(111) and (√3 x √3) R30° Au/Si(111) surfaces are investigated using first principles total energy calculations. We have tested almost all experimentally proposed structural models for both surfaces and found the energetically most favorable model for each of them. The lowest energy model structure of the (√3 x √3) R30° Ag/Si(111) surface consists of a top layer of Ag atoms arranged as ``honeycomb-chained-trimers`` lying above a distorted ``missing top layer`` Si(111) substrate. The coverage of Ag is 1 monolayer (ML). We find that the honeycomb structure observed in STM imagesmore » arise from the electronic charge densities of an empty surface band near the Fermi level. The electronic density of states of this model gives a ``pseudo-gap`` around the Fermi level, which is consistent with experimental results. The lowest energy model for the (√3 x √3) R30° Au/Si(111) surface is a conjugate honeycomb-chained-trimer (CHCT-1) configuration which consists of a top layer of trimers formed by 1 ML Au atoms lying above a ``missing top layer`` Si(111) substrate with a honeycomb-chained-trimer structure for its first layer. The structures of Au and Ag are in fact quite similar and belong to the same class of structural models. However, small variation in the structural details gives rise to quite different observed STM images, as revealed in the theoretical calculations. The electronic charge density from bands around the Fermi level for the (√3 x √3) R30°, Au/Si(111) surface also gives a good description of the images observed in STM experiments. First principles calculations are performed to study the electronic and structural properties of a series of Ti-base binary alloys TiFe, TiNi, TiPd, TiMo, and TiAu in the B2 structure.« less

Application of semiempirical electronic structure theory to compute the force generated by a single surface-mounted switchable rotaxane.

PubMed

Sohlberg, Karl; Bazargan, Gloria; Angelo, Joseph P; Lee, Choongkeun

2017-01-01

Herein we report a study of the switchable [3]rotaxane reported by Huang et al. (Appl Phys Lett 85(22):5391-5393, 1) that can be mounted to a surface to form a nanomechanical, linear, molecular motor. We demonstrate the application of semiempirical electronic structure theory to predict the average and instantaneous force generated by redox-induced ring shuttling. Detailed analysis of the geometric and electronic structure of the system reveals technical considerations essential to success of the approach. The force is found to be in the 100-200 pN range, consistent with published experimental estimates. Graphical Abstract A single surface-mounted switchable rotaxane.

Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide

DOE PAGES

Mishra, Rohan; Kim, Young -Min; He, Qian; ...

2016-07-18

Here, the surfaces of transition-metal oxides with the perovskite structure are fertile grounds for the discovery of novel electronic and magnetic phenomena. In this article, we combine scanning transmission electron microscopy (STEM) with density functional theory (DFT) calculations to obtain the electronic and magnetic properties of the (001) surface of a (LaFeO 3) 8/(SrFeO 3) 1 superlattice film capped with four layers of LaFeO 3. Simultaneously acquired STEM images and electron-energy-loss spectra reveal the surface structure and a reduction in the oxidation state of iron from Fe 3+ in the bulk to Fe 2+ at the surface, extending over severalmore » atomic layers, which signals the presence of oxygen vacancies. The DFT calculations confirm the reduction in terms of oxygen vacancies and further demonstrate the stabilization of an exotic phase in which the surface layer is half metallic and ferromagnetic, while the bulk remains antiferromagnetic and insulating. Based on the calculations, we predict that the surface magnetism and conductivity can be controlled by tuning the partial pressure of oxygen.« less

First-principles study of native defects in bulk Sm2CuO4 and its (001) surface structure

NASA Astrophysics Data System (ADS)

Zheng, Fubao; Zhang, Qinfang; Meng, Qiangqiang; Wang, Baolin; Song, Fengqi; Yunoki, Seiji; Wang, Guanghou

2018-04-01

Using the first-principles calculations based on the density functional theory, we have studied the bulk defect formation and surface structures of Sm2CuO4. To ensure the accuracy of calculations, the spin order of Cu atoms is rechecked and it is the well-known nearest-neighbor antiferromagnetic ground state, which can be attributed to the hole-mediated superexchange through the strong pdσ hybridization interaction between Cu dx2-y2 electron and the neighboring oxygen px (or py) electron. Under each present experimental condition, the Sm vacancy has a very high formation energy and is unlikely to be stable. The Cu vacancy is a shallow acceptor, which is preferred under O-rich conditions, whereas the O vacancy is a donor and energetically favorable under O-poor conditions. To construct its (001) surface structure, CuOO, CuO, and Cu terminated surfaces are found to be most favorable under different experimental conditions. The stable surface structures are always accompanied by significant surface atomic reconstructions and electron charge redistribution, which are intimately correlated to each other.

Effect of Surface Termination on the Electonic Properties of LaNiO₃ Films

DOE PAGES

Kumah, Divine P.; Malashevich, Andrei; Disa, Ankit S.; ...

2014-11-06

The electronic and structural properties of thin LaNiO₃ films grown by using molecular beam epitaxy are studied as a function of the net ionic charge of the surface terminating layer. We demonstrate that electronic transport in nickelate heterostructures can be manipulated through changes in the surface termination due to a strong coupling of the surface electrostatic properties to the structural properties of the Ni—O bonds that govern electronic conduction. We observe experimentally and from first-principles theory an asymmetric response of the structural properties of the films to the sign of the surface charge, which results from a strong interplay betweenmore » electrostatic and mechanical boundary conditions governing the system. The structural response results in ionic buckling in the near-surface NiO₂ planes for films terminated with negatively charged NiO₂ and bulklike NiO₂ planes for films terminated with positively charged LaO planes. The ability to modify transport properties by the deposition of a single atomic layer can be used as a guiding principle for nanoscale device fabrication.« less

Electronic structures of U X3 (X =Al , Ga, and In) studied by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Fujimori, Shin-ichi; Kobata, Masaaki; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Haga, Yoshinori; Yamamoto, Etsuji; Ōnuki, Yoshichika

2017-09-01

The electronic structures of U X3 (X =Al , Ga , and In ) were studied by photoelectron spectroscopy to understand the relationship between their electronic structures and magnetic properties. The band structures and Fermi surfaces of UAl3 and UGa3 were revealed experimentally by angle-resolved photoelectron spectroscopy (ARPES), and they were compared with the result of band-structure calculations. The topologies of the Fermi surfaces and the band structures of UAl3 and UGa3 were explained reasonably well by the calculation, although bands near the Fermi level (EF) were renormalized owing to the finite electron correlation effect. The topologies of the Fermi surfaces of UAl3 and UGa3 are very similar to each other, except for some minor differences. Such minor differences in their Fermi surface or electron correlation effect might take an essential role in their different magnetic properties. No significant changes were observed between the ARPES spectra of UGa3 in the paramagnetic and antiferromagnetic phases, suggesting that UGa3 is an itinerant weak antiferromagnet. The effect of chemical pressure on the electronic structures of U X3 compounds was also studied by utilizing the smaller lattice constants of UAl3 and UGa3 than that of UIn3. The valence band spectrum of UIn3 is accompanied by a satellitelike structure on the high-binding-energy side. The core-level spectrum of UIn3 is also qualitatively different from those of UAl3 and UGa3. These findings suggest that the U 5 f states in UIn3 are more localized than those in UAl3 and UGa3.

Effective mass and Fermi surface complexity factor from ab initio band structure calculations

NASA Astrophysics Data System (ADS)

Gibbs, Zachary M.; Ricci, Francesco; Li, Guodong; Zhu, Hong; Persson, Kristin; Ceder, Gerbrand; Hautier, Geoffroy; Jain, Anubhav; Snyder, G. Jeffrey

2017-02-01

The effective mass is a convenient descriptor of the electronic band structure used to characterize the density of states and electron transport based on a free electron model. While effective mass is an excellent first-order descriptor in real systems, the exact value can have several definitions, each of which describe a different aspect of electron transport. Here we use Boltzmann transport calculations applied to ab initio band structures to extract a density-of-states effective mass from the Seebeck Coefficient and an inertial mass from the electrical conductivity to characterize the band structure irrespective of the exact scattering mechanism. We identify a Fermi Surface Complexity Factor: Nv*K* from the ratio of these two masses, which in simple cases depends on the number of Fermi surface pockets (Nv* ) and their anisotropy K*, both of which are beneficial to high thermoelectric performance as exemplified by the high values found in PbTe. The Fermi Surface Complexity factor can be used in high-throughput search of promising thermoelectric materials.

Chemical, electronic, and magnetic structure of LaFeCoSi alloy: Surface and bulk properties

NASA Astrophysics Data System (ADS)

Lollobrigida, V.; Basso, V.; Borgatti, F.; Torelli, P.; Kuepferling, M.; Coïsson, M.; Olivetti, E. S.; Celegato, F.; Tortora, L.; Stefani, G.; Panaccione, G.; Offi, F.

2014-05-01

We investigate the chemical, electronic, and magnetic structure of the magnetocaloric LaFeCoSi compound with bulk and surface sensitive techniques. We put in evidence that the surface retains a soft ferromagnetic behavior at temperatures higher than the Curie temperature of the bulk due to the presence of Fe clusters at the surface only. This peculiar magnetic surface effect is attributed to the exchange interaction between the ferromagnetic Fe clusters located at the surface and the bulk magnetocaloric alloy, and it is used here to monitor the magnetic properties of the alloy itself.

First-principles investigation on the structures, energies, electronic and defective properties of Ti2AlN surfaces

NASA Astrophysics Data System (ADS)

Liu, Pei; Han, Xiuli; Sun, Dongli; Wang, Qing

2018-03-01

In this research work, the structures, energies, electronic and defective properties of (0001), (10 1 bar 0) , (11 2 bar 0) and (10 1 bar 3) surfaces of Ti2AlN were investigated systematically by the first-principles calculations based on density functional theory. The (0001) and (10 1 bar 0) are polar surfaces and have different kinds of surface terminations, while the (11 2 bar 0) and (10 1 bar 3) are non-polar surfaces. The calculated results show that the Ti(Al)-, Al- terminated (0001) surfaces experience the least relaxation, and N- terminated (0001) surface experiences the greatest relaxation. The calculated surface energies of non-polar surfaces are independent on the constituent element chemical potential, while surface energies of polar surfaces are correlated with the constituent element chemical potential. It is found that the (0001)-Ti(Al), (0001)-Al, (10 1 bar 0) -TiAl and (10 1 bar 3) surface are stable under the condition of Ti- and Al- rich environments, the (0001)-N surface is the most stable one under the Ti- and Al- poor condition. The electronic structures of all the surfaces except (10 1 bar 3) are significantly influenced by structure relaxations. Furthermore, the monovacancy formation energies on the surface layer are lower than that in the bulk, the monovacancies are most difficult to exist on the (10 1 bar 3) surface among all the surfaces.

Defect Induced Electronic Structure of Uranofullerene

PubMed Central

Dai, Xing; Cheng, Cheng; Zhang, Wei; Xin, Minsi; Huai, Ping; Zhang, Ruiqin; Wang, Zhigang

2013-01-01

The interaction between the inner atoms/cluster and the outer fullerene cage is the source of various novel properties of endohedral metallofullerenes. Herein, we introduce an adatom-type spin polarization defect on the surface of a typical endohedral stable U2@C60 to predict the associated structure and electronic properties of U2@C61 based on the density functional theory method. We found that defect induces obvious changes in the electronic structure of this metallofullerene. More interestingly, the ground state of U2@C61 is nonet spin in contrast to the septet of U2@C60. Electronic structure analysis shows that the inner U atoms and the C ad-atom on the surface of the cage contribute together to this spin state, which is brought about by a ferromagnetic coupling between the spin of the unpaired electrons of the U atoms and the C ad-atom. This discovery may provide a possible approach to adapt the electronic structure properties of endohedral metallofullerenes. PMID:23439318

The structural and electronic properties of metal atoms adsorbed on graphene

NASA Astrophysics Data System (ADS)

Liu, Wenjiang; Zhang, Cheng; Deng, Mingsen; Cai, Shaohong

2017-09-01

Based on density functional theory (DFT), we studied the structural and electronic properties of seven different metal atoms adsorbed on graphene (M + graphene). The geometries, adsorption energies, density of states (DOS), band structures, electronic dipole moment, magnetic moment and work function (WF) of M + graphene were calculated. The adsorption energies ΔE indicated that Li, Na, K, Ca and Fe adsorbed on graphene were tending to form stable structures. However, diffusion would occur on Cu and Ag adsorbed on graphene. In addition, the electronic structure near the Fermi level of graphene was significantly affected by Fe (Cu and Ag), compared with Li (Na, K and Ca). The electronic dipole moment and magnetic moment of M + graphene were sensitive to the adsorbed metal atoms. Moreover, we found electropositive (electronegative) adsorption can decrease (increase) the WF of the surface. Specially, the WF of Ag + graphene and Fe + graphene would increase because surface dipole moment make a contribution to electron.

Au-induced deep groove nanowire structure on the Ge(001) surface: DFT calculations

NASA Astrophysics Data System (ADS)

Tsay, Shiow-Fon

2016-09-01

The atomic geometry, stability, and electronic properties of self-organized Au induced nanowires on the Ge(001) surface are investigated based on the density-functional theory in GGA and the stoichiometry of Au. A giant Ge zigzag chain structure is suggested for 0.75 ML Au coverage, which displays c(8 × 2) deep groove zigzag nanowire structure simulated STM images. The top layer Ge and Au atomic disorder introduces the chevron units into the zigzag nanowire structure STM image as per the experimental observations. The zigzag Ge nanowire exhibits a semi-metallic characteristic, and the electric transport occurs in between the Ge zigzag nanowire and the subsurface. The system exhibits obvious electronic correlations among the Ge nanowire, the nano-facet Au trimers and the deeper layer Ge atoms, that play an important role in the electronic structure. At surface Brillouin zone boundaries, an anisotropic two-dimensional upward parabolic surface-state band is consistent with the ARPES spectra reported by Nakatsuji et al. [Phys. Rev. B 80, 081406(R) (2009); Phys. Rev. B 84, 115411 (2011)]; this electronic structure is different from the quasi-one-dimensional energy trough reported by Schäfer et al. [Phys. Rev. Lett. 101, 236802 (2008); Phys. Rev. B 83, 121411(R) (2011)].

Femtosecond laser-induced periodic surface structural formation on sapphire with nanolayered gold coating

NASA Astrophysics Data System (ADS)

Yin, Kai; Wang, Cong; Duan, Ji'an; Guo, Chunlei

2016-09-01

Sapphire has a potential as a new generation of electronics display. However, direct processing of sapphire surface by visible or near-IR laser light is challenging since sapphire is transparent to these wavelengths. In this study, we investigate the formation of femtosecond laser-induced periodic surface structures (LIPSSs) on sapphire coated with nanolayered gold film. We found a reduced threshold by about 25 % in generating uniform LIPSSs on sapphire due to the nanolayered gold film. Different thickness of nanolayered gold films are studied, and it is shown that the change in thickness does not significantly affect the threshold reduction. It is believed that the diffusion of hot electrons in the gold films increases interfacial carrier density and electron-phonon coupling that results in a reduced threshold and more uniform periodic surface structure generation.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

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

Fazleev, N. G.; Department of Physics, Kazan State University, Kazan 420008; Nadesalingam, M. P.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to {approx}550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M{sub 2,3}VV and O KLL Auger transitions. PAESmore » results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.« less

Structure Evolution and Distributions of Grain-Boundary Misorientainons in Submicrocrystalline Molybdenum Irradiated with a Pulsed Electron Beam

NASA Astrophysics Data System (ADS)

Stepanova, E. N.; Grabovetskaya, G. P.; Teresov, A. D.; Mishin, I. P.

2018-05-01

Using the methods of electron backscatter diffraction, electron microscopy and X-ray diffraction analysis, it is demonstrated that irradiation of the surface of a submicrocrystalline molybdenum specimen with a pulsed electron beam in a non-melt regime results in the formation of a gradient structure in its bulk. The irradiation temperature is shown to affect the density of defects, the value of stress, and the distributions of grain-boundary misorientations in the surface and bulk of the submicrocrystalline molybdenum specimens.

Microstructure, tribological and strength properties of the surface layer in metal-ceramic composite nano-structured by electron irradiation

NASA Astrophysics Data System (ADS)

Ovcharenko, V. E.; Ivanov, K. V.; Mokhovikov, A. A.

2017-12-01

Exemplified by metal-ceramic composite TiC-(Ni-Cr) with the ratio of components 50:50, the paper presents findings of the study on patterns of nanoscale structural-phase state formation in the surface layer of the composite under pulsed electron irradiation in inert gas plasmas with different ionization energies and atomic weights and their influence on tribological and strength properties of the surface layer.

Structure of a bacterial cell surface decaheme electron conduit

USDA-ARS?s Scientific Manuscript database

Some bacterial species are able to utilize extracellular mineral forms of iron and manganese as respiratory electron acceptors. In Shewanella oneidensis this involves decaheme cytochromes that are located on the bacterial cell surface at the termini of trans-outer-membrane electron transfer conduits...

Metallic surface states in elemental electrides

NASA Astrophysics Data System (ADS)

Naumov, Ivan I.; Hemley, Russell J.

2017-07-01

Recent high-pressure studies have uncovered an alternative class of materials, insulating electride phases created by compression of simple metals. These exotic insulating phases develop an unusual electronic structure: the valence electrons move away from the nuclei and condense at interstitial sites, thereby acquiring the role of atomic anions or even molecules. We show that they are also topological phases as they exhibit a wide diversity of metallic surface states (SSs) that are controlled by the bulk electronic structure. The electronic reconstruction occurs that involves charge transfer between the surfaces of opposite polarity making both of them metallic, resembling the appearance of the two-dimensional gas at the renowned SrTi O3 /LaAl O3 interface. Remarkably, these materials thus embody seemingly disparate physical concepts—chemical electron localization, topological control of bulk-surface conductivity, and the two-dimensional electron gas. Such metallic SSs could be probed by direct electrical resistance or by standard photoemission measurements on recovery to ambient conditions.

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.

Positron Annihilation Studies of the Electronic Structure of Selected High-Temperature Cuprate and Organic Superconductors.

NASA Astrophysics Data System (ADS)

Chan, Lie Ping

The understanding of the electronic structure of the high-T_{c} superconductors could be important for a full theoretical description of the mechanism behind superconductivity in these materials. In this thesis, we present our measurements of the positron -electron momentum distributions of the cuprate superconductors Bi_2Sr_2CaCu _2O_8, Tl _2Ba_2Ca _2Cu_3O_ {10}, and the organic superconductor kappa-(BEDT)_2Cu(NCS) _2. We use the positron Two-dimensional Angular Correlation of Annihilation Radiation technique to make the measurements on single crystals and compare our high-statistics data with band structure calculations to determine the existence and nature of the respective Fermi surfaces. The spectra from unannealed Bi _2Sr_2CaCu _2O_8 exhibit effects of the superlattice modulation in the BiO_2 layers, and a theoretical understanding of the modulation effects on the electronic band structure is required to interpret these spectra. Since the present theory does not consider the modulation, we have developed a technique to remove the modulation effects from our spectra, and the resultant data when compared with the positron -electron momentum distribution calculation, yield features consistent with the predicted CuO_2 and BiO_2 Fermi surfaces. In the data from unannealed Tl_2Ba _2Ca_2Cu_3 O_{10}, we only observe indications of the TlO Fermi surfaces, and attribute the absence of the predicted CuO_2 Fermi surfaces to the poor sample quality. In the absence of positron-electron momentum calculations for kappa-(BEDT)_2Cu(NCS) _2, we compare our data to electronic band structure calculations, and observed features suggestive of the predicted Fermi surface contributions from the BEDT cation layers. A complete positron-electron calculation for kappa-(BEDT)_2 Cu(NCS)_2 is required to understand the positron wavefunction effects in this material.

Interfacial Coupling and Electronic Structure of Two-Dimensional Silicon Grown on the Ag(111) Surface at High Temperature

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

Feng, Jiagui; Wagner, Sean R.; Zhang, Pengpeng

Freestanding silicene, a monolayer of Si arranged in a honeycomb structure, has been predicted to give rise to massless Dirac fermions, akin to graphene. However, Si structures grown on a supporting substrate can show properties that strongly deviate from the freestanding case. Here, combining scanning tunneling microscopy/spectroscopy and differential conductance mapping, we show that the electrical properties of the (√3 x √3) phase of few-layer Si grown on Ag(111) strongly depend on film thickness, where the electron phase coherence length decreases and the free-electron-like surface state gradually diminishes when approaching the interface. These features are presumably attributable to the inelasticmore » inter-band electron-electron scattering originating from the overlap between the surface state, interface state and the bulk state of the substrate. We further demonstrate that the intrinsic electronic structure of the as grown (√3 x √3) phase is identical to that of the (√3 x √3) R30° reconstructed Ag on Si(111), both of which exhibit the parabolic energy-momentum dispersion relation with comparable electron effective masses. Lastly, these findings highlight the essential role of interfacial coupling on the properties of two-dimensional Si structures grown on supporting substrates, which should be thoroughly scrutinized in pursuit of silicene.« less

Effect of Surface Treatments on Electron Beam Freeform Fabricated Aluminum Structures

NASA Technical Reports Server (NTRS)

Taminger, Karen M. B.; Hafley, Robert A.; Fahringer, David T.; Martin, Richard E.

2004-01-01

Electron beam freeform fabrication (EBF3) parts exhibit a ridged surface finish typical of many layer-additive processes. This, post-processing is required to produce a net shape with a smooth surface finish. High speed milling wire electrical discharge machining (EDM), electron beam glazing, and glass bead blasting were performed on EBF3-build 2219 aluminum alloy parts to reduce or eliminate the ridged surface features. Surface roughness, surface residual stress state, and microstructural characteristics were examined for each of the different surface treatment to assess the quality and effect of the surface treatments on the underlying material. The analysis evaluated the effectivenes of the different surface finishing techniques for achieving a smooth surface finish on an electron beam freeform fabricated part.

Electron beam enhanced surface modification for making highly resolved structures

DOEpatents

Pitts, John R.

1986-01-01

A method for forming high resolution submicron structures on a substrate is provided by direct writing with a submicron electron beam in a partial pressure of a selected gas phase characterized by the ability to dissociate under the beam into a stable gaseous leaving group and a reactant fragment that combines with the substrate material under beam energy to form at least a surface compound. Variations of the method provide semiconductor device regions on doped silicon substrates, interconnect lines between active sites, three dimensional electronic chip structures, electron beam and optical read mass storage devices that may include color differentiated data areas, and resist areas for use with selective etching techniques.

Electron beam enhanced surface modification for making highly resolved structures

DOEpatents

Pitts, J.R.

1984-10-10

A method for forming high resolution submicron structures on a substrate is provided by direct writing with a submicron electron beam in a partial pressure of a selected gas phase characterized by the ability to dissociate under the beam into a stable gaseous leaving group and a reactant fragment that combines with the substrate material under beam energy to form at least a surface compound. Variations of the method provide semiconductor device regions on doped silicon substrates, interconnect lines between active sites, three dimensional electronic chip structures, electron beam and optical read mass storage devices that may include color differentiated data areas, and resist areas for use with selective etching techniques.

Seamless growth of a supramolecular carpet

PubMed Central

Kim, Ju-Hyung; Ribierre, Jean-Charles; Yang, Yu Seok; Adachi, Chihaya; Kawai, Maki; Jung, Jaehoon; Fukushima, Takanori; Kim, Yousoo

2016-01-01

Organic/metal interfaces play crucial roles in the formation of intermolecular networks on metal surfaces and the performance of organic devices. Although their purity and uniformity have profound effects on the operation of organic devices, the formation of organic thin films with high interfacial uniformity on metal surfaces has suffered from the intrinsic limitation of molecular ordering imposed by irregular surface structures. Here we demonstrate a supramolecular carpet with widely uniform interfacial structure and high adaptability on a metal surface via a one-step process. The high uniformity is achieved with well-balanced interfacial interactions and site-specific molecular rearrangements, even on a pre-annealed amorphous gold surface. Co-existing electronic structures show selective availability corresponding to the energy region and the local position of the system. These findings provide not only a deeper insight into organic thin films with high structural integrity, but also a new way to tailor interfacial geometric and electronic structures. PMID:26839053

SPE-LEEM Studies on the Surface and Electronic Structure of 2-D Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Yeh, Po-Chun; Jin, Wencan; Zaki, Nader; Zhang, Datong; Sadowski, Jerzy; Al-Mahboob, Abdullah; van de Zande, Arend; Chenet, Daniel; Dadap, Jerry; Herman, Irving; Sutter, Petter; Hone, James; Osgood, Richard

2014-03-01

In this work, we studied the surface and electronic structure of monolayer and few-layer exfoliated MoS2 and WSe2, as well as chemical-vapor-deposition (CVD) grown MoS2, using Spectroscopic Photoemission and Low Energy Electron Microscope (SPE-LEEM). LEEM measurements reveal that, unlike exfoliated MoS2, CVD-grown MoS2 exhibits grain-boundary alterations due to surface strain. However, LEEM and micro-probe low energy electron diffraction show that the quality of CVD-grown MoS2 is comparable to that of exfoliated MoS2. Micrometer-scale angle-resolved photoemission spectroscopy (ARPES) measurement on exfoliated MoS2 and WSe2 single-crystals provides direct evidence for the shifting of the valence band maximum from Γ to K, when the layer number is thinned down to one, as predicted by density functional theory. Our measurements of the k-space resolved electronic structure allow for further comparison with other theoretical predictions and with transport measurements. Session I and II

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

Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri

Using in situ transmission electron microscopy that spatially and temporally resolves the evolution of the atomic structure in the surface and subsurface regions, we Find that the surface segregation of Au atoms in a Cu(Au) solid solution results in the nucleation and growth of a (2 × 1) missing-row reconstructed, half-unit-cell thick L1 2 Cu 3Au(110) surface alloy. Our in situ electron microscopy observations and atomistic simulations demonstrate that the (2 × 1) reconstruction of the Cu 3Au(110) surface alloy remains as a stable surface structure as a result of the favored Cu-Au diatom configuration.

Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure

NASA Astrophysics Data System (ADS)

Dai, Zhongwei; Jin, Wencan; Yu, Jie-Xiang; Grady, Maxwell; Sadowski, Jerzy T.; Kim, Young Duck; Hone, James; Dadap, Jerry I.; Zang, Jiadong; Osgood, Richard M.; Pohl, Karsten

2017-12-01

The surface structure of black phosphorus materials is determined using surface-sensitive dynamical microspot low energy electron diffraction (μ LEED ) analysis using a high spatial resolution low energy electron microscopy (LEEM) system. Samples of (i) crystalline cleaved black phosphorus (BP) at 300 K and (ii) exfoliated few-layer phosphorene (FLP) of about 10 nm thickness which were annealed at 573 K in vacuum were studied. In both samples, a significant surface buckling of 0.22 Å and 0.30 Å, respectively, is measured, which is one order of magnitude larger than previously reported. As direct evidence for large buckling, we observe a set of (for the flat surface forbidden) diffraction spots. Using first-principles calculations, we find that the presence of surface vacancies is responsible for the surface buckling in both BP and FLP, and is related to the intrinsic hole doping of phosphoresce materials previously reported.

Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure

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

Dai, Zhongwei; Jin, Wencan; Yu, Jie-Xiang

The surface structure of black phosphorus materials is determined using surface-sensitive dynamical microspot low energy electron diffraction ( μ LEED ) analysis using a high spatial resolution low energy electron microscopy (LEEM) system. Samples of (i) crystalline cleaved black phosphorus (BP) at 300 K and (ii) exfoliated few-layer phosphorene (FLP) of about 10 nm thickness which were annealed at 573 K in vacuum were studied. In both samples, a significant surface buckling of 0.22 Å and 0.30 Å, respectively, is measured, which is one order of magnitude larger than previously reported. As direct evidence for large buckling, we observe amore » set of (for the flat surface forbidden) diffraction spots. Using first-principles calculations, we find that the presence of surface vacancies is responsible for the surface buckling in both BP and FLP, and is related to the intrinsic hole doping of phosphoresce materials previously reported.« less

Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure

DOE PAGES

Dai, Zhongwei; Jin, Wencan; Yu, Jie-Xiang; ...

2017-12-29

The surface structure of black phosphorus materials is determined using surface-sensitive dynamical microspot low energy electron diffraction ( μ LEED ) analysis using a high spatial resolution low energy electron microscopy (LEEM) system. Samples of (i) crystalline cleaved black phosphorus (BP) at 300 K and (ii) exfoliated few-layer phosphorene (FLP) of about 10 nm thickness which were annealed at 573 K in vacuum were studied. In both samples, a significant surface buckling of 0.22 Å and 0.30 Å, respectively, is measured, which is one order of magnitude larger than previously reported. As direct evidence for large buckling, we observe amore » set of (for the flat surface forbidden) diffraction spots. Using first-principles calculations, we find that the presence of surface vacancies is responsible for the surface buckling in both BP and FLP, and is related to the intrinsic hole doping of phosphoresce materials previously reported.« less

Surface structure of bulk 2H-MoS2(0001) and exfoliated suspended monolayer MoS2: A selected area low energy electron diffraction study

NASA Astrophysics Data System (ADS)

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

2017-06-01

We have used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS2) and mechanically exfoliated and suspended monolayer MoS2. Our results show that the surface structure of bulk 2H-MoS2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS2 shows a large interlayer relaxation compared to the MoS2 sandwich layer terminating the bulk surface. The Debye temperature of MoS2 was concluded to be about 600 K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.

Surface structure of bulk 2H-MoS 2 (0001) and exfoliated suspended monolayer MoS 2 : A selected area low energy electron diffraction study

DOE PAGES

Dai, Zhongwei; Jin, Wencan; Grady, Maxwell; ...

2017-02-10

Here, we used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS 2) and mechanically exfoliated and suspended monolayer MoS 2. Our results show that the surface structure of bulk 2H-MoS 2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS 2 shows a large interlayer relaxation compared to the MoS 2 sandwich layer terminating the bulk surface. The Debye temperature of MoS 2 was concluded to be aboutmore » 600 K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.« less

The role of electro-explosion alloying with titanium diboride and treatment with pulsed electron beam in the surface modification of VT6 alloy

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

Konovalov, Sergey, E-mail: konovserg@gmail.com; Gromov, Victor, E-mail: gromov@physics.sibsiu.ru; Kobzareva, Tatyana

The paper presents the results of the investigation of VT6 titanium alloy subjected to electro-explosion alloying with TiB{sub 2} and irradiation with pulsed electron beam. It was established that electro-explosion alloying resulted in a high level of roughness of the surface layer with high adhesion of the modified layer and matrix. Further irradiation of the material with electron beam resulted in the smoothing of the surface of alloying and formation of a porous structure with various scale levels in the surface layer. It was also established that the energetic exposure causes the formation of a gradient structure with a changingmore » elemental composition along the direction from the surface of alloying.« less

Atomically Visualizing Elemental Segregation-Induced Surface Alloying and Restructuring

DOE PAGES

Zou, Lianfeng; Li, Jonathan; Zakharov, Dmitri; ...

2017-12-01

Using in situ transmission electron microscopy that spatially and temporally resolves the evolution of the atomic structure in the surface and subsurface regions, we Find that the surface segregation of Au atoms in a Cu(Au) solid solution results in the nucleation and growth of a (2 × 1) missing-row reconstructed, half-unit-cell thick L1 2 Cu 3Au(110) surface alloy. Our in situ electron microscopy observations and atomistic simulations demonstrate that the (2 × 1) reconstruction of the Cu 3Au(110) surface alloy remains as a stable surface structure as a result of the favored Cu-Au diatom configuration.

Surface electronic structure of SmB6(111)

NASA Astrophysics Data System (ADS)

Ohtsubo, Yoshiyuki; Hagiwara, Kenta; Wang, Chengwei; Yukawa, Ryu; Horiba, Koji; Kumigashira, Hiroshi; Hirano, Wataru; Iga, Fumitoshi; Kimura, Shin-ichi

2018-05-01

Samarium hexaboride (SmB6) is the most extensively studied candidate of topological Kondo insulators. To clarify the topological origin of metallic surface states observed on the SmB6(001) surfaces, we studied the surface electronic structure of SmB6 on the other surface orientation, SmB6(111). Although the SmB6(111) surface cannot be obtained by cleaving, we successfully obtained the well-defined clean surface by high-temperature annealing of the mechanically polished single crystal of SmB6(111) in an ultra-high vacuum. The valence band spectra obtained by photoelectron spectroscopy with the bulk and surface-sensitive incident photon energies imply that the surface is covered with B6 cluster without Sm atoms.

Surface structures of L10-MnGa (001) by scanning tunneling microscopy and first-principles theory

NASA Astrophysics Data System (ADS)

Corbett, J. P.; Guerrero-Sanchez, J.; Richard, A. L.; Ingram, D. C.; Takeuchi, N.; Smith, A. R.

2017-11-01

We report on the surface reconstructions of L10-ordered MnGa (001) thin films grown by molecular beam epitaxy on a 50 nm Mn3N2 (001) layer freshly grown on a magnesium oxide (001) substrate. Scanning tunneling microscopy, Auger electron spectroscopy, and reflection high energy electron diffraction are combined with first-principles density functional theory calculations to determine the reconstructions of the L10-ordered MnGa (001) surface. We find two lowest energy reconstructions of the MnGa (001) face: a 1 × 1 Ga-terminated structure and a 1 × 2 structure with a Mn replacing a Ga in the 1 × 1 Ga-terminated surface. The 1 × 2 reconstruction forms a row structure along [100]. The manganese:gallium stoichiometry within the surface based on theoretical modeling is in good agreement with experiment. Magnetic moment calculations for the two lowest energy structures reveal important surface and bulk effects leading to oscillatory total magnetization for ultra-thin MnGa (001) films.

Fabrication of large area plasmonic nanoparticle grating structure on silver halide based transmission electron microscope film and its application as a surface enhanced Raman spectroscopy substrate

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

Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Singh, M. N.

The plasmonic responses of silver nanoparticle grating structures of different periods made on silver halide based electron microscope film are investigated. Raster scan of the conventional scanning electron microscope (SEM) is used to carry out electron beam lithography for fabricating the plasmonic nanoparticle grating (PNG) structures. Morphological characterization of the PNG structures, carried out by the SEM and the atomic force microscope, indicates that the depth of the groove decreases with a decrease in the grating period. Elemental characterization performed by the energy dispersive spectroscopy and the x-ray diffraction shows the presence of nanoparticles of silver in the PNG grating.more » The optical characterization of the gratings shows that the localized surface plasmon resonance peak shifts from 366 to 378 nm and broadens with a decrease in grating period from 10 to 2.5 μm. The surface enhanced Raman spectroscopy of the Rhodamine-6G dye coated PNG structure shows the maximum enhancement by two orders of magnitude in comparison to the randomly distributed silver nanoparticles having similar size and shape as the PNG structure.« less

Modification of the titanium alloy surface in electroexplosive alloying with boron carbide and subsequent electron-beam treatment

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

Gromov, Victor E., E-mail: gromov@physics.sibsiu.ru; Budovskikh, Evgeniy A., E-mail: budovskikh-ea@physics.sibsiu.ru; Bashchenko, Lyudmila P., E-mail: gromov@physics.sibsiu.ru

2015-10-27

The modification of the VT6 titanium alloy surface in electroexplosion alloying with plasma being formed in titanium foil with a weighed powder of boron carbide with subsequent irradiation by a pulsed electron beam has been carried out. An electroexplosive alloying zone of a thickness up to 50 μm with a gradient structure is found to form. The subsequent electron-beam treatment of the alloying zone results in smoothing of the alloying surface and is accompanied by the formation of the multilayer structure with alternating layers of various alloying degree at a depth of 30 μm.

Doping of the step-edge Si chain: Ag on a Si(557)-Au surface

NASA Astrophysics Data System (ADS)

Krawiec, M.; Jałochowski, M.

2010-11-01

Structural and electronic properties of monatomic Ag chains on the Au-induced, highly ordered Si(557) surface are investigated by scanning tunneling microscopy (STM)/spectroscopy and first-principles density functional theory (DFT) calculations. The STM topography data show that a small amount of Ag (0.25 ML) very weakly modifies the one-dimensional structure induced by Au atoms. However, the bias-dependent STM topography and spectroscopy point to the importance of the electronic effects in this system, which are further corroborated by the DFT calculations. The obtained results suggest that Ag atoms act as electron donors leaving the geometry of the surface almost unchanged.

Spin-polarized surface resonances accompanying topological surface state formation

PubMed Central

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; Kemper, Alexander F.; Rotundu, Costel R.; Birgeneau, Robert J.; Hussain, Zahid; Lee, Dung-Hai; Shen, Zhi-Xun; Lanzara, Alessandra

2016-01-01

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi2Se3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states can emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. This work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure. PMID:27739428

Dynamical simulation of electron transfer processes in self-assembled monolayers at metal surfaces using a density matrix approach.

PubMed

Prucker, V; Bockstedte, M; Thoss, M; Coto, P B

2018-03-28

A single-particle density matrix approach is introduced to simulate the dynamics of heterogeneous electron transfer (ET) processes at interfaces. The characterization of the systems is based on a model Hamiltonian parametrized by electronic structure calculations and a partitioning method. The method is applied to investigate ET in a series of nitrile-substituted (poly)(p-phenylene)thiolate self-assembled monolayers adsorbed at the Au(111) surface. The results show a significant dependence of the ET on the orbital symmetry of the donor state and on the molecular and electronic structure of the spacer.

Ready to use bioinformatics analysis as a tool to predict immobilisation strategies for protein direct electron transfer (DET).

PubMed

Cazelles, R; Lalaoui, N; Hartmann, T; Leimkühler, S; Wollenberger, U; Antonietti, M; Cosnier, S

2016-11-15

Direct electron transfer (DET) to proteins is of considerable interest for the development of biosensors and bioelectrocatalysts. While protein structure is mainly used as a method of attaching the protein to the electrode surface, we employed bioinformatics analysis to predict the suitable orientation of the enzymes to promote DET. Structure similarity and secondary structure prediction were combined underlying localized amino-acids able to direct one of the enzyme's electron relays toward the electrode surface by creating a suitable bioelectrocatalytic nanostructure. The electro-polymerization of pyrene pyrrole onto a fluorine-doped tin oxide (FTO) electrode allowed the targeted orientation of the formate dehydrogenase enzyme from Rhodobacter capsulatus (RcFDH) by means of hydrophobic interactions. Its electron relays were directed to the FTO surface, thus promoting DET. The reduction of nicotinamide adenine dinucleotide (NAD(+)) generating a maximum current density of 1μAcm(-2) with 10mM NAD(+) leads to a turnover number of 0.09electron/s/molRcFDH. This work represents a practical approach to evaluate electrode surface modification strategies in order to create valuable bioelectrocatalysts. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermodynamic Control of Two-Dimensional Molecular Ionic Nanostructures on Metal Surfaces

DOE PAGES

Jeon, Seokmin; Doak, Peter W.; Sumpter, Bobby G.; ...

2016-07-26

Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions and superconducting ground states. In contrast, few of these phenomena have so far been observed in low-dimensional molecular structures, including thin films, nanoparticles and molecular blends, not in the least because most of such structures have so far been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional molecular structures of ionic molecules toward fundamental studies and potential applications. Here we present detailed analysis of monolayer-thick structures of the canonical TTF-TCNQ (tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane) system grown on low-index gold and silver surfaces. The most distinctivemore » property of the epitaxial growth is the wide abundance of stable TTF/TCNQ ratios, in sharp contrast to the predominance of 1:1 ratio in the bulk. We propose the existence of the surface phase-diagram that controls the structures of TTF-TCNQ on the surfaces, and demonstrate phase-transitions that occur upon progressively increasing the density of TCNQ while keeping the surface coverage of TTF fixed. Based on direct observations, we propose the binding motif behind the stable phases and infer the dominant interactions that enable the existence of the rich spectrum of surface structures. Finally, we also show that the surface phase diagram will control the epitaxy beyond monolayer coverage. Multiplicity of stable surface structures, the corollary rich phase diagram and the corresponding phase-transitions present an interesting opportunity for low-dimensional molecular systems, particularly if some of the electronic properties of the bulk can be preserved or modified in the surface phases.« less

Pb chains on reconstructed Si(335) surface

NASA Astrophysics Data System (ADS)

Krawiec, Mariusz

2009-04-01

The structural and electronic properties of Si(335)-Au surface decorated with Pb atoms are studied by means of density-functional theory. The resulting structural model features Pb atoms bonded to neighboring Si and Au surface atoms, forming monoatomic chain located 0.2 nm above the surface. The presence of Pb chain leads to a strong rebonding of Si atoms at the step edge. The fact that Pb atoms occupy positions in the middle of terrace is consistent with scanning tunneling microscopy (STM) data and also confirmed by simulated STM images. The calculated band structure clearly shows one-dimensional metallic character. The calculated electronic bands remain in very good agreement with photoemission data.

Experimental evidence and structural modeling of nonstoichiometric (010) surfaces coexisting in hydroxyapatite nano-crystals.

PubMed

Ospina, C A; Terra, J; Ramirez, A J; Farina, M; Ellis, D E; Rossi, A M

2012-01-01

High-resolution transmission electron microscopy (HRTEM) and ab initio quantum-mechanical calculations of electronic structure were combined to investigate the structure of the hydroxyapatite (HA) (010) surface, which plays an important role in HA interactions with biological media. HA was synthesized by in vitro precipitation at 37°C. HRTEM images revealed thin elongated rod nanoparticles with preferential growth along the [001] direction and terminations parallel to the (010) plane. The focal series reconstruction (FSR) technique was applied to develop an atomic-scale structural model of the high-resolution images. The HRTEM simulations identified the coexistence of two structurally distinct terminations for (010) surfaces: a rather flat Ca(II)-terminated surface and a zig-zag structure with open OH channels. Density functional theory (DFT) was applied in a periodic slab plane-wave pseudopotential approach to refine details of atomic coordination and bond lengths of Ca(I) and Ca(II) sites in hydrated HA (010) surfaces, starting from the HRTEM model. Copyright © 2011 Elsevier B.V. All rights reserved.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

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

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less

Formation, structure, and orientation of gold silicide on gold surfaces

NASA Technical Reports Server (NTRS)

Green, A. K.; Bauer, E.

1976-01-01

The formation of gold silicide on Au films evaporated onto Si(111) surfaces is studied by Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED). Surface condition, film thickness, deposition temperature, annealing temperature, and heating rate during annealing are varied. Several oriented crystalline silicide layers are observed.

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

DOE PAGES

Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel; ...

2017-01-06

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li 1.2Ni 0.13Mn 0.54Co 0.13O 2 crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-definedmore » model system of battery materials. Here, we report the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. Finally, the intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.« less

Spatially Resolved Nano-Scale Characterization of Electronic States in SrTiO3(001) Surfaces by STM/STS

NASA Astrophysics Data System (ADS)

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Hashizume, Tomihiro; Hitosugi, Taro

2012-02-01

We have performed low temperature scanning tunneling microscopy/spectroscopy (STM/STS) measurements on TiO2-terminated SrTiO3(001) thin film surfaces. The conductance map exhibited electronic modulations that were completely different from the surface structure. We also found that the electronic modulations were strongly dependent on temperature and the density of atomic defects associated with oxygen vacancies. These results suggest the existence of strongly correlated two-dimensional electronic states near the SrTiO3 surface, implying the importance of electron correlation at the interfaces of SrTiO3-related heterostructures.

Real-space visualization of conformation-independent oligothiophene electronic structure

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

Taber, Benjamen N.; Kislitsyn, Dmitry A.; Gervasi, Christian F.

2016-05-21

We present scanning tunneling microscopy and spectroscopy (STM/STS) investigations of the electronic structures of different alkyl-substituted oligothiophenes on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes adopted distinct straight and bent conformations. By combining STS maps with STM images, we visualize, in real space, particle-in-a-box-like oligothiophene molecular orbitals. We demonstrate that different planar conformers with significant geometrical distortions of oligothiophene backbones surprisingly exhibit very similar electronic structures, indicating a low degree of conformation-induced electronic disorder. The agreement of these results with gas-phase density functional theory calculations implies that the oligothiophene interaction with the Au(111) surface is generally insensitivemore » to molecular conformation.« less

Antimonene: Experiments and theory of surface conductivity

NASA Astrophysics Data System (ADS)

Palacios, Juan Jose; Ares, Pablo; Pakdel, Sahar; Paz, Wendel; Zamora, Felix; Gomez-Herrero, Julio

Very recently antimony has been demonstrated to be amenable to standard exfoliation procedures opening the possibility of studying the electronic properties of isolated few-layers flakes of this material, a.k.a. antimonene. Antimony is a topological semimetal, meaning that its electronic structure presents spin-split helical states (or Dirac cones) on the surface, but it is still trivially metallic in bulk. Antimonene, on the other hand, may present a much reduced electronic bulk contribution for a small number of layers. A novel technique to make electrical contacts on the surface of individual thin flakes (5-10 monolayers) has allowed us to measure the (surface) conductivity of these in ambient conditions. Our measurements show a high conductivity in the range of 1 - 2e2 / h , which we attribute to the surface Dirac electrons. We have also carried out theoretical work to address the origin of this value, in particular, the importance of scattering between the Dirac electrons and the bulk bands. Our calculations are based on density functional theory for the electronic structure and Kubo formalism for the conductivity, the latter considering random disorder and the presence of water. Ministerio de Economia y Competitividad, Grant FIS2016-80434-P.

XPS and UPS studies on electronic structure of Li 2O

NASA Astrophysics Data System (ADS)

Tanaka, Satoru; Taniguchi, Masaki; Tanigawa, Hisashi

2000-12-01

The adsorption behavior of H 2O on Li 2O was studied by X-ray photo electron spectroscopy (XPS) and ultraviolet photo electron spectroscopy (UPS). XPS and UPS spectra of Li 2O single crystals which were exposed to different pressure of H 2O vapor were observed. In O(1s) region, two peaks were observed and they were assigned to O(1s) in precipitated LiOH on the surface and O(1s) in Li 2O. After H 2O exposure, a peak broadening and an appearance of a new peak were observed at the higher binding energy region than O(1s) in Li 2O. They were attributed to surface -OH and H 2O molecule adsorbed on the surface. The adsorption behavior of H 2O was discussed from the observation of electronic structure in Li 2O surface.

Scanning ultrafast electron microscopy.

PubMed

Yang, Ding-Shyue; Mohammed, Omar F; Zewail, Ahmed H

2010-08-24

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability.

Density-functional theory applied to d- and f-electron systems

NASA Astrophysics Data System (ADS)

Wu, Xueyuan

Density functional theory (DFT) has been applied to study the electronic and geometric structures of prototype d- and f-electron systems. For the d-electron system, all electron DFT with gradient corrections to the exchange and correlation functionals has been used to investigate the properties of small neutral and cationic vanadium clusters. Results are in good agreement with available experimental and other theoretical data. For the f-electron system, a hybrid DFT, namely, B3LYP (Becke's 3-parameter hybrid functional using the correlation functional of Lee, Yang and Parr) with relativistic effective core potentials and cluster models has been applied to investigate the nature of chemical bonding of both the bulk and the surfaces of plutonium monoxide and dioxide. Using periodic models, the electronic and geometric structures of PuO2 and its (110) surface, as well as water adsorption on this surface have also been investigated using DFT in both local density approximation (LDA) and generalized gradient approximation (GGA) formalisms.

The use of analytical surface tools in the fundamental study of wear. [atomic nature of wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1977-01-01

Various techniques and surface tools available for the study of the atomic nature of the wear of materials are reviewed These include chemical etching, x-ray diffraction, electron diffraction, scanning electron microscopy, low-energy electron diffraction, Auger emission spectroscopy analysis, electron spectroscopy for chemical analysis, field ion microscopy, and the atom probe. Properties of the surface and wear surface regions which affect wear, such as surface energy, crystal structure, crystallographic orientation, mode of dislocation behavior, and cohesive binding, are discussed. A number of mechanisms involved in the generation of wear particles are identified with the aid of the aforementioned tools.

Two-dimensional Si nanosheets with local hexagonal structure on a MoS(2) surface.

PubMed

Chiappe, Daniele; Scalise, Emilio; Cinquanta, Eugenio; Grazianetti, Carlo; van den Broek, Bas; Fanciulli, Marco; Houssa, Michel; Molle, Alessandro

2014-04-02

The structural and electronic properties of a Si nanosheet (NS) grown onto a MoS2 substrate by means of molecular beam epitaxy are assessed. Epitaxially grown Si is shown to adapt to the trigonal prismatic surface lattice of MoS2 by forming two-dimensional nanodomains. The Si layer structure is distinguished from the underlying MoS2 surface structure. The local electronic properties of the Si nanosheet are dictated by the atomistic arrangement of the layer and unlike the MoS2 hosting substrate they are qualified by a gap-less density of states. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lateral engineering of surface states - towards surface-state nanoelectronics.

PubMed

García de Abajo, F J; Cordón, J; Corso, M; Schiller, F; Ortega, J E

2010-05-01

Patterned metal surfaces can host electron quantum waves that display interference phenomena over distances of a few nanometres, thus providing excellent information carriers for future atomic-scale devices. Here we demonstrate that collimation and waveguiding of surface electrons can be realized in silver-induced strain dislocation networks on Cu(111) surfaces, as a conceptual proof-of-principle of surface-state nanoelectronics (SSNE). The Ag/Cu(111) system exhibits featured surface bands with gaps at the Fermi energy, which are basic requirements for a potential SSNE material. We establish a solid analogy between the behavior of surface-state electrons and surface plasmons in patterned metal surfaces, thus facilitating the transfer of existing knowledge on plasmonic structures to the new scenario presented by engineered electronic surface-state nanostructures, with the advantage of a 1000-fold reduction in wavelength and geometrical parameters.

Electronic structures of Plutonium compounds with the NaCl-type monochalcogenides structure

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Tatetsu, Yasutomi

2012-12-01

We calculate the energy band structure and the Fermi surface of PuS, PuSe and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in a local density approximation. It is found in common that the energy bands in the vicinity of the Fermi level are mainly due to the hybridization between Pu 5/ and monochalcogenide p electrons. The obtained main Fermi surfaces are composed of two hole sheets and one electron sheet, all of which are constructed from the band having the Pu 5/ state and the monochalcogenide p state.

Structural and phase transformation of A{sup III}B{sup V}(100) semiconductor surface in interaction with selenium

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

Bezryadin, N. N.; Kotov, G. I., E-mail: giktv@mail.ru; Kuzubov, S. V., E-mail: kuzub@land.ru

2015-03-15

Surfaces of GaAs(100), InAs(100), and GaP(100) substrates thermally treated in selenium vapor have been investigated by transmission electron microscopy and electron probe X-ray microanalysis. Some specific features and regularities of the formation of A{sub 3}{sup III}B{sub 4}{sup VI} (100)c(2 × 2) surface phases and thin layers of gallium or indium selenides A{sub 2}{sup III}B{sub 3}{sup VI} (100) on surfaces of different A{sup III}B{sup V}(100) semiconductors are discussed within the vacancy model of surface atomic structure.

Rotational Parameters from Vibronic Eigenfunctions of Jahn-Teller Active Molecules

NASA Astrophysics Data System (ADS)

Garner, Scott M.; Miller, Terry A.

2017-06-01

The structure in rotational spectra of many free radical molecules is complicated by Jahn-Teller distortions. Understanding the magnitudes of these distortions is vital to determining the equilibrium geometric structure and details of potential energy surfaces predicted from electronic structure calculations. For example, in the recently studied {\\widetilde{A}^2E^{''} } state of the NO_3 radical, the magnitudes of distortions are yet to be well understood as results from experimental spectroscopic studies of its vibrational and rotational structure disagree with results from electronic structure calculations of the potential energy surface. By fitting either vibrationally resolved spectra or vibronic levels determined by a calculated potential energy surface, we obtain vibronic eigenfunctions for the system as linear combinations of basis functions from products of harmonic oscillators and the degenerate components of the electronic state. Using these vibronic eigenfunctions we are able to predict parameters in the rotational Hamiltonian such as the Watson Jahn-Teller distortion term, h_1, and compare with the results from the analysis of rotational experiments.

Pseudogap and electronic structure of electron-doped Sr2IrO4

NASA Astrophysics Data System (ADS)

Moutenet, Alice; Georges, Antoine; Ferrero, Michel

2018-04-01

We present a theoretical investigation of the effects of correlations on the electronic structure of the Mott insulator Sr2IrO4 upon electron doping. A rapid collapse of the Mott gap upon doping is found, and the electronic structure displays a strong momentum-space differentiation at low doping level: The Fermi surface consists of pockets centered around (π /2 ,π /2 ) , while a pseudogap opens near (π ,0 ) . Its physical origin is shown to be related to short-range spin correlations. The pseudogap closes upon increasing doping, but a differentiated regime characterized by a modulation of the spectral intensity along the Fermi surface persists to higher doping levels. These results, obtained within the cellular dynamical mean-field-theory framework, are discussed in comparison to recent photoemission experiments and an overall good agreement is found.

Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam

DOE PAGES

Lin, Feng; Markus, Isaac M.; Doeff, Marca M.; ...

2014-07-16

Our investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. But, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi 0.4Mn 0.4Co 0.18Ti 0.02O 2 particles, repeated electron beam irradiation induced a phase transition from an Rmore » $$\\bar{3}$$m layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from R$$\\bar{3}$$m 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, in using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results.« less

Direct observation for atomically flat and ordered vertical {111} side-surfaces on three-dimensionally figured Si(110) substrate using scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Yang, Haoyu; Hattori, Azusa N.; Ohata, Akinori; Takemoto, Shohei; Hattori, Ken; Daimon, Hiroshi; Tanaka, Hidekazu

2017-11-01

A three-dimensional Si{111} vertical side-surface structure on a Si(110) wafer was fabricated by reactive ion etching (RIE) followed by wet-etching and flash-annealing treatments. The side-surface was studied with scanning tunneling microscopy (STM) in atomic scale for the first time, in addition to atomic force microscopy (AFM), scanning electron microscopy (SEM), and low-energy electron diffraction (LEED). AFM and SEM showed flat and smooth vertical side-surfaces without scallops, and STM proved the realization of an atomically-flat 7 × 7-reconstructed structure, under optimized RIE and wet-etching conditions. STM also showed that a step-bunching occurred on the produced {111} side-surface corresponding to a reversely taped side-surface with a tilt angle of a few degrees, but did not show disordered structures. Characteristic LEED patterns from both side- and top-reconstructed surfaces were also demonstrated.

Structure analysis of the single-domain Si(111)4 × 1-In surface by μ-probe Auger electron diffraction and μ-probe reflection high energy electron diffraction

NASA Astrophysics Data System (ADS)

Nakamura, N.; Anno, K.; Kono, S.

1991-10-01

A single-domain Si(111)4 × 1-In surface has been studied by μ-probe reflection high-energy electron diffraction (RHEED) to elucidate the symmetry of the 4 × 1 surface. Azimuthal diffraction patterns of In MNN Auger electron have been obtained by a μ-probe Auger electron diffraction (AED) apparatus from the single-domain Si(111)4 × 1-In surface. On the basis of information from scanning tunneling microscopy [J. Microsc. 152 (1988) 727] and under the assumption that the 4 × 1 surface is composed of In-overlayers, the μ-probe AED patterns were kinematically analyzed to reach a concrete model of indium arrangement.

High-dose MeV electron irradiation of Si-SiO2 structures implanted with high doses Si+

NASA Astrophysics Data System (ADS)

Kaschieva, S.; Angelov, Ch; Dmitriev, S. N.

2018-03-01

The influence was studied of 22-MeV electron irradiation on Si-SiO2 structures implanted with high-fluence Si+ ions. Our earlier works demonstrated that Si redistribution is observed in Si+-ion-implanted Si-SiO2 structures (after MeV electron irradiation) only in the case when ion implantation is carried out with a higher fluence (1016 cm-2). We focused our attention on the interaction of high-dose MeV electron irradiation (6.0×1016 cm-2) with n-Si-SiO2 structures implanted with Si+ ions (fluence 5.4×1016 cm-2 of the same order magnitude). The redistribution of both oxygen and silicon atoms in the implanted Si-SiO2 samples after MeV electron irradiation was studied by Rutherford back-scattering (RBS) spectroscopy in combination with a channeling technique (RBS/C). Our results demonstrated that the redistribution of oxygen and silicon atoms in the implanted samples reaches saturation after these high doses of MeV electron irradiation. The transformation of amorphous SiO2 surface into crystalline Si nanostructures (after MeV electron irradiation) was evidenced by atomic force microscopy (AFM). Silicon nanocrystals are formed on the SiO2 surface after MeV electron irradiation. The shape and number of the Si nanocrystals on the SiO2 surface depend on the MeV electron irradiation, while their size increases with the dose. The mean Si nanocrystals height is 16-20 nm after irradiation with MeV electrons at the dose of 6.0×1016 cm-2.

Structural Assembly for Cold Plate Cooling

NASA Technical Reports Server (NTRS)

Zaffetti, Mark A. (Inventor); Taddey, Edmund P. (Inventor)

2014-01-01

A device including a structural member having a heat spreader and an electronic device mounted directly to a first surface of the heat spreader of the structural member. The device also includes a cold plate mounted directly to the first surface of the heat spreader of the structural member.

Superconductivity across Lifshitz transition and anomalous insulating state in surface K-dosed (Li0.8Fe0.2OH)FeSe.

PubMed

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-07-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity ( T c of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li 0.8 Fe 0.2 OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level ( E F ), can be continuously tuned to cross E F and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors.

Superconductivity across Lifshitz transition and anomalous insulating state in surface K–dosed (Li0.8Fe0.2OH)FeSe

PubMed Central

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-01-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity (Tc of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li0.8Fe0.2OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level (EF), can be continuously tuned to cross EF and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors. PMID:28740865

Studies by immune electron microscopy of hepatitis B surface antigen in PLC/PRF/5 cells.

PubMed

Shibayama, T; Watanabe, T; Kojima, H; Yoshikawa, A; Watanabe, S; Kamimura, T; Suzuki, S; Ichida, F

1984-01-01

Electron microscopic studies of the morphology of hepatitis B surface antigen (HBsAg) produced by PLC/PRF/5 cells in vitro were carried out. Aggregates of 20-nm spherical particles in 3-day culture supernatants were observed by immune electron microscopy (IEM). Aggregates of tubular structures were found with IEM in the extracts of the cells. Tubular structures 18 to 22 nm in diameter were seen by electron microscopy (EM) in the cisternae of the endoplasmic reticulum in 2-3% of the cells. The tubular structures in the cytoplasm and extracts of PLC/PRF/5 cells resembled those observed in the hepatocytes of human carriers of hepatitis B virus (HBV). Intracellular localization of HBsAg in PLC/PRF/5 cells by direct peroxidase-conjugated antibody staining was observed on the tubular structures and the cisternal wall, which contained these structures. Rotation technique analysis indicated that the tubular structures were composed of 11 or 12 subunits.

Structure and electronic properties of Cu nanoclusters supported on Mo 2C(001) and MoC(001) surfaces

DOE PAGES

Posada-Pérez, Sergio; Viñes, Francesc; Rodríguez, José A.; ...

2015-09-15

In this study, the atomic structure and electronic properties of Cu n nanoclusters (n = 4, 6, 7, and 10) supported on cubic nonpolar δ-MoC(001) and orthorhombic C- or Mo-terminated polar β-Mo 2C(001) surfaces have been investigated by means of periodic density functional theory based calculations. The electronic properties have been analyzed by means of the density of states, Bader charges, and electron localization function plots. The Cu nanoparticles supported on β-Mo 2C(001), either Mo- or C-terminated, tend to present a two-dimensional structure whereas a three-dimensional geometry is preferred when supported on δ-MoC(001), indicating that the Mo:C ratio and themore » surface polarity play a key role determining the structure of supported clusters. Nevertheless, calculations also reveal important differences between the C- and Mo-terminated β-Mo 2C(001) supports to the point that supported Cu particles exhibit different charge states, which opens a way to control the reactivity of these potential catalysts.« less

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-04-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sites of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.

Theoretical studies of positron states and annihilation characteristics at the oxidized Cu(100) surface

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

Fazleev, N. G.; Weiss, A. H.

2013-04-19

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. An ab-initio study of the electronic properties of the Cu(100) missing row reconstructed surface at various on surface and sub-surface oxygen coverages has been performed on the basis of the density functional theory (DFT) using the Dmol3 code and the generalized gradient approximation (GGA). Surface structures in calculations have been constructed by adding oxygen atoms to various surface hollow and sub-surface octahedral sitesmore » of the 0.5 monolayer (ML) missing row reconstructed phase of the Cu(100) surface with oxygen coverages ranging from 0.5 to 1.5 ML. The charge redistribution at the surface and variations in atomic structure and chemical composition of the topmost layers associated with oxidation and surface reconstruction have been found to affect the spatial extent and localization of the positron surface state wave function and annihilation probabilities of surface trapped positrons with relevant core electrons. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). It has been shown that positron annihilation probabilities with Cu 3s and 3p core electrons decrease when total (on-surface and sub-surface) oxygen coverage of the Cu(100) surface increases up to 1 ML. The calculations show that for high oxygen coverage when total oxygen coverage is 1. 5 ML the positron is not bound to the surface.« less

Electronic Structure and Surface Physics of Two-dimensional Material Molybdenum Disulfide

NASA Astrophysics Data System (ADS)

Jin, Wencan

The interest in two-dimensional materials and materials physics has grown dramatically over the past decade. The family of two-dimensional materials, which includes graphene, transition metal dichalcogenides, phosphorene, hexagonal boron nitride, etc., can be fabricated into atomically thin films since the intralayer bonding arises from their strong covalent character, while the interlayer interaction is mediated by weak van der Waals forces. Among them, molybdenum disulfide (MoS2) has attracted much interest for its potential applications in opto-electronic and valleytronics devices. Previously, much of the experimental studies have concentrated on optical and transport measurements while neglecting direct experimental determination of the electronic structure of MoS2, which is crucial to the full understanding of its distinctive properties. In particular, like other atomically thin materials, the interactions with substrate impact the surface structure and morphology of MoS2, and as a result, its structural and physical properties can be affected. In this dissertation, the electronic structure and surface structure of MoS2 are directly investigated using angle-resolved photoemission spectroscopy and cathode lens microscopy. Local-probe angle-resolved photoemission spectroscopy measurements of monolayer, bilayer, trilayer, and bulk MoS 2 directly demonstrate the indirect-to-direct bandgap transition due to quantum confinement as the MoS2 thickness is decreased from multilayer to monolayer. The evolution of the interlayer coupling in this transition is also investigated using density functional theory calculations. Also, the thickness-dependent surface roughness is characterized using selected-area low energy electron diffraction (LEED) and the surface structural relaxation is investigated using LEED I-V measurements combined with dynamical LEED calculations. Finally, bandgap engineering is demonstrated via tuning of the interlayer interactions in van der Waals interfaces by twisting the relative orientation in bilayer-MoS2 and graphene-MoS 2-heterostructure systems.

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

DOE PAGES

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly; ...

2017-08-14

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

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

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

Studies in electron phenomena in MOS structures: The pulsed C-V method. M.S. Thesis. Abstract Only

NASA Technical Reports Server (NTRS)

Kaplan, G.

1983-01-01

The pulse hysteresis capacitance voltage (C-V) provides a straight forward technique for measuring the change of various charges in MOS structures and a tool for investigating the kinetics of various electron phenomena is developed and described. The method can be used for measuring the energy distribution and kinetics of surface states with the resolution of about 1/5 x 10 to the -9 power cm eV. Some transients in an MOS structure, particularly, the thermal generation of minority charge carriers via surface states and the relaxation of minority charge carriers supplied from the inversion layer outside the MOS structure are theoretically investigated. Analytical expressions which clearly present the physics of those electron phenomena are derived.

Interaction between adatoms on surfaces: Application to the system H/Ni(111)

NASA Astrophysics Data System (ADS)

Muscat, J. P.; Newns, D. M.

1981-04-01

The interaction of adatoms on a metal surface is looked at from a novel viewpoint, using the techniques of the embedded cluster model of chemisorption. Application is made to the problem of two hydrogen atoms on a free electron surface with simple derivation of the well known R-5 asymptotic behaviour for the interaction, at large inter-adatom distances R, compared to the corresponding R-3 behaviour for two impurities in a bulk free electron gas. Application of the free electron model to the case of H/Ni(111) does not reproduce the experimental observation of formation of a graphitic structure on the surface. Inclusion of the l = 2 nickel muffin tins corrects for this anomaly, and is seen to favour the formation of the above mentioned structure.

Water adsorption on the P-rich GaP(100) surface: optical spectroscopy from first principles

NASA Astrophysics Data System (ADS)

May, Matthias M.; Sprik, Michiel

2018-03-01

The contact of water with semiconductors typically changes its surface electronic structure by oxidation or corrosion processes. A detailed knowledge—or even control of—the surface structure is highly desirable, as it impacts the performance of opto-electronic devices from gas-sensing to energy conversion applications. It is also a prerequisite for density functional theory-based modelling of the electronic structure in contact with an electrolyte. The P-rich GaP(100) surface is extraordinary with respect to its contact with gas-phase water, as it undergoes a surface reordering, but does not oxidise. We investigate the underlying changes of the surface in contact with water by means of theoretically derived reflection anisotropy spectroscopy (RAS). A comparison of our results with experiment reveals that a water-induced hydrogen-rich phase on the surface is compatible with the boundary conditions from experiment, reproducing the optical spectra. We discuss potential reaction paths that comprise a water-enhanced hydrogen mobility on the surface. Our results also show that computational RAS—required for the interpretation of experimental signatures—is feasible for GaP in contact with water double layers. Here, RAS is sensitive to surface electric fields, which are an important ingredient of the Helmholtz-layer. This paves the way for future investigations of RAS at the semiconductor–electrolyte interface.

Photoemission study of electronic structure of the half-metallic ferromagnet Co3Sn2S2

NASA Astrophysics Data System (ADS)

Holder, M.; Dedkov, Yu. S.; Kade, A.; Rosner, H.; Schnelle, W.; Leithe-Jasper, A.; Weihrich, R.; Molodtsov, S. L.

2009-05-01

Surface electronic structure of polycrystalline and single-crystalline samples of the half-metallic ferromagnet Co3Sn2S2 was studied by means of angle-resolved and core-level photoemissions. The experiments were performed in temperature regimes both above and below a Curie temperature of 176.9 K. The spectroscopic results are compared to local-spin density approximation band-structure calculations for the bulk samples. It is found that the surface sensitive experimental data are generally reproduced by the bulk computation suggesting that the theoretically predicted half-metallic properties of Co3Sn2S2 are retained at the surface.

Effects of front-surface target structures on properties of relativistic laser-plasma electrons.

PubMed

Jiang, S; Krygier, A G; Schumacher, D W; Akli, K U; Freeman, R R

2014-01-01

We report the results of a study of the role of prescribed geometrical structures on the front of a target in determining the energy and spatial distribution of relativistic laser-plasma electrons. Our three-dimensional particle-in-cell simulation studies apply to short-pulse, high-intensity laser pulses, and indicate that a judicious choice of target front-surface geometry provides the realistic possibility of greatly enhancing the yield of high-energy electrons while simultaneously confining the emission to narrow (<5°) angular cones.

A Study of the Surface Structure of Polymorphic Graphene and Other Two-Dimensional Materials for Use in Novel Electronics and Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Grady, Maxwell

For some time there has been interest in the fundamental physical properties of low- dimensional material systems. The discovery of graphene as a stable two-dimensional form of solid carbon lead to an exponential increase in research in two-dimensional and other re- duced dimensional systems. It is now known that there is a wide range of materials which are stable in two-dimensional form. These materials span a large configuration space of struc- tural, mechanical, and electronic properties, which results in the potential to create novel electronic devices from nano-scale heterostructures with exactly tailored device properties. Understanding the material properties at the nanoscale level requires specialized tools to probe materials with atomic precision. Here I present the growth and analysis of a novel graphene-ruthenium system which exhibits unique polymorphism in its surface structure, hereby referred to as polymorphic graphene. Scanning Tunneling Microscopy (STM) investigations of the polymorphic graphene surface reveal a periodically rippled structure with a vast array of domains, each exhibiting xvia unique moire period. The majority of moire domains found in this polymorphic graphene system are previously unreported in past studies of the structure of graphene on ruthenium. To better understand many of the structural properties of this system, characterization methods beyond those available at the UNH surface science lab are employed. Further investigation using Low Energy Electron Microscopy (LEEM) has been carried out at Sandia National Laboratory's Center for Integrated Nanotechnology and the Brookhaven National Laboratory Center for Functional Nanomaterials. To aid in analysis of the LEEM data, I have developed an open source software package to automate extraction of electron reflectivity curves from real space and reciprocal space data sets. This software has been used in the study of numerous other two-dimensional materials beyond graphene. When combined with computational modeling, the analysis of electron I(V) curves presents a method to quantify structural parameters in a material with angstrom level precision. While many materials studied in this thesis offer unique electronic properties, my work focuses primarily on their structural aspects, as well as the instrumentation required to characterize the structure with ultra high resolution.

The Electronic Structure of the Cs/ n-GaN(0001) Nano-Interface

NASA Astrophysics Data System (ADS)

Benemanskaya, G. V.; Lapushkin, M. N.; Marchenko, D. E.; Timoshnev, S. N.

2018-03-01

Electronic structures of the n-GaN(0001) surface and Cs/ n-GaN(0001) interface with submonolayer Cs coverages were studied for the first time in situ by the photoelectron spectroscopy (PES) method. The spectra of photoemission from the valence band, surface electron states, and core levels (Ga 3 d, Cs 4 d, Cs 5 p) under synchrotron excitation were measured in a range of photon energies within 50-150 eV. Evolution of the spectrum of surface states near the valence-band maximum was revealed by PES during the adsorption of Cs atoms. A metallic character of the Cs/ n-GaN(0001) nano-interface is demonstrated.

Graphene-on-semiconductor substrates for analog electronics

DOEpatents

Lagally, Max G.; Cavallo, Francesca; Rojas-Delgado, Richard

2016-04-26

Electrically conductive material structures, analog electronic devices incorporating the structures and methods for making the structures are provided. The structures include a layer of graphene on a semiconductor substrate. The graphene layer and the substrate are separated by an interfacial region that promotes transfer of charge carriers from the surface of the substrate to the graphene.

Controlled electron doping into metallic atomic wires: Si(111)4×1-In

NASA Astrophysics Data System (ADS)

Morikawa, Harumo; Hwang, C. C.; Yeom, Han Woong

2010-02-01

We demonstrate the controllable electron doping into metallic atomic wires, indium wires self-assembled on the Si(111) surface, which feature one-dimensional (1D) band structure and temperature-driven metal-insulator transition. The electron filling of 1D metallic bands is systematically increased by alkali-metal adsorption, which, in turn, tunes the macroscopic property, that is, suppresses the metal-insulator transition. On the other hand, the dopant atoms induce a local lattice distortion without a band-gap opening, leading to a microscopic phase separation on the surface. The distinct bifunctional, electronic and structural, roles of dopants in different length scales are thus disclosed.

Multi-MHz time-of-flight electronic bandstructure imaging of graphene on Ir(111)

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

Tusche, C., E-mail: c.tusche@fz-juelich.de; Peter Grünberg Institut; Goslawski, P.

2016-06-27

In the quest for detailed spectroscopic insight into the electronic structure at solid surfaces in a large momentum range, we have developed an advanced experimental approach. It combines the 3D detection scheme of a time-of-flight momentum microscope with an optimized filling pattern of the BESSY II storage ring. Here, comprehensive data sets covering the full surface Brillouin zone have been used to study faint substrate-film hybridization effects in the electronic structure of graphene on Ir(111), revealed by a pronounced linear dichroism in angular distribution. The method paves the way to 3D electronic bandmapping with unprecedented data recording efficiency.

Analogies in electronic properties of graphene wormhole and perturbed nanocylinder

NASA Astrophysics Data System (ADS)

Pincak, R.; Smotlacha, J.

2013-11-01

The electronic properties of the wormhole and the perturbed nanocylinder were investigated using two different methods: the continuum gauge field-theory model that deals with the continuum approximation of the surface and the Haydock recursion method that transforms the surface into a simplier structure and deals with the nearest-neighbor interactions. Furthermore, the changes of the electronic properties were investigated for the case of enclosing the appropriate structure, and possible substitutes for the encloser were derived. Finally, the character of the electron flux through the perturbed wormhole was predicted from the model based on the multiwalled nanotubes. The effect of the "graphene blackhole" is introduced.

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

NASA Astrophysics Data System (ADS)

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

2007-02-01

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

Periodicity in Attachment Organelle Revealed by Electron Cryotomography Suggests Conformational Changes in Gliding Mechanism of Mycoplasma pneumoniae

PubMed Central

Kawamoto, Akihiro; Matsuo, Lisa; Kato, Takayuki; Yamamoto, Hiroki

2016-01-01

ABSTRACT Mycoplasma pneumoniae, a pathogenic bacterium, glides on host surfaces using a unique mechanism. It forms an attachment organelle at a cell pole as a protrusion comprised of knoblike surface structures and an internal core. Here, we analyzed the three-dimensional structure of the organelle in detail by electron cryotomography. On the surface, knoblike particles formed a two-dimensional array, albeit with limited regularity. Analyses using a nonbinding mutant and an antibody showed that the knoblike particles correspond to a naplike structure that has been observed by negative-staining electron microscopy and is likely to be formed as a complex of P1 adhesin, the key protein for binding and gliding. The paired thin and thick plates feature a rigid hexagonal lattice and striations with highly variable repeat distances, respectively. The combination of variable and invariant structures in the internal core and the P1 adhesin array on the surface suggest a model in which axial extension and compression of the thick plate along a rigid thin plate is coupled with attachment to and detachment from the substrate during gliding. PMID:27073090

Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Ito, S.; Feng, B.; Arita, M.; Someya, T.; Chen, W.-C.; Takayama, A.; Iimori, T.; Namatame, H.; Taniguchi, M.; Cheng, C.-M.; Tang, S.-J.; Komori, F.; Matsuda, I.

2018-04-01

Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

Surface hardening of 30CrMnSiA steel using continuous electron beam

NASA Astrophysics Data System (ADS)

Fu, Yulei; Hu, Jing; Shen, Xianfeng; Wang, Yingying; Zhao, Wansheng

2017-11-01

30CrMnSiA high strength low alloy (HSLA) carbon structural steel is typically applied in equipment manufacturing and aerospace industries. In this work, the effects of continuous electron beam treatment on the surface hardening and microstructure modifications of 30CrMnSiA are investigated experimentally via a multi-purpose electron beam machine Pro-beam system. Micro hardness value in the electron beam treated area shows a double to triple increase, from 208 HV0.2 on the base metal to 520 HV0.2 on the irradiated area, while the surface roughness is relatively unchanged. Surface hardening parameters and mechanisms are clarified by investigation of the microstructural modification and the phase transformation both pre and post irradiation. The base metal is composed of ferrite and troostite. After continuous electron beam irradiation, the micro structure of the electron beam hardened area is composed of acicular lower bainite, feathered upper bainite and part of lath martensite. The optimal input energy density for 30CrMnSiA steel in this study is of 2.5 kJ/cm2 to attain the proper hardened depth and peak hardness without the surface quality deterioration. When the input irradiation energy exceeds 2.5 kJ/cm2 the convective mixing of the melted zone will become dominant. In the area with convective mixing, the cooling rate is relatively lower, thus the micro hardness is lower. The surface quality will deteriorate. Chemical composition and surface roughness pre and post electron beam treatment are also compared. The technology discussed give a picture of the potential of electron beam surface treatment for improving service life and reliability of the 30CrMnSiA steel.

TiO 2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

DOE PAGES

Liu, Jing; Hosseinpour, Pegah M.; Luo, Si; ...

2014-11-19

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO₂ nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O₂ (oxidizing), Ar (inert), and H₂ (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO₂ nanotube samplesmore » partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO₂ nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H₂-annealed nanotubes than with the Ar- and O₂-annealed nanotube samples. This enhanced photocatalytic response of the H₂-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti 3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

Charging of Basic Structural Shapes in a Simulated Lunar Environment

NASA Technical Reports Server (NTRS)

Craven, P.; Schneider, T.; Vaughn, J.; Wang, J.; Polansky, J.

2012-01-01

In order to understand the effect of the charging environment on and around structures on the lunar surface, we have exposed basic structural shapes to electrons and Vacuum Ultra-Violet (VUV) radiation. The objects were, in separate runs, isolated, grounded, and placed on dielectric surfaces. In this presentation, the effects of electron energy, VUV flux, and sample orientation, on the charging of the objects will be examined. The potential of each of the object surfaces was monitored in order to determine the magnitude of the ram and wake effects under different orientations relative to the incoming beams (solar wind). This is a part of, and complementary to, the study of the group at USC under Dr. J. Wang, the purpose of which is to model the effects of the charging environment on structures on the lunar surface.

Conductivity and local structure in LaNiO3

NASA Astrophysics Data System (ADS)

Fowlie, Jennifer; Gibert, Marta; Tieri, Giulio; Gloter, Alexandre; à+/-Iguez, Jorge; Filippetti, Alessio; Catalano, Sara; Gariglio, Stefano; StéPhan, Odile; Triscone, Jean-Marc

In this study we approach the thickness-dependence of the properties of LaNiO3 films along multiple, complementary avenues: sophisticated ab initio calculations, scanning transmission electron microscopy and electronic transport. Specifically, we find an unexpected maximum in conductivity in films of thickness 6 - 10 unit cells (3 nm) for several series of LaNiO3 films. Ab initio transport based on the detailed crystal structure also reveals a maximum in conductivity at the same thickness. In agreement with the structure obtained from scanning transmission electron microscopy (STEM), our simulated structures reveal that the substrate- and surface-induced distortions lead to three types of local structure (heterointerface, interior-layer, surface). Based on this observation, a 3-element parallel conductor model neatly reproduces the trend of conductivity with thickness. This study addresses the question of how structural distortions at the atomic scale evolve in a thin film under the influence of the substrate and the surface. This topic is key to the understanding of the physics of heterostructures and the design of functional oxides.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

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

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

PubMed

Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

2017-05-01

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

Formation of structure, phase composition and properties of electro explosion resistant coatings using electron-beam processing

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

Romanov, Denis A., E-mail: romanov-da@physics.sibsiu.ru, E-mail: kos2906@mail.ru, E-mail: budovskih-ea@physics.sibsiu.ru, E-mail: gromov@physics.sibsiu.ru, E-mail: da-rom@live.ru; Sosnin, Kirill V., E-mail: romanov-da@physics.sibsiu.ru, E-mail: kos2906@mail.ru, E-mail: budovskih-ea@physics.sibsiu.ru, E-mail: gromov@physics.sibsiu.ru, E-mail: da-rom@live.ru; Budovskikh, Evgenij A., E-mail: romanov-da@physics.sibsiu.ru, E-mail: kos2906@mail.ru, E-mail: budovskih-ea@physics.sibsiu.ru, E-mail: gromov@physics.sibsiu.ru, E-mail: da-rom@live.ru

2014-11-14

For the first time, the high intensity electron beam modification of electroexplosion composite coatings of MoCu, MoCCu, WCu, WCCu and TiB{sub 2}Cu systems was done. The studies of phase and elemental composition, defective structure conditions of these coatings were carried out. The regimes of electron-beam processing making possible to form the dense, specular luster surface layers having a submicrocrystalline structure were revealed. It was established that electron-beam processing of elecroexplosion spraying of layer of elecroexplosion spraying carried out in the regime of melting results in the formation of structurally and contrationally homogeneous surface layer. Investigation of the effect of electron-beammore » processing of electroexplosion electroerosion resistant coatings on their tribological properties (wear resistanse and coefficient of friction) and electroerosion resistance was done. It was shown that all the examined costings demonstrate the increase of electroerosion resistance in spark erosion up to 10 times.« less

Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy

NASA Astrophysics Data System (ADS)

Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

2017-05-01

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

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

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe[sub 2] and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

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

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe{sub 2} and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

Understanding of the Formation of Micro/Nanoscale Structures on Metal Surfaces by Ultrafast Pulse Laser Processing

NASA Astrophysics Data System (ADS)

Peng, Edwin

In the recent decades, there has been much interest in functionalized surfaces produced by ultrafast laser processing. Using pulse lasers with nanosecond to femtosecond time scale, a wide range of micro/nanoscale structures can be produced on virtually all metal surfaces. These surface structures create special optoelectronic, wetting, and tribological properties with a diverse range of potential applications. The formation mechanisms of these surface structures, especially microscale, mound-like structures, are not fully understood. There has been wide study of ultrafast laser processing of metals. Yet, the proposed formation models present in current literature often lack sufficient experimental verification. Specifically, many studies are limited to surface characterization, e.g. scanning electron microscopy of the surfaces of these micro/nanoscale structures. Valuable insight into the physical processes responsible for formation can be obtained if standard material science characterization methods are performed across the entire mound. In our study, we examined mound-like structures formed on three metal alloys. Using cross section and 3D slice and view operations by a dual beam scanning electron microscope-focused ion beam, the interior microstructures of these mounds are revealed. Taking advantage of amorphous phase formation during laser processing of Ni60Nb40, we verified the fluence-dependent formation model: mounds formed at low fluence are primarily the result of ablation while mounds formed at high fluence are formed by both ablation and rapid resolidification by hydrodynamical fluid flow. For the first time, we revealed the cross section of a wide variety of mound-like structures on titanium surfaces. The increased contribution to mound formation by fluid flow with increasing fluence was observed. Finally, a 3D scanning electron microscopy technique was applied for mounds produced on silver surface by delayed-pulse laser processing. The interior microstructure demonstrated that most of the volume comprised of resolidified silver grains with 1% porosity.

Donor defects and small polarons on the TiO2(110) surface

NASA Astrophysics Data System (ADS)

Moses, P. G.; Janotti, A.; Franchini, C.; Kresse, G.; Van de Walle, C. G.

2016-05-01

The role of defects in the chemical activity of the rutile TiO2(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend to localize in the form of small polarons, which are the factual cause of the deep states ˜1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO2 and related oxides.

Ab initio surface properties of Ag-Sn alloys: implications for lead-free soldering.

PubMed

Saleh, Gabriele; Xu, Chen; Sanvito, Stefano

2018-02-07

Ag and Sn are the major components of solder alloys adopted to assemble printed circuit boards. The qualities that make them the alloys of choice for the modern electronic industry are related to their physical and chemical properties. For corrosion resistance and solderability, surface properties are particularly important. Yet, atomic-level information about the surfaces of these alloys is not known. Here we fill this gap by presenting an extensive ab initio investigation of composition, energetics, structure and reactivity of Ag-Sn alloy surfaces. The structure and stability of various surfaces is evaluated, and the main factors determining the energetics of surface formation are uncovered. Oxygen and sulphur chemisorptions are studied and discussed in the framework of corrosion tendency, an important issue for printed circuit boards. Adsorption energy trends are rationalized based on the analysis of structural and electronic features.

First-principles study of electronic structure and Fermi surface in semimetallic YAs

DOE PAGES

Swatek, Przemys?aw Wojciech

2018-03-23

In the course of searching for new systems, which exhibit nonsaturating and extremely large positive magnetoresistance, electronic structure, Fermi surface, and de Haas-van Alphen characteristics of the semimetallic YAs compound were studied using the all-electron full-potential linearized augmented-plane wave (FP–LAPW) approach in the framework of the generalized gradient approximation (GGA). In the scalar-relativistic calculation, the cubic symmetry splits fivefold degenerate Y- d orbital into low-energy threefold-degenerate and twofold degenerate doublet states at point around the Fermi energy. Furthermore one of them, together with the threefold degenerate character of As-p orbital, render the YAs semimetal with a topologically trivial band ordermore » and fairly low density of states at the Fermi level. Including spin–orbit (SO) coupling into the calculation leads to pronounced splitting of the state and shifting the bands in the energy scale. Consequently, the determined four different 3-dimensional Fermi surface sheets of YAs consists of three concentric hole-like bands at and one ellipsoidal electron-like sheet centred at the X points. In full accordance with the previous first-principles calculations for isostructural YSb and YBi, the calculated Fermi surface of YAs originates from fairly compensated multi-band electronic structures.« less

First-principles study of electronic structure and Fermi surface in semimetallic YAs

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

Swatek, Przemys?aw Wojciech

In the course of searching for new systems, which exhibit nonsaturating and extremely large positive magnetoresistance, electronic structure, Fermi surface, and de Haas-van Alphen characteristics of the semimetallic YAs compound were studied using the all-electron full-potential linearized augmented-plane wave (FP–LAPW) approach in the framework of the generalized gradient approximation (GGA). In the scalar-relativistic calculation, the cubic symmetry splits fivefold degenerate Y- d orbital into low-energy threefold-degenerate and twofold degenerate doublet states at point around the Fermi energy. Furthermore one of them, together with the threefold degenerate character of As-p orbital, render the YAs semimetal with a topologically trivial band ordermore » and fairly low density of states at the Fermi level. Including spin–orbit (SO) coupling into the calculation leads to pronounced splitting of the state and shifting the bands in the energy scale. Consequently, the determined four different 3-dimensional Fermi surface sheets of YAs consists of three concentric hole-like bands at and one ellipsoidal electron-like sheet centred at the X points. In full accordance with the previous first-principles calculations for isostructural YSb and YBi, the calculated Fermi surface of YAs originates from fairly compensated multi-band electronic structures.« less

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.

The Electrical Structure of Discharges Modified by Electron Beams

NASA Astrophysics Data System (ADS)

Haas, F. A.; Braithwaite, N. St. J.

1997-10-01

Injection of an electron beam into a low pressure plasma modifies both the electrical structure and the distributions of charged particle energies. The electrical structure is investigated here in a one-dimensional model by representing the discharge as two collisionless sheaths with a monenergetic electron beam, linked by a quasi-neutral collisional region. The latter is modelled by fluid equations in which the beam current decreases with position. Since the electrodes are connected by an external conductor this implies through Kirchoff's laws that the thermal electron current must correspondingly increase with position. Given the boundary conditions and beam input at the first electrode then the rest of the system is uniquely described. The model reveals the dependence of the sheath potentials at the emitting and absorbing surfaces on the beam current. The model is relevant to externally injected beams and to electron beams originating from secondary processes on surfaces exposed to the plasma.

Imaging quasiperiodic electronic states in a synthetic Penrose tiling

NASA Astrophysics Data System (ADS)

Collins, Laura C.; Witte, Thomas G.; Silverman, Rochelle; Green, David B.; Gomes, Kenjiro K.

2017-06-01

Quasicrystals possess long-range order but lack the translational symmetry of crystalline solids. In solid state physics, periodicity is one of the fundamental properties that prescribes the electronic band structure in crystals. In the absence of periodicity and the presence of quasicrystalline order, the ways that electronic states change remain a mystery. Scanning tunnelling microscopy and atomic manipulation can be used to assemble a two-dimensional quasicrystalline structure mapped upon the Penrose tiling. Here, carbon monoxide molecules are arranged on the surface of Cu(111) one at a time to form the potential landscape that mimics the ionic potential of atoms in natural materials by constraining the electrons in the two-dimensional surface state of Cu(111). The real-space images reveal the presence of the quasiperiodic order in the electronic wave functions and the Fourier analysis of our results links the energy of the resonant states to the local vertex structure of the quasicrystal.

Imaging quasiperiodic electronic states in a synthetic Penrose tiling.

PubMed

Collins, Laura C; Witte, Thomas G; Silverman, Rochelle; Green, David B; Gomes, Kenjiro K

2017-06-22

Quasicrystals possess long-range order but lack the translational symmetry of crystalline solids. In solid state physics, periodicity is one of the fundamental properties that prescribes the electronic band structure in crystals. In the absence of periodicity and the presence of quasicrystalline order, the ways that electronic states change remain a mystery. Scanning tunnelling microscopy and atomic manipulation can be used to assemble a two-dimensional quasicrystalline structure mapped upon the Penrose tiling. Here, carbon monoxide molecules are arranged on the surface of Cu(111) one at a time to form the potential landscape that mimics the ionic potential of atoms in natural materials by constraining the electrons in the two-dimensional surface state of Cu(111). The real-space images reveal the presence of the quasiperiodic order in the electronic wave functions and the Fourier analysis of our results links the energy of the resonant states to the local vertex structure of the quasicrystal.

Bulk-surface relationship of an electronic structure for high-throughput screening of metal oxide catalysts

NASA Astrophysics Data System (ADS)

Kweun, Joshua Minwoo; Li, Chenzhe; Zheng, Yongping; Cho, Maenghyo; Kim, Yoon Young; Cho, Kyeongjae

2016-05-01

Designing metal-oxides consisting of earth-abundant elements has been a crucial issue to replace precious metal catalysts. To achieve efficient screening of metal-oxide catalysts via bulk descriptors rather than surface descriptors, we investigated the relationship between the electronic structure of bulk and that of the surface for lanthanum-based perovskite oxides, LaMO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu). Through density functional theory calculations, we examined the d-band occupancy of the bulk and surface transition-metal atoms (nBulk and nSurf) and the adsorption energy of an oxygen atom (Eads) on (001), (110), and (111) surfaces. For the (001) surface, we observed strong correlation between the nBulk and nSurf with an R-squared value over 94%, and the result was interpreted in terms of ligand field splitting and antibonding/bonding level splitting. Moreover, the Eads on the surfaces was highly correlated with the nBulk with an R-squared value of more than 94%, and different surface relaxations could be explained by the bulk electronic structure (e.g., LaMnO3 vs. LaTiO3). These results suggest that a bulk-derived descriptor such as nBulk can be used to screen metal-oxide catalysts.

Characterizing water-metal interfaces and machine learning potential energy surfaces

NASA Astrophysics Data System (ADS)

Ryczko, Kevin

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Fabrication of meso- and nano-scale structures on surfaces of chalcogenide semiconductors by surface hydrodynamic interference patterning

NASA Astrophysics Data System (ADS)

Bilanych, V.; Komanicky, V.; Lacková, M.; Feher, A.; Kuzma, V.; Rizak, V.

2015-10-01

We observe the change of surface relief on amorphous Ge-As-Se thin films after irradiation with an electron beam. The beam softens the glass and induces various topological surface changes in the irradiated area. The film relief change depends on the film thickness, deposited charge, and film composition. Various structures are formed: Gausian-like cones, extremely sharp Taylor cones, deep craters, and craters with large spires grown on the side. Our investigation shows that these effects can be at least partially a result of electro-hydrodynamic material flow, but the observed phenomena are likely more complex. When we irradiated structural patterns formed by the electron beam with a red laser beam, we could not only fully relax the produced patterns, but also form very complex and intricate superstructures. These organized meso- and nano-scale structures are formed by a combination of photo-induced structural relaxation, light interference on structures fabricated by the e-beam, and photo-induced material flow.

Spin-polarized surface resonances accompanying topological surface state formation

DOE PAGES

Jozwiak, Chris; Sobota, Jonathan A.; Gotlieb, Kenneth; ...

2016-10-14

Topological insulators host spin-polarized surface states born out of the energetic inversion of bulk bands driven by the spin-orbit interaction. Here we discover previously unidentified consequences of band-inversion on the surface electronic structure of the topological insulator Bi 2Se 3. By performing simultaneous spin, time, and angle-resolved photoemission spectroscopy, we map the spin-polarized unoccupied electronic structure and identify a surface resonance which is distinct from the topological surface state, yet shares a similar spin-orbital texture with opposite orientation. Its momentum dependence and spin texture imply an intimate connection with the topological surface state. Calculations show these two distinct states canmore » emerge from trivial Rashba-like states that change topology through the spin-orbit-induced band inversion. As a result, this work thus provides a compelling view of the coevolution of surface states through a topological phase transition, enabled by the unique capability of directly measuring the spin-polarized unoccupied band structure.« less

Final Technical Report

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

Dr. Asok K. Ray

2012-05-22

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compoundsmore » and understanding the quantum mechanics of the 5f electrons is the defining issue in the chemistry and physics of actinide elements. These elements are also characterized by the increasing prominence of relativistic effects and their studies can, in fact, help us understand the role of relativity throughout the periodic table. However, the electronic and geometric structures of the actinides, specifically the trans-uranium actinides and the roles of the 5f electrons in chemical bonding are still not well understood. This is crucial not only for our understanding of the actinides but also for the fact that the actinides constitute 'the missing link' between the d transition elements and the lanthanides. The 5f orbitals have properties intermediate between those of localized 4f and delocalized 3d orbitals. Thus, a proper understanding of the actinides will help us understand the behavior of the lanthanides and transition metals as well. In fact, there is an urgent need for continued extensive and detailed theoretical research in this area to provide significant and deep understandings of the electronic and geometric structures of the actinides. In this work, we have performed electronic structure studies for plutonium (Pu), americium (Am), and curium (Cm) surfaces, and molecular adsorptions on Pu and Am surfaces. In particular, the region at the boundary of Pu and Am, is widely believed to be the crossover region between d-like itinerant and f-like localized behavior The eventual goal is a complete understanding of the surface chemistry and physics processes of all actinide surfaces, defining the chemistry and physics of such heavy elements. Among the actinides, plutonium, with five 5f electrons in the solid state, is arguably the most complex, fascinating, and enigmatic element known to mankind and has attracted extraordinary scientific and technological interests because of its unique properties, generating a significant body of research in diverse areas, including superconductivity. Pu has, at least, six stable allotropes between room temperature and melting at atmospheric pressure, indicating that the valence electrons can hybridize into a number of complex bonding arrangements. Central and critical questions relate to the electronic structure, localization of the 5f electrons and the magnetism of Pu. For the light-actinides, from Th to Pu, the 5f electrons are believed to be delocalized, hybridizing with the 6d and 7s electrons. For the heavier actinides, Am and beyond, the 5f electrons are localized with the 5f orbitals progressively lower in energy relative to the 6d configuration. Hence, Pu is in a position where the 5f electronic behavior changes from itinerant to localized. As far as magnetism is concerned, a majority of the theoretical calculations continues to claim the existence of magnetism while almost all the experimental results do not find any support for such claims. The second element of interest to us, namely americium, occupies a central position in the actinide series with respect to the involvement of 5f electrons in metallic bonding. It is widely believed that the 5f electrons in Am are localized and that Am undergoes a series of crystallographic phase changes with pressure. Fully-relativistic all electron surface studies of the different phases of Am, initially for the dhcp and the fcc surfaces, can and have provided us with valuable information about chemical bonding in Am and the transitions from f-electron delocalization to f-electron localization in trans-uranium compounds. In particular, a comparative study of the electronic structures of the Pu and Am surfaces using the techniques of all-electron modern density functional theory and beyond can provide significant information about the role of 5f electrons in bond formation as also the localization of the 5f electrons, matters of considerable controversies. The change from metallic 5f bonding into local-moment nonbonding configurations that takes place between Pu and Am is rather unique in the periodic table and is at the very heart of our understanding of electronic structure. We believe that, considering the narrow bandwidth of surface states, any transition from itinerant to localized behavior first takes place at the actinide surfaces with possible reconstructions.« less

Electron spectroscopy imaging and surface defect configuration of zinc oxide nanostructures under different annealing ambient

NASA Astrophysics Data System (ADS)

Ann, Ling Chuo; Mahmud, Shahrom; Bakhori, Siti Khadijah Mohd

2013-01-01

In this study, electron spectroscopy imaging was used to visualize the elemental distribution of zinc oxide nanopowder. Surface modification in zinc oxide was done through annealing treatment and type of surface defect was also inferred from the electron spectroscopy imaging investigation. The micrographs revealed the non-stoichiometric distribution of the elements in the unannealed samples. Annealing the samples in nitrogen and oxygen ambient at 700 °C would alter the density of the elements in the samples as a result of removal or absorption of oxygen. The electrical measurement showed that nitrogen annealing treatment improved surface electrical conductivity, whereas oxygen treatment showed an adverse effect. Observed change in the photoluminescence green emission suggested that oxygen vacancies play a significant role as surface defects. Structural investigation carried out through X-ray diffraction revealed the polycrystalline nature of both zinc oxide samples with hexagonal phase whereby annealing process increased the crystallinity of both zinc oxide specimens. Due to the different morphologies of the two types of zinc oxide nanopowders, X-ray diffraction results showed different stress levels in their structures and the annealing treatment give significant effect to the structural stress. Electron spectroscopy imaging was a useful technique to identify the elemental distribution as well as oxygen defect in zinc oxide nanopowder.

Tailoring Dirac Fermions in Molecular Graphene

NASA Astrophysics Data System (ADS)

Gomes, Kenjiro K.; Mar, Warren; Ko, Wonhee; Camp, Charlie D.; Rastawicki, Dominik K.; Guinea, Francisco; Manoharan, Hari C.

2012-02-01

The dynamics of electrons in solids is tied to the band structure created by a periodic atomic potential. The design of artificial lattices, assembled through atomic manipulation, opens the door to engineer electronic band structure and to create novel quantum states. We present scanning tunneling spectroscopic measurements of a nanoassembled honeycomb lattice displaying a Dirac fermion band structure. The artificial lattice is created by atomic manipulation of single CO molecules with the scanning tunneling microscope on the surface of Cu(111). The periodic potential generated by the assembled CO molecules reshapes the band structure of the two-dimensional electron gas, present as a surface state of Cu(111), into a ``molecular graphene'' system. We create local defects in the lattice to observe the quasiparticle interference patterns that unveil the underlying band structure. We present direct comparison between the tunneling data, first-principles calculations of the band structure, and tight-binding models.

Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111).

PubMed

Fernández, Cynthia C; Pensa, Evangelina; Carro, Pilar; Salvarezza, Roberto; Williams, Federico J

2018-05-22

The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV).

Spectroscopic studies of nanomaterials with a liquid-helium-free high-stability cryogenic scanning tunneling microscope

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry Anatolevich

This dissertation presents results of a project bringing Scanning Tunneling Microscope (STM) into a regime of unlimited operational time at cryogenic conditions. Freedom from liquid helium consumption was achieved and technical characteristics of the instrument are reported, including record low noise for a scanning probe instrument coupled to a close-cycle cryostat, which allows for atomically resolved imaging, and record low thermal drift. Subsequent studies showed that the new STM opened new prospects in nanoscience research by enabling Scanning Tunneling Spectroscopic (STS) spatial mapping to reveal details of the electronic structure in real space for molecules and low-dimensional nanomaterials, for which this depth of investigation was previously prohibitively expensive. Quantum-confined electronic states were studied in single-walled carbon nanotubes (SWCNTs) deposited on the Au(111) surface. Localization on the nanometer-scale was discovered to produce a local vibronic manifold resulting from the localization-enhanced electron-vibrational coupling. STS showed the vibrational overtones, identified as D-band Kekule vibrational modes and K-point transverse out-of plane phonons. This study experimentally connected the properties of well-defined localized electronic states to the properties of associated vibronic states. Electronic structures of alkyl-substituted oligothiophenes with different backbone lengths were studied and correlated with torsional conformations assumed on the Au(111) surface. The molecules adopted distinct planar conformations with alkyl ligands forming cis- or trans-mutual orientations and at higher coverage self-assembled into ordered structures, binding to each other via interdigitated alkyl ligands. STS maps visualized, in real space, particle-in-a-box-like molecular orbitals. Shorter quaterthiophenes have substantially varying orbital energies because of local variations in surface reactivity. Different conformers of longer oligothiophenes with significant geometrical distortions of the oligothiophene backbones surprisingly exhibited similar electronic structures, indicating insensitivity of interaction with the surface to molecular conformation. Electronic states for annealed ligand-free lead sulfide nanocrystals were investigated, as well as hydrogen-passivated silicon nanocrystals, supported on the Au(111) surface. Delocalized quantum-confined states and localized defect-related states were identified, for the first time, via STS spatial mapping. Physical mechanisms, involving surface reconstruction or single-atom defects, were proposed for surface state formation to explain the observed spatial behavior of the electronic density of states. This dissertation includes previously published co-authored material.

Total photoelectron yield spectroscopy of energy distribution of electronic states density at GaN surface and SiO2/GaN interface

NASA Astrophysics Data System (ADS)

Ohta, Akio; Truyen, Nguyen Xuan; Fujimura, Nobuyuki; Ikeda, Mitsuhisa; Makihara, Katsunori; Miyazaki, Seiichi

2018-06-01

The energy distribution of the electronic state density of wet-cleaned epitaxial GaN surfaces and SiO2/GaN structures has been studied by total photoelectron yield spectroscopy (PYS). By X-ray photoelectron spectroscopy (XPS) analysis, the energy band diagram for a wet-cleaned epitaxial GaN surface such as the energy level of the valence band top and electron affinity has been determined to obtain a better understanding of the measured PYS signals. The electronic state density of GaN surface with different carrier concentrations in the energy region corresponding to the GaN bandgap has been evaluated. Also, the interface defect state density of SiO2/GaN structures was also estimated by not only PYS analysis but also capacitance–voltage (C–V) characteristics. We have demonstrated that PYS analysis enables the evaluation of defect state density filled with electrons at the SiO2/GaN interface in the energy region corresponding to the GaN midgap, which is difficult to estimate by C–V measurement of MOS capacitors.

Multi-scale predictive modeling of nano-material and realistic electron devices

NASA Astrophysics Data System (ADS)

Palaria, Amritanshu

Among the challenges faced in further miniaturization of electronic devices, heavy influence of the detailed atomic configuration of the material(s) involved, which often differs significantly from that of the bulk material(s), is prominent. Device design has therefore become highly interrelated with material engineering at the atomic level. This thesis aims at outlining, with examples, a multi-scale simulation procedure that allows one to integrate material and device aspects of nano-electronic design to predict behavior of novel devices with novel material. This is followed in four parts: (1) An approach that combines a higher time scale reactive force field analysis with density functional theory to predict structure of new material is demonstrated for the first time for nanowires. Novel stable structures for very small diameter silicon nanowires are predicted. (2) Density functional theory is used to show that the new nanowire structures derived in 1 above have properties different from diamond core wires even though the surface bonds in some may be similar to the surface of bulk silicon. (3) Electronic structure of relatively large-scale germanium sections of realistically strained Si/strained Ge/ strained Si nanowire heterostructures is computed using empirical tight binding and it is shown that the average non-homogeneous strain in these structures drives their interesting non-conventional electronic characteristics such as hole effective masses which decrease as the wire cross-section is reduced. (4) It is shown that tight binding, though empirical in nature, is not necessarily limited to the material and atomic structure for which the parameters have been empirically derived, but that simple changes may adapt the derived parameters to new bond environments. Si (100) surface electronic structure is obtained from bulk Si parameters.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

PubMed

Hong, Woong-Ki; Park, Jong Bae; Yoon, Jongwon; Kim, Bong-Joong; Sohn, Jung Inn; Lee, Young Boo; Bae, Tae-Sung; Chang, Sung-Jin; Huh, Yun Suk; Son, Byoungchul; Stach, Eric A; Lee, Takhee; Welland, Mark E

2013-04-10

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

3D morphology of Au and Au@Ag nanobipyramids

NASA Astrophysics Data System (ADS)

Burgin, Julien; Florea, Ileana; Majimel, Jérôme; Dobri, Adam; Ersen, Ovidiu; Tréguer-Delapierre, Mona

2012-02-01

The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance.The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11454b

Scanning ultrafast electron microscopy

PubMed Central

Yang, Ding-Shyue; Mohammed, Omar F.; Zewail, Ahmed H.

2010-01-01

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability. PMID:20696933

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

DOE PAGES

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung; ...

2018-05-24

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

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

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Laser-induced generation of surface periodic structures in media with nonlinear diffusion

NASA Astrophysics Data System (ADS)

Zhuravlev, V. M.; Zolotovskii, I. O.; Korobko, D. A.; Morozov, V. M.; Svetukhin, V. V.; Yavtushenko, I. O.; Yavtushenko, M. S.

2017-12-01

A model of fast formation of high-contrast periodic structure appearing on a semiconductor surface under action of laser radiation is proposed. The process of growing a surface structure due to the interaction surface plasmon- polaritons excited on nonequilibrium electrons with incident laser radiation are considered in the framework of a medium with nonlinear diffusion of nonequilibrium carriers (defects). A resonance effect of superfast pico- and subpicosecond amplification of the plasmon-polariton structure generated on the surface, the realization of which can result in a high-contrast defect lattice.

Surface alloying of aluminum with molybdenum by high-current pulsed electron beam

NASA Astrophysics Data System (ADS)

Xia, Han; Zhang, Conglin; Lv, Peng; Cai, Jie; Jin, Yunxue; Guan, Qingfeng

2018-02-01

The surface alloying of pre-coated molybdenum (Mo) film on aluminum (Al) substrate by high-current pulsed electron beam (HCPEB) was investigated. The microstructure and phase analysis were conducted by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that Mo particles were dissolved into Al matrix to form alloying layer, which was composed of Mo, Al and acicular or equiaxed Al5Mo phases after surface alloying. Meanwhile, various structure defects such as dislocation loops, high-density dislocations and dislocation walls were observed in the alloying surface. The corrosion resistance was tested by using potentiodynamic polarization curves and electrochemical impedance spectra (EIS). Electrochemical results indicate that all the alloying samples had better corrosion resistance in 3.5 wt% NaCl solution compared to initial sample. The excellent corrosion resistance is mainly attributed to the combined effect of the structure defects and the addition of Mo element to form a more stable passive film.

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

Single ion induced surface nanostructures: a comparison between slow highly charged and swift heavy ions.

PubMed

Aumayr, Friedrich; Facsko, Stefan; El-Said, Ayman S; Trautmann, Christina; Schleberger, Marika

2011-10-05

This topical review focuses on recent advances in the understanding of the formation of surface nanostructures, an intriguing phenomenon in ion-surface interaction due to the impact of individual ions. In many solid targets, swift heavy ions produce narrow cylindrical tracks accompanied by the formation of a surface nanostructure. More recently, a similar nanometric surface effect has been revealed for the impact of individual, very slow but highly charged ions. While swift ions transfer their large kinetic energy to the target via ionization and electronic excitation processes (electronic stopping), slow highly charged ions produce surface structures due to potential energy deposited at the top surface layers. Despite the differences in primary excitation, the similarity between the nanostructures is striking and strongly points to a common mechanism related to the energy transfer from the electronic to the lattice system of the target. A comparison of surface structures induced by swift heavy ions and slow highly charged ions provides a valuable insight to better understand the formation mechanisms. © 2011 IOP Publishing Ltd

Surface and local electronic structure modification of MgO film using Zn and Fe ion implantation

NASA Astrophysics Data System (ADS)

Singh, Jitendra Pal; Lim, Weon Cheol; Lee, Jihye; Song, Jonghan; Lee, Ik-Jae; Chae, Keun Hwa

2018-02-01

Present work is motivated to investigate the surface and local electronic structure modifications of MgO films implanted with Zn and Fe ions. MgO film was deposited using radio frequency sputtering method. Atomic force microscopy measurements exhibit morphological changes associated with implantation. Implantation of Fe and Zn ions leads to the reduction of co-ordination geometry of Mg2+ ions in host lattice. The effect is dominant at bulk of film rather than surface as the large concentration of implanted ions resides inside bulk. Moreover, the evidences of interaction among implanted ions and oxygen are not being observed using near edge fine structure measurements.

Graphite carbon nitride/boron-doped graphene hybrid for efficient hydrogen generation reaction.

PubMed

Yang, Liang; Wang, Xin; Wang, Juan; Cui, Guomin; Liu, Daoping

2018-08-24

Metal-free carbon materials, with tuned surface chemical and electronic properties, hold great potential for the hydrogen evolution reaction (HER). We designed and synthesized a CN/BG hybrid electrocatalytic system with a porous and active graphite carbon nitride (CN) layer on boron-doped graphene (BG). A porous CN layer on graphene could provide exposed defects and edges that act as active sites for proton adsorption and reduction. The composition, structure, surface electronics, and chemical properties of this CN/BG hybrid system were tuned to obtain excellent HER activity and stability. Detailed surface chemical, morphological, and structural analyses demonstrated the synergetic effect arising from the electronic interaction between CN and BG, which contributed to the enhanced electrocatalytic performances.

Surface atomic structure characterization of SnSe and black phosphorus using selected area uLEED-IV via LEEM

NASA Astrophysics Data System (ADS)

Dai, Zhongwei; Grady, Maxwell; Yu, Jiexiang; Zang, Jiadong; Pohl, Karsten; Jin, Wencan; Kim, Young Duck; Hone, James; Dadap, Jerry; Osgood, Richard; Sadowski, Jerzy; Vishwanath, Suresh; Xing, Huili

Selected area diffraction intensity-voltage (μLEED-IV) analysis via low energy electron microscopy (LEEM) has the combined functionality of atomic surface structure determination and μm area selectivity, making it ideal for structural investigations of 2-D materials. SnSe thin films have been predicted and observed to be topological crystalline insulators. Previous studies suggested that SnSe has a preferred Se-terminated surface configuration. Using μLEED-IV, we determined that SnSe has, on the contrary, a stable Sn termination. This surface is stabilized through an oscillatory interlayer relaxation, which agrees with previous DFT predictions. Black phosphorus (BP) has an intrinsic layer-dependent bandgap ranging from 0.3 eV to 2 eV. Previous STM and DFT studies suggested BP surfaces have a buckling of 0.02 Å to 0.06 Å. We experimentally determined that the surface buckling of BP to be near 0.2 Å. We further propose, using DFT calculations, that this large surface buckling is induced by the presence of surface defects. The influence of this surface buckling on the electronic structures of BP is under investigation.

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.

Electronic structures of of PuX (X=S, Se, Te)

NASA Astrophysics Data System (ADS)

Maehira, Takahiro; Sakai, Eijiro; Tatetsu, Yasutomi

2013-08-01

We have calculated the energy band structures and the Fermi surfaces of PuS, PuSe, and PuTe by using a self-consistent relativistic linear augmented-plane-wave method with the exchange and correlation potential in the local density approximation. In general, the energy bands near the Fermi level are mainly caused by the hybridization between the Pu 5 f and the monochalcogenide p electrons. The obtained main Fermi surfaces consisted of two hole sheets and one electron sheet, which were constructed from the band having both the Pu 5 f state and the monochalcogenide p state.

Spin-dependent electron scattering at graphene edges on Ni(111).

PubMed

Garcia-Lekue, A; Balashov, T; Olle, M; Ceballos, G; Arnau, A; Gambardella, P; Sanchez-Portal, D; Mugarza, A

2014-02-14

We investigate the scattering of surface electrons by the edges of graphene islands grown on Ni(111). By combining local tunneling spectroscopy and ab initio electronic structure calculations we find that the hybridization between graphene and Ni states results in strongly reflecting graphene edges. Quantum interference patterns formed around the islands reveal a spin-dependent scattering of the Shockley bands of Ni, which we attribute to their distinct coupling to bulk states. Moreover, we find a strong dependence of the scattering amplitude on the atomic structure of the edges, depending on the orbital character and energy of the surface states.

Atomic-scale visualization of oxide thin-film surfaces.

PubMed

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Okada, Yoshinori; Hitosugi, Taro

2018-01-01

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.

Ordered water structure at hydrophobic graphite interfaces observed by 4D, ultrafast electron crystallography

PubMed Central

Yang, Ding-Shyue; Zewail, Ahmed H.

2009-01-01

Interfacial water has unique properties in various functions. Here, using 4-dimensional (4D), ultrafast electron crystallography with atomic-scale spatial and temporal resolution, we report study of structure and dynamics of interfacial water assembly on a hydrophobic surface. Structurally, vertically stacked bilayers on highly oriented pyrolytic graphite surface were determined to be ordered, contrary to the expectation that the strong hydrogen bonding of water on hydrophobic surfaces would dominate with suppressed interfacial order. Because of its terrace morphology, graphite plays the role of a template. The dynamics is also surprising. After the excitation of graphite by an ultrafast infrared pulse, the interfacial ice structure undergoes nonequilibrium “phase transformation” identified in the hydrogen-bond network through the observation of structural isosbestic point. We provide the time scales involved, the nature of ice-graphite structural dynamics, and relevance to properties related to confined water. PMID:19246378

Formation of nano-laminated structures in a dry sliding wear-induced layer under different wear mechanisms of 20CrNi2Mo steel

NASA Astrophysics Data System (ADS)

Yin, Cun-hong; Liang, Yi-long; Jiang, Yun; Yang, Ming; Long, Shao-lei

2017-11-01

The microstructures of 20CrNi2Mo steel underneath the contact surface were examined after dry sliding. Scanning Electronic Microscopy (SEM), Transmission Electron Microscopy (TEM), Electron Backscattered Diffraction (EBSD) and an ultra-micro-hardness tester were used to characterize the worn surface and dry sliding wear-induced layer. Martensite laths were ultra-refined due to cumulative strains and a large strain gradient that occurred during cyclic loading in wear near the surface. The microstructure evolution in dominant abrasive wear differs from that in adhesive wear. In dominant abrasive wear, only bent martensite laths with high-density deformation dislocations were observed. In contrast, in dominant adhesive wear, gradient structures were formed along the depth from the wear surface. Cross-sectional TEM foils were prepared in a focused ion beam (FIB) to observe the gradient structures in a dry sliding wear-induced layer at depths of approximately 1-5 μm and 5-20 μm. The gradient structures contained nano-laminated structures with an average thickness of 30-50 nm and bent martensite laths. We found that the original martensite laths coordinated with the strain energy and provided origin boundaries for the formation of gradient structures. Geometrically necessary boundaries (GNBs) and isolated dislocation boundaries (IDBs) play important roles in forming the nano-laminated structures.

Electronic structure reconstruction across the antiferromagnetic transition in TaFe₁̣₂₃Te₃ spin ladder

DOE PAGES

Xu, Min; Wang, Li -Min; Peng, Rui; ...

2015-02-01

With angle-resolved photoemission spectroscopy, we studied the electronic structure of TaFe₁̣₂₃Te₃, a two-leg spin ladder compound with a novel antiferromagnetic ground state. Quasi-two-dimensional Fermi surface is observed, with sizable inter-ladder hopping. Moreover, instead of observing an energy gap at the Fermi surface in the antiferromagnetic state, we observed the shifts of various bands. Combining these observations with density-functional-theory calculations, we propose that the large scale reconstruction of the electronic structure, caused by the interactions between coexisting itinerant electrons and local moments, is most likely the driving force of the magnetic transition. Thus TaFe₁̣₂₃Te₃ serves as a simpler platform that containsmore » similar ingredients as the parent compounds of iron-based superconductors.« less

InP and GaAs characterization with variable stoichiometry obtained by molecular spray

NASA Technical Reports Server (NTRS)

Massies, J.; Linh, N. T.; Olivier, J.; Faulconnier, P.; Poirier, R.

1979-01-01

Both InP and GaAs surfaces were studied in parallel. A molecular spray technique was used to obtain two semiconductor surfaces with different superficial compositions. The structures of these surfaces were examined by electron diffraction. Electron energy loss was measured spectroscopically in order to determine surface electrical characteristics. The results are used to support conclusions relative to the role of surface composition in establishing a Schottky barrier effect in semiconductor devices.

Gradient changes in structural condition of the B2 phase of NiTi surface layers after electron-beam treatments

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

Meisner, Ludmila L., E-mail: llm@ispms.tsc.ru, E-mail: egu@ispms.tsc.ru; Gudimova, Ekaterina Yu., E-mail: llm@ispms.tsc.ru, E-mail: egu@ispms.tsc.ru; Ostapenko, Marina G., E-mail: artifact@ispms.tsc.ru

2014-11-14

Structural conditions of the B2 phase of the Ti{sub 49.5}Ni{sub 50.5} alloy surface layers before and after electron-beam treatments (pulse duration τ = 150 μs, number of pulses n = 5, beam energy density E ≤ 20 J/cm{sup 2}) were studied by X-ray diffraction analysis. Analysis of the X-ray patterns demonstrates that surface layers modified by electron beam treatment contain phase with B2{sup surf} structure. It is revealed that the lattice parameter of the B2{sup surf} phase in the surface (modified) layer is also higher than the lattice parameter of the B2 phase in the underlying layer (a{sub B2} = 3.0159±0.0005). Themore » values of lattice parameter of phase B2{sup surf} amounted a{sub B2}{sup surf} = 3.0316±0.0005 Å and a{sub B2}{sup surf} = 3.0252±0.0005 Å, for the specimens after electron-beam treatment at E{sub 1} = 15 J/cm{sup 2} and E{sub 2} = 20 J/cm{sup 2}, respectively. Inflated lattice parameters a{sub B2}{sup surf} are associated with changes in the chemical composition and the presence of residual stresses in the surface region of the samples after electron-beam treatments.« less

Surface morphology of Al0.3Ga0.7N/Al2O3-high electron mobility transistor structure.

PubMed

Cörekçi, S; Usanmaz, D; Tekeli, Z; Cakmak, M; Ozçelik, S; Ozbay, E

2008-02-01

We present surface properties of buffer films (AIN and GaN) and Al0.3Gao.zN/Al2O3-High Electron Mobility Transistor (HEMT) structures with/without AIN interlayer grown on High Temperature (HT)-AIN buffer/Al2O3 substrate and Al2O3 substrate. We have found that the GaN surface morphology is step-flow in character and the density of dislocations was about 10(8)-10(9) cm(-2). The AFM measurements also exhibited that the presence of atomic steps with large lateral step dimension and the surface of samples was smooth. The lateral step sizes are in the range of 100-250 nm. The typical rms values of HEMT structures were found as 0.27, 0.30, and 0.70 nm. HT-AIN buffer layer can have a significant impact on the surface morphology of Al0.3Ga0.7N/Al2O3-HEMT structures.

Angle-resolved photoemission spectroscopy studies of metallic surface and interface states of oxide insulators

NASA Astrophysics Data System (ADS)

Plumb, Nicholas C.; Radović, Milan

2017-11-01

Over the last decade, conducting states embedded in insulating transition metal oxides (TMOs) have served as gateways to discovering and probing surprising phenomena that can emerge in complex oxides, while also opening opportunities for engineering advanced devices. These states are commonly realized at thin film interfaces, such as the well-known case of LaAlO3 (LAO) grown on SrTiO3 (STO). In recent years, the use of angle-resolved photoemission spectroscopy (ARPES) to investigate the k-space electronic structure of such materials led to the discovery that metallic states can also be formed on the bare surfaces of certain TMOs. In this topical review, we report on recent studies of low-dimensional metallic states confined at insulating oxide surfaces and interfaces as seen from the perspective of ARPES, which provides a direct view of the occupied band structure. While offering a fairly broad survey of progress in the field, we draw particular attention to STO, whose surface is so far the best-studied, and whose electronic structure is probably of the most immediate interest, given the ubiquitous use of STO substrates as the basis for conducting oxide interfaces. The ARPES studies provide crucial insights into the electronic band structure, orbital character, dimensionality/confinement, spin structure, and collective excitations in STO surfaces and related oxide surface/interface systems. The obtained knowledge increases our understanding of these complex materials and gives new perspectives on how to manipulate their properties.

Investigations of surface structural, dynamical, and magnetic properties of systems exhibiting multiferroicity, and topological phases by helium scattering spectroscopies

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

El-Batanouny, Maged

2015-08-03

We propose to investigate the surface structural, dynamics and magnetic properties of the novel class of topological insulator crystals, as well as crystals that exhibit multiferroicity, magnetoelectricity and thermoelectricity. Topological insulators (TIs) are a new class of insulators in which a bulk gap for electronic excitations is generated because of the strong spin-orbit coupling inherent to these systems. These materials are distinguished from ordinary insulators by the presence of gapless metallic surface states, resembling chiral edge modes in quantum Hall systems, but with unconventional spin textures. These exotic metallic states are formed by topological conditions that also render the electrons travelling on such surfaces insensitive to scattering by impurities. The electronic quasi-particles populating the topological surface state are Dirac fermions; they have a linear dispersion and thus are massless just like photons. We propose to investigate the interaction of these massless Dirac fermions with the massive lattice in the newly discovered crystals, Bi2Se3, Bi2Te3 and Sb2Te3. We shall use inelastic helium beam scattering from surfaces to search for related signatures in surface phonon dispersions mappings that cover the entire surface Brillouin zone of these materials. Our recent investigations of the (001) surface of the multiferroic crystals (Li/Na)Cu2O2 revealed an anomalous surface structural behavior where surface Cumore » $$^{2+}$$ row rise above the surface plane as the crystal was cooled. Subsequent worming revealed the onset of a thermally activated incommensurate surface phase, driven by the elevated rows. We are currently investigating the structure of the magnetic phases in these quasi-one-dimensional magnetic rows. Multiferroics are excellent candidates for large magnetoelectric response. We propose to extend this investigation to the class of delafossites which are also multiferroics and have been investigated as good candidates for thermoelectric power devices. They are also typical triangular lattice antiferromagnets with geometric magnetic frustration that leads to helimagnetic structures.« less

Ab initio theory of point defects in oxide materials: structure, properties, chemical reactivity

NASA Astrophysics Data System (ADS)

Pacchioni, Gianfranco

2000-05-01

Point defects play a fundamental role in determining the physical and chemical properties of inorganic materials. This holds not only for the bulk properties but also for the surface of oxides where several kinds of point defects exist and exhibit a rich and complex chemistry. A particularly important defect in oxides is the oxygen vacancy. Depending on the electronic structure of the material the nature of oxygen vacancies changes dramatically. In this article we provide a rationalization of the very different electronic structure of neutral and charged oxygen vacancies in SiO 2 and MgO, two oxide materials with completely different electronic structure (from very ionic, MgO, to largely covalent, SiO 2). We used methods of ab initio quantum chemistry, from density functional theory (DFT) to configuration interaction (CI), to determine the ground and excited state properties of these defects. The theoretical results are combined with recent spectroscopic measurements. A series of observable properties has been determined in this way: defect formation energies, hyperfine interactions in electron paramagnetic resonance (EPR) spectra of paramagnetic centers, optical spectra, surface chemical reactivity. The interplay between experimental and theoretical information allows one to unambiguously identify the structure of oxygen vacancies in these binary oxides and on their surfaces.

THz radiation from two electron-beams interaction within a bi-grating and a sub-wavelength holes array composite sandwich structure.

PubMed

Zhang, Yaxin; Zhou, Y; Dong, L

2013-09-23

Two electron-beams' interaction in a sandwich structure composed of a bi-grating and a sub-wavelength holes array is suggested to generate THz radiation in this paper. It shows that this system takes advantage of both bi-grating and sub-wavelength holes array structures. The results demonstrate that surface waves on a bi-grating can couple with mimicking surface plasmons of a sub-wavelength holes array so that the wave-coupling is strong and the field intensity is high in this structure. Moreover, compared with the interaction in the bi-grating structure and sub-wavelength holes array structure, respectively, it shows that in this composite system the two electron-beams' interaction is more efficient and the modulation depth and radiation intensity have been enhanced significantly. The modulation depth and efficiency can reach 22% and 4%, respectively, and the starting current density is only 12 A/cm². This radiation system may provide good opportunities for development of multi-electron beam-driven THz radiation sources.

Accurate electron gun-positioning mechanism for electron beam-mapping of large cross-section magnetic surfaces

NASA Astrophysics Data System (ADS)

Anderson, F. S. B.; Middleton, F.; Colchin, R. J.; Million, D.

1989-04-01

A method of accurately supporting and positioning an electron source inside a large cross-sectional area magnetic field which provides very low electron beam occlusion is reported. The application of electrical discharge machining to the fabrication of a 1-m truss support structure has provided an extremely long, rigid and mechanically strong electron gun support. Reproducible electron gun positioning to within 1 mm has been achieved at any location within a 1×0.6-m2 area. The extremely thin sections of the support truss (≤1.5 mm) have kept the electron beam occlusion to less than 3 mm. The support and drive mechanism have been designed and fabricated at the University of Wisconsin for application to the mapping of the magnetic surface structure of the Advanced Toroidal Facility torsatron1 at the Oak Ridge National Laboratory.

Fine structure of the copulatory apparatus of the tapeworm Tetrabothrius erostris (Cestoda: Tetrabothriidea).

PubMed

Korneva, Janetta V; Jones, Malcolm K; Kuklin, Vadim V

2015-05-01

The organization and fine structure of the complex copulatory apparatus of Tetrabothrius erostris (Tetrabothriidea) is investigated by light and transmission electron microscopy. A diversity of microstructures was found on the surface of genital ducts. The apical surfaces of male gonadoducts possess tubular and blade-like microtriches that have specific structure in each section of the duct. The apical part of the tubular microtriches contains numerous constrictions in the proximal section of the sperm duct; blade-like microtriches of cirrus possess longitudinal striation in the apical part, and their basal part is reinforced with electron-dense strands. Two types of microtriches occur on the surface of cirrus, and their presence may be considered as systematic features. Prostate glands containing granules of medium electron density (up to 130 nm diameter) are localized in the cirrus sac. The genital atrium contains numerous non-ciliated receptors. Paramyosin-like fibers (up to 200 nm) were found in the muscle fibers surrounding the male atrium canal. Microtriches on the surface of the distal region of the male atrial canal are covered by a glycocalyx. Electron-dense, membrane-like structures (up to 40 nm) lie under the apical membrane of the genital atrium and vagina. These structures do not form a continuous layer; its edges turn down and sink into the apical invaginations of epithelium. Hypotheses on the possible ways of copulation in T. erostris based on the observed ultrastructure are discussed.

Model of photoinduced structural change induced by THz pulse irradiation

NASA Astrophysics Data System (ADS)

Ishida, Kunio; Nasu, Keiichiro

Recently intense optical pulses with THz frequency have been obtained, and it is of interest to study the effect of irradiated THz pulses on electronic systems. We theoretically study the photoinduced cooperative dynamics triggered by irradiation of THz pulses. We employed a model of two-level localized electrons coupled with an optical phonon mode taking into account the nonadiabaticity of the electron dynamics, and solved the time-dependent Schrödinger equation numerically. We consider the cases in which the THz pulses create phonons near the surface of the system, and pursue the electronic transitions induced by the propagation of the phonons. We found that they are able to induce excited-state domain growth, and that the interference between them plays an important role in the growth dynamics. Hence, the domain growth is affected by the geometry of the surface of the system, which is different from the photoinduced structural change by visible/UV pulses. We also show that the nonadiabatic/adiabatic electronic transitions should be taken into account though the domain growth mainly proceeds on the ground-state potential energy surfaces(PESs). In other words, the energy level/structure of excited-state PESs are relevant to the domain-growth dynamics.

SPE-LEEM Studies on the Surface and Electronic Structure of 2-D Transition Metal Dichalcogenides (Part II)

NASA Astrophysics Data System (ADS)

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

2014-03-01

In this work, we studied the surface and electronic structure of monolayer and few-layer exfoliated MoS2 and WSe2, as well as chemical-vapor-deposition (CVD) grown MoS2, using Spectroscopic Photoemission and Low Energy Electron Microscope (SPE-LEEM). LEEM measurements reveal that, unlike exfoliated MoS2, CVD-grown MoS2 exhibits grain-boundary alterations due to surface strain. However, LEEM and micro-probe low energy electron diffraction show that the quality of CVD-grown MoS2 is comparable to that of exfoliated MoS2. Micrometer-scale angle-resolved photoemission spectroscopy (ARPES) measurement on exfoliated MoS2 and WSe2 single-crystals provides direct evidence for the shifting of the valence band maximum from Γ to K, when the layer number is thinned down to one, as predicted by density functional theory. Our measurements of the k-space resolved electronic structure allow for further comparison with other theoretical predictions and with transport measurements. This work is supported by DOE grant DE-FG 02-04-ER-46157, research carried out in part at the CFN and NSLS, Brookhaven National Laboratory.

The structural, electronic and optical properties of Au-ZnO interface structure from the first-principles calculation

NASA Astrophysics Data System (ADS)

Huo, Jin-Rong; Li, Lu; Cheng, Hai-Xia; Wang, Xiao-Xu; Zhang, Guo-Hua; Qian, Ping

2018-03-01

The interface structure, electronic and optical properties of Au-ZnO are studied using the first-principles calculation based on density functional theory (DFT). Given the interfacial distance, bonding configurations and terminated surface, we built the optimal interface structure and calculated the electronic and optical properties of the interface. The total density of states, partial electronic density of states, electric charge density and atomic populations (Mulliken) are also displayed. The results show that the electrons converge at O atoms at the interface, leading to a stronger binding of interfaces and thereby affecting the optical properties of interface structures. In addition, we present the binding energies of different interface structures. When the interface structure of Au-ZnO gets changed, furthermore, varying optical properties are exhibited.

Study of RF breakdown and multipacting in accelerator components

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

Pande, Manjiri; Singh, P., E-mail: manjiri@barc.gov.in, E-mail: psingh@barc.gov.in

2014-07-01

Radio frequency (RF) structures that are part of accelerators and energy sources, operate with sinusoidally varying electromagnetic fields under high RF energy. Here, RF breakdown and multipacting take place in RF structures and limit their performance. Electron field emission processes in a RF structure are precursors for breakdown processes. RF breakdown is a major phenomena affecting and causing the irreversible damage to RF structures. Breakdown rate and the damage induced by the breakdowns are its important properties. The damage is related to power absorbed during breakdown, while the breakdown rate is determined by the amplitudes of surface electric and magneticmore » fields, geometry, metal surface preparation and conditioning history. It limits working power and produces irreversible surface damage. The breakdown limit depends on the RF circuit, structure geometry, RF frequency, input RF power, pulse width, materials used, surface processing technique and surface electric and magnetic fields. Multipactor (MP) is a low power, electron multiplication based resonance breakdown phenomenon in vacuum and is often observed in RF structures. A multipactor discharge is undesirable, as it can create a reactive component that detunes the resonant cavities and components, generates noise in communication system and induces gas desorption from the conductor surfaces. In RF structures, certain conditions are required to generate multipacting. (author)« less

Atomic structures of B20 FeGe thin films grown on the Si(111) surface

NASA Astrophysics Data System (ADS)

Kim, Wondong; Noh, Seungkyun; Yoon, Jisoo; Kim, Young Heon; Lee, Inho; Kim, Jae-Sung; Hwang, Chanyong

We investigated the growth and atomic structures of FeGe thin films on the Si (111) surface by using scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). The 2 5nm- thick FeGe thin films were prepared on the clean Si(111) 7x7 surface by co-deposition of Fe and Ge from separated electron-beam evaporators. With direct deposition on the substrate at the temperature above 550 K, the surface of FeGe films was not smooth and consisted of coarse grains. By the combination of room-temperature annealing and post-annealing process around 800 K, the structure of FeGe thin films evolved into the well crystalized structures. Atom-resolved STM images revealed that there are at least four different surface terminations. We constructed atomic models for each surface terminations based on the bulk atomic arrangement of a B20 chiral structure and confirmed that the observed STM images are successfully reproduced by using computational simulations employing Vienna Ab Initio Simulation package (VASP) with a B20 chiral structure model. TEM cross-sectional images also support our atomic models by revealing clearly the characteristic zigzag features of B20 structures of FeGe(111) thin films.

Theoretical investigation of the electronic structure and quantum transport in the graphene-C(111) diamond surface system.

PubMed

Selli, Daniele; Baburin, Igor; Leoni, Stefano; Zhu, Zhen; Tománek, David; Seifert, Gotthard

2013-10-30

We investigate the interaction of a graphene monolayer with the C(111) diamond surface using ab initio density functional theory. To accommodate the lattice mismatch between graphene and diamond, the overlayer deforms into a wavy structure that binds strongly to the diamond substrate. The detached ridges of the wavy graphene overlayer behave electronically as free-standing polyacetylene chains with delocalized π electrons, separated by regions containing only sp(3) carbon atoms covalently bonded to the (111) diamond surface. We performed quantum transport calculations for different geometries of the system to study how the buckling of the graphene layer and the associated bonding to the diamond substrate affect the transport properties. The system displays high carrier mobility along the ridges and a wide transport gap in the direction normal to the ridges. These intriguing, strongly anisotropic transport properties qualify the hybrid graphene-diamond system as a viable candidate for electronic nanodevices.

Interface electronic structures of reversible double-docking self-assembled monolayers on an Au(111) surface

PubMed Central

Zhang, Tian; Ma, Zhongyun; Wang, Linjun; Xi, Jinyang; Shuai, Zhigang

2014-01-01

Double-docking self-assembled monolayers (DDSAMs), namely self-assembled monolayers (SAMs) formed by molecules possessing two docking groups, provide great flexibility to tune the work function of metal electrodes and the tunnelling barrier between metal electrodes and the SAMs, and thus offer promising applications in both organic and molecular electronics. Based on the dispersion-corrected density functional theory (DFT) in comparison with conventional DFT, we carry out a systematic investigation on the dual configurations of a series of DDSAMs on an Au(111) surface. Through analysing the interface electronic structures, we obtain the relationship between single molecular properties and the SAM-induced work-function modification as well as the level alignment between the metal Fermi level and molecular frontier states. The two possible conformations of one type of DDSAM on a metal surface reveal a strong difference in the work-function modification and the electron/hole tunnelling barriers. Fermi-level pinning is found to be a key factor to understand the interface electronic properties. PMID:24615153

A new series of two-dimensional silicon crystals with versatile electronic properties

NASA Astrophysics Data System (ADS)

Chae, Kisung; Kim, Duck Young; Son, Young-Woo

2018-04-01

Silicon (Si) is one of the most extensively studied materials owing to its significance to semiconductor science and technology. While efforts to find a new three-dimensional (3D) Si crystal with unusual properties have made some progress, its two-dimensional (2D) phases have not yet been explored as much. Here, based on a newly developed systematic ab initio materials searching strategy, we report a series of novel 2D Si crystals with unprecedented structural and electronic properties. The new structures exhibit perfectly planar outermost surface layers of a distorted hexagonal network with their thicknesses varying with the atomic arrangement inside. Dramatic changes in electronic properties ranging from semimetal to semiconducting with indirect energy gaps and even to one with direct energy gaps are realized by varying thickness as well as by surface oxidation. Our predicted 2D Si crystals with flat surfaces and tunable electronic properties will shed light on the development of silicon-based 2D electronics technology.

Mechanism of equivalent electric dipole oscillation for high-order harmonic generation from grating-structured solid-surface by femtosecond laser pulse

NASA Astrophysics Data System (ADS)

Wang, Yang; Song, Hai-Ying; Liu, H. Y.; Liu, Shi-Bing

2017-07-01

We theoretically study high-order harmonic generation (HHG) from relativistically driven overdense plasma targets with rectangularly grating-structured surfaces by femtosecond laser pulses. Our particle-in-cell (PIC) simulations show that, under the conditions of low laser intensity and plasma density, the harmonics emit principally along small angles deviating from the target surface. Further investigation of the surface electron dynamics reveals that the electron bunches are formed by the interaction between the laser field and the target surface, giving rise to the oscillation of equivalent electric-dipole (OEED), which enhances specific harmonic orders. Our work helps understand the mechanism of harmonic emissions from grating targets and the distinction from the planar harmonic scheme.

The Influence of the Surface Neutralization of Active Impurities on the Field-Electron Emission Properties of p-Type Silicon Crystals

NASA Astrophysics Data System (ADS)

Yafarov, R. K.

2017-12-01

Correlation dependences between variations of the structural-phase composition, morphology characteristics, and field-electron-emission (FEE) properties of surface-structured p-type silicon singlecrystalline (100)-oriented wafers have been studied during their stepwise high-dose carbon-ion-beam irradiation. It is established that the stepwise implantation of carbon decreases the FEE threshold and favors an increase in the maximum FEE-current density by more than two orders of magnitude. Physicochemical mechanisms involved in this modification of the properties of near-surface layers of silicon under carbon-ion implantation are considered.

Dependency of magnetic microwave absorption on surface architecture of Co20Ni80 hierarchical structures studied by electron holography

NASA Astrophysics Data System (ADS)

Liu, Qinhe; Xu, Xianhui; Xia, Weixing; Che, Renchao; Chen, Chen; Cao, Qi; He, Jingang

2015-01-01

To design and fabricate rational surface architecture of individual particles is one of the key factors that affect their magnetic properties and microwave absorption capability, which is still a great challenge. Herein, a series of Co20Ni80 hierarchical structures with different surface morphologies, including flower-, urchin-, ball-, and chain-like morphologies, were obtained using structure-directing templates via a facile one-step solvothermal treatment. The microwave reflection loss (RL) of urchin-like Co20Ni80 hierarchical structures reaches as high as -33.5 dB at 3 GHz, with almost twice the RL intensity of the ball- and chain-like structures, and the absorption bandwidth (<-10 dB) is about 5.5 GHz for the flower-like morphology, indicating that the surface nanospikes and nanoflakes on the Co20Ni80 microsphere surfaces have great influences on their magnetic microwave absorption properties. Electron holography analysis reveals that the surface nanospikes and nanoflakes could generate a high density of stray magnetic flux lines and contribute a large saturation magnetization (105.62 emu g-1 for urchin-like and 96.41 emu g-1 for flower-like morphology), leading the urchin-like and flower-like Co20Ni80 to possess stronger microwave RL compared with the ball-like and chain-like Co20Ni80 alloys. The eddy-current absorption mechanism μ''(μ')-2(f)-1 is dominant in the frequency region above 8 GHz, implying that eddy-current loss is a vital factor for microwave RL in the high frequency range. It can be supposed from our findings that different surface morphologies of magnetic hierarchical structures might become an effective path to achieve high-performance microwave absorption for electromagnetic shielding and stealth camouflage applications.To design and fabricate rational surface architecture of individual particles is one of the key factors that affect their magnetic properties and microwave absorption capability, which is still a great challenge. Herein, a series of Co20Ni80 hierarchical structures with different surface morphologies, including flower-, urchin-, ball-, and chain-like morphologies, were obtained using structure-directing templates via a facile one-step solvothermal treatment. The microwave reflection loss (RL) of urchin-like Co20Ni80 hierarchical structures reaches as high as -33.5 dB at 3 GHz, with almost twice the RL intensity of the ball- and chain-like structures, and the absorption bandwidth (<-10 dB) is about 5.5 GHz for the flower-like morphology, indicating that the surface nanospikes and nanoflakes on the Co20Ni80 microsphere surfaces have great influences on their magnetic microwave absorption properties. Electron holography analysis reveals that the surface nanospikes and nanoflakes could generate a high density of stray magnetic flux lines and contribute a large saturation magnetization (105.62 emu g-1 for urchin-like and 96.41 emu g-1 for flower-like morphology), leading the urchin-like and flower-like Co20Ni80 to possess stronger microwave RL compared with the ball-like and chain-like Co20Ni80 alloys. The eddy-current absorption mechanism μ''(μ')-2(f)-1 is dominant in the frequency region above 8 GHz, implying that eddy-current loss is a vital factor for microwave RL in the high frequency range. It can be supposed from our findings that different surface morphologies of magnetic hierarchical structures might become an effective path to achieve high-performance microwave absorption for electromagnetic shielding and stealth camouflage applications. Electronic supplementary information (ESI) available: EDS analysis data, SEM images, electron holography schematic diagram, electron holography and magnetic hysteresis loops. See DOI: 10.1039/c4nr05547k

Effect of surface Fe-S hybrid structure on the activity of the perfect and reduced α-Fe2O3(001) for chemical looping combustion

NASA Astrophysics Data System (ADS)

Xiao, Xianbin; Qin, Wu; Wang, Jianye; Li, Junhao; Dong, Changqing

2018-05-01

Sulfurization of the gradually reduced Fe2O3 surfaces is inevitable while Fe2O3 is used as an oxygen carrier (OC) for coal chemical looping combustion (CLC), which will result in formation of Fe-S hybrid structure on the surfaces. The Fe-S hybrid structure will directly alter the reactivity of the surfaces. Therefore, detailed properties of Fe-S hybrid structure over the perfect and reduced Fe2O3(001) surfaces, and its effect on the interfacial interactions, including CO oxidization and decomposition on the surfaces, were investigated by using density functional theory (DFT) calculations. The S atom prefers to chemically bind to Fe site with electron transfer from the surfaces to the S atom, and a deeper reduction of Fe2O3(001) leads to an increasing interaction between S and Fe. The formation of Fe-S hybrid structure alters the electronic properties of the gradually reduced Fe2O3(001) surfaces, promoting CO oxidation on the surfaces ranging from Fe2O3 to FeO, but depressing carbon deposition on the surfaces ranging from FeO to Fe. The sulfurized FeO acts as a watershed to realize relatively high CO oxidation rate and low carbon deposition. Results provided a fundamental understanding for controlling and optimizing the CLC processes.

RF and structural characterization of new SRF films

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

A.-M. Valente-Feliciano,H. L. Phillips,C. E. Reece,X. Zhao,D. Gu,R. Lukaszew,B. Xiao,K. Seo

2009-09-01

In the past years, energetic vacuum deposition methods have been developed in different laboratories to improve Nb/Cu technology for superconducting cavities. Jefferson Lab is pursuing energetic condensation deposition via Electron Cyclotron Resonance. As part of this study, the influence of the deposition energy on the material and RF properties of the Nb thin film is investigated. The film surface and structure analyses are conducted with various techniques like X-ray diffraction, Transmission Electron Microscopy, Auger Electron Spectroscopy and RHEED. The microwave properties of the films are characterized on 50 mm disk samples with a 7.5 GHz surface impedance characterization system. Thismore » paper presents surface impedance measurements in correlation with surface and material characterization for Nb films produced on copper substrates with different bias voltages and also highlights emerging opportunities for developing multilayer SRF films with a new deposition system.« less

Missing dimer defects investigated by adsorption of nitric oxide (NO) on silicon (100) 2 × 1

NASA Astrophysics Data System (ADS)

Sasse, A. G. B. M.; Kleinherenbrink, P. M.; Van Silfhout, A.

This paper describes a study concerning the interaction of nitric oxide (NO) with the clean Si(100)2×1 surface in ultra-high vacuum at room temperature. Differential reflectometry (DR) in the photon energy range of 2.4-4.4 eV. Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) have been used to investigate the chemisorption of NO on Si(100)2×1. With this combination of techniques it is possible to make an analysis of the geometric and electronic structure and chemical composition of the surface layer. The aim of the present study was to explain the experimental results of the adsorption of NO on the clean Si(100)2×1 at 300 K. Analysing the electronic and geometric structure of a simplified stepped 2×1 reconstructed Si(100) surface and of the NO molecule in combination with the use of Woodward-Hoffmann rules (WHR) we were able to model a surface defect specific adsorption mechanism. Surface defects such as missing dimer defects seem to play an important role in the adsorption mechanism of NO on the silicon surface. The experimental results are consistent with this developed model. We also suggest a relation between the missing dimer defects and the number of steps on the silicon surface.

Common electronic origin of superconductivity in (Li,Fe)OHFeSe bulk superconductor and single-layer FeSe/SrTiO3 films.

PubMed

Zhao, Lin; Liang, Aiji; Yuan, Dongna; Hu, Yong; Liu, Defa; Huang, Jianwei; He, Shaolong; Shen, Bing; Xu, Yu; Liu, Xu; Yu, Li; Liu, Guodong; Zhou, Huaxue; Huang, Yulong; Dong, Xiaoli; Zhou, Fang; Liu, Kai; Lu, Zhongyi; Zhao, Zhongxian; Chen, Chuangtian; Xu, Zuyan; Zhou, X J

2016-02-08

The mechanism of high-temperature superconductivity in the iron-based superconductors remains an outstanding issue in condensed matter physics. The electronic structure plays an essential role in dictating superconductivity. Recent revelation of distinct electronic structure and high-temperature superconductivity in the single-layer FeSe/SrTiO3 films provides key information on the role of Fermi surface topology and interface in inducing or enhancing superconductivity. Here we report high-resolution angle-resolved photoemission measurements on the electronic structure and superconducting gap of an FeSe-based superconductor, (Li0.84Fe0.16)OHFe0.98Se, with a Tc at 41 K. We find that this single-phase bulk superconductor shows remarkably similar electronic behaviours to that of the superconducting single-layer FeSe/SrTiO3 films in terms of Fermi surface topology, band structure and the gap symmetry. These observations provide new insights in understanding high-temperature superconductivity in the single-layer FeSe/SrTiO3 films and the mechanism of superconductivity in the bulk iron-based superconductors.

Oxide surfaces in practical and model catalytic systems

NASA Astrophysics Data System (ADS)

Lanier, Courtney H.

Oxide surface structures play a key role in many technological processes, including catalysis, thin film growth, and layered structures, and a thorough understanding of surface structures and surface structure dynamics is required in order to better engineer materials systems for these processes. This research works towards understanding these fundamental principles through an investigation of practical and model catalytic systems. In this work, the surface structures and dynamics of Mg3(VO4)2, LaAlO3, SrTiO3, and alpha-Fe2O3/Fe3O 4 are investigated under a variety of conditions and by a range of experimental and computational techniques. The structure and morphology of LaAlO3 has been investigated over a range of annealing temperatures, and the ( 5x5 )R26.6° reconstruction of LaAlO3 (001) has been determined using transmission electron diffraction combined with direct methods. The structure is relatively simple, consisting of a lanthanum oxide termination with one lanthanum cation vacancy per surface unit cell. The electronic structure is unusual since a fractional number of holes or atomic occupancies per surface unit cell are required to achieve charge neutrality. The reconstruction can be understood in terms of expulsion of the more electropositive cation from the surface followed by an increased covalency between the remaining surface lanthanum atoms and adjacent oxygen atoms. The c(6x2) is a reconstruction of the SrTiO3 (001) surface that is formed between 1050-1100°C in oxidizing annealing conditions. This work proposes a model for the atomic structure for the c(6x2) obtained through a combination of results from transmission electron diffraction, surface x-ray diffraction, direct methods analysis, computational combinational screening, and density functional theory. As it is formed at high temperatures, the surface is complex and can be described as a short-range ordered phase featuring microscopic domains composed of four main structural motifs. Additionally, non-periodic TiO2 units are present on the surface. The surface and bulk of oriented single crystal Mg3(VO 4)2 have been characterized after treatment in a reducing environment. Annealing in a flow of 7% H2 in N2 causes the reduction of Mg3(VO4)2 to Mg3V 2O6, which is shown to be single-crystal to single-crystal and occurs in such a way that the oxygen framework of the crystal is preserved. Transmission electron microscopy images of crystals at the early stages of reduction show low angle grain boundaries and the formation of channels approximately 50nm in diameter. A model for reduction of Mg3(VO4) 2 to Mg3V2O6 based on the experimental observations and derived from classic nucleation theory is proposed. The so-called Biphase structure on alpha-Fe2O3 has been previously reported and described as islands of Fe1-xO and alpha-Fe2O3 arranged in a 40A periodic unit cell. Based on thermodynamic arguments and experimental evidence, including transmission electron diffraction, we find that the previous structure model was incorrect. Rather, it is found that the Biphase structure is, in fact, related to the reduction of alpha-Fe2O3 to Fe 3O4, is a layered structure, and does not contain islands of Fe1-xO. A model for the Biphase termination consisting of bulk alpha-Fe 2O3 with an Fe3O4 -derived overlayer is developed and is consistent with all current and previously reported experimental findings.

Electron-Beam Lithographic Grafting of Functional Polymer Structures from Fluoropolymer Substrates.

PubMed

Gajos, Katarzyna; Guzenko, Vitaliy A; Dübner, Matthias; Haberko, Jakub; Budkowski, Andrzej; Padeste, Celestino

2016-10-07

Well-defined submicrometer structures of poly(dimethylaminoethyl methacrylate) (PDMAEMA) were grafted from 100 μm thick films of poly(ethene-alt-tetrafluoroethene) after electron-beam lithographic exposure. To explore the possibilities and limits of the method under different exposure conditions, two different acceleration voltages (2.5 and 100 keV) were employed. First, the influence of electron energy and dose on the extent of grafting and on the structure's morphology was determined via atomic force microscopy. The surface grafting with PDMAEMA was confirmed by advanced surface analytical techniques such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy. Additionally, the possibility of effective postpolymerization modification of grafted structures was demonstrated by quaternization of the grafted PDMAEMA to the polycationic QPDMAEMA form and by exploiting electrostatic interactions to bind charged organic dyes and functional proteins.

An automatic chip structure optical inspection system for electronic components

NASA Astrophysics Data System (ADS)

Song, Zhichao; Xue, Bindang; Liang, Jiyuan; Wang, Ke; Chen, Junzhang; Liu, Yunhe

2018-01-01

An automatic chip structure inspection system based on machine vision is presented to ensure the reliability of electronic components. It consists of four major modules, including a metallographic microscope, a Gigabit Ethernet high-resolution camera, a control system and a high performance computer. An auto-focusing technique is presented to solve the problem that the chip surface is not on the same focusing surface under the high magnification of the microscope. A panoramic high-resolution image stitching algorithm is adopted to deal with the contradiction between resolution and field of view, caused by different sizes of electronic components. In addition, we establish a database to storage and callback appropriate parameters to ensure the consistency of chip images of electronic components with the same model. We use image change detection technology to realize the detection of chip images of electronic components. The system can achieve high-resolution imaging for chips of electronic components with various sizes, and clearly imaging for the surface of chip with different horizontal and standardized imaging for ones with the same model, and can recognize chip defects.

InN/GaN quantum dot superlattices: Charge-carrier states and surface electronic structure

NASA Astrophysics Data System (ADS)

Kanouni, F.; Brezini, A.; Djenane, M.; Zou, Q.

2018-03-01

We have theoretically investigated the electron energy spectra and surface states energy in the three dimensionally ordered quantum dot superlattices (QDSLs) made of InN and GaN semiconductors. The QDSL is assumed in this model to be a matrix of GaN containing cubic dots of InN of the same size and uniformly distributed. For the miniband’s structure calculation, the resolution of the effective mass Schrödinger equation is done by decoupling it in the three directions within the framework of Kronig-Penney model. We found that the electrons minibands in infinite ODSLs are clearly different from those in the conventional quantum-well superlattices. The electrons localization and charge-carrier states are very dependent on the quasicrystallographic directions, the size and the shape of the dots which play a role of the artificial atoms in such QD supracrystal. The energy spectrum of the electron states localized at the surface of InN/GaN QDSL is represented by Kronig-Penney like-model, calculated via direct matching procedure. The calculation results show that the substrate breaks symmetrical shape of QDSL on which some localized electronic surface states can be produced in minigap regions. Furthermore, we have noticed that the surface states degeneracy is achieved in like very thin bands located in the minigaps, identified by different quantum numbers nx, ny, nz. Moreover, the surface energy bands split due to the reduction of the symmetry of the QDSL in z-direction.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Reed, J. A.

2011-03-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to more complex structures which results from diffusion of oxygen into the sub-surface regions. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the Cu(100) missing row reconstructed surface under conditions of high oxygen coverage. Calculations are performed for various surface and subsurface oxygen coverages ranging from 0.50 to 1.50 monolayers. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. Estimates of the positron binding energy, positron work function, and annihilation characteristics reveal their sensitivity to atomic structure of the topmost layers of the surface and charge transfer. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Tailoring the Electrochemical Properties of Carbon Nanotube Modified Indium Tin Oxide via in Situ Grafting of Aryl Diazonium.

PubMed

Hicks, Jacqueline M; Wong, Zhi Yi; Scurr, David J; Silman, Nigel; Jackson, Simon K; Mendes, Paula M; Aylott, Jonathan W; Rawson, Frankie J

2017-05-23

Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

General mechanism involved in subwavelength optics of conducting microstructures: charge-oscillation-induced light emission and interference.

PubMed

Huang, Xian-Rong; Peng, Ru-Wen

2010-04-01

Interactions between light and conducting microstructures or nanostructures can result in a variety of novel phenomena, but their underlying mechanisms have not been completely understood. From calculations of surface charge density waves on conducting gratings and by comparing them with classical surface plasmons, we revealed a general yet concrete picture regarding the coupling of light to free electron oscillation on structured conducting surfaces that can lead to oscillating subwavelength charge patterns (i.e., structured surface plasmons). New wavelets emitted from these light sources then destructively interfere to form evanescent waves. This principle, usually combined with other mechanisms, is mainly a geometrical effect that can be universally involved in light scattering from all periodic and non-periodic structures containing free electrons. This picture may provide clear guidelines for developing conductor-based nano-optical devices.

Structure and Electronic Properties of Interface-Confined Oxide Nanostructures

DOE PAGES

Liu, Yun; Ning, Yanxiao; Yu, Liang; ...

2017-09-16

The controlled fabrication of nanostructures has often made use of a substrate template to mediate and control the growth kinetics. Electronic substrate-mediated interactions have been demonstrated to guide the assembly of organic molecules or the nucleation of metal atoms but usually at cryogenic temperatures, where the diffusion has been limited. Combining STM, STS, and DFT studies, we report that the strong electronic interaction between transition metals and oxides could indeed govern the growth of low-dimensional oxide nanostructures. As a demonstration, a series of FeO triangles, which are of the same structure and electronic properties but with different sizes (side lengthmore » >3 nm), are synthesized on Pt(111). The strong interfacial interaction confines the growth of FeO nanostructures, leading to a discrete size distribution and a uniform step structure. Given the same interfacial configuration, as-grown FeO nanostructures not only expose identical edge/surface structure but also exhibit the same electronic properties, as manifested by the local density of states and local work functions. We expect the interfacial confinement effect can be generally applied to control the growth of oxide nanostructures on transition metal surfaces. These oxide nanostructures of the same structure and electronic properties are excellent models for studies of nanoscale effects and applications.« less

Structure and Electronic Properties of Interface-Confined Oxide Nanostructures

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

Liu, Yun; Ning, Yanxiao; Yu, Liang

The controlled fabrication of nanostructures has often made use of a substrate template to mediate and control the growth kinetics. Electronic substrate-mediated interactions have been demonstrated to guide the assembly of organic molecules or the nucleation of metal atoms but usually at cryogenic temperatures, where the diffusion has been limited. Combining STM, STS, and DFT studies, we report that the strong electronic interaction between transition metals and oxides could indeed govern the growth of low-dimensional oxide nanostructures. As a demonstration, a series of FeO triangles, which are of the same structure and electronic properties but with different sizes (side lengthmore » >3 nm), are synthesized on Pt(111). The strong interfacial interaction confines the growth of FeO nanostructures, leading to a discrete size distribution and a uniform step structure. Given the same interfacial configuration, as-grown FeO nanostructures not only expose identical edge/surface structure but also exhibit the same electronic properties, as manifested by the local density of states and local work functions. We expect the interfacial confinement effect can be generally applied to control the growth of oxide nanostructures on transition metal surfaces. These oxide nanostructures of the same structure and electronic properties are excellent models for studies of nanoscale effects and applications.« less

Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

NASA Astrophysics Data System (ADS)

Maurer, Reinhard J.; Ruiz, Victor G.; Camarillo-Cisneros, Javier; Liu, Wei; Ferri, Nicola; Reuter, Karsten; Tkatchenko, Alexandre

2016-05-01

Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdWsurf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdWsurf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

Atomic Mechanism of Hybridization-Dependent Surface Reconstruction with Tailored Functionality in Hexagonal Multiferroics.

PubMed

Deng, Shiqing; Cheng, Shaobo; Xu, Changsong; Ge, Binghui; Sun, Xuefeng; Yu, Rong; Duan, Wenhui; Zhu, Jing

2017-08-16

The broken symmetry along with anomalous defect structures and charging conditions at multiferroics surface can alter both crystal structures and electronic configurations, bringing in emergent physical properties. Extraordinary surface states are induced into original mutually coupled order parameters in such strongly correlated oxides, which flourish in diverse properties but remain less explored. Here, we report the peculiar surface ferroelectric states and reconfigurable functionalities driven by the relaxation of surface and consequent changes in O 2p and Y 4d orbital (p-d) hybridization within a representative hexagonal multiferroics, YMnO 3 . An unprecedented surface reconstruction is achieved by tailored p-d hybridization coupling with in-plane oxygen vacancies, which is atomically revealed on the basis of the advantages of state-of-the-art aberration-corrected (scanning) transmission electron microscopy. Further ab initio density functional theory calculations verify the key roles of in-plane oxygen vacancies in modulating polarization properties and electronic structure, which should be regarded as the atomic multiferroic element. This surface configuration is found to induce tunable functionalities, such as surface ferromagnetism and conductivity. Meanwhile, the controversial origin of improper ferroelectricity that is unexpectedly free from critical size has also been atomically unraveled. Our findings provide new insights into the design and implementation of surface chemistry devices by simply controlling the oxygen stoichiometry, greatly advance our understandings of surface science in strongly correlated oxides, and enable exciting innovations and new technological functionality paradigms.

Structural stability of coplanar 1T-2H superlattice MoS2 under high energy electron beam.

PubMed

Reshmi, S; Akshaya, M V; Satpati, Biswarup; Basu, Palash Kumar; Bhattacharjee, K

2018-05-18

Coplanar heterojunctions composed of van der Waals layered materials with different structural polymorphs have drawn immense interest recently due to low contact resistance and high carrier injection rate owing to low Schottky barrier height. Present research has largely focused on efficient exfoliation of these layered materials and their restacking to achieve better performances. We present here a microwave assisted easy, fast and efficient route to induce high concentration of metallic 1T phase in the original 2H matrix of exfoliated MoS 2 layers and thus facilitating the formation of a 1T-2H coplanar superlattice phase. High resolution transmission electron microscopy (HRTEM) investigations reveal formation of highly crystalline 1T-2H hybridized structure with sharp interface and disclose the evidence of surface ripplocations within the same exfoliated layer of MoS 2 . In this work, the structural stability of 1T-2H superlattice phase during HRTEM measurements under an electron beam of energy 300 keV is reported. This structural stability could be either associated to the change in electronic configuration due to induction of the restacked hybridized phase with 1T- and 2H-regions or to the formation of the surface ripplocations. Surface ripplocations can act as an additional source of scattering centers to the electron beam and also it is possible that a pulse train of propagating ripplocations can sweep out the defects via interaction from specific areas of MoS 2 sheets.

Structural stability of coplanar 1T-2H superlattice MoS2 under high energy electron beam

NASA Astrophysics Data System (ADS)

Reshmi, S.; Akshaya, M. V.; Satpati, Biswarup; Basu, Palash Kumar; Bhattacharjee, K.

2018-05-01

Coplanar heterojunctions composed of van der Waals layered materials with different structural polymorphs have drawn immense interest recently due to low contact resistance and high carrier injection rate owing to low Schottky barrier height. Present research has largely focused on efficient exfoliation of these layered materials and their restacking to achieve better performances. We present here a microwave assisted easy, fast and efficient route to induce high concentration of metallic 1T phase in the original 2H matrix of exfoliated MoS2 layers and thus facilitating the formation of a 1T-2H coplanar superlattice phase. High resolution transmission electron microscopy (HRTEM) investigations reveal formation of highly crystalline 1T-2H hybridized structure with sharp interface and disclose the evidence of surface ripplocations within the same exfoliated layer of MoS2. In this work, the structural stability of 1T-2H superlattice phase during HRTEM measurements under an electron beam of energy 300 keV is reported. This structural stability could be either associated to the change in electronic configuration due to induction of the restacked hybridized phase with 1T- and 2H-regions or to the formation of the surface ripplocations. Surface ripplocations can act as an additional source of scattering centers to the electron beam and also it is possible that a pulse train of propagating ripplocations can sweep out the defects via interaction from specific areas of MoS2 sheets.

AlGaN/GaN heterostructures with an AlGaN layer grown directly on reactive-ion-etched GaN showing a high electron mobility (>1300 cm2 V-1 s-1)

NASA Astrophysics Data System (ADS)

Yamamoto, Akio; Makino, Shinya; Kanatani, Keito; Kuzuhara, Masaaki

2018-04-01

In this study, the metal-organic-vapor-phase-epitaxial growth behavior and electrical properties of AlGaN/GaN structures prepared by the growth of an AlGaN layer on a reactive-ion-etched (RIE) GaN surface without regrown GaN layers were investigated. The annealing of RIE-GaN surfaces in NH3 + H2 atmosphere, employed immediately before AlGaN growth, was a key process in obtaining a clean GaN surface for AlGaN growth, that is, in obtaining an electron mobility as high as 1350 cm2 V-1 s-1 in a fabricated AlGaN/RIE-GaN structure. High-electron-mobility transistors (HEMTs) were successfully fabricated with AlGaN/RIE-GaN wafers. With decreasing density of dotlike defects observed on the surfaces of AlGaN/RIE-GaN wafers, both two-dimensional electron gas properties of AlGaN/RIE-GaN structures and DC characteristics of HEMTs were markedly improved. Since dotlike defect density was markedly dependent on RIE lot, rather than on growth lot, surface contaminations of GaN during RIE were believed to be responsible for the formation of dotlike defects and, therefore, for the inferior electrical properties.

Low-Dimensional Materials for Optoelectronic and Bioelectronic Applications

NASA Astrophysics Data System (ADS)

Hong, Tu

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

A novel fabrication method for surface integration of metal structures into polymers (SIMSIP)

NASA Astrophysics Data System (ADS)

Carrion-Gonzalez, Hector

Recently developed flexible electronics applications require that the thin metal films embedded on elastomer substrates also be flexible. These electronic systems are radically different in terms of performance and functionality than conventional silicon-based devices. A key question is whether the metal deposited on flexible films can survive large strains without rupture. Cumbersome macro-fabrication methods have been developed for functional and bendable electronics (e.g., interconnects) encapsulated between layers of polymer films. However, future electronic applications may require electronic flexible devices to be in intimate contact with curved surfaces (e.g., retinal implants) and to be robust enough to withstand large and repeated mechanical deformations. In this research, a novel technique for surface integration of metal structures into polymers (SIMSIP) was developed. Surface embedding, as opposed to placing metal on polymers, provides better adherence while leaving the surface accessible for contacts. This was accomplished by first fabricating the micro-scale metal patterns on a quartz or Teflon mother substrate, and then embedding them to a flexible polyimide thin film. The technique was successfully used to embed micro-metal structures of gold (Au), silver (Ag), and copper (Cu) into polyimide films without affecting the functional properties of the either the metals or the polymers. Experimental results confirm the successful surface-embedding of metal structures as narrow as 0.6 microm wide for different geometries commonly used in circuit design. Although similar approaches exist in literature, the proposed methodology provides a simpler and more reliable way of producing flexible circuits/electronics that is also suitable for high volume manufacturing. In order to demonstrate the flexibility of metal interconnects fabricated using the SIMSIP technique, multiple Au electrodes (5 microm and 2.5 microm wide) were tested using the X-theta bending methodology. The X-theta bending test captures data on the electrical resistivity of micro Au electrodes fabricated using the proposed SIMSIP technique by bending them at different angles between 0o and 180o up to 50 times. The data shows that the electrical resistivity of the Au electrodes remains constant (<1% variation) despite the interconnects being repeatedly subjected to extreme tensile and compressive forces during the X-theta bending test. These results are significant from the perspective of flexible electronics and biotechnology applications since the fabricated thin films exhibit significant electrical stability, reliability and wear resistance. These surface-embedded, flexible, and mechanically stable metal interconnects will enable the further development of new electronic products with applications in biotechnology (e.g., e-skin), space exploration (e.g., satellites), and microelectronics (e.g., flat panel displays). The SIMSIP technique is also a suitable process for the nanofabrication of flexible electronic devices in applications that require intimate contact with bendable curved surfaces (e.g., retinal implants).

Electronic structure of BaO/W cathode surfaces

NASA Technical Reports Server (NTRS)

Muller, Wolfgang

1989-01-01

The local electronic structure of the emissive layer of barium dispenser thermionic cathodes is investigated theoretically using the relativistic scattered-wave approach. The interaction of Ba and O with W, Os, and W-Os alloy surfaces is studied with atomic clusters modeling different absorption environments representative of B- and M-type cathodes. Ba is found to be strongly oxidized, while O and the metal substrate are in a reduced chemical state. The presence of O enhances the surface dipole and Ba binding energy relative to Ba on W. Model results for W-Os alloy substrates show only relatively small changes in Ba and O for identical geometries, but very large charge redistributions inside the substrate, which are attributed to the electronegativity difference between Os and W. If Os is present in the surface layer, the charge transfer from Ba to the substrate and the Ba binding energy increase relative to W. Explanations are offered for the improved electron emission from alloy surfaces and the different emission enhancement for different alloy substrates.

Donor defects and small polarons on the TiO{sub 2}(110) surface

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

Moses, P. G.; Janotti, A., E-mail: janotti@udel.edu; Van de Walle, C. G.

2016-05-14

The role of defects in the chemical activity of the rutile TiO{sub 2}(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend tomore » localize in the form of small polarons, which are the factual cause of the deep states ∼1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO{sub 2} and related oxides.« less

Reflection high energy electron diffraction study of nitrogen plasma interactions with a GaAs (100) surface

NASA Astrophysics Data System (ADS)

Hauenstein, R. J.; Collins, D. A.; Cai, X. P.; O'Steen, M. L.; McGill, T. C.

1995-05-01

Effect of a nitrogen electron-cyclotron-resonance (ECR) microwave plasma on near-surface composition, crystal structure, and morphology of the As-stabilized GaAs (100) surface is investigated with the use of digitally image-processed in situ reflection high energy electron diffraction. Nitridation is performed on molecular beam epitaxially (MBE) grown GaAs surfaces near 600 °C under typical conditions for ECR microwave plasma-assisted MBE growth of GaN films on GaAs. Brief plasma exposures (≊3-5 s) are shown to result in a specular, coherently strained, relatively stable, GaN film approximately one monolayer in thickness, which can be commensurately overgrown with GaAs while longer exposures (up to 1 min) result in incommensurate zincblende epitaxial GaN island structures. Specular and nonspecular film formations are explained in terms of N-for-As surface and subsurface anion exchange reactions, respectively. Commensurate growth of ultrathin buried GaN layers in GaAs is achieved.

A density functional theory study of CO oxidation on CuO1-x(111).

PubMed

Yang, Bing-Xing; Ye, Li-Ping; Gu, Hui-Jie; Huang, Jin-Hua; Li, Hui-Ying; Luo, Yong

2015-08-01

The surface structures, CO adsorption, and oxidation-reaction properties of CuO1-x(111) with different reduction degree have been investigated by using density functional theory including on-site Coulomb corrections (DFT + U). Results indicate that the reduction of Cu has a great influence on the adsorption of CO. Electron localization caused by the reduction turns Cu(2+) to Cu(+), which interacts much stronger with CO, and the adsorption strength of CO is related to the electronic interaction with the substrate as well as the structural relaxation. In particular, the electronic interaction is proved to be the decisive factor. The surfaces of CuO1-x(111) with different reduction degree all have good adsorption to CO. With the expansion of the surface reduction degree, the amount of CO that is stably adsorbed on the surface increases, while the number of surface active lattice O decreases. In general, the activity of CO oxidation first rises and then declines.

Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

On-chip surface modified nanostructured ZnO as functional pH sensors

NASA Astrophysics Data System (ADS)

Zhang, Qing; Liu, Wenpeng; Sun, Chongling; Zhang, Hao; Pang, Wei; Zhang, Daihua; Duan, Xuexin

2015-09-01

Zinc oxide (ZnO) nanostructures are promising candidates as electronic components for biological and chemical applications. In this study, ZnO ultra-fine nanowire (NW) and nanoflake (NF) hybrid structures have been prepared by Au-assisted chemical vapor deposition (CVD) under ambient pressure. Their surface morphology, lattice structures, and crystal orientation were investigated by scanning electron microscopy (SEM), x-ray diffraction (XRD), and transmission electron microscopy (TEM). Two types of ZnO nanostructures were successfully integrated as gate electrodes in extended-gate field-effect transistors (EGFETs). Due to the amphoteric properties of ZnO, such devices function as pH sensors. We found that the ultra-fine NWs, which were more than 50 μm in length and less than 100 nm in diameter, performed better in the pH sensing process than NW-NF hybrid structures because of their higher surface-to-volume ratio, considering the Nernst equation and the Gouy-Chapman-Stern model. Furthermore, the surface coating of (3-Aminopropyl)triethoxysilane (APTES) protects ZnO nanostructures in both acidic and alkaline environments, thus enhancing the device stability and extending its pH sensing dynamic range.

Structural dynamics of surfaces by ultrafast electron crystallography: experimental and multiple scattering theory.

PubMed

Schäfer, Sascha; Liang, Wenxi; Zewail, Ahmed H

2011-12-07

Recent studies in ultrafast electron crystallography (UEC) using a reflection diffraction geometry have enabled the investigation of a wide range of phenomena on the femtosecond and picosecond time scales. In all these studies, the analysis of the diffraction patterns and their temporal change after excitation was performed within the kinematical scattering theory. In this contribution, we address the question, to what extent dynamical scattering effects have to be included in order to obtain quantitative information about structural dynamics. We discuss different scattering regimes and provide diffraction maps that describe all essential features of scatterings and observables. The effects are quantified by dynamical scattering simulations and examined by direct comparison to the results of ultrafast electron diffraction experiments on an in situ prepared Ni(100) surface, for which structural dynamics can be well described by a two-temperature model. We also report calculations for graphite surfaces. The theoretical framework provided here allows for further UEC studies of surfaces especially at larger penetration depths and for those of heavy-atom materials. © 2011 American Institute of Physics

Monoatomic and dimer Mn adsorption on the Au(111) surface from first principles

NASA Astrophysics Data System (ADS)

Muñoz, Francisco; Romero, Aldo H.; Mejía-López, Jose; Morán-López, J. L.

2011-05-01

A theoretical study based on the density functional theory of the adsorption of Mn monomers and dimers on a Au-(111) surface is presented. As necessary preliminary steps, the bulk and clean surface electronic structure are calculated, which agree well with previous reports. Then, the electronic structure of the Mn adatom, chemisorbed on four different surface geometries, is analyzed. It is found that the most stable geometry is when the Mn atom is chemisorbed on threefold coordinated sites. Using this geometry for a single adatom a second Mn atom is chemisorbed and the most stable dimer geometrical structure is calculated. The lowest-energy configuration corresponds to the molecule lying parallel to the surface, adsorbed on two topological equivalent threefold coordinated sites. It is also found that the lowest-energy magnetic configuration corresponds to the antiferromagnetic arrangement with individual magnetic moments of 4.64μB. Finally, it is concluded that the dimer is not stable and should fragment at the surface.

Auger electron diffraction in thin CoO films on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Chassé, A.; Niebergall, L.; Heiler, M.; Neddermeyer, H.; Schindler, K.-M.

The local structure of thin CoO films grown on a single crystal Au(1 1 1) surface has been studied by Auger electron diffraction (AED). Therefore, the angular dependence of the Auger electron intensity of Co-LMM and O-KLL Auger electrons was recorded in the total half-space above the film. Such 2 π-scans immediately reflect the symmetry of the surface and the local structure of the film. The experimental data are compared to multiple-scattering cluster calculations, where both the influence of multiple-scattering effects and effects of Auger transition matrix elements have been investigated. We have found that the AED patterns of a CoO film in forward-scattering conditions do not always provide straightforward information on the local structure of the film, whereas the multiple-scattering approximation applied gives very good agreement between experimental and theoretical results.

Improved protein surface comparison and application to low-resolution protein structure data.

PubMed

Sael, Lee; Kihara, Daisuke

2010-12-14

Recent advancements of experimental techniques for determining protein tertiary structures raise significant challenges for protein bioinformatics. With the number of known structures of unknown function expanding at a rapid pace, an urgent task is to provide reliable clues to their biological function on a large scale. Conventional approaches for structure comparison are not suitable for a real-time database search due to their slow speed. Moreover, a new challenge has arisen from recent techniques such as electron microscopy (EM), which provide low-resolution structure data. Previously, we have introduced a method for protein surface shape representation using the 3D Zernike descriptors (3DZDs). The 3DZD enables fast structure database searches, taking advantage of its rotation invariance and compact representation. The search results of protein surface represented with the 3DZD has showngood agreement with the existing structure classifications, but some discrepancies were also observed. The three new surface representations of backbone atoms, originally devised all-atom-surface representation, and the combination of all-atom surface with the backbone representation are examined. All representations are encoded with the 3DZD. Also, we have investigated the applicability of the 3DZD for searching protein EM density maps of varying resolutions. The surface representations are evaluated on structure retrieval using two existing classifications, SCOP and the CE-based classification. Overall, the 3DZDs representing backbone atoms show better retrieval performance than the original all-atom surface representation. The performance further improved when the two representations are combined. Moreover, we observed that the 3DZD is also powerful in comparing low-resolution structures obtained by electron microscopy.

Electronic structure and dynamics of thin Ge/GaAs(110) heterostructures

NASA Astrophysics Data System (ADS)

Haight, R.; Silberman, J. A.

1990-10-01

Using angle-resolved picosecond laser photoemission we have investigated both occupied and transiently excited empty states at the surface of Ge grown epitaxially on GaAs(110). We observe a normally unoccupied, Ge layer derived state whose separation from the valence-band maximum of the system is 700±50 meV at six monolayers Ge coverage. The evolution of the electronic structure is followed as a function of coverage and correlated with low-energy electron diffraction. The time dependence of the transiently occupied Ge signal is compared with that of the clean GaAs(110) surface and shows that electrons are prevented from diffusing into the GaAs bulk by the conduction-band offset of 330±40 meV.

Observation of topological surface states and strong electron/hole imbalance in extreme magnetoresistance compound LaBi

NASA Astrophysics Data System (ADS)

Jiang, J.; Schröter, N. B. M.; Wu, S.-C.; Kumar, N.; Shekhar, C.; Peng, H.; Xu, X.; Chen, C.; Yang, H. F.; Hwang, C.-C.; Mo, S.-K.; Felser, C.; Yan, B. H.; Liu, Z. K.; Yang, L. X.; Chen, Y. L.

2018-02-01

The recent discovery of the extreme magnetoresistance (XMR) in the nonmagnetic rare-earth monopnictides La X (X = P, As, Sb, Bi,), a recently proposed new topological semimetal family, has inspired intensive research effort in the exploration of the correlation between the XMR and their electronic structures. In this work, using angle-resolved photoemission spectroscopy to investigate the three-dimensional band structure of LaBi, we unraveled its topologically nontrivial nature with the observation of multiple topological surface Dirac fermions, as supported by our ab initio calculations. Furthermore, we observed substantial imbalance between the volume of electron and hole pockets, which rules out the electron-hole compensation as the primary cause of the XMR in LaBi.

Adsorption and Electronic Structure of Sr and Ag Atoms on Graphite Surfaces: a First-Principles Study

NASA Astrophysics Data System (ADS)

Luo, Xiao-Feng; Fang, Chao; Li, Xin; Lai, Wen-Sheng; Sun, Li-Feng; Liang, Tong-Xiang

2013-06-01

The adsorption behaviors of radioactive strontium and silver nuclides on the graphite surface in a high-temperature gas-cooled reactor are studied by first-principles theory using generalized gradient approximation (GGA) and local density approximation (LDA) pseudo-potentials. It turns out that Sr prefers to be absorbed at the hollow of the carbon hexagonal cell by 0.54 eV (GGA), while Ag likes to sit right above the carbon atom with an adsorption energy of almost zero (GGA) and 0.45 eV (LDA). Electronic structure analysis reveals that Sr donates its partial electrons of the 4p and 5s states to the graphite substrate, while Ag on graphite is a physical adsorption without any electron transfer.

Electronic structure studies of adsorbate-induced surface reconstructions: oxygen on Rh(1 0 0)

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2004-03-01

Solid-state Fenske-Hall band structure calculations have been used to study the electronic structure and bonding that occur on an "asymmetric" clock reconstructed Rh(1 0 0) surface with a half-monolayer of O atom adsorbates. The displacement of the top-layer Rh atoms on reconstructed O/Rh(1 0 0) is similar to that observed when a half-monolayer of C or N atoms adsorb onto clean Ni(1 0 0). Unlike the five-coordinate C or N adsorbates that adsorb into effectively coplanar sites on the Ni(1 0 0) surface, however, O atoms sit well above the Rh surface plane and occupy three-coordinate adsorption sites. The results of these calculations show that the asymmetric clock reconstruction of O/Rh(1 0 0) increases the negative charge localized on the highly electronegative O atoms and strengthens the O-Rh bonding relative to an unreconstructed surface. This suggests that, in contrast to the C(N)/Ni(1 0 0) clock, which appears to be driven primarily by the restoration of metal-metal bonding, the asymmetric O/Rh(1 0 0) clock reconstruction is driven by the optimization of the O atom bonding environment. Comparisons of the O/Rh(1 0 0) and C(N, O)/Ni(1 0 0) surfaces further indicate that the electronegativity and electron count of the adsorbed species, as well as the electron count and physical size of the metal, all play a role in determining the preferred atomic geometries of these adsorbate-covered transition metal surfaces.

Interface and Electronic Characterization of Thin Epitaxial Co3O4 Films

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

Vaz, C.A.; Zhu, Y.; Wang, H.-Q.

2009-01-15

The interface and electronic structure of thin ({approx} 20-74 nm) Co{sub 3}O{sub 4}(1 1 0) epitaxial films grown by oxygen-assisted molecular beam epitaxy on MgAl{sub 2}O{sub 4}(1 1 0) single crystal substrates have been investigated by means of real and reciprocal space techniques. As-grown film surfaces are found to be relatively disordered and exhibit an oblique low energy electron diffraction (LEED) pattern associated with the O-rich CoO{sub 2} bulk termination of the (1 1 0) surface. Interface and bulk film structure are found to improve significantly with post-growth annealing at 820 K in air and display sharp rectangular LEED patterns,more » suggesting a surface stoichiometry of the alternative Co{sub 2}O{sub 2} bulk termination of the (1 1 0) surface. Non-contact atomic force microscopy demonstrates the presence of wide terraces separated by atomic steps in the annealed films that are not present in the as-grown structures; the step height of {approx}2.7 {angstrom} corresponds to two atomic layers and confirms a single termination for the annealed films, consistent with the LEED results. A model of the (1 x 1) surfaces that allows for compensation of the polar surfaces is presented.« less

Accurate anharmonic zero-point energies for some combustion-related species from diffusion Monte Carlo

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

Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.

Full dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic, zero point energies. Here, the resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower level electronic structure methods (B3LYP and MP2).

Accurate Anharmonic Zero-Point Energies for Some Combustion-Related Species from Diffusion Monte Carlo.

PubMed

Harding, Lawrence B; Georgievskii, Yuri; Klippenstein, Stephen J

2017-06-08

Full-dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion-related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic zero-point energies. The resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower-level electronic structure methods (B3LYP and MP2).

Accurate anharmonic zero-point energies for some combustion-related species from diffusion Monte Carlo

DOE PAGES

Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.

2017-05-17

Full dimensional analytic potential energy surfaces based on CCSD(T)/cc-pVTZ calculations have been determined for 48 small combustion related molecules. The analytic surfaces have been used in Diffusion Monte Carlo calculations of the anharmonic, zero point energies. Here, the resulting anharmonicity corrections are compared to vibrational perturbation theory results based both on the same level of electronic structure theory and on lower level electronic structure methods (B3LYP and MP2).

Variational nonadiabatic dynamics in the moving crude adiabatic representation: Further merging of nuclear dynamics and electronic structure

NASA Astrophysics Data System (ADS)

Joubert-Doriol, Loïc; Izmaylov, Artur F.

2018-03-01

A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new approach is the elimination of any global or local model representation of electronic potential energy surfaces; instead, the electron-nuclear interaction is treated explicitly using the Gaussian integration. As a result, the new scheme does not introduce any uncontrolled approximations. The employed variational principle ensures the energy conservation and leaves the number of electronic and nuclear basis functions as the only parameter determining the accuracy. To assess performance of the approach, a model with two electronic and two nuclear spacial degrees of freedom containing conical intersections between potential energy surfaces has been considered. Dynamical features associated with nonadiabatic transitions and nontrivial geometric (or Berry) phases were successfully reproduced within a limited basis expansion.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Surface and Internal Structure of Pristine Presolar Silicon Carbide

NASA Astrophysics Data System (ADS)

Stroud, R. M.; Bernatowicz, T. J.

2005-03-01

We report results from transmission electron microcopy studies of the surface and internal structure of two pristine presolar SiC grains, including definitive evidence of an oxide rim on one grain, and the presence of internal TiC and AlN grains.

Electronic structure and photoabsorption of Ti 3+ ions in reduced anatase and rutile TiO 2

DOE PAGES

Wen, Bo; Hao, Qunqing; Yin, Wen-Jin; ...

2018-01-01

We have used two-photon photoemission (2PPE) spectroscopy and first-principles density functional theory calculations to investigate the electronic structure and photoabsorption of the reduced anatase TiO 2 (101) and rutile TiO 2 (110) surfaces.

The Key Ingredients of the Electronic Structure of FeSe

NASA Astrophysics Data System (ADS)

Coldea, Amalia I.; Watson, Matthew D.

2018-03-01

FeSe is a fascinating superconducting material at the frontier of research in condensed matter physics. Here, we provide an overview of the current understanding of the electronic structure of FeSe, focusing in particular on its low-energy electronic structure as determined from angle-resolved photoemission spectroscopy, quantum oscillations, and magnetotransport measurements of single-crystal samples. We discuss the unique place of FeSe among iron-based superconductors, as it is a multiband system exhibiting strong orbitally dependent electronic correlations and unusually small Fermi surfaces and is prone to different electronic instabilities. We pay particular attention to the evolution of the electronic structure that accompanies the tetragonal-orthorhombic structural distortion of the lattice around 90 K, which stabilizes a unique nematic electronic state. Finally, we discuss how the multiband multiorbital nematic electronic structure impacts our understanding of the superconductivity, and show that the tunability of the nematic state with chemical and physical pressure helps to disentangle the role of different competing interactions relevant for enhancing superconductivity.

a Study of the Tungsten (001) Surface Using Low Energy Electron Diffraction and Other Electron Spectroscopies.

NASA Astrophysics Data System (ADS)

Kalceff, Marion Anne Stevens

The properties of the clean Tungsten (001) surfaces (both (1 x 1) and reconstructed (SQRT.(2 x SQRT.(2)R45(DEGREES) phases) and the effects of the common absorbates Hydrogen and Oxygen have been investigated using the techniques of Low Energy Electron Diffraction, Auger Electron Spectroscopy and Characteristic Electron Energy Loss Spectroscopy. The origins of features observed in Characteristic Energy Loss Spectra, very low energy (<10 eV) Secondary Electron Emission spectra and low energy (<40 eV) Auger spectra, are deduced and compared with recent relevant independently obtained theoretical data and with other, sometimes conflicting, analyses. The use of these spectroscopies as monitors of surface cleanliness is evaluated. In particular a previously unreported emission, observed during Oxygen adsorption, is attributed to an Auger transition involving the Oxygen 2s and 2p adsorbate levels. Experimental conventional LEED and improved resolution very low energy intensity versus energy spectra are compared with Dynamical spectra, calculated using the program package of M. A. Van Hove and S. Y. Tong or calculated by R. O. Jones using a previously determined saturated image barrier, within a spin dependent scattering model, respectively. Structural information about the clean (1 x 1), clean reconstructed (SQRT.(2 x SQRT.(2)R45(DEGREES) and Hydrogen saturated (1 x 1)-H surfaces have been obtained via visual comparison or R factor (E. Zanazzi and F. Jona) analysis of the conventional data. The conventional methods of LEED Intensity data collection are assessed and procedures to improve experimental reproducibility are proposed. From the analysis of the improved resolution data, and with reference to the corresponding set of very low energy electron reflection data also obtained for comparison, conclusions are made about the origins of fine structure observed in the experimental profiles and about the W(001) surface order before and after the temperature dependent reconstruction and during Hydrogen adsorption. Further information about the clean W(001)-(SQRT.(2 x SQRT.(2)R45(DEGREES) surface, including the clean surface transition temperature, the mode of reconstruction, and structural information is determined from the analyses of the LEED intensity pattern and temperature dependence. In particular it is found that the reconstruction involves both vertical and horizontal components of atomic displacement and is dependent upon the surface topography and defect structure. All results are evaluated in comparison with other relevant independent experimental or theoretical analyses, where possible.

Self-assembly patterning of organic molecules on a surface

DOEpatents

Pan, Minghu; Fuentes-Cabrera, Miguel; Maksymovych, Petro; Sumpter, Bobby G.; Li, Qing

2017-04-04

The embodiments disclosed herein include all-electron control over a chemical attachment and the subsequent self-assembly of an organic molecule into a well-ordered three-dimensional monolayer on a metal surface. The ordering or assembly of the organic molecule may be through electron excitation. Hot-electron and hot-hole excitation enables tethering of the organic molecule to a metal substrate, such as an alkyne group to a gold surface. All-electron reactions may allow a direct control over the size and shape of the self-assembly, defect structures and the reverse process of molecular disassembly from single molecular level to mesoscopic scale.

Modeling of reduced secondary electron emission yield from a foam or fuzz surface

DOE PAGES

Swanson, Charles; Kaganovich, Igor D.

2018-01-10

Complex structures on a material surface can significantly reduce the total secondary electron emission yield from that surface. A foam or fuzz is a solid surface above which is placed a layer of isotropically aligned whiskers. Primary electrons that penetrate into this layer produce secondary electrons that become trapped and do not escape into the bulk plasma. In this manner the secondary electron yield (SEY) may be reduced. We developed an analytic model and conducted numerical simulations of secondary electron emission from a foam to determine the extent of SEY reduction. We find that the relevant condition for SEY minimization ismore » $$\\bar{u}$$≡AD/2>>1 while D <<1, where D is the volume fill fraction and A is the aspect ratio of the whisker layer, the ratio of the thickness of the layer to the radius of the fibers. As a result, we find that foam cannot reduce the SEY from a surface to less than 0.3 of its flat value.« less

Modeling of reduced secondary electron emission yield from a foam or fuzz surface

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

Swanson, Charles; Kaganovich, Igor D.

Complex structures on a material surface can significantly reduce the total secondary electron emission yield from that surface. A foam or fuzz is a solid surface above which is placed a layer of isotropically aligned whiskers. Primary electrons that penetrate into this layer produce secondary electrons that become trapped and do not escape into the bulk plasma. In this manner the secondary electron yield (SEY) may be reduced. We developed an analytic model and conducted numerical simulations of secondary electron emission from a foam to determine the extent of SEY reduction. We find that the relevant condition for SEY minimization ismore » $$\\bar{u}$$≡AD/2>>1 while D <<1, where D is the volume fill fraction and A is the aspect ratio of the whisker layer, the ratio of the thickness of the layer to the radius of the fibers. As a result, we find that foam cannot reduce the SEY from a surface to less than 0.3 of its flat value.« less

Electronic, magnetic and structural properties of Co3O4 (100) surface: a DFT+U study

NASA Astrophysics Data System (ADS)

Hashim, Ameerul Hazeeq; Zayed, Ala'Omar Hasan; Zain, Sharifuddin Md; Lee, Vannajan Sanghiran; Said, Suhana Mohd

2018-01-01

The three most stable (100), (110), and (111) surfaces exposed by Co3O4 are effective catalysts for various oxidation reactions. Among these surfaces, (100) has not yet received ample attention. In this study, we investigated the structural, electronic and magnetic properties of Co3O4 (100) surface using density functional theory calculations. By considering both stoichiometric and nonstoichiometric surface structures of the two possible terminations, A and B. Besides the greater stability of the newly proposed stoichiometric models compared to nonstoichiometric models reported in previous studies, the results show that the B termination is energetically preferred over the entire range of oxygen chemical potentials. Unlike the bulk, Co3+ octahedral ions become magnetic at the surface, which leads to interesting surface magnetic properties. Density of states (DOS) indicate a small band gap of 1.15 eV for the B-stoichiometric model, due to the presence of surface states in the bulk band gap. More polar surface with a very narrow band gap is found in the A-nonstoichiometric model. These surface states may play an important role in the magnetism and metallicity observed experimentally in several Co3O4 systems.

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

2017-02-17

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry, but are challenging to probe experimentally with atomic-scale understanding. Here we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO surface is more reactive toward water, forming hydroxyl species andmore » adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight into the design of catalyst materials.« less

In situ KPFM imaging of local photovoltaic characteristics of structured organic photovoltaic devices.

PubMed

Watanabe, Satoshi; Fukuchi, Yasumasa; Fukasawa, Masako; Sassa, Takafumi; Kimoto, Atsushi; Tajima, Yusuke; Uchiyama, Masanobu; Yamashita, Takashi; Matsumoto, Mutsuyoshi; Aoyama, Tetsuya

2014-02-12

Here, we discuss the local photovoltaic characteristics of a structured bulk heterojunction, organic photovoltaic devices fabricated with a liquid carbazole, and a fullerene derivative based on analysis by scanning kelvin probe force microscopy (KPFM). Periodic photopolymerization induced by an interference pattern from two laser beams formed surface relief gratings (SRG) in the structured films. The surface potential distribution in the SRGs indicates the formation of donor and acceptor spatial distribution. Under illumination, the surface potential reversibly changed because of the generation of fullerene anions and hole transport from the films to substrates, which indicates that we successfully imaged the local photovoltaic characteristics of the structured photovoltaic devices. Using atomic force microscopy, we confirmed the formation of the SRG because of the material migration to the photopolymerized region of the films, which was induced by light exposure through photomasks. The structuring technique allows for the direct fabrication and the control of donor and acceptor spatial distribution in organic photonic and electronic devices with minimized material consumption. This in situ KPFM technique is indispensable to the fabrication of nanoscale electron donor and electron acceptor spatial distribution in the devices.

First-principles study of structure, electronic properties and stability of tungsten adsorption on TiC(111) surface with disordered vacancies

NASA Astrophysics Data System (ADS)

Ilyasov, Victor V.; Pham, Khang D.; Zhdanova, Tatiana P.; Phuc, Huynh V.; Hieu, Nguyen N.; Nguyen, Chuong V.

2017-12-01

In this paper, we systematically investigate the atomic structure, electronic and thermodynamic properties of adsorbed W atoms on the polar Ti-terminated TixCy (111) surface with different configurations of adsorptions using first principle calculations. The bond length, adsorption energy, and formation energy for different reconstructions of the atomic structure of the W/TixCy (111) systems were established. The effect of the tungsten coverage on the electronic structure and the adsorption mechanism of tungsten atom on the TixCy (111) are also investigated. We also suggest the possible mechanisms of W nucleation on the TixCy (111) surface. The effective charges on W atoms and nearest-neighbor atoms in the examined reconstructions were identified. Additionally, we have established the charge transfer from titanium atom to tungsten and carbon atoms which determine by the reconstruction of the local atomic and electronic structures. Our calculations showed that the charge transfer correlates with the electronegativity of tungsten and nearest-neighbor atoms. We also determined the effective charge per atom of titanium, carbon atoms, and neighboring adsorbed tungsten atom in different binding configurations. We found that, with reduction of the lattice symmetry associated with titanium and carbon vacancies, the adsorption energy increases by 1.2 times in the binding site A of W/TixCy systems.

Structural and electrical properties of AlN layers grown on silicon by reactive RF magnetron sputtering

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

Bazlov, N., E-mail: n.bazlov@spbu.ru; Pilipenko, N., E-mail: nelly.pilipenko@gmail.com; Vyvenko, O.

2016-06-17

AlN films of different thicknesses were deposited on n-Si (100) substrates by reactive radio frequency (rf) magnetron sputtering. Dependences of structure and electrical properties on thickness of deposited films were researched. The structures of the films were analyzed with scanning electron microscopy (SEM) and with transmitting electron microscopy (TEM). Electrical properties of the films were investigated on Au-AlN-(n-Si) structures by means of current-voltage (I-V), capacitance-voltage (C-V) and deep level transient spectroscopy (DLTS) techniques. Electron microscopy investigations had shown that structure and chemical composition of the films were thickness stratified. Near silicon surface layer was amorphous aluminum oxide one contained trapsmore » of positive charges with concentration of about 4 × 10{sup 18} cm{sup −3}. Upper layers were nanocrystalline ones consisted of both wurzite AlN and cubic AlON nanocrystals. They contained traps both positive and negative charges which were situated within 30 nm distance from silicon surface. Surface densities of these traps were about 10{sup 12} cm{sup −2}. Electron traps with activation energies of (0.2 ÷ 0.4) eV and densities of about 10{sup 10} cm{sup −2} were revealed on interface between aluminum oxide layer and silicon substrate. Their densities varied weakly with the film thickness.« less

Superconducting surface impedance under radiofrequency field

DOE PAGES

Xiao, Binping P.; Reece, Charles E.; Kelley, Michael J.

2013-04-26

Based on BCS theory with moving Cooper pairs, the electron states distribution at 0K and the probability of electron occupation with finite temperature have been derived and applied to anomalous skin effect theory to obtain the surface impedance of a superconductor under radiofrequency (RF) field. We present the numerical results for Nb and compare these with representative RF field-dependent effective surface resistance measurements from a 1.5 GHz resonant structure.

Fabrication of frequency selective surface for band stop IR-filter

NASA Astrophysics Data System (ADS)

Mishra, Akshita; Sudheer, Tiwari, P.; Mondal, P.; Bhatt, H.; Rai, V. N.; Srivastava, A. K.

2016-05-01

Fabrication and characterization of frequency selective surfaces (FSS) on silicon dioxide/ silicon is reported. Electron beam lithography based techniques are used for the fabrication of periodic slot structure in tungsten layer on silicon dioxide/silicon. The fabrication process consists of growth of SiO2 on silicon, tungsten deposition, electron beam lithography, and wet etching of tungsten. The optical characterization of the structural pattern was carried out using fourier transform infrared spectroscopy (FTIR). The reflectance spectra clearly show a resonance peak at 9.09 µm in the mid infrared region. This indicates that the patterned surface acts as band stop filter in the mid-infrared region.

Structural phase transitions and time-resolved dynamics of solid-supported interfacial methanol observed by reflection electron diffraction

NASA Astrophysics Data System (ADS)

Yang, Ding-Shyue; He, Xing; Wu, Chengyi

Due to their large scattering cross sections with matter, electrons are suitable for contactless probing of solid-supported surface assemblies, especially in a reflection geometry. Direct visualization of assembly structures through electron diffraction further enables studies of ultrafast structural dynamics through the pump-probe scheme as well as discoveries of hidden phase changes in equilibrium that have been obscure in spectroscopic measurements. In this presentation, we report our first observation of unique two-stage transformations of interfacial methanol on smooth hydrophobic surfaces. The finding may reconcile the inconsistent previous reports of the crystallization temperature using various indirect methods. Dynamically, energy transfer across a solid-molecule interface following photoexcitation of the substrate is found to be highly dependent on the structure of interfacial methanol. If it is only 2-dimensionally ordered, as the film thickness increases, a prolonged time in the decrease of diffraction intensity is seen, signifying an inefficient vibrational coupling in the surface normal direction. Implications of the dynamics results and an outlook of interfacial studies using time-resolved and averaged electron diffraction will be discussed. We gratefully acknowledge the support from the R. A. Welch Foundation (Grant No. E-1860), the Donors of the American Chemical Society Petroleum Research Fund (ACS-PRF), and the University of Houston.

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

Liu, Jing; Hosseinpour, Pegah M.; Lewis, Laura H., E-mail: lhlewis@neu.edu

To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO{sub 2} nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O{sub 2} (oxidizing), Ar (inert), and H{sub 2} (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO{submore » 2} nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (∼5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO{sub 2} nanotubes regardless of their length. However, the annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H{sub 2}-annealed nanotubes than with the Ar- and O{sub 2}-annealed nanotube samples. This enhanced photocatalytic response of the H{sub 2}-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti{sup 3+} and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

Crystal Structure Variations of Sn Nanoparticles upon Heating

NASA Astrophysics Data System (ADS)

Mittal, Jagjiwan; Lin, Kwang-Lung

2018-04-01

Structural changes in Sn nanoparticles during heating below the melting point have been investigated using differential scanning calorimetry (DSC), x-ray diffraction (XRD) analysis, electron diffraction (ED), and high-resolution transmission electron microscopy (HRTEM). DSC revealed that the heat required to melt the nanoparticles (28.43 J/g) was about half compared with Sn metal (52.80 J/g), which was attributed to the large surface energy contribution for the nanoparticles. ED and XRD analyses of the Sn nanoparticles revealed increased intensity for crystal planes having large interplaner distances compared with regular crystal planes with increasing heat treatment temperature (HTT). HRTEM revealed an increase in interlayer spacing at the surface and near joints between nanoparticles with the HTT, leading to an amorphous structure of nanoparticles at the surface at 220°C. These results highlight the changes that occur in the morphology and crystal structure of Sn nanoparticles at the surface and in the interior with increase of the heat treatment temperature.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

NASA Astrophysics Data System (ADS)

Meng, Jianbing; Dong, Xiaojuan; Wei, Xiuting; Yin, Zhanmin

2014-03-01

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The results show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.

Preparation of anti-adhesion surfaces on aluminium substrates of rubber plastic moulds using a coupling method of liquid plasma and electrochemical machining

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

Meng, Jianbing, E-mail: jianbingmeng@126.com; Dong, Xiaojuan; Wei, Xiuting

Hard anti-adhesion surfaces, with low roughness and wear resistance, on aluminium substrates of rubber plastic moulds were fabricated via a new coupling method of liquid plasma and electrochemical machining. With the aid of liquid plasma thermal polishing and electrochemical anodic dissolution, micro/nano-scale binary structures were prepared as the base of the anti-adhesion surfaces. The anti-adhesion behaviours of the resulting aluminium surfaces were analysed by a surface roughness measuring instrument, a scanning electron microscope (SEM), a Fourier-transform infrared spectrophotometer (FTIR), an X-ray diffractometer (XRD), an optical contact angle meter, a digital Vickers micro-hardness (Hv) tester, and electronic universal testing. The resultsmore » show that, after the liquid plasma and electrochemical machining, micro/nano-scale binary structures composed of micro-scale pits and nano-scale elongated boss structures were present on the sample surfaces. As a result, the anti-adhesion surfaces fabricated by the above coupling method have good anti-adhesion properties, better wear resistance and lower roughness.« less

Role of organic cations on hybrid halide perovskite CH3NH3PbI3 surfaces

NASA Astrophysics Data System (ADS)

Teng, Qiang; Shi, Ting-Ting; Tian, Ren-Yu; Yang, Xiao-Bao; Zhao, Yu-Jun

2018-02-01

Organic-inorganic hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has received rapid progress in power conversion efficiency as promising photovoltaic materials, yet the surface structures and the role of MA cations are not well understood. In this work, we investigated the structural stability and electronic properties of (001) surface of cubic, (001) and (110) surfaces of tetragonal and orthorhombic phases of MAPbI3 with considering the orientation of MA cations, by density functional theory calculations. We demonstrate that the orientation of MA cations has profound consequences on the structural stability and the electronic properties of the surfaces, in contrast to the bulk phases. Compared with the MA-I terminated surfaces, the Pb-I2 terminated ones generally have smaller band gaps and the advantage to enable the photo-excited holes to transfer to the hole-transport materials in both tetragonal and orthorhombic phases. Overall, we suggest that the films with Pb-I2 terminated surfaces would prevail in high performance solar energy absorbers.

Characterization and evaluation of femtosecond laser-induced sub-micron periodic structures generated on titanium to improve osseointegration of implants

NASA Astrophysics Data System (ADS)

Lee, Bryan E. J.; Exir, Hourieh; Weck, Arnaud; Grandfield, Kathryn

2018-05-01

Reproducible and controllable methods of modifying titanium surfaces for dental and orthopaedic applications are of interest to prevent poor implant outcomes by improving osseointegration. This study made use of a femtosecond laser to generate laser-induced periodic surface structures with periodicities of 300, 620 and 760 nm on titanium substrates. The reproducible rippled patterns showed consistent submicron scale roughness and relatively hydrophobic surfaces as measured by atomic force microscopy and contact angle, respectively. Transmission electron microscopy and Auger electron spectroscopy identified a thicker oxide layer on ablated surfaces compared to controls. In vitro testing was conducted using osteosarcoma Saos-2 cells. Cell metabolism on the laser-ablated surfaces was comparable to controls and alkaline phosphatase activity was notably increased at late time points for the 620 and 760 nm surfaces compared to controls. Cells showed a more elongated shape on laser-ablated surfaces compared to controls and showed perpendicular alignment to the periodic structures. This work has demonstrated the feasibility of generating submicron features on an implant material with the ability to influence cell response and improve implant outcomes.

Surface structural reconstruction of SrVO3 thin films on SrTiO3 (001)

NASA Astrophysics Data System (ADS)

Wang, Gaomin; Saghayezhian, Mohammad; Chen, Lina; Guo, Hangwen; Zhang, Jiandi

Paramagnetic metallic oxide SrVO3>(SVO) is an itinerant system known to undergo thickness-induced metal-insulator-transition (MIT) in ultrathin film form, which makes it a prototype system for the study of the mechanism behind metal-insulator-transition like structure distortion, electron correlations and disorder-induced localization. We have grown SrVO3 thin film with atomically flat surface through the layer-by-layer deposition by laser Molecular Beam Epitaxy (laser-MBE) on SrTiO3 (001) surface. Low Energy Electron Diffraction (LEED) measurements reveal that there is a (√2X √2) R45°surface reconstruction independent of film thickness. By using LEED-I(V) structure refinement, we determine the surface structure. In combination with X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM), we discuss the implication on the MIT in ultrathin films below 2-3 unit cell thickness. This work is supported by the National Science Foundation under the NSF EPSCoR Cooperative Agreement No. EPS-1003897 with additional support from the Louisiana Board of Regents.

Electromers of the benzene dimer radical cation.

PubMed

Błoch-Mechkour, Anna; Bally, Thomas

2015-04-28

The well-studied benzene dimer radical cation, which is prototypical for this class of species, has been reinvestigated computationally. Thereby it turned out that both the σ-hemibonded and the half-shifted sandwich structures of the benzene dimer cation, which had been independently proposed, represent stationary points on the B2PLYP-D potential energy surfaces. However, these structures belong to distinct electronic states, both of which are associated with potential surfaces that are very flat with regard to rotation of the two benzene rings in an opposite sense relative to each other. The surfaces of these two "electromers" of the benzene dimer cation are separated by only 3-4 kcal mol(-1) and do not intersect along the rotation coordinate, which represents a rather unique electronic structure situation. When moving on either of the two surfaces the title complex is an extremely fluxional species, in spite of its being bound by over 20 kcal mol(-1).

Metallic rare-earth silicide nanowires on silicon surfaces.

PubMed

Dähne, Mario; Wanke, Martina

2013-01-09

The formation, atomic structure, and electronic properties of self-assembled rare-earth silicide nanowires on silicon surfaces were studied by scanning tunneling microscopy and angle-resolved photoelectron spectroscopy. Metallic dysprosium and erbium silicide nanowires were observed on both the Si(001) and Si(557) surfaces. It was found that they consist of hexagonal rare-earth disilicides for both surface orientations. On Si(001), the nanowires are characterized by a one-dimensional band structure, while the electronic dispersion is two-dimensional for the nanowires formed on Si(557). This behavior is explained by the different orientations of the hexagonal c axis of the silicide leading to different conditions for the carrier confinement. By considering this carrier confinement it is demonstrated how the one-dimensional band structure of the nanowires on Si(001) can be derived from the two-dimensional one of the silicide monolayer on Si(111).

Atomic scale morphology, growth behaviour and electronic properties of semipolar {101[overline]3} GaN surfaces.

PubMed

Kioseoglou, J; Kalesaki, E; Lymperakis, L; Karakostas, Th; Komninou, Ph

2013-01-30

First-principles calculations relating to the atomic structure and electronic properties of {101[overline]3} GaN surfaces reveal significant differentiations between the two polarity orientations. The (101[overline]3) surface exhibits a remarkable morphological stability, stabilizing a metallic structure (Ga adlayer) over the entire range of the Ga chemical potential. In contrast, the semiconducting, cleaved surface is favoured on (101[overline]3[overline]) under extremely and moderately N-rich conditions, a Ga bilayer is stabilized under corresponding Ga-rich conditions and various transitions between metallic reconstructions take place in intermediate growth stoichiometries. Efficient growth schemes for smooth, two-dimensional GaN layers and the isolation of {101[overline]3} material from parasitic orientations are identified.

Structural and electronic properties of low-index stoichiometric Cu2ZnSnS4 surfaces

NASA Astrophysics Data System (ADS)

Jia, Zhan-Ju; Wang, Yu-An; Zhao, Zong-Yan; Liu, Qing-Ju

2018-05-01

Over the past few years, quaternary Cu2ZnSnS4 (CZTS) has attracted a great deal of attention as the most promising photovoltaic absorber layer, due to its abundance and non-toxic properties. However, the significant surface structures and properties for photo-catalytic absorption layers have not yet been studied in detail for CZTS. Hence, the surface structure and electronic properties of low-index stoichiometric CZTS surfaces are calculated based on density functional theory. The relaxation is much large for the (001), (100), (101) and (112) surfaces. Moreover, more surface states appear at the bottom of conduction band and the top of valence band. The conduction band is mainly composed of S-3p and Sn-5p orbits. The valence band top is mainly composed of S-3p and Cu-3d orbits. The band gap values of five surfaces do not vary greatly. The dangling bond density for the (112) surfaces is minimal, resulting in minimum surface energy. Finally, the equilibrium morphology of CZTS is constructed by the Wulff rule. It is found that the {101} surface is the dominant surface (72.6%). These results will help us to better understand the surface properties of absorption layer that is related to CZTS surface and provide theoretical support for future experimental studies.

Quantum interference measurement of spin interactions in a bio-organic/semiconductor device structure

DOE PAGES

Deo, Vincent; Zhang, Yao; Soghomonian, Victoria; ...

2015-03-30

Quantum interference is used to measure the spin interactions between an InAs surface electron system and the iron center in the biomolecule hemin in nanometer proximity in a bio-organic/semiconductor device structure. The interference quantifies the influence of hemin on the spin decoherence properties of the surface electrons. The decoherence times of the electrons serve to characterize the biomolecule, in an electronic complement to the use of spin decoherence times in magnetic resonance. Hemin, prototypical for the heme group in hemoglobin, is used to demonstrate the method, as a representative biomolecule where the spin state of a metal ion affects biologicalmore » functions. The electronic determination of spin decoherence properties relies on the quantum correction of antilocalization, a result of quantum interference in the electron system. Spin-flip scattering is found to increase with temperature due to hemin, signifying a spin exchange between the iron center and the electrons, thus implying interactions between a biomolecule and a solid-state system in the hemin/InAs hybrid structure. The results also indicate the feasibility of artificial bioinspired materials using tunable carrier systems to mediate interactions between biological entities.« less

Electronic structure of uracil-like nucleobases adsorbed on Si(001): uracil, thymine and 5-fluorouracil

NASA Astrophysics Data System (ADS)

Molteni, Elena; Onida, Giovanni; Cappellini, Giancarlo

2016-04-01

We study the electronic properties of the Si(001):Uracil, Si(001):Thymine, and Si(001):5-Fluorouracil systems, focusing on the Si dimer-bridging configuration with adsorption governed by carbonyl groups. While the overall structural and electronic properties are similar, with small differences due to chemical substitutions, much larger effects on the surface band dispersion and bandgap show up as a function of the molecular orientation with respect to the surface. An off-normal orientation of the molecular planes is favored, showing larger bandgap and lower total energy than the upright position. We also analyze the localization of gap-edge occupied and unoccupied surface states. Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjb/e2016-70011-1

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

PubMed

Monazami, Ehsan; McClimon, John B; Rondinelli, James; Reinke, Petra

2016-12-21

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C 60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 10 4 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C 60 and isolated C 60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C 60 -W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

Formation of a conducting LaAlO3/SrTiO3 interface studied by low-energy electron reflection during growth

NASA Astrophysics Data System (ADS)

van der Torren, A. J. H.; Liao, Z.; Xu, C.; Gauquelin, N.; Yin, C.; Aarts, J.; van der Molen, S. J.

2017-12-01

The two-dimensional electron gas occurring between the band insulators SrTiO3 and LaAlO3 continues to attract considerable interest, due to the possibility of dynamic control over the carrier density and due to ensuing phenomena such as magnetism and superconductivity. The formation of this conducting interface is sensitive to the growth conditions, but despite numerous investigations there are still questions about the details of the physics involved. In particular, not much is known about the electronic structure of the growing LaAlO3 layer at the growth temperature (around 800°C) in oxygen (pressure around 5 ×10-5 mbar), since analysis techniques at these conditions are not readily available. We developed a pulsed laser deposition system inside a low-energy electron microscope in order to study this issue. The setup allows for layer-by-layer growth control and in situ measurements of the angle-dependent electron reflection intensity, which can be used as a fingerprint of the electronic structure of the surface layers during growth. By using different substrate terminations and growth conditions we observe two families of reflectivity maps, which we can connect either to samples with an AlO2-rich surface and a conducting interface or to samples with a LaO-rich surface and an insulating interface. Our observations emphasize that substrate termination and stoichiometry determine the electronic structure of the growing layer, and thereby the conductance of the interface.

Oxygen adsorption on Cu-9 at. %Al(111) studied by low energy electron diffraction and Auger electron spectroscopy

NASA Astrophysics Data System (ADS)

Yoshitake, Michiko; Bera, Santanu; Yamauchi, Yasuhiro; Song, Weijie

2003-07-01

Cu-based alloys have been used for electric cables for long time. In the field of microelectronics, Al had been used for electrical wiring. However, it became clear that electromigration occurs in Al that causes breaking of wires in minute wirings. Due to this problem, Cu wiring is used in most advanced microprocessors. Cu metal is more corrosive than Al and Cu-based alloys with a small amount of Al is expected to solve problems both on electromigration and corrosion. The initial stage of corrosion is oxygen adsorption. We studied surface segregation of Al on Cu-9% Al(111) and oxygen adsorption on the surface with/without Al segregation in ultrahigh vacuum by low energy electron diffraction (LEED) and Auger electron spectroscopy. It was found that Al segregates on the surface to form (√3×√3)R30° structure and the structure vanishes above 595 K to give (1×1) structure while Al still segregates. The specimen was exposed to oxygen at different temperatures. The amount of oxygen uptake was not structure dependent but temperature dependent. Below 595 K, only a small amount of oxygen adsorbed. Between 595 and 870 K, oxygen adsorbed surface showed amorphous LEED pattern. The specimen was annealed at 1070 K after oxygen exposure. When the specimen was exposed oxygen below 870 K, the oxygen Auger intensity decreased significantly by annealing and the annealed surface showed (√3×√3)R30° structure at room temperature. When the specimen was exposed to oxygen at 870 K, diffused spots developed newly in LEED pattern but the pattern disappeared after 1070 K annealing while oxygen Auger intensity remained almost constant. Exposing the specimen to oxygen at 995 K resulted in clear spots in the LEED pattern, which were attributed to the (7/√3×7√3)R30° structure.

Stimuli-responsive polyaniline coated silica microspheres and their electrorheology

NASA Astrophysics Data System (ADS)

Park, Dae Eun; Choi, Hyoung Jin; Vu, Cuong Manh

2016-05-01

Silica/polyaniline (PANI) core-shell structured microspheres were synthesized by coating the surface of silica micro-beads with PANI and applied as a candidate inorganic/polymer composite electrorheological (ER) material. The silica micro-beads were initially modified using N-[(3-trimethoxysilyl)-propyl] aniline to activate an aniline functional group on the silica surface for a better PANI coating. The morphology of the PANI coating on the silica surface was examined by scanning electron microscopy and the silica/PANI core-shell structure was confirmed by transmission electron microscopy. The chemical structure of the particles was confirmed by Fourier transform infrared spectroscopy. Rotational rheometry was performed to confirm the difference in the ER properties between pure silica and silica/PANI microsphere-based ER fluids when dispersed in silicone oil.

Structure determination of the ordered (2 × 1) phase of NiSi surface alloy on Ni(111) using low-energy electron diffraction

NASA Astrophysics Data System (ADS)

Sazzadur Rahman, Md.; Amirul Islam, Md.; Saha, Bidyut Baran; Nakagawa, Takeshi; Mizuno, Seigi

2015-12-01

The (2 × 1) structure of the two-dimensional nickel silicide surface alloy on Ni(111) was investigated using quantitative low-energy electron diffraction analysis. The unit cell of the determined silicide structure contains one Si and one Ni atom, corresponding to a chemical formula of NiSi. The Si atoms adopt substitutional face-centered cubic hollow sites on the Ni(111) substrate. The Ni-Si bond lengths were determined to be 2.37 and 2.34 Å. Both the alloy surface and the underlying first layers of Ni atoms exhibit slight corrugation. The Ni-Si interlayer distance is smaller than the Ni-Ni interlayer distance, which indicates that Si atoms and underlying Ni atoms strongly interact.

Photoemission and Photoabsorption Investigation of the Electronic Structure of Ytterbium Doped Strontium Fluoroapatite

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

Nelson, A J; van Buuren, T; Bostedt, C

X-ray photoemission and x-ray photoabsorption were used to study the composition and the electronic structure of ytterbium doped strontium fluoroapatite (Yb:S-FAP). High resolution photoemission measurements on the valence band electronic structure was used to evaluate the density of occupied states of this fluoroapatite. Element specific density of unoccupied electronic states in Yb:S-FAP were probed by x-ray absorption spectroscopy (XAS) at the Yb 4d (N{sub 4,5}-edge), Sr 3d (M{sub 4,5}-edge), P 2p (L{sub 2,3}-edge), F 1s and O 1s (K-edges) absorption edges. These results provide the first measurements of the electronic structure and surface chemistry of this material.

A theoretical study of structural and electronic properties of pentacene/Al(100) interface.

PubMed

Saranya, G; Nair, Shiny; Natarajan, V; Kolandaivel, P; Senthilkumar, K

2012-09-01

The first principle calculations within the framework of density functional theory have been performed for the pentacene molecule deposited on the aluminum Al(100) substrate to study the structural and electronic properties of the pentacene/Al(100) interface. The most stable configuration was found at bridge site with 45° rotation of the pentacene molecule on Al(100) surface with a vertical distance of 3.4 Å within LDA and 3.8 Å within GGA functionals. The calculated adsorption energy reveals that the adsorption of pentacene molecule on Al(100) surface is physisorption. For the stable adsorption geometry the electronic properties such as density of states (DOS), partial density of states (PDOS), Mulliken population analysis and Schottky barrier height are studied. The analysis of atomic charge, DOS and PDOS show that the charge is transferred from the Al(100) surface to pentacene molecule, and the transferred charge is about -0.05 electrons. For the adsorbed system, the calculated Schottky barrier height for hole and electron transport is 0.27 and 1.55 eV, respectively. Copyright © 2012 Elsevier Inc. All rights reserved.

Temperature-driven topological transition in 1T'-MoTe2

NASA Astrophysics Data System (ADS)

Berger, Ayelet Notis; Andrade, Erick; Kerelsky, Alexander; Edelberg, Drew; Li, Jian; Wang, Zhijun; Zhang, Lunyong; Kim, Jaewook; Zaki, Nader; Avila, Jose; Chen, Chaoyu; Asensio, Maria C.; Cheong, Sang-Wook; Bernevig, Bogdan A.; Pasupathy, Abhay N.

2018-01-01

The topology of Weyl semimetals requires the existence of unique surface states. Surface states have been visualized in spectroscopy measurements, but their connection to the topological character of the material remains largely unexplored. 1T'-MoTe2, presents a unique opportunity to study this connection. This material undergoes a phase transition at 240 K that changes the structure from orthorhombic (putative Weyl semimetal) to monoclinic (trivial metal), while largely maintaining its bulk electronic structure. Here, we show from temperature-dependent quasiparticle interference measurements that this structural transition also acts as a topological switch for surface states in 1T'-MoTe2. At low temperature, we observe strong quasiparticle scattering, consistent with theoretical predictions and photoemission measurements for the surface states in this material. In contrast, measurements performed at room temperature show the complete absence of the scattering wavevectors associated with the trivial surface states. These distinct quasiparticle scattering behaviors show that 1T'-MoTe2 is ideal for separating topological and trivial electronic phenomena via temperature-dependent measurements.

Formation of Surface and Quantum-Well States in Ultra Thin Pt Films on the Au(111) Surface

PubMed Central

Silkin, Igor V.; Koroteev, Yury M.; Echenique, Pedro M.; Chulkov, Evgueni V.

2017-01-01

The electronic structure of the Pt/Au(111) heterostructures with a number of Pt monolayers n ranging from one to three is studied in the density-functional-theory framework. The calculations demonstrate that the deposition of the Pt atomic thin films on gold substrate results in strong modifications of the electronic structure at the surface. In particular, the Au(111) s-p-type Shockley surface state becomes completely unoccupied at deposition of any number of Pt monolayers. The Pt adlayer generates numerous quantum-well states in various energy gaps of Au(111) with strong spatial confinement at the surface. As a result, strong enhancement in the local density of state at the surface Pt atomic layer in comparison with clean Pt surface is obtained. The excess in the density of states has maximal magnitude in the case of one monolayer Pt adlayer and gradually reduces with increasing number of Pt atomic layers. The spin–orbit coupling produces strong modification of the energy dispersion of the electronic states generated by the Pt adlayer and gives rise to certain quantum states with a characteristic Dirac-cone shape. PMID:29232833

Improved protein surface comparison and application to low-resolution protein structure data

PubMed Central

2010-01-01

Background Recent advancements of experimental techniques for determining protein tertiary structures raise significant challenges for protein bioinformatics. With the number of known structures of unknown function expanding at a rapid pace, an urgent task is to provide reliable clues to their biological function on a large scale. Conventional approaches for structure comparison are not suitable for a real-time database search due to their slow speed. Moreover, a new challenge has arisen from recent techniques such as electron microscopy (EM), which provide low-resolution structure data. Previously, we have introduced a method for protein surface shape representation using the 3D Zernike descriptors (3DZDs). The 3DZD enables fast structure database searches, taking advantage of its rotation invariance and compact representation. The search results of protein surface represented with the 3DZD has showngood agreement with the existing structure classifications, but some discrepancies were also observed. Results The three new surface representations of backbone atoms, originally devised all-atom-surface representation, and the combination of all-atom surface with the backbone representation are examined. All representations are encoded with the 3DZD. Also, we have investigated the applicability of the 3DZD for searching protein EM density maps of varying resolutions. The surface representations are evaluated on structure retrieval using two existing classifications, SCOP and the CE-based classification. Conclusions Overall, the 3DZDs representing backbone atoms show better retrieval performance than the original all-atom surface representation. The performance further improved when the two representations are combined. Moreover, we observed that the 3DZD is also powerful in comparing low-resolution structures obtained by electron microscopy. PMID:21172052

Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

PubMed

Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

2014-06-25

Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated oxygen atoms on the surface of the super-reduced POM(27-) polyanion allows the huge Coulombic repulsion due to the presence of the excess electrons to be counterbalanced by the presence of Li countercations, which partially penetrate into the outer oxygen shell. This "semiporous molecular capacitor" structure is likely the reason for the effective electron uptake in POMs.

Direct, experimental evidence of the Fermi surface in YBa2Cu3O(7-x)

NASA Astrophysics Data System (ADS)

Haghighi, H.; Kaiser, J. H.; Rayner, S. L.; West, R. N.; Liu, J. Z.; Shelton, R.; Howell, R. H.; Sterne, P. A.; Solal, F. R.; Fluss, M. J.

1991-04-01

We report new measurements of the electron positron momentum spectra of YBa2Cu3O(7-x) performed with ultra-high statistical precision. These data differ from previous results in two significant respects: They show the D(sub 2) symmetry appropriate for untwinned crystals and, more importantly, they show unmistakable, statistically significant, discontinuities that are evidence of a major Fermi surface section. These results provide a partial answer to a question of special significance to the study of high temperature superconductors i.e., the distribution of the electrons in the material, the electronic structure. Special consideration has been given both experimentally and theoretically to the existence and shape of a Fermi surface in the materials and to the superconducting gap. There are only three experimental techniques that can provide details of the electronic structure at useful resolutions. They are angular correlation of positron annihilation radiation, ACAR, angle resolved photo emission, PE, and de Haas van Alphen measurements.

Improvements of electronic and optical characteristics of n-GaN-based structures by photoelectrochemical oxidation in glycol solution

NASA Astrophysics Data System (ADS)

Shiozaki, Nanako; Hashizume, Tamotsu

2009-03-01

Surface control of n-GaN was performed by applying a photoelectrochemical oxidation method in a glycol solution to improve the optical and electronic characteristics. The fundamental properties of the oxidation were investigated. The oxidation, chemical composition, and bonding states were analyzed by x-ray photoelectron spectroscopy and micro-Auger electron spectroscopy, in which confirmed the formation of gallium oxide on the surface. The oxide formation rate was about 8 nm/min under UV illumination of 4 mW/cm2. After establishing the basic properties for control of n-GaN oxidation, the surface control technique was applied to achieve low-damage etching, enhancement of the photoluminescence intensity, and selective passivation of the air-exposed sidewalls in an AlGaN/GaN high electron mobility transistor wire structure. The capacitance-voltage measurement revealed the minimum interface-state density between GaN and anodic oxide to be about 5×1011 cm-2 eV-1, which is rather low value for compound semiconductors.

Effects of surface functionalization on the electronic and structural properties of carbon nanotubes: A computational approach

NASA Astrophysics Data System (ADS)

Ribeiro, M. S.; Pascoini, A. L.; Knupp, W. G.; Camps, I.

2017-12-01

Carbon nanotubes (CNTs) have important electronic, mechanical and optical properties. These features may be different when comparing a pristine nanotube with other presenting its surface functionalized. These changes can be explored in areas of research and application, such as construction of nanodevices that act as sensors and filters. Following this idea, in the current work, we present the results from a systematic study of CNT's surface functionalized with hydroxyl and carboxyl groups. Using the entropy as selection criterion, we filtered a library of 10k stochastically generated complexes for each functional concentration (5, 10, 15, 20 and 25%). The structurally related parameters (root-mean-square deviation, entropy, and volume/area) have a monotonic relationship with functionalization concentration. Differently, the electronic parameters (frontier molecular orbital energies, electronic gap, molecular hardness, and electrophilicity index) present and oscillatory behavior. For a set of concentrations, the nanotubes present spin polarized properties that can be used in spintronics.

Fermi arcs vs. fermi pockets in electron-doped perovskite iridates

DOE PAGES

He, Junfeng; Hafiz, H.; Mion, Thomas R.; ...

2015-02-23

We report on an angle resolved photoemission (ARPES) study of bulk electron-doped perovskite iridate, (Sr 1-xLa x)₃Ir₂O₇. Fermi surface pockets are observed with a total electron count in keeping with that expected from La substitution. Depending on the energy and polarization of the incident photons, these pockets show up in the form of disconnected “Fermi arcs”, reminiscent of those reported recently in surface electron-doped Sr₂IrO₄. Our observed spectral variation is consistent with the coexistence of an electronic supermodulation with structural distortion in the system.

Common electronic origin of superconductivity in (Li,Fe)OHFeSe bulk superconductor and single-layer FeSe/SrTiO3 films

PubMed Central

Zhao, Lin; Liang, Aiji; Yuan, Dongna; Hu, Yong; Liu, Defa; Huang, Jianwei; He, Shaolong; Shen, Bing; Xu, Yu; Liu, Xu; Yu, Li; Liu, Guodong; Zhou, Huaxue; Huang, Yulong; Dong, Xiaoli; Zhou, Fang; Liu, Kai; Lu, Zhongyi; Zhao, Zhongxian; Chen, Chuangtian; Xu, Zuyan; Zhou, X. J.

2016-01-01

The mechanism of high-temperature superconductivity in the iron-based superconductors remains an outstanding issue in condensed matter physics. The electronic structure plays an essential role in dictating superconductivity. Recent revelation of distinct electronic structure and high-temperature superconductivity in the single-layer FeSe/SrTiO3 films provides key information on the role of Fermi surface topology and interface in inducing or enhancing superconductivity. Here we report high-resolution angle-resolved photoemission measurements on the electronic structure and superconducting gap of an FeSe-based superconductor, (Li0.84Fe0.16)OHFe0.98Se, with a Tc at 41 K. We find that this single-phase bulk superconductor shows remarkably similar electronic behaviours to that of the superconducting single-layer FeSe/SrTiO3 films in terms of Fermi surface topology, band structure and the gap symmetry. These observations provide new insights in understanding high-temperature superconductivity in the single-layer FeSe/SrTiO3 films and the mechanism of superconductivity in the bulk iron-based superconductors. PMID:26853801

Hierarchical micro-nano structured Ti6Al4V surface topography via two-step etching process for enhanced hydrophilicity and osteoblastic responses.

PubMed

Moon, Byeong-Seok; Kim, Sungwon; Kim, Hyoun-Ee; Jang, Tae-Sik

2017-04-01

Hierarchical micro-nano (HMN) surface structuring of dental implants is a fascinating strategy for achieving fast and mechanically stable fixation due to the synergetic effect of micro- and nano-scale surface roughness with surrounding tissues. However, the introduction of a well-defined nanostructure on a microstructure having complex surface geometry is still challenging. As a means of fabricating HMN surface on Ti6Al4V-ELI, target-ion induced plasma sputtering (TIPS) was used onto a sand-blasted, large-grit and acid-etched substrate. The HMN surface topography was simply controlled by adjusting the tantalum (Ta) target power of the TIPS technique, which is directly related to the Ta ion flux and the surface chemical composition of the substrate. Characterization using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and laser scanning microscopy (LSM) verified that well-defined nano-patterned surface structures with a depth of ~300 to 400nm and a width of ~60 to 70nm were uniformly distributed and followed the complex micron-sized surface geometry. In vitro cellular responses of pre-osteoblast cells (MC3T3-E1) were assessed by attachment and proliferation of cells on flat, nano-roughened, micro-roughened, and an HMN surface structure of Ti6Al4V-ELI. Moreover, an in vivo dog mandible defect model study was used to investigate the biological effect of the HMN surface structure compared with the micro-roughened surface. The results showed that the surface nanostructure significantly increased the cellular activities of flat and micro-roughened Ti, and the bone-to-implant contact area and new bone volume were significantly improved on the HMN surface structured Ti. These results support the idea that an HMN surface structure on Ti6Al4V-ELI alloy has great potential for enhancing the biological performance of dental implants. Copyright © 2016 Elsevier B.V. All rights reserved.

Potassium-induced effect on structure and chemical activity of Cu xO/Cu(111) (x≤2) surface: A combined scanning tunneling microscopy and density functional theory study

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

Liu, Ping; An, Wei; Stacchiola, Dario

2015-10-16

Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of Cu xO/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on Cu xO/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on themore » Cu xO rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of Cu xO/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on Cu xO/Cu(111), but being able to accelerate the activation of CO 2. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.« less

Study of positron annihilation with core electrons at the clean and oxygen covered Ag(001) surface

NASA Astrophysics Data System (ADS)

Joglekar, P.; Shastry, K.; Olenga, A.; Fazleev, N. G.; Weiss, A. H.

2013-03-01

In this paper we present measurements of the energy spectrum of electrons emitted as a result of Positron Annihilation Induce Auger Electron Emission from a clean and oxygen covered Ag (100) surface using a series of incident beam energies ranging from 20 eV down to 2 eV. A peak was observed at ~ 40 eV corresponding to the N23VV Auger transition in agreement with previous PAES studies. Experimental results were investigated theoretically by calculations of positron states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the clean and oxygen covered Ag(100) surface. An ab-initio investigation of stability and associated electronic properties of different adsorption phases of oxygen on Ag(100) has been performed on the basis of density functional theory and using DMOl3 code. The computed positron binding energy, positron surface state wave function, and positron annihilation probabilities of surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, elemental content, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data. This work was supported in part by the National Science Foundation Grant # DMR-0907679.

Ultrastructure of the surface structures and haptor of Empleurosoma pyriforme (Ancyrocephalinae; Monopisthocotylea: Monogenea) from the gills of the teleost fish Therapon jarbua.

PubMed

Ramasamy, P; Brennan, G P

2000-02-01

Infections with Empleurosoma pyriforme occur between successive secondary gill lamellae on both sides of the primary lamella of Therapon jarbua. The haptoral disc bears two pairs of anchors and a pair of connecting transverse bars. The attachment of the parasite to the host gill causes inflammation, erosion and degeneration of the gill epithelia. The ventral anchors consist of an inner core of irregularly arranged, electron-dense fibrils and a smooth outer core of electron-lucent fibrils, whereas the surface of the dorsal anchors is ridged. Both the dorsal and the ventral anchors may be extended or withdrawn. The connecting transverse bars consist of longitudinally arranged fibrils in an electron-dense matrix, whereas the tendons consist of fibrils, supported in a less electron-dense matrix, which interconnect the anchor erector-protractor muscles and the haptor muscles. Two types of perikarya are present. The less common type contain large multivesicular bodies and small electron-dense granules and are located only in the haptor region. The second and more common perikarya are present throughout the body surface. The cytoplasmic syncytium contains numerous electron-dense granules and electron-lucent vesicles. Beneath the syncytium, unicellular epidermal gland cells contain electron-dense granules. Neurones containing numerous electron-dense vesicles are present in the haptor region. Uniciliate presumed sensory receptors are distributed over the body surface. Groups of ciliated sensory structures are present in the forebody. Ciliated and non-ciliated presumed sensory receptors are present in the sleeve cavity of the anchors, on the haptor and in the vicinity of the oral apertures.

Ab initio investigation of barium-scandium-oxygen coatings on tungsten for electron emitting cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Booske, John H.; Morgan, Dane

2010-02-01

Microwave, x-ray, and radio-frequency radiation sources require a cathode emitting electrons into vacuum. Thermionic B-type dispenser cathodes consist of BaxOz coatings on tungsten (W), where the surface coatings lower the W work function and enhance electron emission. The new and promising class of scandate cathodes modifies the B-type surface through inclusion of Sc, and their superior emissive properties are also believed to stem from the formation of a low work function surface alloy. In order to better understand these cathode systems, density-functional theory (DFT)-based ab initio modeling is used to explore the stability and work function of BaxScyOz on W(001) monolayer-type surface structures. It is demonstrated how surface depolarization effects can be calculated easily using ab initio calculations and fitted to an analytic depolarization equation. This approach enables the rapid extraction of the complete depolarization curve (work function versus coverage relation) from relatively few DFT calculations, useful for understanding and characterizing the emitting properties of novel cathode materials. It is generally believed that the B-type cathode has some concentration of Ba-O dimers on the W surface, although their structure is not known. Calculations suggest that tilted Ba-O dimers are the stable dimer surface configuration and can explain the observed work function reduction corresponding to various dimer coverages. Tilted Ba-O dimers represent a new surface coating structure not previously proposed for the activated B-type cathode. The thermodynamically stable phase of Ba and O on the W surface was identified to be the Ba0.25O configuration, possessing a significantly lower Φ value than any of the Ba-O dimer configurations investigated. The identification of a more stable Ba0.25O phase implies that if Ba-O dimers cover the surface of emitting B-type cathodes, then a nonequilibrium steady state must dominate the emitting surface. The identification of a stable and low work function Ba0.25Sc0.25O structure suggests that addition of Sc to the B-type cathode surface could form this alloy structure under operating conditions, leading to improved cathode performance and stability. Detailed comparison to previous experimental results of BaxScyOz on W surface coatings are made to both validate the modeling and aid in interpretation of experimental data. The studies presented here demonstrate that ab initio methods are powerful for understanding the fundamental physics of electron emitting materials systems and can potentially aid in the development of improved cathodes.

Electronic structure and Fermi surface topology of WTe2 in a magnetic field

NASA Astrophysics Data System (ADS)

Krishna, Jyoti; Maitra, T.

2018-05-01

Two dimensional (2D) layered transition metal dichalcogenides (TMDs) have recently become the foremost candidate for future electronic device applications overcoming graphene as latter has no bandgap which limits some of the applications. WTe2 is one such TMD whose magnetoresistance (MR) continue to increase with magnetic field without any indication of saturation. Inspired by this, we have theoretically investigated the material using first principle density functional theory (DFT) approach to study the effect of magnetic field on electronic structure of the compound. The magnetic field is seen to enhance the hole pockets' size along Γ-Z direction, which brings in significant change in the Fermi surface topology.

The study of the modes of Ta-Zr powder mixture non-vacuum electron-beam cladding on the surface of the cp-titanium plates

NASA Astrophysics Data System (ADS)

Samoylenko, V. V.; Lozhkina, E. A.; Polyakov, I. A.; Lenivtseva, O. G.; Ivanchik, I. S.; Matts, O. E.

2016-11-01

The effect of the modes of non-vacuum electron-beam cladding of Ta-Zr powder mixtures on the structure and properties of the layers formed on the surface of cp-titanium were studied. The mode of the electron-beam alloying of titanium with zirconium and tantalum, which ensured the formation of a defect-free layer with a high content of alloying elements was selected. Metallographic examination indicated the presence of a dendritic- and plate-type structure of cladded layers. The microhardness of the layers, formed at the optimum mode, was not changed in the cross section and was equal to 450 HV.

Solar Wind Access to Lunar Polar Craters: Feedback Between Surface Charging and Plasma Expansion

NASA Technical Reports Server (NTRS)

Zimmerman, M. I.; Farrell, W. M.; Stubbs, T. J.; Halekas, J. S.; Jackson, T. L.

2011-01-01

Determining the plasma environment within permanently shadowed lunar craters is critical to understanding local processes such as surface charging, electrostatic dust transport, volatile sequestration, and space weathering. In order to investigate the nature of this plasma environment, the first two-dimensional kinetic simulations of solar wind expansion into a lunar crater with a self-consistent plasma-surface interaction have been undertaken. The present results reveal how the plasma expansion into a crater couples with the electrically-charged lunar surface to produce a quasi-steady wake structure. In particular, there is a negative feedback between surface charging and ambipolar wake potential that allows an equilibrium to be achieved, with secondary electron emission strongly moderating the process. A range of secondary electron yields is explored, and two distinct limits are highlighted in which either surface charging or ambipoiar expansion is responsible for determining the overall wake structure.

Transition in discharge plasma of Hall thruster type in presence of secondary electron emissive surface

NASA Astrophysics Data System (ADS)

Schweigert, I. V.; Yadrenkin, M. A.; Fomichev, V. P.

2017-11-01

Modification of the sheath structure near the emissive plate placed in magnetized DC discharge plasma of Hall thruster type was studied in the experiment and in kinetic simulations. The plate is made from Al2O3 which has enhanced secondary electron emission yield. The energetic electrons emitted by heated cathode provide the volume ionization and the secondary electron emission from the plate. An increase of the electron beam energy leads to an increase of the secondary electron generation, which initiates the transition in sheath structure over the emissive plate.

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces.

PubMed

Hattori, Azusa N; Okamoto, Takeshi; Sadakuni, Shun; Murata, Junji; Oi, Hideo; Arima, Kenta; Sano, Yasuhisa; Hattori, Ken; Daimon, Hiroshi; Endo, Katsuyoshi; Yamauchi, Kazuto

2011-04-01

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.

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

Zhuang, Jinda; Ju, Y. Sungtaek, E-mail: just@seas.ucla.edu

One major challenge in incorporating flexible electronics or optoelectronics on curved surfaces is the requirement of significant stretchability. We report a tunable platform for incorporating flexible and yet non-stretching device layers on a hemisphere. In this configuration, an array of planar petals contractively maps onto the surface of an inflatable hemisphere through elastocapillary interactions mediated by an interface liquid. A mechanical model is developed to elucidate the dependence of the conformality of the petal structures on their elastic modulus and thickness and the liquid surface tension. The modeling results are validated against experimental results obtained using petal structures of differentmore » thicknesses, restoring elastic spring elements of different spring constants, and liquids with different surface tension coefficients. Our platform will enable facile integration of non-stretching electronic and optoelectronic components prepared using established planar fabrication techniques on tunable hemispherical surfaces.« less

A New Technique to Produce Clean and Thin Silicon Films In Situ in a UHV Electron Microscope for TEM-TED Studies of Surfaces

NASA Astrophysics Data System (ADS)

Ozawa, Soh-ichiro; Yamanaka, Akira; Kobayashi, Kunio; Tanishiro, Yasumasa; Yagi, Katsumichi

1990-04-01

A new technique of in situ oxygen gas reaction thinning of Si films at around 750-800°C in an ultrahigh-vacuum electron microscope was developed. The technique produced films as thin as 10 to 20 nm. Such a thin film allows us to observe surface atomic steps, out-of-phase boundaries and {1/7 0}, {1/7 1/7} and {2/7 0} spots from the Si(111)7× 7 surface. These spots were not observed in previous studies, having been masked by strong inelastic scattering. The technique is useful not only for detecting clear diffraction spots of kinematical intensity for surface structure analysis but also for observation of high-resolution plan-view structure images of clean and adsorbed surfaces.

Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

NASA Technical Reports Server (NTRS)

Poppa, H.; Soria, F.

1983-01-01

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.

Localized variations in electronic structure of AlGaN/GaN heterostructures grown by molecular-beam epitaxy

NASA Astrophysics Data System (ADS)

Smith, K. V.; Yu, E. T.; Elsass, C. R.; Heying, B.; Speck, J. S.

2001-10-01

Local electronic properties in a molecular-beam-epitaxy-grown AlxGa1-xN/GaN heterostructure field-effect transistor epitaxial layer structure are probed using depth-resolved scanning capacitance microscopy. Theoretical analysis of contrast observed in scanning capacitance images acquired over a range of bias voltages is used to assess the possible structural origins of local inhomogeneities in electronic structure, which are shown to be concentrated in areas where Ga droplets had formed on the surface during growth. Within these regions, there are significant variations in the local electronic structure that are attributed to variations in both AlxGa1-xN layer thickness and Al composition. Increased charge trapping is also observed in these regions.

Electronic structure of R Sb ( R = Y , Ce, Gd, Dy, Ho, Tm, Lu) studied by angle-resolved photoemission spectroscopy

DOE PAGES

Wu, Yun; Lee, Yongbin; Kong, Tai; ...

2017-07-15

Here, we use high-resolution angle-resolved photoemission spectroscopy (ARPES) and electronic structure calculations to study the electronic properties of rare-earth monoantimonides RSb (R = Y, Ce, Gd, Dy, Ho, Tm, Lu). The experimentally measured Fermi surface (FS) of RSb consists of at least two concentric hole pockets at the Γ point and two intersecting electron pockets at the X point. These data agree relatively well with the electronic structure calculations. Detailed photon energy dependence measurements using both synchrotron and laser ARPES systems indicate that there is at least one Fermi surface sheet with strong three-dimensionality centered at the Γ point. Duemore » to the “lanthanide contraction”, the unit cell of different rare-earth monoantimonides shrinks when changing the rare-earth ion from CeSb to LuSb. This results in the differences in the chemical potentials in these compounds, which are demonstrated by both ARPES measurements and electronic structure calculations. Interestingly, in CeSb, the intersecting electron pockets at the X point seem to be touching the valence bands, forming a fourfold-degenerate Dirac-like feature. On the other hand, the remaining rare-earth monoantimonides show significant gaps between the upper and lower bands at the X point. Furthermore, similar to the previously reported results of LaBi, a Dirac-like structure was observed at the Γ point in YSb, CeSb, and GdSb, compounds showing relatively high magnetoresistance. This Dirac-like structure may contribute to the unusually large magnetoresistance in these compounds.« less

Electronic structure of R Sb ( R = Y , Ce, Gd, Dy, Ho, Tm, Lu) studied by angle-resolved photoemission spectroscopy

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

Wu, Yun; Lee, Yongbin; Kong, Tai

Here, we use high-resolution angle-resolved photoemission spectroscopy (ARPES) and electronic structure calculations to study the electronic properties of rare-earth monoantimonides RSb (R = Y, Ce, Gd, Dy, Ho, Tm, Lu). The experimentally measured Fermi surface (FS) of RSb consists of at least two concentric hole pockets at the Γ point and two intersecting electron pockets at the X point. These data agree relatively well with the electronic structure calculations. Detailed photon energy dependence measurements using both synchrotron and laser ARPES systems indicate that there is at least one Fermi surface sheet with strong three-dimensionality centered at the Γ point. Duemore » to the “lanthanide contraction”, the unit cell of different rare-earth monoantimonides shrinks when changing the rare-earth ion from CeSb to LuSb. This results in the differences in the chemical potentials in these compounds, which are demonstrated by both ARPES measurements and electronic structure calculations. Interestingly, in CeSb, the intersecting electron pockets at the X point seem to be touching the valence bands, forming a fourfold-degenerate Dirac-like feature. On the other hand, the remaining rare-earth monoantimonides show significant gaps between the upper and lower bands at the X point. Furthermore, similar to the previously reported results of LaBi, a Dirac-like structure was observed at the Γ point in YSb, CeSb, and GdSb, compounds showing relatively high magnetoresistance. This Dirac-like structure may contribute to the unusually large magnetoresistance in these compounds.« less

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Correlation study of nanocrystalline carbon doped thin films prepared by a thermionic vacuum arc deposition technique

NASA Astrophysics Data System (ADS)

Dinca-Balan, Virginia; Vladoiu, Rodica; Mandes, Aurelia; Prodan, Gabriel

2017-11-01

The synthesis of Ag, Mg and Si nanocrystalline, embedded in a hydrogen-free amorphous carbon (a-C) matrix, deposited by a high vacuum and free buffer gas technique, were investigated. The films with compact structures and extremely smooth surfaces were prepared using the thermionic vacuum arc method in one electron gun configuration, on glass and silicon substrates. The surface morphology and wettability of the obtained multifunctional thin films were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and free surface energy (FSE) by See System. The results from the TEM measurements show how the Ag, Mg and Si interacted with carbon and the influence these materials have on the thin film structure formation and the grain size distribution. SEM correlated with EDX results reveal a very precise comparative study, regarding the quantity of the elements that morphed into carbides nanostructures. Also, the FSE results prove how different materials in combination with carbon can make changes to the surface properties.

Study of the electronic structure of electron accepting cyano-films: TCNQversusTCNE.

PubMed

Capitán, Maria J; Álvarez, Jesús; Navio, Cristina

2018-04-18

In this article, we perform systematic research on the electronic structure of two closely related organic electron acceptor molecules (TCNQ and TCNE), which are of technological interest due to their outstanding electronic properties. These studies have been performed from the experimental point of view by the use electron spectroscopies (XPS and UPS) and supported theoretically by the use of ab-initio DFT calculations. The cross-check between both molecules allows us to identify the characteristic electronic features of each part of the molecules and their contribution to the final electronic structure. We can describe the nature of the band gap of these materials, and we relate this with the appearance of the shake-up features in the core level spectra. A band bending and energy gap reduction of the aforementioned electronic structure in contact with a metal surface are seen in the experimental results as well in the theoretical calculations. This behavior implies that the TCNQ thin film accepts electrons from the metal substrate becoming a Schottky n-junction.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Laboratory studies of magnetic anomaly effects on electric potential distributions near the lunar surface

NASA Astrophysics Data System (ADS)

Wang, X.; Robertson, S. H.; Horanyi, M.; NASA Lunar Science Institute: Colorado CenterLunar Dust; Atmospheric Studies

2011-12-01

The Moon does not have a global magnetic field, unlike the Earth, rather it has strong crustal magnetic anomalies. Data from Lunar Prospector and SELENE (Kaguya) observed strong interactions between the solar wind and these localized magnetic fields. In the laboratory, a configuration of a horseshoe permanent magnet below an insulating surface is used as an analogue of lunar crustal magnetic anomalies. Plasmas are created above the surface by a hot filament discharge. Potential distributions are measured with an emissive probe and show complex spatial structures. In our experiments, electrons are magnetized with gyro-radii r smaller than the distance from the surface d (r < d) and ions are un-magnetized with r > d. Unlike negative charging on surfaces with no magnetic fields, the surface potential at the center of the magnetic dipole is found close to the plasma bulk potential. The surface charging is dominated by the cold unmagnetized ions, while the electrons are shielded away. A potential minimum is formed between the center of the surface and the bulk plasma, most likely caused by the trapped electrons between the two magnetic mirrors at the cusps. The value of the potential minimum with respect to the bulk plasma potential decreases with increasing plasma density and neutral pressure, indicating that the mirror-trapped electrons are scattered by electron-electron and electron-neutral collisions. The potential at the two cusps are found to be more negative due to the electrons following the magnetic field lines onto the surface.

3-D readout-electronics packaging for high-bandwidth massively paralleled imager

DOEpatents

Kwiatkowski, Kris; Lyke, James

2007-12-18

Dense, massively parallel signal processing electronics are co-packaged behind associated sensor pixels. Microchips containing a linear or bilinear arrangement of photo-sensors, together with associated complex electronics, are integrated into a simple 3-D structure (a "mirror cube"). An array of photo-sensitive cells are disposed on a stacked CMOS chip's surface at a 45.degree. angle from light reflecting mirror surfaces formed on a neighboring CMOS chip surface. Image processing electronics are held within the stacked CMOS chip layers. Electrical connections couple each of said stacked CMOS chip layers and a distribution grid, the connections for distributing power and signals to components associated with each stacked CSMO chip layer.

Instructional Text: The Transition from Page to Screen.

ERIC Educational Resources Information Center

Kerr, Stephen T.

1986-01-01

Discusses the types of problems that arise when text is presented in electronic form: (1) surface design, which involves typography, layout, graphics and illustrations, and the quality of language; and (2) interface design, which is manifested on the levels of immediate surface of the text, internal structure, and external structure. (SKC)

Electron and positron states in HgBa2CuO4

NASA Astrophysics Data System (ADS)

Barbiellini, B.; Jarlborg, T.

1994-08-01

Local-density-calculations of the electronic structure of HgBa2CuO4 have been performed with the self-consistent linear muffin-tin orbital method. The positron-density distribution and its sensitivity due to different potentials are calculated. The annihilation rates are computed in order to study the chemical bonding and to predict the Fermi-surface signal. Comparisons are made with previous calculations on other high-Tc copper oxides concerning the Fermi-surface properties and electron-positron overlap. We discuss the possibility of observing the Fermi surface associated with the Cu-O planes in positron-annihilation experiments.

Growth Twinning and Generation of High-Frequency Surface Nanostructures in Ultrafast Laser-Induced Transient Melting and Resolidification.

PubMed

Sedao, Xxx; Shugaev, Maxim V; Wu, Chengping; Douillard, Thierry; Esnouf, Claude; Maurice, Claire; Reynaud, Stéphanie; Pigeon, Florent; Garrelie, Florence; Zhigilei, Leonid V; Colombier, Jean-Philippe

2016-07-26

The structural changes generated in surface regions of single crystal Ni targets by femtosecond laser irradiation are investigated experimentally and computationally for laser fluences that, in the multipulse irradiation regime, produce sub-100 nm high spatial frequency surface structures. Detailed experimental characterization of the irradiated targets combining electron back scattered diffraction analysis with high-resolution transmission electron microscopy reveals the presence of multiple nanoscale twinned domains in the irradiated surface regions of single crystal targets with (111) surface orientation. Atomistic- and continuum-level simulations performed for experimental irradiation conditions reproduce the generation of twinned domains and establish the conditions leading to the formation of growth twin boundaries in the course of the fast transient melting and epitaxial regrowth of the surface regions of the irradiated targets. The observation of growth twins in the irradiated Ni(111) targets provides strong evidence of the role of surface melting and resolidification in the formation of high spatial frequency surface structures. This also suggests that the formation of twinned domains can be used as a sensitive measure of the levels of liquid undercooling achieved in short pulse laser processing of metals.

Ion-bombardment of nickel (110) at elevated temperature

NASA Astrophysics Data System (ADS)

Peddinti, Vijay Kumar

The goal of this thesis is to study the behavior of ion-induced defects at the Y point on the Ni (110) surface at elevated temperatures. The electronic structure of the surface is examined using inverse photoemission spectroscopy (IPES), and the geometric structure is observed using low energy electron diffraction (LEED). These measurements lead to a better understanding of the surface properties. The clean Ni (110) surface exhibits a peak ˜ 2.6 eV above the Fermi level, indicating an unoccupied surface state near the Y point of the surface Brillouin zone (SBZ). Defects are induced by low energy ion bombardment at various temperatures, which result in a decrease of the peak intensity. The surface state eventually disappears when bombarded for longer times. We also observed that the surface heals faster when the crystal is being simultaneously sputtered and annealed at higher versus lower temperature. Finally the data for annealing while sputtering versus annealing after sputtering does not seem to exhibit much difference.

Quantum Chemical Study of Water Adsorption on the Surfaces of SrTiO3 Nanotubes.

PubMed

Bandura, Andrei V; Kuruch, Dmitry D; Evarestov, Robert A

2015-07-20

We have studied the adsorption of water molecules on the inner and outer surfaces of nanotubes generated by rolling (001) layers of SrTiO3 cubic crystals. The stability and the atomic and electronic structures of the adsorbed layers are determined by using hybrid density functional theory. The absorption energy and the preferred adsorbate structure are essentially governed by the nature of the surface of the nanotube. Dissociative adsorption prevails on the outer nanotube surfaces. The stability of the adsorbed layers on the inner surfaces is related to the possibility of the formation of hydrogen bonds between water molecules and surface oxygen atoms, and depends on the surface curvature. The presence of water molecules on the inner surface of the nanotubes leads to an increase of the electronic band gap. Externally TiO2 -terminated nanotubes could be used for the photocatalytic decomposition of water by ultraviolet radiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy

PubMed Central

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H.

2014-01-01

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material’s electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier–carrier scatterings which are mirrored in the energy of material’s secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces. PMID:24469803

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy.

PubMed

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H

2014-02-11

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material's electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier-carrier scatterings which are mirrored in the energy of material's secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces.

Localized versus itinerant states created by multiple oxygen vacancies in SrTiO3

NASA Astrophysics Data System (ADS)

Jeschke, Harald O.; Shen, Juan; Valentí, Roser

2015-02-01

Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti {{t}2g} states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.

Epitaxial Growth of an Organic p-n Heterojunction: C60 on Single-Crystal Pentacene.

PubMed

Nakayama, Yasuo; Mizuno, Yuta; Hosokai, Takuya; Koganezawa, Tomoyuki; Tsuruta, Ryohei; Hinderhofer, Alexander; Gerlach, Alexander; Broch, Katharina; Belova, Valentina; Frank, Heiko; Yamamoto, Masayuki; Niederhausen, Jens; Glowatzki, Hendrik; Rabe, Jürgen P; Koch, Norbert; Ishii, Hisao; Schreiber, Frank; Ueno, Nobuo

2016-06-01

Designing molecular p-n heterojunction structures, i.e., electron donor-acceptor contacts, is one of the central challenges for further development of organic electronic devices. In the present study, a well-defined p-n heterojunction of two representative molecular semiconductors, pentacene and C60, formed on the single-crystal surface of pentacene is precisely investigated in terms of its growth behavior and crystallographic structure. C60 assembles into a (111)-oriented face-centered-cubic crystal structure with a specific epitaxial orientation on the (001) surface of the pentacene single crystal. The present experimental findings provide molecular scale insights into the formation mechanisms of the organic p-n heterojunction through an accurate structural analysis of the single-crystalline molecular contact.

Shift of semimetal-semiconductor bond direction on “0 1 1” to “1 1 1” Bismuth quazi-two-dimension system

NASA Astrophysics Data System (ADS)

Yazdani, Ahmad; Hamreh, Sajad

2018-03-01

The electronic structure of the nanocrystallines and quasi-two-dimensional systems strongly impressed by the thermodynamic- behavior mainly due to excess of hidden surface free energy. Therefore, the stability of crystalline structure’s change could be related to band-offset of bond rupturing of atomic displacements. whereas for the electronic-structure of "Bi" it seams the competition of L.S and bond exchange should be effectively dominated. Besides all of the characters behave spatial like strong sensitive oxidation here it is supposed that strong correlated electronic structure in the absence of oxygen is resulted on direction of redistribution of surface chemical bond formation before any reconstructive structure. Where • The metallic direction of electronic structure “0 1 1” is changed to “1 1 1” semiconductor direction. • the effect of L.S is more evident on the local density of state while it is not observable around the fermi level. • Strong effect of spin-orbit interaction on splitting of the valance to nearly conduction band around the fermi level is more evident.

Sustainable resource recovery and energy conversion processes using microbial electrochemical technologies

NASA Astrophysics Data System (ADS)

Yates, Matthew D.

Microbial Electrochemical Technologies (METs) are emerging technological platforms for the conversion of waste into usable products. METs utilize naturally occurring bacteria, called exoelectrogens, capable of transferring electrons to insoluble terminal electron acceptors. Electron transfer processes in the exoelectrogen Geobacter sulfurreducens were exploited here to develop sustainable processes for synthesis of industrially and socially relevant end products. The first process examined was the removal of soluble metals from solution to form catalytic nanoparticles and nanoporous structures. The second process examined was the biocatalytic conversion of electrons into hydrogen gas using electrons supplied directly to an electrode. Nanoparticle formation is desirable because materials on the nanoscale possess different physical, optical, electronic, and mechanical properties compared to bulk materials. In the first process, soluble palladium was used to form catalytic palladium nanoparticles using extracellular electron transfer (EET) processes of G. sulfurreducens, typically the dominant member of mixedculture METs. Geobacter cells reduced the palladium extracellularly using naturally produced pili, which provided extracellular adsorption and reduction sites to help delay the diffusion of soluble metals into the cell. The extracellular reduction prevented cell inactivation due to formation of intracellular particles, and therefore the cells could be reused in multiple palladium reduction cycles. A G. sulfurreducens biofilm was next investigated as a biotemplate for the formation of a nanoporous catalytic palladium structure. G. sulfurreducens biofilms have a dense network of pili and extracellular cytochromes capable of high rates of electron transfer directly to an electrode surface. These pili and cytochromes provide a dense number of reduction sites for nanoparticle formation without the need for any synthetic components. The cells within the biofilm also can act as natural agents for preventing agglomeration of nanoparticles, and subsequent decrease of active surface area, on the electrode surface. The cell template was carbonized and removed via thermal treatments, leaving a catalytically active mesoporous palladium structure. The biotemplated mesoporous structure had a high surface area composed of nanoparticles, and a high pore volume and surface area. The biotemplated porous structure also exhibited an increased catalytic activity compared to an electroplated palladium electrode and an electrode coated with synthetically produced palladium nanoparticles attached to the surface with a Nafion binder. The biotemplated mesoporous structure was found to be an alternative process to form a porous structure directly on an electrode using only materials and processes that naturally occur in G. sulfurreducens biofilms. Biotemplated catalytic structures are an alternative method to form a porous structure with high catalytic activity without using any synthetic compounds. However, their uses in large scale processes require that the catalyst layer be durable. The electrochemical and mechanical stability of biotemplated mesoporous structures was tested on different support materials (polished graphite, carbon paper, carbon cloth, and stainless steel) subjected to electrochemical and/or mechanical stress. Carbon paper was found to withstand the most electrochemical and mechanical stress of the four different support materials tested. Polished graphite was able to withstand electrochemical stress, but deteriorated under a combination of electrochemical and mechanical stress. Different readily available and inexpensive polymers (polyaniline and polydimethylsiloxane) were also tested against a widely used polymer (NafionRTM) to stabilize the palladium catalyst on the polished graphite surface. The polyaniline was the most effective binder because it enhanced the catalytic activity and could be electropolymerized around the catalyst, giving the greatest amount of control over the thickness of the polymer layer. The second process studied used exoelectrogenic bacteria in METs for the conversion of electrons to hydrogen via water electrolysis in a biocathodic system. Naturally occurring biocatalytic cell material on the cathode surface was used to lower the cathode overpotential. Different cell cultures ( G. sulfurreducens, Methanosarcina barkeri, and Escherichia coli) were tested for their effect on hydrogen formation using electrons supplied to an insoluble electrode. The mode of hydrogen production was investigated by monitoring hydrogen production over three to five months using G. sulfurreducens biofilms (pregrown under anodic conditions with acetate) that were: (1) not supplied with an organic carbon source for cell growth and maintenance, (2) killed with ethanol, or (3) supplied with lactate, an organic carbon source and electron donor for G. sulfurreducens. Hydrogen was produced at a rate 10--20 times higher over five months in reactors that were either not given organic carbon or killed with ethanol, compared to reactors with lactate added. The methanogen, M. barkeri, was also tested as a biocatalyst because it is able to grow autotrophically. However, M. barkeri cells did not grow in the reactor with the electrode potential poised, based on the lack of evidence for methane production. Despite the lack of cell activity, the rate of hydrogen production with M. barkeri was similar to the rate observed in killed G. sulfurreducens reactors. The addition of E. coli, a non-exoelectrogenic bacteria, resulted in an initial elevated hydrogen gas production, but hydrogen production rates similar to background levels after three months. No cells were detected on the electrode surfaces after five months using scanning electron microscopy and unique metals, such as iron, nickel, cobalt, and zinc, were detected on the electrode surfaces exposed to cells. The identifiable peptides extracted from the electrodes were found to be derived primarily from metalloproteins produced by G. sulfurreducens and M. barkeri cells. These findings show that hydrogen can be produced in a biocathodic system by abiotic cell material attached to a graphite electrode surface and that it does not require electron uptake by living cells.

The influence of photoelectron processes in a semiconductor substrate on the adsorption of polycationic and polyanionic molecules

NASA Astrophysics Data System (ADS)

Stetsyura, S. V.; Kozlowski, A. V.

2017-03-01

White-light illumination during the adsorption of polyanionic molecules of glucose oxidase (GO x ) enzyme on the surface of p-Si/SiO2/polyethylenimine structure leads to a threefold decrease in the surface concentration of GO x molecules. Same illumination during the GO x adsorption on the n-Si/SiO2/PEI structure leads to a sevenfold increase in the surface concentration of enzyme molecules. Changes in the amount of adsorbed GO x molecules depending on the intensity of irradiation are explained by electron transfer processes and recharging of electronic states at the Si/SiO2 interface and within SiO2 layer.

Fermi Surface as a Driver for the Shape-Memory Effect in AuZn

NASA Astrophysics Data System (ADS)

Lashley, Jason

2005-03-01

Martensites are materials that undergo diffusionless, solid-state transitions. The martensitic transition yields properties that depend on the history of the material and if reversible can allow it to recover its previous shape after plastic deformation. This is known as the shape-memory effect (SME). We have succeeded in identifying the operative electronic mechanism responsible for the martensitic transition in the shape-memory alloy AuZn by using Fermi-surface measurements (de Haas-van Alphen oscillations) and band-structure calculations. Our findings suggest that electronic band structure gives rise to special features on the Fermi surface that is important to consider in the design of SME alloys.

Fabrication of frequency selective surface for band stop IR-filter

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

Mishra, Akshita, E-mail: akshitamishra27@gmail.com; Sudheer,; Tiwari, P.

2016-05-23

Fabrication and characterization of frequency selective surfaces (FSS) on silicon dioxide/ silicon is reported. Electron beam lithography based techniques are used for the fabrication of periodic slot structure in tungsten layer on silicon dioxide/silicon. The fabrication process consists of growth of SiO{sub 2} on silicon, tungsten deposition, electron beam lithography, and wet etching of tungsten. The optical characterization of the structural pattern was carried out using fourier transform infrared spectroscopy (FTIR). The reflectance spectra clearly show a resonance peak at 9.09 µm in the mid infrared region. This indicates that the patterned surface acts as band stop filter in the mid-infraredmore » region.« less

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Synchrotron studies of top-down grown silicon nanowires

NASA Astrophysics Data System (ADS)

Turishchev, S. Yu.; Parinova, E. V.; Nesterov, D. N.; Koyuda, D. A.; Sivakov, V.; Schleusener, A.; Terekhov, V. A.

2018-06-01

Morphology of the top-down grown silicon nanowires obtained by metal-assisted wet-chemical approach on silicon substrates with different resistance were studied by scanning electron microscopy. Obtained arrays of compact grown Si nanowires were a subject for the high resolution electronic structures studies by X-ray absorption near edge structure technique performed with the usage of high intensity synchrotron radiation of the SRC storage ring of the University of Wisconsin-Madison. The different oxidation rates were found by investigation of silicon atoms local surrounding specificity of the highly developed surface and near surface layer that is not exceeded 70 nm. Flexibility of the wires arrays surface morphology and its composition is demonstrated allowing smoothly form necessary surface oxidation rate and using Si nanowires as a useful matrixes for a wide range of further functionalization.

Scanning electron microscope investigation of the structural growth in thick sputtered coatings

NASA Technical Reports Server (NTRS)

Spalvins, T.

1975-01-01

Sputtered S-Monel, silver, and 304 stainless steel coatings and molybdenum disulfide coatings were deposited on mica and metal substrates with various surface finishes to investigate the structural growth of the coating by scanning electron microscopy. The geometry and the surface morphology of the nodules are characterized. Compositional changes within the coating were analyzed by energy dispersive X-ray analysis. Defects in the surface finish act as preferential nucleation sites and form isolated overlapping and complex nodules and various unusual surface overgrowths on the coating. The nodule boundaries are very vulnerable to chemical etching and these nodules do not disappear after full annealing. Further, they have undesirable effects on mechanical properties; cracks are initiated at the nodules when the coating is stressed by mechanical forces.

Heterogeneous catalysis with lasers

NASA Astrophysics Data System (ADS)

George, T. F.

1986-06-01

Theoretical techniques have been developed to describe a variety of laser-induced molecular rate processes occurring at solid surfaces which are involved in heterogeneous catalysis. Such processes include adsorption, migration, chemical reactions and desorption. The role of surface phonons in laser-selective processes and laser heating has been analyzed. The importance of electronic degrees of freedom has been considered for semiconductor and metal substrates, with special emphasis on the laser excitation of surface states. Surface-modified photochemistry has also been investigated, where the effect of a metal surface on the resonance fluorescence spectrum of a laser-driven atom/molecule has been assessed by means of surface-dressed optical Bloch equations. It is seen that the spectrum can be significantly different from the gas-phase case. Two related gas-surface collision processes have also been studied. First, the feasibility of the formation of the electron-hole pairs in a semiconductor by vibrationally excited molecules has been explored. Second, charge transfer in ion-surface collisions has been examined for both one-electron and two-electron transfer processes. Work has been initiated on microstructures and rough structures, including clusters and surface gratings.

Structure-phase state and mechanical properties of surface layers in titanium nikelide single crystals after shock mechanical treatment

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

Surikova, N., E-mail: surikova@ispms.tsc.ru; Panin, V., E-mail: paninve@ispms.tsc.ru; Vlasov, I.

2015-10-27

The influence of ultrasonic shock surface treatment (USST) on refine structure and mechanical characteristics of surface layers and deformation behaviour of volume samples of TiNi(Fe, Mo) shape memory effect alloy single crystals is studied using optical and transmission electron microscope, X-ray diffraction, nanoindentation, mechanical attrition testing and experiments on uniaxial tension.

Structure-phase state and mechanical properties of surface layers in titanium nikelide single crystals after shock mechanical treatment

NASA Astrophysics Data System (ADS)

Surikova, N.; Panin, V.; Vlasov, I.; Narkevich, N.; Surikov, N.; Tolmachev, A.

2015-10-01

The influence of ultrasonic shock surface treatment (USST) on refine structure and mechanical characteristics of surface layers and deformation behaviour of volume samples of TiNi(Fe, Mo) shape memory effect alloy single crystals is studied using optical and transmission electron microscope, X-ray diffraction, nanoindentation, mechanical attrition testing and experiments on uniaxial tension.

Theoretical aspects of studies of high coverage oxidation of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.

2010-10-01

The study of adsorption of oxygen on transition metal surface is important for the understanding of oxidation, heterogeneous catalysis, and metal corrosion. The structures formed on transition metal surfaces vary from simple adlayers of chemisorbed oxygen to oxygen diffusion into the sub-surface region and the formation of oxides. In this work we present the results of an ab-initio investigation of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Calculations are performed for various high coverage missing row structures ranging between 0.50 and 1.50 ML oxygen coverage. Calculations are also performed for the on-surface adsorption of oxygen on the unreconstructed Cu(001) surface for coverages up to one monolayer to use for comparison. The geometry of the surfaces with adsorbed oxygen is fully optimized. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy.

Surface plasmon induced direct detection of long wavelength photons.

PubMed

Tong, Jinchao; Zhou, Wei; Qu, Yue; Xu, Zhengji; Huang, Zhiming; Zhang, Dao Hua

2017-11-21

Millimeter and terahertz wave photodetectors have long been of great interest due to a wide range of applications, but they still face challenges in detection performance. Here, we propose a new strategy for the direct detection of millimeter and terahertz wave photons based on localized surface-plasmon-polariton (SPP)-induced non-equilibrium electrons in antenna-assisted subwavelength ohmic metal-semiconductor-metal (OMSM) structures. The subwavelength OMSM structure is used to convert the absorbed photons into localized SPPs, which then induce non-equilibrium electrons in the structure, while the antenna increases the number of photons coupled into the OMSM structure. When the structure is biased and illuminated, the unidirectional flow of the SPP-induced non-equilibrium electrons forms a photocurrent. The energy of the detected photons is determined by the structure rather than the band gap of the semiconductor. The detection scheme is confirmed by simulation and experimental results from the devices, made of gold and InSb, and a room temperature noise equivalent power (NEP) of 1.5 × 10 -13 W Hz -1/2 is achieved.

Computational modeling of the effect of external electron injection into a direct-current microdischarge

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

Panneer Chelvam, Prem Kumar; Raja, Laxminarayan L.

2015-12-28

Electron emission from the electrode surface plays an important role in determining the structure of a direct-current microdischarge. Here we have developed a computational model of a direct-current microdischarge to study the effect of external electron injection from the cathode surface into the discharge to manipulate its properties. The model provides a self-consistent, multi-species, multi-temperature fluid representation of the plasma. A microdischarge with a metal-insulator-metal configuration is chosen for this study. The effect of external electron injection on the structure and properties of the microdischarge is described. The transient behavior of the microdischarge during the electron injection is examined. Themore » nonlinearities in the dynamics of the plasma result in a large increase of conduction current after active electron injection. For the conditions simulated a switching time of ∼100 ns from a low-current to high-current discharge state is realized.« less

Theoretical predictions for hot-carrier generation from surface plasmon decay

PubMed Central

Sundararaman, Ravishankar; Narang, Prineha; Jermyn, Adam S.; Goddard III, William A.; Atwater, Harry A.

2014-01-01

Decay of surface plasmons to hot carriers finds a wide variety of applications in energy conversion, photocatalysis and photodetection. However, a detailed theoretical description of plasmonic hot-carrier generation in real materials has remained incomplete. Here we report predictions for the prompt distributions of excited ‘hot’ electrons and holes generated by plasmon decay, before inelastic relaxation, using a quantized plasmon model with detailed electronic structure. We find that carrier energy distributions are sensitive to the electronic band structure of the metal: gold and copper produce holes hotter than electrons by 1–2 eV, while silver and aluminium distribute energies more equitably between electrons and holes. Momentum-direction distributions for hot carriers are anisotropic, dominated by the plasmon polarization for aluminium and by the crystal orientation for noble metals. We show that in thin metallic films intraband transitions can alter the carrier distributions, producing hotter electrons in gold, but interband transitions remain dominant. PMID:25511713

First principles studies on anatase surfaces

NASA Astrophysics Data System (ADS)

Selcuk, Sencer

TiO2 is one of the most widely studied metal oxides from both the fundamental and the technological points of view. A variety of applications have already been developed in the fields of energy production, environmental remediation, and electronics. Still, it is considered to have a high potential for further improvement and continues to be of great interest. This thesis describes our theoretical studies on the structural and electronic properties of anatase surfaces, and their (photo)chemical behavior. Recently much attention has been focused on anatase crystals synthesized by hydrofluoric acid assisted methods. These crystals exhibit a high percentage of {001} facets, generally considered to be highly reactive. We used first principles methods to investigate the structure of these facets, which is not yet well understood. Our results suggest that (001) surfaces exhibit the bulk-terminated structure when in contact with concentrated HF solutions. However, 1x4-reconstructed surfaces, as observed in UHV, become always more stable at the typical temperatures used to clean the as-prepared crystals in experiments. Since the reconstructed surfaces are only weakly reactive, we predict that synthetic anatase crystals with dominant {001} facets should not exhibit enhanced photocatalytic activity. Understanding how defects in solids interact with external electric fields is important for technological applications such as memristor devices. We studied the influence of an external electric field on the formation energies and diffusion barriers of the surface and the subsurface oxygen vacancies at the anatase (101) surface from first principles. Our results show that the applied field can have a significant influence on the relative stabilities of these defects, whereas the effect on the subsurface-to-surface defect migration is found to be relatively minor. Charge carriers play a key role in the transport properties and the surface chemistry of TiO2. Understanding their behavior is essential for further improving the technologically relevant features of this material. We used first principles simulations to study the dynamical behavior of excess electrons near the anatase (101) and (001) surfaces, and their interfaces with water. Excess electrons prefer localizing on the (101) surface, also triggering water dissociation on this surface, while they strongly avoid the (001) surface.

Electron solvation and localization at interfaces

NASA Astrophysics Data System (ADS)

Harris, Charles B.; Szymanski, Paul; Garrett-Roe, Sean; Miller, Andre D.; Gaffney, Kelly J.; Liu, Simon H.; Bezel, Ilya

2003-12-01

Two-photon photoemission of thiolate/Ag(111), nitrile/Ag(111), and alcohol/Ag(111) interfaces elucidates electron solvation and localization in two dimensions. For low coverages of thiolates on Ag(111), the occupied (HOMO) and unoccupied (LUMO) electronic states of the sulfer-silver bond are localized due to the lattice gas structure of the adsorbate. As the coverage saturates and the adsorbate-adsorbate nearest neighbor distance decreases, the HOMO and LUMO delocalize across many adsorbate molecules. Alcohol- and nitrile-covered Ag(111) surfaces solvate excess image potential state (IPS) electrons. In the case of alcohol-covered surfaces, this solvation is due to a shift in the local workfunction of the surface. For two-monolayer coverages of nitriles/Ag(111), localization accompanies solvation of the IPS. The size of the localized electron can be estimated by Fourier transformation of the wavefunction from momentum- to position-space. The IPS electron localizes to 15 +/- 4 angstroms full-width at half maximum in the plane of the surface, i.e., to a single lattice site.

Facile preparation of dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil for application as a SERS-substrate

NASA Astrophysics Data System (ADS)

Yi, Zao; Tan, Xiulan; Niu, Gao; Xu, Xibin; Li, Xibo; Ye, Xin; Luo, Jiangshan; Luo, Binchi; Wu, Weidong; Tang, Yongjian; Yi, Yougen

2012-05-01

Dendritic Ag-Pd bimetallic nanostructures have been synthesized on the surface of Cu foil via a multi-stage galvanic replacement reaction (MGRR) of Ag dendrites in a Na2PdCl4 solution. After five stages of replacement reaction, one obtained structures with protruding Ag-Pd flakes; these will mature into many porous structures with a few Ag atoms that are left over dendrites. The dendritic Ag-Pd bimetallic nanostructures were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), selected area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS). The morphology of the products strongly depended on the stage of galvanic replacement reaction and reaction temperature. The morphology and composition-dependent surface-enhanced Raman scattering (SERS) of the as-synthesized Ag-Pd bimetallic nanostructures were investigated. The effectiveness of these dendritic Ag-Pd bimetallic nanostructures on the surface of Cu foil as substrates toward SERS detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. The results indicate that as-synthesized dendritic Ag-Pd bimetallic nanostructures are good candidates for SERS spectroscopy.

Effect of abrasive water jet on the structure of the surface layer of Al-Mg alloy

NASA Astrophysics Data System (ADS)

Tabatchikova, T. I.; Tereshchenko, N. A.; Yakovleva, I. L.; Gudnev, N. Z.

2017-09-01

Optical, scanning, and transmission electron microscopy methods, and X-ray diffraction analysis have been used to study the changes in the structure and the microhardness in the surface layer of the Al-Mg (5.8-6.8 wt %) alloy after water jet cutting. The dislocation density, the sizes of coherent scattering regions, and microdistortions have been determined. The transformation of the fine structure has been revealed in the displacement from the alloy volume to the abrasive-waterjet cutting surface.

Structural changes caused by H 2 adsorption on the Si(111)7 × 7 surface

NASA Astrophysics Data System (ADS)

Wolff, S. H.; Wagner, S.; Gibson, J. M.; Loretto, D.; Robinson, I. K.; Bean, J. C.

1990-12-01

Structural changes caused by the adsorption of molecular hydrogen adsorption onto the Si(111)7 × 7 surface reconstruction are quantified using the first structure parameter refinement on transmission electron diffraction (TED) data. We find that initial adsorption of molecular hydrogen onto the Si(111)7 × 7 surface causes a preferential decrease in the occupancy of the center adatoms. Further adsorption of hydrogen results in the breaking of the dimer bonds and the removal of the corner adatoms.

On-surface formation of one-dimensional polyphenylene through Bergman cyclization.

PubMed

Sun, Qiang; Zhang, Chi; Li, Zhiwen; Kong, Huihui; Tan, Qinggang; Hu, Aiguo; Xu, Wei

2013-06-12

On-surface fabrication of covalently interlinked conjugated nanostructures has attracted significant attention, mainly because of the high stability and efficient electron transport ability of these structures. Here, from the interplay of scanning tunneling microscopy imaging and density functional theory calculations, we report for the first time on-surface formation of one-dimensional polyphenylene chains through Bergman cyclization followed by radical polymerization on Cu(110). The formed surface nanostructures were further corroborated by the results for the ex situ-synthesized molecular product after Bergman cyclization. These findings are of particular interest and importance for the construction of molecular electronic nanodevices on surfaces.

The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

PubMed

Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

2005-03-01

The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and substrate bands. Significant implications are described for density-functional calculations of through-molecule electron transport in molecular electronics.

Enhanced superconductivity in the high pressure phase of SnAs studied from first principles

NASA Astrophysics Data System (ADS)

Sreenivasa Reddy, P. V.; Kanchana, V.; Millichamp, T. E.; Vaitheeswaran, G.; Dugdale, S. B.

2017-01-01

First principles calculations are performed using density functional theory and density functional perturbation theory for SnAs. Total energy calculations show the first order phase transition from an NaCl structure to a CsCl one at around 37 GPa, which is also confirmed from enthalpy calculations and agrees well with experimental work. Calculations of the phonon structure and hence the electron-phonon coupling, λep, and superconducting transition temperature, Tc, across the phase diagram are performed. These calculations give an ambient pressure Tc, in the NaCl structure, of 3.08 K, in good agreement with experiment whilst at the transition pressure, in the CsCl structure, a drastically increased value of Tc = 12.2 K is found. Calculations also show a dramatic increase in the electronic density of states at this pressure. The lowest energy acoustic phonon branch in each structure also demonstrates some softening effects. Electronic structure calculations of the Fermi surface in both phases are presented for the first time as well as further calculations of the generalised susceptibility with the inclusion of matrix elements. These calculations indicate that the softening is not derived from Fermi surface nesting and it is concluded to be due to a wavevector-dependent enhancement of the electron-phonon coupling.

Induced Infiltration of Hole-Transporting Polymer into Photocatalyst for Staunch Polymer-Metal Oxide Hybrid Solar Cells.

PubMed

Park, Jong Hwan; Jung, Youngsuk; Yang, Yooseong; Shin, Hyun Suk; Kwon, Soonchul

2016-10-05

For efficient solar cells based on organic semiconductors, a good mixture of photoactive materials in the bulk heterojunction on the length scale of several tens of nanometers is an important requirement to prevent exciton recombination. Herein, we demonstrate that nanoporous titanium dioxide inverse opal structures fabricated using a self-assembled monolayer method and with enhanced infiltration of electron-donating polymers is an efficient electron-extracting layer, which enhances the photovoltaic performance. A calcination process generates an inverse opal structure of titanium dioxide (<70 nm of pore diameters) providing three-dimensional (3D) electron transport pathways. Hole-transporting polymers was successfully infiltrated into the pores of the surface-modified titanium dioxide under vacuum conditions at 200 °C. The resulting geometry expands the interfacial area between hole- and electron-transport materials, increasing the thickness of the active layer. The controlled polymer-coating process over titanium dioxide materials enhanced photocurrent of the solar cell device. Density functional theory calculations show improved interfacial adhesion between the self-assembled monolayer-modified surface and polymer molecules, supporting the experimental result of enhanced polymer infiltration into the voids. These results suggest that the 3D inverse opal structure of the surface-modified titanium dioxide can serve as a favorable electron-extracting layer in further enhancing optoelectronic performance based on organic or organic-inorganic hybrid solar cell.

Computational simulation of the effects of oxygen on the electronic states of hydrogenated 3C-porous SiC

PubMed Central

2012-01-01

A computational study of the dependence of the electronic band structure and density of states on the chemical surface passivation of cubic porous silicon carbide (pSiC) was performed using ab initio density functional theory and the supercell method. The effects of the porosity and the surface chemistry composition on the energetic stability of pSiC were also investigated. The porous structures were modeled by removing atoms in the [001] direction to produce two different surface chemistries: one fully composed of silicon atoms and one composed of only carbon atoms. The changes in the electronic states of the porous structures as a function of the oxygen (O) content at the surface were studied. Specifically, the oxygen content was increased by replacing pairs of hydrogen (H) atoms on the pore surface with O atoms attached to the surface via either a double bond (X = O) or a bridge bond (X-O-X, X = Si or C). The calculations show that for the fully H-passivated surfaces, the forbidden energy band is larger for the C-rich phase than for the Si-rich phase. For the partially oxygenated Si-rich surfaces, the band gap behavior depends on the O bond type. The energy gap increases as the number of O atoms increases in the supercell if the O atoms are bridge-bonded, whereas the band gap energy does not exhibit a clear trend if O is double-bonded to the surface. In all cases, the gradual oxygenation decreases the band gap of the C-rich surface due to the presence of trap-like states. PMID:22913486

Electronic Structure of the Metastable Epitaxial Rock-Salt SnSe {111 } Topological Crystalline Insulator

NASA Astrophysics Data System (ADS)

Jin, Wencan; Vishwanath, Suresh; Liu, Jianpeng; Kong, Lingyuan; Lou, Rui; Dai, Zhongwei; Sadowski, Jerzy T.; Liu, Xinyu; Lien, Huai-Hsun; Chaney, Alexander; Han, Yimo; Cao, Michael; Ma, Junzhang; Qian, Tian; Wang, Shancai; Dobrowolska, Malgorzata; Furdyna, Jacek; Muller, David A.; Pohl, Karsten; Ding, Hong; Dadap, Jerry I.; Xing, Huili Grace; Osgood, Richard M.

2017-10-01

Topological crystalline insulators have been recently predicted and observed in rock-salt structure SnSe {111 } thin films. Previous studies have suggested that the Se-terminated surface of this thin film with hydrogen passivation has a reduced surface energy and is thus a preferred configuration. In this paper, synchrotron-based angle-resolved photoemission spectroscopy, along with density functional theory calculations, is used to demonstrate that a rock-salt SnSe {111 } thin film epitaxially grown on Bi2Se3 has a stable Sn-terminated surface. These observations are supported by low-energy electron diffraction (LEED) intensity-voltage measurements and dynamical LEED calculations, which further show that the Sn-terminated SnSe {111 } thin film has undergone a surface structural relaxation of the interlayer spacing between the Sn and Se atomic planes. In sharp contrast to the Se-terminated counterpart, the observed Dirac surface state in the Sn-terminated SnSe {111 } thin film is shown to yield a high Fermi velocity, 0.50 ×106 m /s , which suggests a potential mechanism of engineering the Dirac surface state of topological materials by tuning the surface configuration.

Electronic Structure of the Metastable Epitaxial Rock-Salt SnSe { 111 } Topological Crystalline Insulator

DOE PAGES

Jin, Wencan; Vishwanath, Suresh; Liu, Jianpeng; ...

2017-10-25

Topological crystalline insulators have been recently predicted and observed in rock-salt structure SnSe {111} thin films. Previous studies have suggested that the Se-terminated surface of this thin film with hydrogen passivation has a reduced surface energy and is thus a preferred configuration. In this paper, synchrotron-based angle-resolved photoemission spectroscopy, along with density functional theory calculations, is used to demonstrate that a rock-salt SnSe {111} thin film epitaxially grown on Bi 2Se 3 has a stable Sn-terminated surface. These observations are supported by low-energy electron diffraction (LEED) intensity-voltage measurements and dynamical LEED calculations, which further show that the Sn-terminated SnSe {111}more » thin film has undergone a surface structural relaxation of the interlayer spacing between the Sn and Se atomic planes. In sharp contrast to the Se-terminated counterpart, the observed Dirac surface state in the Sn-terminated SnSe {111} thin film is shown to yield a high Fermi velocity, 0.50 x 10 6 m/s, which suggests a potential mechanism of engineering the Dirac surface state of topological materials by tuning the surface configuration.« less

Surface effect investigation on multipactor in microwave components using the EM-PIC method

NASA Astrophysics Data System (ADS)

Li, Yun; Ye, Ming; He, Yong-Ning; Cui, Wan-Zhao; Wang, Dan

2017-11-01

Multipactor poses a great risk to microwave components in space and its accurate controllable suppression is still lacking. To evaluate the secondary electron emission (SEE) of arbitrary surface states on multipactor, metal samples fabricated with ideal smoothness, random roughness, and micro-structures on the surface are investigated through SEE experiments and multipactor simulations. An accurate quantitative relationship between the SEE parameters and the multipactor discharge threshold in practical components has been established through Electromagnetic Particle-In-Cell (EM-PIC) simulation. Simulation results of microwave components, including the impedance transformer and the coaxial filter, exhibit an intuitive correlation between the critical SEE parameters, varied due to different surface states, and multipactor thresholds. It is demonstrated that it is the surface micro-structures with certain depth and morphology that determine the average yield of secondaries, other than the random surface relieves. Both the random surface relieves and micro-structures have a scattering effect on SEE, and the yield is prone to be identical upon different elevation angles of incident electrons. It possesses a great potential in the optimization and improvement of suppression technology without the exhaustion of the technological parameter.

Electrodeposition of Highly Porous Pt Nanoparticles Studied by Quantitative 3D Electron Tomography: Influence of Growth Mechanisms and Potential Cycling on the Active Surface Area.

PubMed

Ustarroz, Jon; Geboes, Bart; Vanrompay, Hans; Sentosun, Kadir; Bals, Sara; Breugelmans, Tom; Hubin, Annick

2017-05-17

Nanoporous Pt nanoparticles (NPs) are promising fuel cell catalysts due to their large surface area and increased electrocatalytic activity toward the oxygen reduction reaction (ORR). Herein, we report on the influence of the growth mechanisms on the surface properties of electrodeposited Pt dendritic NPs with large surface areas. The electrochemically active surface was studied by hydrogen underpotential deposition (H UPD) and compared for the first time to high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) quantitative 3D electron tomography of individual nanoparticles. Large nucleation overpotential leads to a large surface coverage of roughened spheroids, which provide a large roughness factor (R f ) but low mass-specific electrochemically active surface area (EASA). Lowering the nucleation overpotential leads to highly porous Pt NPs with pores stretching to the center of the structure. At the expense of smaller R f , the obtained EASA values of these structures are in the range of those of large surface area supported fuel cell catalysts. The active surface area of the Pt dendritic NPs was measured by electron tomography, and it was found that the potential cycling in the H adsorption/desorption and Pt oxidation/reduction region, which is generally performed to determine the EASA, leads to a significant reduction of that surface area due to a partial collapse of their dendritic and porous morphology. Interestingly, the extrapolation of the microscopic tomography results in macroscopic electrochemical parameters indicates that the surface properties measured by H UPD are comparable to the values measured on individual NPs by electron tomography after the degradation caused by the H UPD measurement. These results highlight that the combination of electrochemical and quantitative 3D surface analysis techniques is essential to provide insights into the surface properties, the electrochemical stability, and, hence, the applicability of these materials. Moreover, it indicates that care must be taken with widely used electrochemical methods of surface area determination, especially in the case of large surface area and possibly unstable nanostructures, since the measured surface can be strongly affected by the measurement itself.

Ultrastructural Study of Some Pollen Grains of Prairie Flowers

ERIC Educational Resources Information Center

Kozar, Frank

1973-01-01

Discusses the importance of the electron microscope, and in particular the scanning electron microscope, in studying the surface topography, sectional substructures, and patterns of development of pollen grains. The production, dispersal methods, and structure of pollen grains are described and illustrated with numerous electron micrographs. (JR)

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

NASA Astrophysics Data System (ADS)

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

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

Stimulated emission of surface plasmons by electron tunneling in metal-barrier-metal structures

NASA Technical Reports Server (NTRS)

Siu, D. P.; Gustafson, T. K.

1978-01-01

It is shown that correlation currents arising from the superposition of pairs of states on distinct sides of a potential barrier in metal-barrier-metal structures can result in inelastic tunneling through the emission of surface plasmons. Net gain of an externally excited plasmon field is possible.

Electron acceleration by surface plasma waves in double metal surface structure

NASA Astrophysics Data System (ADS)

Liu, C. S.; Kumar, Gagan; Singh, D. B.; Tripathi, V. K.

2007-12-01

Two parallel metal sheets, separated by a vacuum region, support a surface plasma wave whose amplitude is maximum on the two parallel interfaces and minimum in the middle. This mode can be excited by a laser using a glass prism. An electron beam launched into the middle region experiences a longitudinal ponderomotive force due to the surface plasma wave and gets accelerated to velocities of the order of phase velocity of the surface wave. The scheme is viable to achieve beams of tens of keV energy. In the case of a surface plasma wave excited on a single metal-vacuum interface, the field gradient normal to the interface pushes the electrons away from the high field region, limiting the acceleration process. The acceleration energy thus achieved is in agreement with the experimental observations.

Spectromicroscopy measurements of surface morphology and band structure of exfoliated graphene

NASA Astrophysics Data System (ADS)

Knox, Kevin; Locatelli, Andrea; Cvetko, Dean; Mentes, Tevfik; Nino, Miguel; Wang, Shancai; Yilmaz, Mehmet; Kim, Philip; Osgood, Richard; Morgante, Alberto

2011-03-01

Monolayer-thick crystals, such as graphene, are an area of intense interest in condensed matter research. ~However, crystal deformations in these 2D systems are known to adversely affect conductivity and increase local chemical reactivity. Additionally, surface roughness in graphene complicates band-mapping and limits resolution in techniques such as angle resolved photoemission spectroscopy (ARPES), the theory of which was developed for atomically flat surfaces. Thus, an understanding of the surface morphology of graphene is essential to making high quality devices and important for interpreting ARPES results. In this talk, we will describe a non-invasive approach to examining the corrugation in exfoliated graphene using a combination of low energy electron microscopy (LEEM) and micro-spot low energy electron diffraction (LEED). We will also describe how such knowledge of surface roughness can be used in the analysis of ARPES data to improve resolution and extract useful information about the band-structure.

Interplay between structure, stoichiometry, and electron transfer dynamics in SILAR-based quantum dot-sensitized oxides.

PubMed

Wang, Hai; Barceló, Irene; Lana-Villarreal, Teresa; Gómez, Roberto; Bonn, Mischa; Cánovas, Enrique

2014-10-08

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor-acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

Influence of metallic surface states on electron affinity of epitaxial AlN films

NASA Astrophysics Data System (ADS)

Mishra, Monu; Krishna, Shibin; Aggarwal, Neha; Gupta, Govind

2017-06-01

The present article investigates surface metallic states induced alteration in the electron affinity of epitaxial AlN films. AlN films grown by plasma-assisted molecular beam epitaxy system with (30% and 16%) and without metallic aluminium on the surface were probed via photoemission spectroscopic measurements. An in-depth analysis exploring the influence of metallic aluminium and native oxide on the electronic structure of the films is performed. It was observed that the metallic states pinned the Fermi Level (FL) near valence band edge and lead to the reduction of electron affinity (EA). These metallic states initiated charge transfer and induced changes in surface and interface dipoles strength. Therefore, the EA of the films varied between 0.6-1.0 eV due to the variation in contribution of metallic states and native oxide. However, the surface barrier height (SBH) increased (4.2-3.5 eV) adversely due to the availability of donor-like surface states in metallic aluminium rich films.

Electronic structure basis for the extraordinary magnetoresistance in WTe 2

DOE PAGES

Pletikosić, I.; Ali, Mazhar N.; Fedorov, A. V.; ...

2014-11-19

The electronic structure basis of the extremely large magnetoresistance in layered non-magnetic tungsten ditelluride has been investigated by angle-resolved photoelectron spectroscopy. Hole and electron pockets of approximately the same size were found at the Fermi level, suggesting that carrier compensation should be considered the primary source of the effect. The material exhibits a highly anisotropic, quasi one-dimensional Fermi surface from which the pronounced anisotropy of the magnetoresistance follows. As a result, a change in the Fermi surface with temperature was found and a high-density-of-states band that may take over conduction at higher temperatures and cause the observed turn-on behavior ofmore » the magnetoresistance in WTe₂ was identified.« less

Method of doping interconnections for electrochemical cells

DOEpatents

Pal, Uday B.; Singhal, Subhash C.; Moon, David M.; Folser, George R.

1990-01-01

A dense, electronically conductive interconnection layer 26 is bonded on a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) forming a layer of oxide particles of at least one of the metals Ca, Sr, Co, Ba or Mg on a part 24 of a first surface of the air electrode 16, (B) heating the electrode structure, (C) applying a halide vapor containing at least lanthanum halide and chromium halide to the first surface and applying a source of oxygen to a second opposite surface of the air electrode so that they contact at said first surface, to cause a reaction of the oxygen and halide and cause a dense lanthanum-chromium oxide structure to grow, from the first electrode surface, between and around the oxide particles, where the metal oxide particles get incoporated into the lanthanum-chromium oxide structure as it grows thicker with time, and the metal ions in the oxide particles diffuse into the bulk of the lanthamum-chromium oxide structure, to provide a dense, top, interconnection layer 26 on top of the air electrode 16. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

Scanning tunneling microscopy of the formation, transformation, and property of oligothiophene self-organizations on graphite and gold surfaces.

PubMed

Yang, Zhi-Yong; Zhang, Hui-Min; Yan, Cun-Ji; Li, Shan-Shan; Yan, Hui-Juan; Song, Wei-Guo; Wan, Li-Jun

2007-03-06

Two alkyl-substituted dual oligothiophenes, quarterthiophene (4T)-trimethylene (tm)-octithiophene (8T) and 4T-tm-4T, were used to fabricate molecular structures on highly oriented pyrolytic graphite and Au(111) surfaces. The resulted structures were investigated by scanning tunneling microscopy. The 4T-tm-8T and 4T-tm-4T molecules self-organize into long-range ordered structures with linear and/or quasi-hexagonal patterns on highly oriented pyrolytic graphite at ambient temperature. Thermal annealing induced a phase transformation from quasi-hexagonal to linear in 4T-tm-8T adlayer. The molecules adsorbed on Au(111) surface in randomly folded and linear conformation. Based on scanning tunneling microscopy results, the structural models for different self-organizations were proposed. Scanning tunneling spectroscopy measurement showed the electronic property of individual molecules in the patterns. These results are significant in understanding the chemistry of molecular structure, including its formation, transformation, and electronic properties. They also help to fabricate oligothiophene assemblies with desired structures for future molecular devices.

Exploring the Electronic Structure and Chemical Homogeneity of Individual Bi2Te3 Nanowires by Nano-Angle-Resolved Photoemission Spectroscopy.

PubMed

Krieg, Janina; Chen, Chaoyu; Avila, José; Zhang, Zeying; Sigle, Wilfried; Zhang, Hongbin; Trautmann, Christina; Asensio, Maria Carmen; Toimil-Molares, Maria Eugenia

2016-07-13

Due to their high surface-to-volume ratio, cylindrical Bi2Te3 nanowires are employed as model systems to investigate the chemistry and the unique conductive surface states of topological insulator nanomaterials. We report on nanoangle-resolved photoemission spectroscopy (nano-ARPES) characterization of individual cylindrical Bi2Te3 nanowires with a diameter of 100 nm. The nanowires are synthesized by electrochemical deposition inside channels of ion-track etched polymer membranes. Core level spectra recorded with submicron resolution indicate a homogeneous chemical composition along individual nanowires, while nano-ARPES intensity maps reveal the valence band structure at the single nanowire level. First-principles electronic structure calculations for chosen crystallographic orientations are in good agreement with those revealed by nano-ARPES. The successful application of nano-ARPES on single one-dimensional nanostructures constitutes a new avenue to achieve a better understanding of the electronic structure of topological insulator nanomaterials.

Theoretical study of porous surfaces derived from graphene and boron nitride

NASA Astrophysics Data System (ADS)

Fabris, G. S. L.; Marana, N. L.; Longo, E.; Sambrano, J. R.

2018-02-01

Porous graphene (PG), graphenylene (GP), inorganic graphenylene (IGP-BN), and porous boron nitride (PBN) single-layer have been studied via periodic density functional theory with a modified B3LYP functional and an all-electron Gaussian basis set. The structural, elastic, electronic, vibrational, and topological properties of the surfaces were investigated. The analysis showed that all porous structures had a nonzero band gap, and only PG exhibited a non-planar shape. All porous structures seem to be more susceptible to longitudinal deformation than their pristine counterparts, and GP exhibits a higher strength than graphene in the transversal direction. In addition, the electron densities of GP and IGP-BN are localized closer to the atoms, in contrast with PG and PBN, whose charge density is shifted towards the pore center; this property could find application in various fields, such as gas adsorption.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Structure Determination of Au on Pt(111) Surface: LEED, STM and DFT Study

PubMed Central

Krupski, Katarzyna; Moors, Marco; Jóźwik, Paweł; Kobiela, Tomasz; Krupski, Aleksander

2015-01-01

Low-energy electron diffraction (LEED), scanning tunneling microscopy (STM) and density functional theory (DFT) calculations have been used to investigate the atomic and electronic structure of gold deposited (between 0.8 and 1.0 monolayer) on the Pt(111) face in ultrahigh vacuum at room temperature. The analysis of LEED and STM measurements indicates two-dimensional growth of the first Au monolayer. Change of the measured surface lattice constant equal to 2.80 Å after Au adsorption was not observed. Based on DFT, the distance between the nearest atoms in the case of bare Pt(111) and Au/Pt(111) surface is equal to 2.83 Å, which gives 1% difference in comparison with STM values. The first and second interlayer spacing of the clean Pt(111) surface are expanded by +0.87% and contracted by −0.43%, respectively. The adsorption energy of the Au atom on the Pt(111) surface is dependent on the adsorption position, and there is a preference for a hollow fcc site. For the Au/Pt(111) surface, the top interlayer spacing is expanded by +2.16% with respect to the ideal bulk value. Changes in the electronic properties of the Au/Pt(111) system below the Fermi level connected to the interaction of Au atoms with Pt(111) surface are observed.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Photoemission study of the electronic structure and charge density waves of Na₂Ti₂Sb₂O

DOE PAGES

Tan, S. Y.; Jiang, J.; Ye, Z. R.; ...

2015-04-30

The electronic structure of Na₂Ti₂Sb₂O single crystal is studied by photon energy and polarization dependent angle-resolved photoemission spectroscopy (ARPES). The obtained band structure and Fermi surface agree well with the band structure calculation of Na₂Ti₂Sb₂O in the non-magnetic state, which indicates that there is no magnetic order in Na₂Ti₂Sb₂O and the electronic correlation is weak. Polarization dependent ARPES results suggest the multi-band and multi-orbital nature of Na₂Ti₂Sb₂O. Photon energy dependent ARPES results suggest that the electronic structure of Na₂Ti₂Sb₂O is rather two-dimensional. Moreover, we find a density wave energy gap forms below the transition temperature and reaches 65 meV atmore » 7 K, indicating that Na₂Ti₂Sb₂O is likely a weakly correlated CDW material in the strong electron-phonon interaction regime. (author)« less

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.

Surface structure of Bi2Sr2CaCu2O(8+delta) high-temperature superconductors studied using low-energy electron diffraction

NASA Astrophysics Data System (ADS)

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

1988-12-01

The surface structure of Bi2Sr2CaCu2O(8+delta) has been studied using low-energy electron diffraction (LEED). Sharp diffraction spots indicative of a well-ordered surface are observed. The LEED patterns unequivocally show that this type of material preferentially cleaves along the a-b planes of the nearly tetragonal unit cell. A superstructure extending along one of the axes in the a-b plane (b) is found to have a periodicity of 27 + or - 0.5 A, in good agreement with earlier studies of the three-dimensional crystal structure. The superstructure at the surface is nonlocal in character and reflects the long-range superlattice of the bulk along the b axis. Intensity modulations of the diffraction spots oriented along the b axis are also reported and discussed in terms of the cell dimension of the unit cell along the b axis.

Surface-structure sensitivity of CeO 2 nanocrystals in photocatalysis and enhancing the reactivity with nanogold

DOE PAGES

Lei, Wanying; Zhang, Tingting; Gu, Lin; ...

2015-06-19

Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this research, using aberration-corrected scanning transmission electron microscopy (STEM), the atomic surface structures of well-defined one-dimensional (1D) CeO 2 nanorods (NRs) and 3D nanocubes (NCs) are directly visualized at subangstrom resolution. CeO 2 NCs predominantly expose the {100} facet, with {110} and {111} as minor cutoff facets at the respective edges and corners. Notably, the outermost surface layer of the {100} facet is nearly O-terminated. Neither surface relaxations nor reconstructions on {100} are observed, indicating unusual polarity compensation, which is primarily mediated by near-surface oxygen vacancies. The surface of CeOmore » 2 NRs is highly stepped, with the enclosed {110} facet exposing Ce cations and O anions on terraces. On the basis of STEM profile-view imaging and electronic structure analysis, the photoreactivity of CeO2 nanocrystals toward aqueous methyl orange degradation under UV is revealed to be surface-structure-sensitive, following the order: {110} >> {100}. The underlying surface-structure sensitivity can be attributed to the variation in low-coordinate surface cerium cations between {110} and {100} facets. To further enhance light absorption, Au nanoparticles (NPs) are deposited on CeO 2 NRs to form Au/CeO 2 plasmonic nanocomposites, which dramatically promotes the photoreactivity that is Au particle size- and excitation light wavelength-dependent. The mechanisms responsible for the enhancement of photocatalytic activity are discussed, highlighting the crucial role of photoexcited charge carrier transfer.« less

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the electrochemical cycling effect, electrolyte exposure also shows non-negligible influence on cathode surface degradation. These chemical and structural changes of the NMC cathode could contribute to the first-cycle coulombic inefficiency, restrict the charge transfer characteristics and ultimately impact the cell capacity.

Excess electrons in ice: a density functional theory study.

PubMed

Bhattacharya, Somesh Kr; Inam, Fakharul; Scandolo, Sandro

2014-02-21

We present a density functional theory study of the localization of excess electrons in the bulk and on the surface of crystalline and amorphous water ice. We analyze the initial stages of electron solvation in crystalline and amorphous ice. In the case of crystalline ice we find that excess electrons favor surface states over bulk states, even when the latter are localized at defect sites. In contrast, in amorphous ice excess electrons find it equally favorable to localize in bulk and in surface states which we attribute to the preexisting precursor states in the disordered structure. In all cases excess electrons are found to occupy the vacuum regions of the molecular network. The electron localization in the bulk of amorphous ice is assisted by its distorted hydrogen bonding network as opposed to the crystalline phase. Although qualitative, our results provide a simple interpretation of the large differences observed in the dynamics and localization of excess electrons in crystalline and amorphous ice films on metals.

Writing silica structures in liquid with scanning transmission electron microscopy.

PubMed

van de Put, Marcel W P; Carcouët, Camille C M C; Bomans, Paul H H; Friedrich, Heiner; de Jonge, Niels; Sommerdijk, Nico A J M

2015-02-04

Silica nanoparticles are imaged in solution with scanning transmission electron microscopy (STEM) using a liquid cell with silicon nitride (SiN) membrane windows. The STEM images reveal that silica structures are deposited in well-defined patches on the upper SiN membranes upon electron beam irradiation. The thickness of the deposits is linear with the applied electron dose. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrate that the deposited patches are a result of the merging of the original 20 nm-diameter nanoparticles, and that the related surface roughness depends on the electron dose rate used. Using this approach, sub-micrometer scale structures are written on the SiN in liquid by controlling the electron exposure as function of the lateral position. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing the Properties of the Molecular Adlayers on Metal Substrates: Scanning Tunneling Microscopy Study of Amine Adsorption on Gold(111) and Graphene Nanoislands on Cobalt(0001)

NASA Astrophysics Data System (ADS)

Zhou, Hui

In this thesis, we present our findings on two major topics, both of which are studies of molecules on metal surfaces by scanning tunneling microscopy (STM). The first topic is on adsorption of a model amine compound, 1,4-benzenediamine (BDA), on the reconstructed Au(111) surface, chosen for its potential application as a molecular electronic device. The molecules were deposited in the gas phase onto the substrate in the vacuum chamber. Five different patterns of BDA molecules on the surface at different coverages, and the preferred adsorption sites of BDA molecules on reconstructed Au(111) surface, were observed. In addition, BDA molecules were susceptible to tip-induced movement, suggesting that BDA molecules on metal surfaces can be a potential candidate in STM molecular manipulations. We also studied graphene nanoislands on Co(0001) in the hope of understanding interaction of expitaxially grown graphene and metal substrates. This topic can shed a light on the potential application of graphene as an electronic device, especially in spintronics. The graphene nanoislands were formed by annealing contorted hexabenzocoronene (HBC) on the Co(0001) surface. In our experiments, we have determined atop registry of graphene atoms with respect to the underlying Co surface. We also investigated the low-energy electronic structures of graphene nanoislands by scanning tunneling spectroscopy. The result was compared with a first-principle calculation using density functional theory (DFT) which suggested strong coupling between graphene pi-bands and cobalt d-electrons. We also observed that the islands exhibit zigzag edges, which exhibits unique electronic structures compared with the center areas of the islands.

Nano-patterned superconducting surface for high quantum efficiency cathode

DOEpatents

Hannon, Fay; Musumeci, Pietro

2017-03-07

A method for providing a superconducting surface on a laser-driven niobium cathode in order to increase the effective quantum efficiency. The enhanced surface increases the effective quantum efficiency by improving the laser absorption of the surface and enhancing the local electric field. The surface preparation method makes feasible the construction of superconducting radio frequency injectors with niobium as the photocathode. An array of nano-structures are provided on a flat surface of niobium. The nano-structures are dimensionally tailored to interact with a laser of specific wavelength to thereby increase the electron yield of the surface.

Ab initio density functional theory study on the atomic and electronic structure of GaP/Si(001) heterointerfaces

NASA Astrophysics Data System (ADS)

Romanyuk, O.; Supplie, O.; Susi, T.; May, M. M.; Hannappel, T.

2016-10-01

The atomic and electronic band structures of GaP/Si(001) heterointerfaces were investigated by ab initio density functional theory calculations. Relative total energies of abrupt interfaces and mixed interfaces with Si substitutional sites within a few GaP layers were derived. It was found that Si diffusion into GaP layers above the first interface layer is energetically unfavorable. An interface with Si/Ga substitution sites in the first layer above the Si substrate is energetically the most stable one in thermodynamic equilibrium. The electronic band structure of the epitaxial GaP/Si(001) heterostructure terminated by the (2 ×2 ) surface reconstruction consists of surface and interface electronic states in the common band gap of two semiconductors. The dispersion of the states is anisotropic and differs for the abrupt Si-Ga, Si-P, and mixed interfaces. Ga 2 p , P 2 p , and Si 2 p core-level binding-energy shifts were computed for the abrupt and the lowest-energy heterointerface structures. Negative and positive core-level shifts due to heterovalent bonds at the interface are predicted for the abrupt Si-Ga and Si-P interfaces, respectively. The distinct features in the heterointerface electronic structure and in the core-level shifts open new perspectives in the experimental characterization of buried polar-on-nonpolar semiconductor heterointerfaces.

Ab initio investigation of the surface properties of dispenser B-type and scandate thermionic emission cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Lee, Yueh-Lin; Booske, John H.; Morgan, Dane; Turek, Ladislav; Kirshner, Mark; Kowalczyk, Richard; Wilsen, Craig

2009-05-01

Scandate cathodes (BaxScyOz on W) are important thermionic electron emission materials whose emission mechanism remains unclear. Ab initio modeling is used to investigate the surface properties of both scandate and traditional B-type (Ba-O on W) cathodes. We demonstrate that the Ba-O dipole surface structure believed to be present in active B-type cathodes is not thermodynamically stable, suggesting that a nonequilibrium steady state dominates the active cathode's surface structure. We identify a stable, low work function BaxScyOz surface structure, which may be responsible for some scandate cathode properties and demonstrate that multicomponent surface coatings can lower cathode work functions.

Exopolysaccharide microchannels direct bacterial motility and organize multicellular behavior

DOE PAGES

Berleman, James E.; Zemla, Marcin; Remis, Jonathan P.; ...

2016-05-06

The myxobacteria are a family of soil bacteria that form biofilms of complex architecture, aligned multilayered swarms or fruiting body structures that are simple or branched aggregates containing myxospores. Here, we examined the structural role of matrix exopolysaccharide (EPS) in the organization of these surface-dwelling bacterial cells. Using time-lapse light and fluorescence microscopy, as well as transmission electron microscopy and focused ion beam/scanning electron microscopy (FIB/SEM) electron microscopy, we found that Myxococcus xanthus cell organization in biofilms is dependent on the formation of EPS microchannels. Cells are highly organized within the three-dimensional structure of EPS microchannels that are required formore » cell alignment and advancement on surfaces. Mutants lacking EPS showed a lack of cell orientation and poor colony migration. Purified, cell-free EPS retains a channel-like structure, and can complement EPS - mutant motility defects. In addition, EPS provides the cooperative structure for fruiting body formation in both the simple mounds of M. xanthus and the complex, tree-like structures of Chondromyces crocatus. We furthermore investigated the possibility that EPS impacts community structure as a shared resource facilitating cooperative migration among closely related isolates of M. xanthus.« less

Geometric modeling of subcellular structures, organelles, and multiprotein complexes

PubMed Central

Feng, Xin; Xia, Kelin; Tong, Yiying; Wei, Guo-Wei

2013-01-01

SUMMARY Recently, the structure, function, stability, and dynamics of subcellular structures, organelles, and multi-protein complexes have emerged as a leading interest in structural biology. Geometric modeling not only provides visualizations of shapes for large biomolecular complexes but also fills the gap between structural information and theoretical modeling, and enables the understanding of function, stability, and dynamics. This paper introduces a suite of computational tools for volumetric data processing, information extraction, surface mesh rendering, geometric measurement, and curvature estimation of biomolecular complexes. Particular emphasis is given to the modeling of cryo-electron microscopy data. Lagrangian-triangle meshes are employed for the surface presentation. On the basis of this representation, algorithms are developed for surface area and surface-enclosed volume calculation, and curvature estimation. Methods for volumetric meshing have also been presented. Because the technological development in computer science and mathematics has led to multiple choices at each stage of the geometric modeling, we discuss the rationales in the design and selection of various algorithms. Analytical models are designed to test the computational accuracy and convergence of proposed algorithms. Finally, we select a set of six cryo-electron microscopy data representing typical subcellular complexes to demonstrate the efficacy of the proposed algorithms in handling biomolecular surfaces and explore their capability of geometric characterization of binding targets. This paper offers a comprehensive protocol for the geometric modeling of subcellular structures, organelles, and multiprotein complexes. PMID:23212797

X-Ray Photoelectron Spectroscopy Study of the Heating Effects on Pd/6H-SiC Schottky Structure

NASA Technical Reports Server (NTRS)

Chen, Liang-Yu; Hunter, Gary W.; Neudeck, Philip G.; Knight, Dak

1998-01-01

X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.

Asymptotic behavior of the Kohn-Sham exchange potential at a metal surface

NASA Astrophysics Data System (ADS)

Qian, Zhixin

2012-03-01

The asymptotic structure of the Kohn-Sham exchange potential vx(r) in the classically forbidden region of a metal surface is investigated, together with that of the Slater exchange potential VxS(r) and those of the approximate Krieger-Li-Iafrate VxKLI(r) and Harbola-Sahni Wx(r) exchange potentials. Particularly, the former is shown to have the form of vx(z→∞)=-αx/z with αx a constant dependent only of bulk electron density. The same result in previous work is thus confirmed; in the meanwhile, a controversy raised recently gets resolved. The structure of the exchange hole ρx(r,r') is examined, and the delocalization of it in the metal bulk when the electron is at large distance from the metal surface is demonstrated with analytical expressions. The asymptotic structures of vx(r), VxS(r), VxKLI(r), and Wx(r) at a slab metal surface are also investigated. Particularly, vx(z→∞)=-1/z in the slab case. The distinction, in this respect, between the semi-infinite and the slab metal surfaces is elucidated.

Simulations of molecular self-assembled monolayers on surfaces: packing structures, formation processes and functions tuned by intermolecular and interfacial interactions.

PubMed

Wen, Jin; Li, Wei; Chen, Shuang; Ma, Jing

2016-08-17

Surfaces modified with a functional molecular monolayer are essential for the fabrication of nano-scale electronics or machines with novel physical, chemical, and/or biological properties. Theoretical simulation based on advanced quantum chemical and classical models is at present a necessary tool in the development, design, and understanding of the interfacial nanostructure. The nanoscale surface morphology, growth processes, and functions are controlled by not only the electronic structures (molecular energy levels, dipole moments, polarizabilities, and optical properties) of building units but also the subtle balance between intermolecular and interfacial interactions. The switchable surfaces are also constructed by introducing stimuli-responsive units like azobenzene derivatives. To bridge the gap between experiments and theoretical models, opportunities and challenges for future development of modelling of ferroelectricity, entropy, and chemical reactions of surface-supported monolayers are also addressed. Theoretical simulations will allow us to obtain important and detailed information about the structure and dynamics of monolayer modified interfaces, which will guide the rational design and optimization of dynamic interfaces to meet challenges of controlling optical, electrical, and biological functions.

Optimization of the nanotwin-induced zigzag surface of copper by electromigration

NASA Astrophysics Data System (ADS)

Chen, Hsin-Ping; Huang, Chun-Wei; Wang, Chun-Wen; Wu, Wen-Wei; Liao, Chien-Neng; Chen, Lih-Juann; Tu, King-Ning

2016-01-01

By adding nanotwins to Cu, the surface electromigration (EM) slows down. The atomic mobility of the surface step-edges is retarded by the triple points where a twin meets a free surface to form a zigzag-type surface. We observed that EM can alter the zigzag surface structure to optimize the reduction of EM, according to Le Chatelier's principle. Statistically, the optimal alternation is to change an arbitrary (111)/(hkl) zigzag pair to a pair having a very low index (hkl) plane, especially the (200) plane. Using in situ ultrahigh vacuum and high-resolution transmission electron microscopy, we examined the effects of different zigzag surfaces on the rate of EM. The calculated rate of surface EM can be decreased by a factor of ten.By adding nanotwins to Cu, the surface electromigration (EM) slows down. The atomic mobility of the surface step-edges is retarded by the triple points where a twin meets a free surface to form a zigzag-type surface. We observed that EM can alter the zigzag surface structure to optimize the reduction of EM, according to Le Chatelier's principle. Statistically, the optimal alternation is to change an arbitrary (111)/(hkl) zigzag pair to a pair having a very low index (hkl) plane, especially the (200) plane. Using in situ ultrahigh vacuum and high-resolution transmission electron microscopy, we examined the effects of different zigzag surfaces on the rate of EM. The calculated rate of surface EM can be decreased by a factor of ten. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05418d

Low-energy surface states in the normal state of α - PdBi 2 superconductor

DOE PAGES

Choi, Hongchul; Neupane, Madhab; Sasagawa, T.; ...

2017-08-25

Topological superconductors as characterized by Majorana surface states have been actively searched for their significance in fundamental science and technological implication. The large spin-orbit coupling in Bi-Pd binaries has stimulated extensive investigations on the topological surface states in these superconducting compounds. Here we report a study of normal-state electronic structure in a centrosymmetric α-PdBi 2 within density functional theory calculations. By investigating the electronic structure from the bulk to slab geometries in this system, we predict for the first time that α-PdBi 2 can host orbital-dependent and asymmetric Rashba surface states near the Fermi energy. This study suggests that α-PdBimore » 2 will be a good candidate to explore the relationship between superconductivity and topology in condensed matter physics.« less

Topological phase diagram and saddle point singularity in a tunable topological crystalline insulator

DOE PAGES

Neupane, Madhab; Xu, Su-Yang; Sankar, R.; ...

2015-08-20

Here we report the evolution of the surface electronic structure and surface material properties of a topological crystalline insulator (TCI), Pb 1more » $${-}$$xSnxSe, as a function of various material parameters including composition x, temperature T , and crystal structure. Our spectroscopic data demonstrate the electronic ground-state condition for the saddle point singularity, the tunability of surface chemical potential, and the surface states’ response to circularly polarized light. Our results show that each material parameter can tune the system between the trivial and topological phase in a distinct way, unlike that seen in Bi 2Se 3 and related compounds, leading to a rich topological phase diagram. Our systematic studies of the TCI Pb 1$${-}$$xSnxSe are a valuable materials guide to realize new topological phenomena.« less

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

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

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

NASA Astrophysics Data System (ADS)

Steiner, Christian; Gebhardt, Julian; Ammon, Maximilian; Yang, Zechao; Heidenreich, Alexander; Hammer, Natalie; Görling, Andreas; Kivala, Milan; Maier, Sabine

2017-03-01

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

Comprehensive surface treatment of high-speed steel tool

NASA Astrophysics Data System (ADS)

Fedorov, Sergey V.; Aleshin, Sergey V.; Swe, Min Htet; Abdirova, Raushan D.; Kapitanov, Alexey V.; Egorov, Sergey B.

2018-03-01

One of the promising directions of hardening of high-speed steel tool is the creation on their surface of the layered structures with the gradient of physic-chemical properties between the wear-resistant coatings to the base material. Among the methods of such surface modification, a special process takes place based on the use of pulsed high-intensity charged particle beams. The high speed of heating and cooling allows structural-phase transformations in the surface layer, which cannot be realized in a stationary mode. The treatment was conducted in a RITM-SP unit, which constitutes a combination of a source of low-energy high-current electron beams "RITM" and two magnetron spraying systems on a single vacuum chamber. The unit enables deposition of films on the surface of the desired product and subsequent liquid-phase mixing of materials of the film and the substrate by an intense pulse electron beam. The article discusses features of the structure of the subsurface layer of high-speed steel M2, modified by surface alloying of a low-energy high-current electron beam, and its effect on the wear resistance of the tool when dry cutting hard to machine Nickel alloy. A significant decrease of intensity of wear of high-speed steel with combined treatment happens due to the displacement of the zone of wear and decrease the radius of rounding of the cutting edge because of changes in conditions of interaction with the material being treated.

Front surface structured targets for enhancing laser-plasma interactions

NASA Astrophysics Data System (ADS)

Snyder, Joseph; George, Kevin; Ji, Liangliang; Yalamanchili, Sasir; Simonoff, Ethan; Cochran, Ginevra; Daskalova, Rebecca; Poole, Patrick; Willis, Christopher; Lewis, Nathan; Schumacher, Douglass

2016-10-01

We present recent progress made using front surface structured interfaces for enhancing ultrashort, relativistic laser-plasma interactions. Structured targets can increase laser absorption and enhance ion acceleration through a number of mechanisms such as direct laser acceleration and laser guiding. We detail experimental results obtained at the Scarlet laser facility on hollow, micron-scale plasma channels for enhancing electron acceleration. These targets show a greater than three times enhancement in the electron cutoff energy as well as an increased slope temperature for the electron distribution when compared to a flat interface. Using three-dimensional particle-in-cell (PIC) simulations, we have modeled the interaction to give insight into the physical processes responsible for the enhancement. Furthermore, we have used PIC simulations to design structures that are more advantageous for ion acceleration. Such targets necessitate advanced target fabrication methods and we describe techniques used to manufacture optimized structures, including vapor-liquid-solid growth, cryogenic etching, and 3D printing using two-photon-polymerization. This material is based upon work supported by the Air Force Office of Scientific Research under Award Number FA9550-14-1-0085.

Highly charged ion based time of flight emission microscope

DOEpatents

Barnes, Alan V.; Schenkel, Thomas; Hamza, Alex V.; Schneider, Dieter H.; Doyle, Barney

2001-01-01

A highly charged ion based time-of-flight emission microscope has been designed, which improves the surface sensitivity of static SIMS measurements because of the higher ionization probability of highly charged ions. Slow, highly charged ions are produced in an electron beam ion trap and are directed to the sample surface. The sputtered secondary ions and electrons pass through a specially designed objective lens to a microchannel plate detector. This new instrument permits high surface sensitivity (10.sup.10 atoms/cm.sup.2), high spatial resolution (100 nm), and chemical structural information due to the high molecular ion yields. The high secondary ion yield permits coincidence counting, which can be used to enhance determination of chemical and topological structure and to correlate specific molecular species.

Real-time observation of morphological transformations in II-VI semiconducting nanobelts via environmental transmission electron microscopy

DOE PAGES

Agarwal, Rahul; Zakharov, Dmitri N.; Krook, Nadia M.; ...

2015-05-01

It has been observed that wurtzite II–VI semiconducting nanobelts transform into single-crystal, periodically branched nanostructures upon heating. The mechanism of this novel transformation has been elucidated by heating II–VI nanobelts in an environmental transmission electron microscope (ETEM) in oxidizing, reducing and inert atmospheres while observing their structural changes with high spatial resolution. The interplay of surface reconstruction of high-energy surfaces of the wurtzite phase and environment-dependent anisotropic chemical etching of certain crystal surfaces in the branching mechanism of nanobelts has been observed. Understanding of structural and chemical transformations of materials via in situ microscopy techniques and their role in designingmore » new nanostructured materials is discussed.« less

Computational Study on Atomic Structures, Electronic Properties, and Chemical Reactions at Surfaces and Interfaces and in Biomaterials

NASA Astrophysics Data System (ADS)

Takano, Yu; Kobayashi, Nobuhiko; Morikawa, Yoshitada

2018-06-01

Through computer simulations using atomistic models, it is becoming possible to calculate the atomic structures of localized defects or dopants in semiconductors, chemically active sites in heterogeneous catalysts, nanoscale structures, and active sites in biological systems precisely. Furthermore, it is also possible to clarify physical and chemical properties possessed by these nanoscale structures such as electronic states, electronic and atomic transport properties, optical properties, and chemical reactivity. It is sometimes quite difficult to clarify these nanoscale structure-function relations experimentally and, therefore, accurate computational studies are indispensable in materials science. In this paper, we review recent studies on the relation between local structures and functions for inorganic, organic, and biological systems by using atomistic computer simulations.

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

NASA Astrophysics Data System (ADS)

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

1988-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Rapid pulse annealing of CdZnTe detectors for reducing electronic noise

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

Voss, Lars; Conway, Adam; Nelson, Art

A combination of doping, rapid pulsed optical and/or thermal annealing, and unique detector structure reduces or eliminates sources of electronic noise in a CdZnTe (CZT) detector. According to several embodiments, methods of forming a detector exhibiting minimal electronic noise include: pulse-annealing at least one surface of a detector comprising CZT for one or more pulses, each pulse having a duration of .about.0.1 seconds or less. The at least one surface may optionally be ion-implanted. In another embodiment, a CZT detector includes a detector surface with two or more electrodes operating at different electric potentials and coupled to the detector surface;more » and one or more ion-implanted CZT surfaces on or in the detector surface, each of the one or more ion-implanted CZT surfaces being independently connected to one of the two or more electrodes and the surface of the detector. At least two of the ion-implanted surfaces are in electrical contact.« less

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

PubMed

Patterson, C H

2015-12-02

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

Subsurface Growth Of Silicide Structures In Silicon

NASA Technical Reports Server (NTRS)

Fathauer, Robert W.; George, Thomas; Pike, William T.; Schowalter, Leo

1993-01-01

Technique shows promise for fabrication of novel electronic, optoelectronic, and electro-optical devices. Experiments demonstrated feasibility of growing microscopic single-crystal CoSi2 structures beneath surfaces of Si substrates.

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

Neiman, Aleksei A., E-mail: nasa@ispms.tsc.ru; Lotkov, Aleksandr I.; Gudimova, Ekaterina Y.

The paper reports on a study of regularities of formation gradient nano-, submicron and microstructural conditions in the surface layers of the samples after pulsed electron-beam melting of tantalum coating on the substrate NiTi alloy. Experimentally revealed the presence of submicron columnar structure in the upper layers of the tantalum coating. After irradiation modified NiTi surface takes on a layered structure in which each layer differs in phase composition and structural phase state.

Lithium effects on the mechanical and electronic properties of germanium nanowires

NASA Astrophysics Data System (ADS)

González-Macías, A.; Salazar, F.; Miranda, A.; Trejo-Baños, A.; Pérez, L. A.; Carvajal, E.; Cruz-Irisson, M.

2018-04-01

Semiconductor nanowire arrays promise rapid development of a new generation of lithium (Li) batteries because they can store more Li atoms than conventional crystals due to their large surface areas. During the charge-discharge process, the electrodes experience internal stresses that fatigue the material and limit the useful life of the battery. The theoretical study of electronic and mechanical properties of lithiated nanowire arrays allows the designing of electrode materials that could improve battery performance. In this work, we present a density functional theory study of the electronic band structure, formation energy, binding energy, and Young’s modulus (Y) of hydrogen passivated germanium nanowires (H-GeNWs) grown along the [111] and [001] crystallographic directions with surface and interstitial Li atoms. The results show that the germanium nanowires (GeNWs) with surface Li atoms maintain their semiconducting behavior but their energy gap size decreases when the Li concentration grows. In contrast, the GeNWs can have semiconductor or metallic behavior depending on the concentration of the interstitial Li atoms. On the other hand, Y is an indicator of the structural changes that GeNWs suffer due to the concentration of Li atoms. For surface Li atoms, Y stays almost constant, whereas for interstitial Li atoms, the Y values indicate important structural changes in the GeNWs.

Near Edge X-Ray Absorption and X-Ray Photoelectron Diffraction Studies of the Structural Environment of Ge-Si Systems

NASA Astrophysics Data System (ADS)

Castrucci, P.; Gunnella, R.; Pinto, N.; Bernardini, R.; de Crescenzi, M.; Sacchi, M.

Near edge X-ray absorption spectroscopy (XAS), X-ray photoelectron diffraction (XPD) and Auger electron diffraction (AED) are powerful techniques for the qualitative study of the structural and electronic properties of several systems. The recent development of a multiple scattering approach to simulating experimental spectra opened a friendly way to the study of structural environments of solids and surfaces. This article reviews recent X-ray absorption experiments using synchrotron radiation which were performed at Ge L edges and core level electron diffraction measurements obtained using a traditional X-ray source from Ge core levels for ultrathin Ge films deposited on silicon substrates. Thermodynamics and surface reconstruction have been found to play a crucial role in the first stages of Ge growth on Si(001) and Si(111) surfaces. Both techniques show the occurrence of intermixing processes even for room-temperature-grown Ge/Si(001) samples and give a straightforward measurement of the overlayer tetragonal distortion. The effects of Sb as a surfactant on the Ge/Si(001) interface have also been investigated. In this case, evidence of layer-by-layer growth of the fully strained Ge overlayer with a reduced intermixing is obtained when one monolayer of Sb is predeposited on the surface.

New catalyst supports prepared by surface modification of graphene- and carbon nanotube structures with nitrogen containing carbon coatings

NASA Astrophysics Data System (ADS)

Oh, Eun-Jin; Hempelmann, Rolf; Nica, Valentin; Radev, Ivan; Natter, Harald

2017-02-01

We present a new and facile method for preparation of nitrogen containing carbon coatings (NCC) on the surface of graphene- and carbon nanotubes (CNT), which has an increased electronic conductivity. The modified carbon system can be used as catalyst support for electrocatalytic applications, especially for polymer electrolyte membrane fuel cells (PEMFC). The surface modification is performed by impregnating carbon structures with a nitrogen containing ionic liquid (IL) with a defined C:N ratio, followed by a thermal treatment under ambient conditions. We investigate the influence of the main experimental parameters (IL amount, temperature, substrate morphology) on the formation of the NCC. Additionally, the structure and the chemical composition of the resulting products are analyzed by electron microscopic techniques (SEM, TEM), energy disperse X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS) and hot extraction analysis. The modified surface has a nitrogen content of 29 wt% which decreases strongly at temperatures above 600 °C. The new catalyst supports are used for the preparation of PEMFC anodes which are characterized by polarization measurements and electrochemical impedance spectroscopy (EIS). Compared to unmodified graphene and CNT samples the electronic conductivity of the modified systems is increased by a factor of 2 and shows improved mass transport properties.

STEM-EELS analysis of multipole surface plasmon modes in symmetry-broken AuAg nanowire dimers

NASA Astrophysics Data System (ADS)

Schubert, Ina; Sigle, Wilfried; van Aken, Peter A.; Trautmann, Christina; Toimil-Molares, Maria Eugenia

2015-03-01

Surface plasmon coupling in nanowires separated by small gaps generates high field enhancements at the position of the gap and is thus of great interest for sensing applications. It is known that the nanowire dimensions and in particular the symmetry of the structures has strong influence on the plasmonic properties of the dimer structure. Here, we report on multipole surface plasmon coupling in symmetry-broken AuAg nanowire dimers. Our dimers, consisting of two nanowires with different lengths and separated by gaps of only 10 to 30 nm, were synthesized by pulsed electrochemical deposition in ion track-etched polymer templates. Electron energy-loss spectroscopy in scanning transmission electron microscopy allows us to resolve up to nine multipole order surface plasmon modes of these dimers spectrally separated from each other. The spectra evidence plasmon coupling between resonances of different multipole order, resulting in the generation of additional plasmonic modes. Since such complex structures require elaborated synthesis techniques, dimer structures with complex composition, morphology and shape are created. We demonstrate that finite element simulations on pure Au dimers can predict the generated resonances in the fabricated structures. The excellent agreement of our experiment on AuAg dimers with finite integration simulations using CST microwave studio manifests great potential to design complex structures for sensing applications.

Ion induced millimetre-scale structures growth on metal surfaces

NASA Astrophysics Data System (ADS)

Girka, O.; Bizyukov, O.; Balkova, Y.; Myroshnyk, M.; Bizyukov, I.; Bogatyrenko, S.

2018-04-01

Polished polycrystalline Plansee tungsten (W) sample with purity 99.99 wt% and 0.75 mm thickness has been exposed to intense argon (Ar) ion beam with average energy of 2 keV and etched through in the centre. As a result, castle-like structures with strong asymmetry and with the height of >200 μm have been formed. Structures can be observed by naked eyes and with scanning-electron microscopy (SEM). It has been revealed, that the structures have been formed not immediately, but at the later stages of irradiation. Primary factors favouring the formation for the structures are relaxation of the surface stresses and activated surface mobility of atoms.

The surface sulfur doping induced enhanced performance of cobalt catalysts in oxygen evolution reactions.

PubMed

Al-Mamun, Mohammad; Zhu, Zhengju; Yin, Huajie; Su, Xintai; Zhang, Haimin; Liu, Porun; Yang, Huagui; Wang, Dan; Tang, Zhiyong; Wang, Yun; Zhao, Huijun

2016-08-04

A novel surface sulfur (S) doped cobalt (Co) catalyst for the oxygen evolution reaction (OER) is theoretically designed through the optimisation of the electronic structure of highly reactive surface atoms which is also validated by electrocatalytic OER experiments.

Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts

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

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

The surface atomic structure of metallic nanoparticles (NPs) plays a key role in shaping their physicochemical properties and response to external stimuli. Not surprisingly, current research increasingly focuses on exploiting its prime characteristics, including the amount, location, coordination, and electronic configuration of distinct surface atomic species, as tunable parameters for improving the functionality of metallic NPs in practical applications. The effort requires clear understanding of the extent to which changes in each of these characteristics would contribute to achieving the targeted functionality. This, in the first place, requires good knowledge of the actual surface of metallic NPs at atomic level.more » Through a case study on Au–Pd nanoalloy catalysts of industrial and environmental importance, we demonstrate that the surface atomic structure of metallic NPs can be determined in good detail by resonant high-energy X-ray diffraction (HE-XRD). Furthermore, using our experimental surface structure and CO oxidation activity data, we shed new light on the elusive origin of the remarkable catalytic synergy between surface Au and Pd atoms in the nanoalloys. In particular, we show that it arises from the formation of a specific “skin” on top of the nanoalloys that involves as many unlike, i.e., Au–Pd and Pd–Au, atomic pairs as possible given the overall chemical composition of the NPs. Moreover, unlike atoms from the “skin” interact strongly, including both changing their size and electronic structure in inverse proportions. That is, Au atoms shrink and acquire a partial positive charge of 5d-character whereas Pd atoms expand and become somewhat 4d-electron deficient. Accordingly, the reactivity of Au increases whereas Pd atoms become less reactive, as compared to atoms at the surface of pure Au and Pd NPs, respectively. Ultimately, this renders Au–Pd alloy NPs superb catalysts for CO oxidation reaction over a broad range of alloy compositions. Our findings are corroborated by DFT calculations based on a refined version of d-band center theory on the catalytic properties of late transition metals and alloys. Here, we discuss opportunities for improving the accuracy of current theory on surface-controlled properties of metallic NPs through augmenting the theory with surface structure data obtained by resonant XRD.« less

Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts

DOE PAGES

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit; ...

2017-03-23

The surface atomic structure of metallic nanoparticles (NPs) plays a key role in shaping their physicochemical properties and response to external stimuli. Not surprisingly, current research increasingly focuses on exploiting its prime characteristics, including the amount, location, coordination, and electronic configuration of distinct surface atomic species, as tunable parameters for improving the functionality of metallic NPs in practical applications. The effort requires clear understanding of the extent to which changes in each of these characteristics would contribute to achieving the targeted functionality. This, in the first place, requires good knowledge of the actual surface of metallic NPs at atomic level.more » Through a case study on Au–Pd nanoalloy catalysts of industrial and environmental importance, we demonstrate that the surface atomic structure of metallic NPs can be determined in good detail by resonant high-energy X-ray diffraction (HE-XRD). Furthermore, using our experimental surface structure and CO oxidation activity data, we shed new light on the elusive origin of the remarkable catalytic synergy between surface Au and Pd atoms in the nanoalloys. In particular, we show that it arises from the formation of a specific “skin” on top of the nanoalloys that involves as many unlike, i.e., Au–Pd and Pd–Au, atomic pairs as possible given the overall chemical composition of the NPs. Moreover, unlike atoms from the “skin” interact strongly, including both changing their size and electronic structure in inverse proportions. That is, Au atoms shrink and acquire a partial positive charge of 5d-character whereas Pd atoms expand and become somewhat 4d-electron deficient. Accordingly, the reactivity of Au increases whereas Pd atoms become less reactive, as compared to atoms at the surface of pure Au and Pd NPs, respectively. Ultimately, this renders Au–Pd alloy NPs superb catalysts for CO oxidation reaction over a broad range of alloy compositions. Our findings are corroborated by DFT calculations based on a refined version of d-band center theory on the catalytic properties of late transition metals and alloys. Here, we discuss opportunities for improving the accuracy of current theory on surface-controlled properties of metallic NPs through augmenting the theory with surface structure data obtained by resonant XRD.« less

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

Theoretical study of adsorption of organic phosphines on transition metal surfaces

NASA Astrophysics Data System (ADS)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

Thin-film chemical sensors based on electron tunneling

NASA Technical Reports Server (NTRS)

Khanna, S. K.; Lambe, J.; Leduc, H. G.; Thakoor, A. P.

1985-01-01

The physical mechanisms underlying a novel chemical sensor based on electron tunneling in metal-insulator-metal (MIM) tunnel junctions were studied. Chemical sensors based on electron tunneling were shown to be sensitive to a variety of substances that include iodine, mercury, bismuth, ethylenedibromide, and ethylenedichloride. A sensitivity of 13 parts per billion of iodine dissolved in hexane was demonstrated. The physical mechanisms involved in the chemical sensitivity of these devices were determined to be the chemical alteration of the surface electronic structure of the top metal electrode in the MIM structure. In addition, electroreflectance spectroscopy (ERS) was studied as a complementary surface-sensitive technique. ERS was shown to be sensitive to both iodine and mercury. Electrolyte electroreflectance and solid-state MIM electroreflectance revealed qualitatively the same chemical response. A modified thin-film structure was also studied in which a chemically active layer was introduced at the top Metal-Insulator interface of the MIM devices. Cobalt phthalocyanine was used for the chemically active layer in this study. Devices modified in this way were shown to be sensitive to iodine and nitrogen dioxide. The chemical sensitivity of the modified structure was due to conductance changes in the active layer.

First-principles surface interaction studies of aluminum-copper and aluminum-copper-magnesium secondary phases in aluminum alloys

NASA Astrophysics Data System (ADS)

da Silva, Thiago H.; Nelson, Eric B.; Williamson, Izaak; Efaw, Corey M.; Sapper, Erik; Hurley, Michael F.; Li, Lan

2018-05-01

First-principles density functional theory-based calculations were performed to study θ-phase Al2Cu, S-phase Al2CuMg surface stability, as well as their interactions with water molecules and chloride (Cl-) ions. These secondary phases are commonly found in aluminum-based alloys and are initiation points for localized corrosion. Density functional theory (DFT)-based simulations provide insight into the origins of localized (pitting) corrosion processes of aluminum-based alloys. For both phases studied, Cl- ions cause atomic distortions on the surface layers. The nature of the distortions could be a factor to weaken the interlayer bonds in the Al2Cu and Al2CuMg secondary phases, facilitating the corrosion process. Electronic structure calculations revealed not only electron charge transfer from Cl- ions to alloy surface but also electron sharing, suggesting ionic and covalent bonding features, respectively. The S-phase Al2CuMg structure has a more active surface than the θ-phase Al2Cu. We also found a higher tendency of formation of new species, such as Al3+, Al(OH)2+, HCl, AlCl2+, Al(OH)Cl+, and Cl2 on the S-phase Al2CuMg surface. Surface chemical reactions and resultant species present contribute to establishment of local surface chemistry that influences the corrosion behavior of aluminum alloys.

Low-energy electron diffraction study of Si(111)-(√3x √3)R30∘ -B

NASA Astrophysics Data System (ADS)

Marino, K. E.; Huang, Y. T.; Diehl, R. D.; Tu, Weison; Mulugeta, Daniel; Snijders, P. C.; Weitering, H. H.

2014-03-01

Metal-semiconductor interfaces are important for the function and manufacture of advanced electronics, such as those used in computers, tablets and phones. They also exhibit many interesting physical phenomena that are interesting from a fundamental point of view, including exotic phases and phase transitions. This study involves the analysis and modeling of the surface structure of a thin film of boron on the Si(111) surface. The addition of metal atoms to the surface of Si(111) simplifies its structure by removing a ``rippling'' that is present on the clean surface. The low-energy electron diffraction (LEED) data were measured at a surface temperature of 80 K at ORNL. The LEED analysis utilized the SATLEED analysis programs. The results are similar to those obtained in an earlier LEED study for this interface, but the precision is higher due to the larger dataset employed., The results of this study will be compared to other studies of this and similar systems. We acknowledge the Eberly College of Science for funding this project. González, Guo, Ortega, Flores, Weitering. Phys. Rev. Lett. 102, 115501 (2009)

A facile bacterial assisted electrochemical self-assembly of polypyrrole micro-pillars: towards underwater low adhesive superoleophobicity

NASA Astrophysics Data System (ADS)

Cheng, Zhe; Ding, Chunmei; Liu, Huan; Zhu, Ying; Jiang, Lei

2013-12-01

By taking advantage of bacterial extracellular electron transfer behavior, a facile method was developed to fabricate oriented polypyrrole micro-pillars (PPy-MP) with nanoscale surface roughness. Microbes acted as a living conductive template on which PPy was in situ polymerized. The as-prepared PPy-MP exhibit the distinctive underwater low adhesive superoleophobicity which is attributable to the unique hierarchical micro/nano-structures and the high surface energy by doping with inorganic small anions.By taking advantage of bacterial extracellular electron transfer behavior, a facile method was developed to fabricate oriented polypyrrole micro-pillars (PPy-MP) with nanoscale surface roughness. Microbes acted as a living conductive template on which PPy was in situ polymerized. The as-prepared PPy-MP exhibit the distinctive underwater low adhesive superoleophobicity which is attributable to the unique hierarchical micro/nano-structures and the high surface energy by doping with inorganic small anions. Electronic supplementary information (ESI) available: The shape of a water drop on PPy-MPA and cauliflower-like PPy film in air. See DOI: 10.1039/c3nr03788f

Nickel electrodes as a cheap and versatile platform for studying structure and function of immobilized redox proteins.

PubMed

Han, Xiao Xia; Li, Junbo; Öner, Ibrahim Halil; Zhao, Bing; Leimkühler, Silke; Hildebrandt, Peter; Weidinger, Inez M

2016-10-19

Practical use of many bioelectronic and bioanalytical devices is limited by the need of expensive materials and time consuming fabrication. Here we demonstrate the use of nickel electrodes as a simple and cheap solid support material for bioelectronic applications. The naturally nanostructured electrodes showed a surprisingly high electromagnetic surface enhancement upon light illumination such that immobilization and electron transfer reactions of the model redox proteins cytochrome b 5 (Cyt b 5 ) and cytochrome c (Cyt c) could be followed via surface enhanced resonance Raman spectroscopy. It could be shown that the nickel surface, when used as received, promotes a very efficient binding of the proteins upon preservation of their native structure. The immobilized redox proteins could efficiently exchange electrons with the electrode and could even act as an electron relay between the electrode and solubilized myoglobin. Our results open up new possibility for nickel electrodes as an exceptional good support for bioelectronic devices and biosensors on the one hand and for surface enhanced spectroscopic investigations on the other hand. Copyright © 2016 Elsevier B.V. All rights reserved.

Electronic structures of rutile (011)(2 × 1) surfaces: A many-body perturbation theory study.

PubMed

Liu, Guokui; Chen, Tingwei; Liu, Xiaobiao; Jin, Fan; Yuan, Shiling; Ma, Yuchen

2017-03-28

Using the GW method within many-body perturbation theory, we investigate the electronic properties of the rutile (011) surfaces with different reconstruction patterns. We find that keeping the Ti:O ratio on the reconstructedsurface to 1:2 enlarges the bandgap of the rutile (011) surface to ca. 4.0 eV. Increasing the content of O atoms in the surface can turn rutile into a semi-metal. For some surfaces, it is important to apply self-consistent GW calculation to get the correct charge distributions for the frontier orbitals, which are relevant to the photocatalytic behavior of TiO 2 .

Electronic Structure, Surface Doping, and Optical Response in Epitaxial WSe2 Thin Films.

PubMed

Zhang, Yi; Ugeda, Miguel M; Jin, Chenhao; Shi, Su-Fei; Bradley, Aaron J; Martín-Recio, Ana; Ryu, Hyejin; Kim, Jonghwan; Tang, Shujie; Kim, Yeongkwan; Zhou, Bo; Hwang, Choongyu; Chen, Yulin; Wang, Feng; Crommie, Michael F; Hussain, Zahid; Shen, Zhi-Xun; Mo, Sung-Kwan

2016-04-13

High quality WSe2 films have been grown on bilayer graphene (BLG) with layer-by-layer control of thickness using molecular beam epitaxy. The combination of angle-resolved photoemission, scanning tunneling microscopy/spectroscopy, and optical absorption measurements reveal the atomic and electronic structures evolution and optical response of WSe2/BLG. We observe that a bilayer of WSe2 is a direct bandgap semiconductor, when integrated in a BLG-based heterostructure, thus shifting the direct-indirect band gap crossover to trilayer WSe2. In the monolayer limit, WSe2 shows a spin-splitting of 475 meV in the valence band at the K point, the largest value observed among all the MX2 (M = Mo, W; X = S, Se) materials. The exciton binding energy of monolayer-WSe2/BLG is found to be 0.21 eV, a value that is orders of magnitude larger than that of conventional three-dimensional semiconductors, yet small as compared to other two-dimensional transition metal dichalcogennides (TMDCs) semiconductors. Finally, our finding regarding the overall modification of the electronic structure by an alkali metal surface electron doping opens a route to further control the electronic properties of TMDCs.

Electronic structure, surface doping, and optical response in epitaxial WSe 2 thin films

DOE PAGES

Zhang, Yi; Ugeda, Miguel M.; Jin, Chenhao; ...

2016-03-14

High quality WSe 2 films have been grown on bilayer graphene (BLG) with layer-by-layer control of thickness using molecular beam epitaxy. The combination of angle-resolved photoemission, scanning tunneling microscopy/spectroscopy, and optical absorption measurements reveal the atomic and electronic structures evolution and optical response of WSe 2/BLG. We observe that a bilayer of WSe 2 is a direct bandgap semiconductor, when integrated in a BLG-based heterostructure, thus shifting the direct–indirect band gap crossover to trilayer WSe 2. In the monolayer limit, WSe 2 shows a spin-splitting of 475 meV in the valence band at the K point, the largest value observedmore » among all the MX 2 (M = Mo, W; X = S, Se) materials. The exciton binding energy of monolayer-WSe 2/BLG is found to be 0.21 eV, a value that is orders of magnitude larger than that of conventional three-dimensional semiconductors, yet small as compared to other two-dimensional transition metal dichalcogennides (TMDCs) semiconductors. Lastly, our finding regarding the overall modification of the electronic structure by an alkali metal surface electron doping opens a route to further control the electronic properties of TMDCs.« less

Synthesis and characterization of high-surface-area millimeter-sized silica beads with hierarchical multi-modal pore structure by the addition of agar

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

Han, Yosep; Choi, Junhyun; Tong, Meiping, E-mail: tongmeiping@iee.pku.edu.cn

2014-04-01

Millimeter-sized spherical silica foams (SSFs) with hierarchical multi-modal pore structure featuring high specific surface area and ordered mesoporous frameworks were successfully prepared using aqueous agar addition, foaming and drop-in-oil processes. The pore-related properties of the prepared spherical silica (SSs) and SSFs were systematically characterized by field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXRD), Hg intrusion porosimetry, and N{sub 2} adsorption–desorption isotherm measurements. Improvements in the BET surface area and total pore volume were observed at 504 m{sup 2} g{sup −1} and 5.45 cm{sup 3} g{sup −1}, respectively, after an agar addition and foaming process. Despitemore » the increase in the BET surface area, the mesopore wall thickness and the pore size of the mesopores generated from the block copolymer with agar addition were unchanged based on the SAXRD, TEM, and BJH methods. The SSFs prepared in the present study were confirmed to have improved BET surface area and micropore volume through the agar loading, and to exhibit interconnected 3-dimensional network macropore structure leading to the enhancement of total porosity and BET surface area via the foaming process. - Highlights: • Millimeter-sized spherical silica foams (SSFs) are successfully prepared. • SSFs exhibit high BET surface area and ordered hierarchical pore structure. • Agar addition improves BET surface area and micropore volume of SSFs. • Foaming process generates interconnected 3-D network macropore structure of SSFs.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

2017-02-16

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Segregation Phenomena on the Crystal Surface of Chemical Compounds

NASA Astrophysics Data System (ADS)

Tomashpol'skii, Yu. Ya.

2018-06-01

The current state of the theoretical and experimental studies of changes in the chemical structure and composition caused by segregation phenomena on the surface of chemical compounds was reviewed. The review considers the experimental data obtained exclusively on single crystals, which were studied by modern instrumental methods, including in situ Auger electron spectrometry, X-ray spectral microanalysis, high-resolution scanning and transmission electron microscopy, secondary electron emission, and atomic force microscopy. The models that suggest the crystal-chemical diffusion and liquid-phase mechanisms of segregation were described. The parameters of the theory include the type of chemical bond, elastic constants, and crystal-chemical characteristics of substances. The models make it possible to predict the nature of changes in the surface composition: segregation tendency, segregant type, and degree of nonstoichiometry. A new direction in surface segregation was considered, which is promising for nanoelectronics and emission electronics.

Disorder enabled band structure engineering of a topological insulator surface

DOE PAGES

Xu, Yishuai; Chiu, Janet; Miao, Lin; ...

2017-02-03

Three-dimensional topological insulators are bulk insulators with Z 2 topological electronic order that gives rise to conducting light-like surface states. These surface electrons are exceptionally resistant to localization by non-magnetic disorder, and have been adopted as the basis for a wide range of proposals to achieve new quasiparticle species and device functionality. Recent studies have yielded a surprise by showing that in spite of resisting localization, topological insulator surface electrons can be reshaped by defects into distinctive resonance states. Here we use numerical simulations and scanning tunnelling microscopy data to show that these resonance states have significance well beyond themore » localized regime usually associated with impurity bands. Lastly, at native densities in the model Bi 2X 3 (X=Bi, Te) compounds, defect resonance states are predicted to generate a new quantum basis for an emergent electron gas that supports diffusive electrical transport.« less

Direct k-space mapping of the electronic structure in an oxide-oxide interface.

PubMed

Berner, G; Sing, M; Fujiwara, H; Yasui, A; Saitoh, Y; Yamasaki, A; Nishitani, Y; Sekiyama, A; Pavlenko, N; Kopp, T; Richter, C; Mannhart, J; Suga, S; Claessen, R

2013-06-14

The interface between LaAlO(3) and SrTiO(3) hosts a two-dimensional electron system of itinerant carriers, although both oxides are band insulators. Interface ferromagnetism coexisting with superconductivity has been found and attributed to local moments. Experimentally, it has been established that Ti 3d electrons are confined to the interface. Using soft x-ray angle-resolved resonant photoelectron spectroscopy we have directly mapped the interface states in k space. Our data demonstrate a charge dichotomy. A mobile fraction contributes to Fermi surface sheets, whereas a localized portion at higher binding energies is tentatively attributed to electrons trapped by O vacancies in the SrTiO(3). While photovoltage effects in the polar LaAlO(3) layers cannot be excluded, the apparent absence of surface-related Fermi surface sheets could also be fully reconciled in a recently proposed electronic reconstruction picture where the built-in potential in the LaAlO(3) is compensated by surface O vacancies serving also as a charge reservoir.

Emerging surface characterization techniques for carbon steel corrosion: a critical brief review.

PubMed

Dwivedi, D; Lepkova, K; Becker, T

2017-03-01

Carbon steel is a preferred construction material in many industrial and domestic applications, including oil and gas pipelines, where corrosion mitigation using film-forming corrosion inhibitor formulations is a widely accepted method. This review identifies surface analytical techniques that are considered suitable for analysis of thin films at metallic substrates, but are yet to be applied to analysis of carbon steel surfaces in corrosive media or treated with corrosion inhibitors. The reviewed methods include time of flight-secondary ion mass spectrometry, X-ray absorption spectroscopy methods, particle-induced X-ray emission, Rutherford backscatter spectroscopy, Auger electron spectroscopy, electron probe microanalysis, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission electron microscopy, low-energy electron diffraction, small-angle neutron scattering and neutron reflectometry, and conversion electron Moessbauer spectrometry. Advantages and limitations of the analytical methods in thin-film surface investigations are discussed. Technical parameters of nominated analytical methods are provided to assist in the selection of suitable methods for analysis of metallic substrates deposited with surface films. The challenges associated with the applications of the emerging analytical methods in corrosion science are also addressed.

Emerging surface characterization techniques for carbon steel corrosion: a critical brief review

NASA Astrophysics Data System (ADS)

Dwivedi, D.; Lepkova, K.; Becker, T.

2017-03-01

Carbon steel is a preferred construction material in many industrial and domestic applications, including oil and gas pipelines, where corrosion mitigation using film-forming corrosion inhibitor formulations is a widely accepted method. This review identifies surface analytical techniques that are considered suitable for analysis of thin films at metallic substrates, but are yet to be applied to analysis of carbon steel surfaces in corrosive media or treated with corrosion inhibitors. The reviewed methods include time of flight-secondary ion mass spectrometry, X-ray absorption spectroscopy methods, particle-induced X-ray emission, Rutherford backscatter spectroscopy, Auger electron spectroscopy, electron probe microanalysis, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission electron microscopy, low-energy electron diffraction, small-angle neutron scattering and neutron reflectometry, and conversion electron Moessbauer spectrometry. Advantages and limitations of the analytical methods in thin-film surface investigations are discussed. Technical parameters of nominated analytical methods are provided to assist in the selection of suitable methods for analysis of metallic substrates deposited with surface films. The challenges associated with the applications of the emerging analytical methods in corrosion science are also addressed.

The molecular shape and the field similarities as criteria to interpret SAR studies for fragment-based design of platinum(IV) anticancer agents. Correlation of physicochemical properties with cytotoxicity.

PubMed

Lorenzo, Julia; Montaña, Ángel M

2016-09-01

Molecular shape similarity and field similarity have been used to interpret, in a qualitative way, the structure-activity relationships in a selected series of platinum(IV) complexes with anticancer activity. MM and QM calculations have been used to estimate the electron density, electrostatic potential maps, partial charges, dipolar moments and other parameters to correlate the stereo-electronic properties with the differential biological activity of complexes. Extended Electron Distribution (XED) field similarity has been also evaluated for the free 1,4-diamino carrier ligands, in a fragment-based drug design approach, comparing Connolly solvent excluded surface, hydrophobicity field surface, Van der Waals field surface, nucleophilicity field surface, electrophilicity field surface and the extended electron-distribution maxima field points. A consistency has been found when comparing the stereo-electronic properties of the studied series of platinum(IV) complexes and/or the free ligands evaluated and their in vitro anticancer activity. Copyright © 2016 Elsevier Inc. All rights reserved.

Emerging surface characterization techniques for carbon steel corrosion: a critical brief review

PubMed Central

Dwivedi, D.; Becker, T.

2017-01-01

Carbon steel is a preferred construction material in many industrial and domestic applications, including oil and gas pipelines, where corrosion mitigation using film-forming corrosion inhibitor formulations is a widely accepted method. This review identifies surface analytical techniques that are considered suitable for analysis of thin films at metallic substrates, but are yet to be applied to analysis of carbon steel surfaces in corrosive media or treated with corrosion inhibitors. The reviewed methods include time of flight-secondary ion mass spectrometry, X-ray absorption spectroscopy methods, particle-induced X-ray emission, Rutherford backscatter spectroscopy, Auger electron spectroscopy, electron probe microanalysis, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission electron microscopy, low-energy electron diffraction, small-angle neutron scattering and neutron reflectometry, and conversion electron Moessbauer spectrometry. Advantages and limitations of the analytical methods in thin-film surface investigations are discussed. Technical parameters of nominated analytical methods are provided to assist in the selection of suitable methods for analysis of metallic substrates deposited with surface films. The challenges associated with the applications of the emerging analytical methods in corrosion science are also addressed. PMID:28413351

High-fidelity large area nano-patterning of silicon with femtosecond light sheet

NASA Astrophysics Data System (ADS)

Sidhu, Mehra S.; Munjal, Pooja; Singh, Kamal P.

2018-01-01

We employ a femtosecond light sheet generated by a cylindrical lens to rapidly produce high-fidelity nano-structures over large area on silicon surface. The Fourier analysis of electron microscopy images of the laser-induced surface structures reveals sharp peaks indicating good homogeneity. We observed an emergence of second-order spatial periodicity on increasing the scan speed. Our reliable approach may rapidly nano-pattern curved solid surfaces and tiny objects for diverse potential applications in optical devices, structural coloring, plasmonic substrates and in high-harmonic generation.

The Effects of Surface Reconstruction and Electron-Positron Correlation on the Annihilation Characteristics of Positrons Trapped at Semiconductor Surfaces

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Jung, E.; Weiss, A. H.

2009-03-01

Experimental positron annihilation induced Auger electron spectroscopy (PAES) data from Ge(100) and Ge(111) surfaces display several strong Auger peaks corresponding to M4,5N1N2,3, M2,3M4,5M4,5, M2,3M4,5V, and M1M4,5M4,5 Auger transitions. The integrated peak intensities of Auger transitions have been used to obtain experimental annihilation probabilities for the Ge 3d and 3p core electrons. The experimental data were analyzed by performing theoretical studies of the effects of surface reconstructions and electron-positron correlations on image potential induced surface states and annihilation characteristics of positrons trapped at the reconstructed Ge(100) and Ge(111) surfaces. Calculations of positron surface states and annihilation characteristics have been performed for Ge(100) surface with (2×1), (2×2), and (4×2) reconstructions, and for Ge(111) surface with c(2×8) reconstruction. Estimates of the positron binding energy and annihilation characteristics reveal their sensitivity to the specific atomic structure of the topmost layers of the semiconductor and to the approximations used to describe electron-positron correlations. The results of these theoretical studies are compared with the ones obtained for the reconstructed Si(100)-(2×1) and Si(111)-(7×7) surfaces.

TED analysis of the Si(113) surface structure

NASA Astrophysics Data System (ADS)

Suzuki, T.; Minoda, H.; Tanishiro, Y.; Yagi, K.

1999-09-01

We carried out a TED (transmission electron diffraction) analysis of the Si(113) surface structure. The TED patterns taken at room temperature showed reflections due to the 3×2 reconstructed structure. The TED pattern indicated that a glide plane parallel to the <332> direction suggested in some models is excluded. We calculated the R-factors (reliability factors) for six surface structure models proposed previously. All structure models with energy-optimized atomic positions have large R-factors. After revision of the atomic positions, the R-factors of all the structure models decreased below 0.3, and the revised version of Dabrowski's 3×2 model has the smallest R-factor of 0.17.

Majorana surface modes of nodal topological pairings in spin-3/2 semimetals

NASA Astrophysics Data System (ADS)

Yang, Wang; Xiang, Tao; Wu, Congjun

2017-10-01

When solid state systems possess active orbital-band structures subject to spin-orbit coupling, their multicomponent electronic structures are often described in terms of effective large-spin fermion models. Their topological structures of superconductivity are beyond the framework of spin singlet and triplet Cooper pairings for spin-1/2 systems. Examples include the half-Heusler compound series of RPtBi, where R stands for a rare-earth element. Their spin-orbit coupled electronic structures are described by the Luttinger-Kohn model with effective spin-3/2 fermions and are characterized by band inversion. Recent experiments provide evidence to unconventional superconductivity in the YPtBi material with nodal spin-septet pairing. We systematically study topological pairing structures in spin-3/2 systems with the cubic group symmetries and calculate the surface Majorana spectra, which exhibit zero energy flat bands, or, cubic dispersion depending on the specific symmetry of the superconducting gap functions. The signatures of these surface states in the quasiparticle interference patterns of tunneling spectroscopy are studied, which can be tested in future experiments.

Low energy positrons as probes of reconstructed semiconductor surfaces.

NASA Astrophysics Data System (ADS)

Fazleev, Nail G.; Weiss, Alex H.

2007-03-01

Positron probes of semiconductor surfaces that play a fundamental role in modern science and technology are capable to non-destructively provide information that is both unique to the probe and complimentary to that extracted using other more standard techniques. We discuss recent progress in studies of the reconstructed Si(100), Si(111), Ge(100), and Ge(111) surfaces, clean and exposed to hydrogen and oxygen, using a surface characterization technique, Positron-Annihilation-Induced Auger-Electron Spectroscopy (PAES). Experimental PAES results are analyzed by performing first-principles calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons for the reconstructed surfaces, taking into account discrete lattice effects, the electronic reorganization due to bonding, and charge redistribution effects at the surface. Effects of the hydrogen and oxygen adsorption on semiconductor surfaces on localization of positron surface state wave functions and annihilation characteristics are also analyzed. Theoretical calculations confirm that PAES intensities, which are proportional to annihilation probabilities of the surface trapped positrons that results in a core hole, are sensitive to the crystal face, surface structure and elemental content of the semiconductors.

The surface stability of Cr 2O 3 (0 0 0 1)

DOE PAGES

Cao, Shi; Wu, Ning; Echtenkamp, William; ...

2015-05-28

The surface of chromia (Cr 2O 3) has a surface electronic structure distinct from the bulk and a packing density distinct from the bulk. More than a demarcation between the solid and the vacuum, the surface differs from the bulk of chromia, not just because of a partial occupancy of chromium sites, but also because of an increased number of unoccupied surface oxygen sites (vacancy sites), evident in angle-resolved core level photoemission. In spite of the structural differences that exist at the surface, there is, as yet, no evidence that these complications affect the surface Debye temperature beyond the mostmore » simple of assumptions regarding the lower coordination of the surface. Using low-energy electron diffraction (LEED), the effective surface Debye temperature (similar to 490 K) is found to be lower than the bulk (similar to 645 K) Debye temperature of Cr 2O 3(0 0 0 1). This surface effective Debye temperature, indicative of vibrations along the surface normal, uncorrected for anharmonic effects, has a value reduced from the effective bulk Debye temperature yet close to the value root 2 expected from a simple mean field argument.« less

Quantum oscillations from the reconstructed Fermi surface in electron-doped cuprate superconductors

NASA Astrophysics Data System (ADS)

Higgins, J. S.; Chan, M. K.; Sarkar, Tarapada; McDonald, R. D.; Greene, R. L.; Butch, N. P.

2018-04-01

We have studied the electronic structure of electron-doped cuprate superconductors via measurements of high-field Shubnikov–de Haas oscillations in thin films. In optimally doped Pr2‑x Ce x CuO4±δ and La2‑x Ce x CuO4±δ , quantum oscillations indicate the presence of a small Fermi surface, demonstrating that electronic reconstruction is a general feature of the electron-doped cuprates, despite the location of the superconducting dome at very different doping levels. Negative high-field magnetoresistance is correlated with an anomalous low-temperature change in scattering that modifies the amplitude of quantum oscillations. This behavior is consistent with effects attributed to spin fluctuations.

Large-angle illumination STEM: Toward three-dimensional atom-by-atom imaging

DOE PAGES

Ishikawa, Ryo; Lupini, Andrew R.; Hinuma, Yoyo; ...

2014-11-26

To completely understand and control materials and their properties, it is of critical importance to determine their atomic structures in all three dimensions. Recent revolutionary advances in electron optics – the inventions of geometric and chromatic aberration correctors as well as electron source monochromators – have provided fertile ground for performing optical depth sectioning at atomic-scale dimensions. In this study we theoretically demonstrate the imaging of top/sub-surface atomic structures and identify the depth of single dopants, single vacancies and the other point defects within materials by large-angle illumination scanning transmission electron microscopy (LAI-STEM). The proposed method also allows us tomore » measure specimen properties such as thickness or three-dimensional surface morphology using observations from a single crystallographic orientation.« less

Predicting the Oxygen-Binding Properties of Platinum Nanoparticle Ensembles by Combining High-Precision Electron Microscopy and Density Functional Theory.

PubMed

Aarons, Jolyon; Jones, Lewys; Varambhia, Aakash; MacArthur, Katherine E; Ozkaya, Dogan; Sarwar, Misbah; Skylaris, Chris-Kriton; Nellist, Peter D

2017-07-12

Many studies of heterogeneous catalysis, both experimental and computational, make use of idealized structures such as extended surfaces or regular polyhedral nanoparticles. This simplification neglects the morphological diversity in real commercial oxygen reduction reaction (ORR) catalysts used in fuel-cell cathodes. Here we introduce an approach that combines 3D nanoparticle structures obtained from high-throughput high-precision electron microscopy with density functional theory. Discrepancies between experimental observations and cuboctahedral/truncated-octahedral particles are revealed and discussed using a range of widely used descriptors, such as electron-density, d-band centers, and generalized coordination numbers. We use this new approach to determine the optimum particle size for which both detrimental surface roughness and particle shape effects are minimized.

Reaction of water with MgO(100) surfaces: Part III. X-ray standing wave studies

NASA Astrophysics Data System (ADS)

Liu, P.; Kendelewicz, T.; Nelson, E. J.; Brown, G. E.

1998-09-01

Clean MgO(100) surfaces cleaved in vacuum and exposed to water vapor or bulk water were studied using the X-ray standing wave (XSW) technique in back reflection mode and surface sensitive, element specific O KLL and Mg KLL Auger electron yield detection. The effects of surface charging were mitigated, but not entirely eliminated, by using a low-energy electron flood gun. Simulation of the XSW signal showed that the effect of surface charging on the XSW data could be minimized with careful experimental design. We demonstrate that the XSW method can be applied to studies of insulating surfaces, and our results for MgO(100) surfaces exposed to water vapor or bulk water indicate the following: (1) the vacuum-cleaved clean surface undergoes no surface reconstruction or significant relaxation perpendicular to the surface; (2) Mg-OH distances on surfaces exposed to water vapor or bulk water measured perpendicular to the (100) surface are the same as in bulk MgO; and (3) the z-position of the surface Mg atoms does not change within the estimated error [±2% of the (200) spacing] after the surface is fully hydroxylated. Our results for the clean, vacuum-cleaved surface disagree with results from impact collision ion-scattering spectroscopy and surface-extended electron-loss fine structure for MgO(100), which indicate 15 and 17% inward relaxation, respectively, and they support results from low-energy electron diffraction, reflection high-energy electron diffraction, and photoelectron diffraction that show little, if any, relaxation or rumpling of the surface.

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

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

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« less

Solution and surface effects on plasma fibronectin structure

PubMed Central

1983-01-01

As assessed by electron microscopy, the reported shape of the plasma fibronectin molecule ranges from that of a compact particle to an elongated, rod-like structure. In this study, we evaluated the effects of solution and surface conditions on fibronectin shape. Freeze-dried, unstained human plasma fibronectin molecules deposited at pH 7.0-7.4 onto carbon films and examined by scanning transmission electron microscopy appeared relatively compact and pleiomorphic, with approximate average dimensions of 24 nm X 16 nm. Negatively stained molecules also had a similar shape but revealed greater detail in that we observed irregular, yarn-like structures. Glutaraldehyde-induced intramolecular cross-linking did not alter the appearance of plasma fibronectin. Molecules deposited at pH 2.8, pH 9.3, or after succinylation were less compact than those deposited at neutral pH. In contrast, fibronectin molecules sprayed onto mica surfaces at pH 7, rotary shadowed, and examined by transmission electron microscopy were elongated and nodular with a contour length of 120-130 nm. Sedimentation velocity experiments and electron microscopic observations indicate that fibronectin unfolds when it is succinylated, when the ionic strength is raised at pH 7, or when the pH is adjusted to 9.3 or 2.8. Greater unfolding is observed at pH 2.8 at low ionic strength (less than 0.01) compared with material at that pH in 0.15 M NaCl solution. We conclude that (a) the shape assumed by the fibronectin molecule can be strongly affected by solution conditions and by deposition onto certain surfaces; and that (b) the images of fibronectin seen by scanning transmission electron microscopy at neutral pH on carbon film are representative of molecules in physiologic solution. PMID:6417145

Effects of magnetic dopants in (Li0.8M0.2OH )FeSe (M =Fe , Mn, Co): Density functional theory study using a band unfolding technique

NASA Astrophysics Data System (ADS)

Chen, M. X.; Chen, Wei; Zhang, Zhenyu; Weinert, M.

2017-12-01

The effects of Fe dopants on the electronic bands structure of (Li0.8Fe0.2OH )FeSe are investigated by a band unfolding (k -projection) technique and first-principles supercell calculations. Doping 20% Fe into the LiOH layers causes electron donation to the FeSe layers, significantly changing the profile of bands around the Fermi level. Because of the weak bonding between the LiOH and FeSe layers the magnetic configuration of the dopants has only minor effects on the band structure. The electronic bands for the surface FeSe layer of (Li0.8Fe0.2OH )FeSe show noticeable differences compared to those of the inner layers, both in the location of the Fermi level and in details of the bands near the high symmetry points, resulting from different effective doping levels and the broken symmetry at the surface. The band structure for the surface FeSe layer with checkerboard antiferromagnetic order is reasonably consistent with angle-resolved photoemission results. The 3 d transition metals Mn and Co have similar doping effects on the band structure of (LiOH)FeSe.

Topological Electride Y2C.

PubMed

Huang, Huaqing; Jin, Kyung-Hwan; Zhang, Shunhong; Liu, Feng

2018-03-14

Two-dimensional (2D) electrides are layered ionic crystals in which anionic electrons are confined in the interlayer space. Here, we report a discovery of nontrivial [Formula: see text] topology in the electronic structures of 2D electride Y 2 C. Based on first-principles calculations, we found a topological [Formula: see text] invariant of (1; 111) for the bulk band and topologically protected surface states in the surfaces of Y 2 C, signifying its nontrivial electronic topology. We suggest a spin-resolved angle-resolved photoemission spectroscopy (ARPES) measurement to detect the unique helical spin texture of the spin-polarized topological surface state, which will provide characteristic evidence for the nontrivial electronic topology of Y 2 C. Furthermore, the coexistence of 2D surface electride states and topological surface state enables us to explain the outstanding discrepancy between the recent ARPES experiments and theoretical calculations. Our findings establish a preliminary link between the electride in chemistry and the band topology in condensed-matter physics, which are expected to inspire further interdisciplinary research between these fields.

Understanding local degradation of cycled Ni-rich cathode materials at high operating temperature for Li-ion batteries

NASA Astrophysics Data System (ADS)

Hwang, Sooyeon; Kim, Dong Hyun; Chung, Kyung Yoon; Chang, Wonyoung

2014-09-01

We utilize transmission electron microscopy in conjunction with electron energy loss spectroscopy to investigate local degradation that occurs in LixNi0.8Co0.15Al0.05O2 cathode materials (NCA) after 30 cycles with cutoff voltages of 4.3 V and 4.8 V at 55 °C. NCA has a homogeneous crystallographic structure before electrochemical reactions; however, we observed that 30 cycles of charge/discharge reactions induced inhomogeneity in the crystallographic and electronic structures and also introduced porosity particularly at surface area. These changes were more noticeable in samples cycled with higher cutoff voltage of 4.8 V. Effect of operating temperature was further examined by comparing electronic structures of oxygen of the NCA particles cycled at both room temperature and 55 °C. The working temperature has a greater impact on the NCA cathode materials at a cutoff voltage of 4.3 V that is the practical the upper limit voltage in most applications, while a cutoff voltage of 4.8 V is high enough to cause surface degradation even at room temperature.

Fermiology and electron dynamics of trilayer nickelate La 4Ni 3O 10

DOE PAGES

Li, Haoxiang; Zhou, Xiaoqing; Nummy, Thomas; ...

2017-09-26

Layered nickelates have the potential for exotic physics similar to high T C superconducting cuprates as they have similar crystal structures and these transition metals are neighbors in the periodic table. Here we present an angle-resolved photoemission spectroscopy (ARPES) study of the trilayer nickelate La 4Ni 3O 10 revealing its electronic structure and correlations, finding strong resemblances to the cuprates as well as a few key differences. We find a large hole Fermi surface that closely resembles the Fermi surface of optimally hole-doped cuprates, including its d x2-y2 orbital character, hole filling level, and strength of electronic correlations. However, inmore » contrast to cuprates, La 4Ni 3O 10 has no pseudogap in the d x2-y2 band, while it has an extra band of principally d 3z2-r2 orbital character, which presents a low temperature energy gap. Furthermore, these aspects drive the nickelate physics, with the differences from the cuprate electronic structure potentially shedding light on the origin of superconductivity in the cuprates.« less

Nanostructured polymer brushes.

PubMed

Schmelmer, Ursula; Paul, Anne; Küller, Alexander; Steenackers, Marin; Ulman, Abraham; Grunze, Michael; Gölzhäuser, Armin; Jordan, Rainer

2007-03-01

Nanopatterned polymer brushes with sub-50-nm resolution were prepared by a combination of electron-beam chemical lithography (EBCL) of self-assembled monolayers (SAMs) and surface-initiated photopolymerization (SIPP). As a further development of our previous work, selective EBCL was performed with a highly focused electron beam and not via a mask, to region-selectively convert a SAM of 4'-nitro-1,1'-biphenyl-4-thiol to defined areas of crosslinked 4'-amino-1,1'-biphenyl-4-thiol. These "written" structures were then used to prepare surface-bonded, asymmetric, azo initiator sites of 4'-azomethylmalonodinitrile-1,1'-biphenyl-4-thiol. In the presence of bulk styrene, SIPP amplified the primary structures of line widths from 500 to 10 nm to polystyrene structures of line widths 530 nm down to approximately 45 nm at a brush height of 10 or 7 nm, respectively, as measured by scanning electron microscopy and atomic force microscopy (AFM). The relative position of individual structures was within a tolerance of a few nanometers, as verified by AFM. At line-to-line spacings down to 50-70 nm, individual polymer brush structures are still observable. Below this threshold, neighboring structures merge due to chain overlap.

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

DOE PAGES

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto; ...

2017-01-30

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

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

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

Influence of grid resolution in fluid-model simulation of nanosecond dielectric barrier discharge plasma actuator

NASA Astrophysics Data System (ADS)

Hua, Weizhuo; Fukagata, Koji

2018-04-01

Two-dimensional numerical simulation of a surface dielectric barrier discharge (SDBD) plasma actuator, driven by a nanosecond voltage pulse, is conducted. A special focus is laid upon the influence of grid resolution on the computational result. It is found that the computational result is not very sensitive to the streamwise grid spacing, whereas the wall-normal grid spacing has a critical influence. In particular, the computed propagation velocity changes discontinuously around the wall-normal grid spacing about 2 μm due to a qualitative change of discharge structure. The present result suggests that a computational grid finer than that was used in most of previous studies is required to correctly capture the structure and dynamics of streamer: when a positive nanosecond voltage pulse is applied to the upper electrode, a streamer forms in the vicinity of upper electrode and propagates along the dielectric surface with a maximum propagation velocity of 2 × 108 cm/s, and a gap with low electron and ion density (i.e., plasma sheath) exists between the streamer and dielectric surface. Difference between the results obtained using the finer and the coarser grid is discussed in detail in terms of the electron transport at a position near the surface. When the finer grid is used, the low electron density near the surface is caused by the absence of ionization avalanche: in that region, the electrons generated by ionization is compensated by drift-diffusion flux. In contrast, when the coarser grid is used, underestimated drift-diffusion flux cannot compensate the electrons generated by ionization, and it leads to an incorrect increase of electron density.

Femtosecond manipulation of spins, charges, and ions in nanostructures, thin films, and surfaces

PubMed Central

Carbone, F.; Hengsberger, M.; Castiglioni, L.; Osterwalder, J.

2017-01-01

Modern ultrafast techniques provide new insights into the dynamics of ions, charges, and spins in photoexcited nanostructures. In this review, we describe the use of time-resolved electron-based methods to address specific questions such as the ordering properties of self-assembled nanoparticles supracrystals, the interplay between electronic and structural dynamics in surfaces and adsorbate layers, the light-induced control of collective electronic modes in nanowires and thin films, and the real-space/real-time evolution of the skyrmion lattice in topological magnets. PMID:29308416

A First Principles Study of H2 Adsorption on LaNiO3(001) Surfaces

PubMed Central

Pan, Changchang; Chen, Yuhong; Wu, Na; Zhang, Meiling; Yuan, Lihua; Zhang, Cairong

2017-01-01

The adsorption of H2 on LaNiO3 was investigated using density functional theory (DFT) calculations. The adsorption sites, adsorption energy, and electronic structure of LaNiO3(001)/H2 systems were calculated and indicated through the calculated surface energy that the (001) surface was the most stable surface. By looking at optimized structure, adsorption energy and dissociation energy, we found that there were three types of adsorption on the surface. First, H2 molecules completely dissociate and then tend to bind with the O atoms, forming two –OH bonds. Second, H2 molecules partially dissociate with the H atoms bonding to the same O atom to form one H2O molecule. These two types are chemical adsorption modes; however, the physical adsorption of H2 molecules can also occur. When analyzing the electron structure of the H2O molecule formed by the partial dissociation of the H2 molecule and the surface O atom, we found that the interaction between H2O and the (001) surface was weaker, thus, H2O was easier to separate from the surface to create an O vacancy. On the (001) surface, a supercell was constructed to accurately study the most stable adsorption site. The results from analyses of the charge population; electron localization function; and density of the states indicated that the dissociated H and O atoms form a typical covalent bond and that the interaction between the H2 molecule and surface is mainly due to the overlap-hybridization among the H 1s, O 2s, and O 2p states. Therefore, the conductivity of LaNiO3(001)/H2 is stronger after adsorption and furthermore, the conductivity of the LaNiO3 surface is better than that of the LaFeO3 surface. PMID:28772396

New Insights into Mechanism of Surface Reactions of ZnO Nanorods During Electrons Beam Irradiation.

PubMed

Cho, Youngseung; Ji, Hyunjin; Kim, Hyoungsub; Yoon, Jinsuop; Choi, Byoungdeog

2018-09-01

This study provides new insight into mechanisms of ionic reactions on the surface of ZnO nanorod networks, which could result in enhanced performance in optical or molecular sensors. The current- voltage characteristics of ZnO nanorod network devices exhibit typical nonlinear behavior in air, which implies the formation of a Schottky barrier when metals are used as contacts. The conductance of the device increased significantly in vacuum, which can be explained by the desorption of hydroxyl groups at very low pressure. While physisorbed water or oxygen-related ions can detach from the ZnO surface during evacuation, exposure to high energy in the electron beam is believed to detach the chemisorbed anions of O- and O-2 from the surface of ZnO nanorods, which releases more electrons into the channel. The increase in available electrons enhances the conductance of the ZnO nanorods. Slow initialization of the conductance under ambient conditions indicates that the ionic re-adsorption is inactive under these conditions. Thus, the electron irradiation process can be used to reset the surface ionic molecules on metal oxide nano-structures by tuning the surface potential prior to the passivation process.

Multilamellar Structures and Filament Bundles Are Found on the Cell Surface during Bunyavirus Egress

PubMed Central

Sanz-Sánchez, Laura; Risco, Cristina

2013-01-01

Inside cells, viruses build specialized compartments for replication and morphogenesis. We observed that virus release associates with specific structures found on the surface of mammalian cells. Cultured adherent cells were infected with a bunyavirus and processed for oriented sectioning and transmission electron microscopy. Imaging of cell basal regions showed sophisticated multilamellar structures (MLS) and extracellular filament bundles with attached viruses. Correlative light and electron microscopy confirmed that both MLS and filaments proliferated during the maximum egress of new viruses. MLS dimensions and structure were reminiscent of those reported for the nanostructures on gecko fingertips, which are responsible for the extraordinary attachment capacity of these lizards. As infected cells with MLS were more resistant to detachment than control cells, we propose an adhesive function for these structures, which would compensate for the loss of adherence during release of new virus progeny. PMID:23799021

Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition

DOE PAGES

Kiraly, Brian T.; Jacobberger, Robert M.; Mannix, Andrew J.; ...

2015-10-27

Epitaxially oriented wafer-scale graphene grown directly on semiconducting Ge substrates is of high interest for both fundamental science and electronic device applications. To date, however, this material system remains relatively unexplored structurally and electronically, particularly at the atomic scale. To further understand the nature of the interface between graphene and Ge, we utilize ultrahigh vacuum scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) along with Raman and X-ray photoelectron spectroscopy to probe interfacial atomic structure and chemistry. STS reveals significant differences in electronic interactions between graphene and Ge(110)/Ge(111), which is consistent with a model of stronger interaction on Ge(110)more » leading to epitaxial growth. Raman spectra indicate that the graphene is considerably strained after growth, with more point-to-point variation on Ge(111). Furthermore, this native strain influences the atomic structure of the interface by inducing metastable and previously unobserved Ge surface reconstructions following annealing. These nonequilibrium reconstructions cover >90% of the surface and, in turn, modify both the electronic and mechanical properties of the graphene overlayer. Finally, graphene on Ge(001) represents the extreme strain case, where graphene drives the reorganization of the Ge surface into [107] facets. From this study, it is clear that the interaction between graphene and the underlying Ge is not only dependent on the substrate crystallographic orientation, but is also tunable and strongly related to the atomic reconfiguration of the graphene–Ge interface.« less

Correlating structural dynamics and catalytic activity of AgAu nanoparticles with ultrafast spectroscopy and all-atom molecular dynamics simulations.

PubMed

Ferbonink, G F; Rodrigues, T S; Dos Santos, D P; Camargo, P H C; Albuquerque, R Q; Nome, R A

2018-05-29

In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.

The electronic structures and work functions of (100) surface of typical binary and doped REB6 single crystals

NASA Astrophysics Data System (ADS)

Liu, Hongliang; Zhang, Xin; Xiao, Yixin; Zhang, Jiuxing

2018-03-01

The density function theory been used to calculate the electronic structures of binary and doped rare earth hexaborides (REB6), which exhibits the large density of states (DOS) near Fermi level. The d orbital elections of RE element contribute the electronic states of election emission near the Fermi level, which imply that the REB6 (RE = La, Ce, Gd) with wide distribution of high density d orbital electrons could provide a lower work function and excellent emission properties. Doping RE elements into binary REB6 can adjust DOS and the position of the Fermi energy level. The calculated work functions of considered REB6 (100) surface show that the REB6 (RE = La, Ce, Gd) have lower work function and doping RE elements with active d orbital electrons can significantly reduce work function of binary REB6. The thermionic emission test results are basically accordant with the calculated value, proving the first principles calculation could provide a good theoretical guidance for the study of electron emission properties of REB6.

Imaging of Norway spruce early somatic embryos with the ESEM, Cryo-SEM and laser scanning microscope.

PubMed

Neděla, Vilém; Hřib, Jiří; Havel, Ladislav; Hudec, Jiří; Runštuk, Jiří

2016-05-01

This article describes the surface structure of Norway spruce early somatic embryos (ESEs) as a typical culture with asynchronous development. The microstructure of extracellular matrix covering ESEs were observed using the environmental scanning electron microscope as a primary tool and using the scanning electron microscope with cryo attachment and laser electron microscope as a complementary tool allowing our results to be proven independently. The fresh samples were observed in conditions of the air environment of the environmental scanning electron microscope (ESEM) with the pressure from 550Pa to 690Pa and the low temperature of the sample from -18°C to -22°C. The samples were studied using two different types of detector to allow studying either the thin surface structure or material composition. The scanning electron microscope with cryo attachment was used for imaging frozen extracellular matrix microstructure with higher resolution. The combination of both electron microscopy methods was suitable for observation of "native" plant samples, allowing correct evaluation of our results, free of error and artifacts. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystallographic perturbations to valence charge density and hydrogen-surface interactions

NASA Astrophysics Data System (ADS)

Ciston, James W.

The subject of surfaces has been the epicenter of numerous studies in recent years, particularly with respect to applications in catalysis, thin films, and self-assembly of nanostructures where the surface-to-volume ratio is large. Understanding how the atomic structure of materials differs at surfaces where the atoms are far less constrained can yield fundamental insight into these interesting nanoscale phenomena. Quantum surface crystallography takes this one step further in an attempt to experimentally measure the structure of the electrons themselves, which is of greater importance than atomic positions in determining material properties. We report a procedure for obtaining a much better initial parameterization of the charge density than what is possible from a neutral atom model. This procedure involves the parameterization of a bulk charge density model in terms of simple variables such as bond lengths, which can then be transferred to the problem of interest, for instance a surface. Parameterization is accomplished through the fitting of Density Functional Theory calculations of a variety of crystal distortions to a bond-centered pseudoatom (BCPA) model. This parameterized model can then be applied to surfaces or for other problems where an initial higher-order model is needed without the addition of any extra fitted parameters. Through the use of the BCPA model, we report a three-dimensional charge density refinement from x-ray diffraction intensities of the Si (001) 2x1H surface. By properly accounting for the covalent bonding effects in the silicon structure, we were able to stably refine the positions of hydrogen atoms at this surface in three dimensions, which had never before been accomplished for any surface. In addition, we found experimentally an increased, slightly localized bond density of approximately 0.31 electrons between each Si atom pair at the surface. Both the atomic positions and the charge density were found to be in remarkably good agreement with density functional theory (DFT) calculations. The BCPA model was also applied to an experimental refinement of the local charge density at the Si (111) 7x7 surface utilizing a combination of x-ray and high energy electron diffraction. By perturbing about the bond-centered pseudoatom model, we found experimentally that the adatoms were in an anti-bonding state with the atoms directly below. We were also able to experimentally refine a charge transfer of 0.26+/-0.04 e- from each adatom site to the underlying layers. This was the first statistically significant refinement of site-specific bonding information at any surface utilizing x-ray diffraction data. Precession electron diffraction (PED) is a technique which is gaining increasing interest due to its ease of use and reduction of the dynamical scattering problem in electron diffraction. To further investigate the usefulness of this technique, we performed a systematic study of the effect of precession angle on the mineral andalusite where the semiangle was varied from 6.5 to 32 mrad in five discrete steps. We have shown that the intensities of kinematically forbidden reflections decayed exponentially as the precession semiangle (ϕ) was increased. Additionally, we have determined that charge density effects were best observed at moderately low angles (6.5-13 mrad) even though PED patterns became more kinematical in nature as the precession angle was increased further. We have also shown that the amount of interpretable information provided by direct methods phase inversion of the diffraction data increases monotonically but non-systematically as ϕ increases. We report an experimental and theoretical analysis of the ✓3x✓3-R30° and 2x2 reconstructions on the MgO (111) surface combining transmission electron microscopy, x-ray photoelectron spectroscopy, and reasonably accurate density functional calculations using the meta-GGA functional TPSS. We have not only conclusively solved the atomic structures of these reconstructions, but have developed a kinetic model for an evolutionary pathway between structures driven entirely by exchange of water molecules between the surface and the environment that does not require the cations to move when the structure transforms. This is the first time an experimentally and theoretically supported kinetic model has described not only all of the structures in a series on a single oxide surface, but also describes why none of the structures pass through the thermodynamically most stable configuration. Lastly, we have investigated the observability of valence bonding effects in aberration-corrected high resolution electron microscopy (HREM) images along the [010] projection of the mineral Forsterite (Mg2SiO 4). Direct observability of bonding effects would be both faster and less ambiguous than the refinement of similar features against diffraction data. Through analysis of simulated high resolution electron microscopy images, we have determined that bonding effects should be observable at levels approaching 20% of the total contrast. Initial experimental results for this material system have also been presented.

Electronic structure and fine structural features of the air-grown UNxOy on nitrogen-rich uranium nitride

NASA Astrophysics Data System (ADS)

Long, Zhong; Zeng, Rongguang; Hu, Yin; Liu, Jing; Wang, Wenyuan; Zhao, Yawen; Luo, Zhipeng; Bai, Bin; Wang, Xiaofang; Liu, Kezhao

2018-06-01

Oxide formation on surface of nitrogen-rich uranium nitride film/particles was investigated using X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), aberration-corrected transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with electron energy-loss spectroscopy (EELS). XPS and AES studies indicated that the oxidized layer on UN2-x film is ternary compound uranium oxynitride (UNxOy) in 5-10 nm thickness. TEM/HAADF-STEM and EELS studies revealed the UNxOy crystallizes in the FCC CaF2-type structure with the lattice parameter close to the CaF2-type UN2-x matrix. The work can provide further information to the oxidation mechanism of uranium nitride.

H2O incorporation in the phosphorene/a-SiO2 interface: a first-principles study

NASA Astrophysics Data System (ADS)

Scopel, Wanderlã L.; Souza, Everson S.; Miwa, R. H.

2017-02-01

Based on first-principles calculations, we investigate (i) the energetic stability and electronic properties of single-layer phosphorene (SLP) adsorbed on an amorphous SiO2 surface (SLP/a-SiO2), and (ii) the further incorporation of water molecules at the phosphorene/a-SiO2 interface. In (i), we find that the phosphorene sheet binds to a-SiO2 through van der Waals interactions, even in the presence of oxygen vacancies on the surface. The SLP/a-SiO2 system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-SiO2 substrate. The structure and the surface-potential corrugations promote the formation of electron-rich and electron-poor regions on the phosphorene sheet and at the SLP/a-SiO2 interface. Such charge density puddles are strengthened by the presence of oxygen vacancies in a-SiO2. In (ii), because of the amorphous structure of the surface, we consider a number of plausible geometries for H2O embedded in the SLP/a-SiO2 interface. There is an energetic preference for the formation of hydroxyl (OH) groups on the a-SiO2 surface. Meanwhile, in the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we observe the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P-O-Si chemical bonds at the SLP/a-SiO2 interface. Further x-ray absorption spectra simulations are performed, which aim to provide additional structural/electronic information on the oxygen atoms forming hydroxyl groups or P-O-Si chemical bonds at the interface region.

H2O incorporation in the phosphorene/a-SiO2 interface: a first-principles study.

PubMed

Scopel, Wanderlã L; Souza, Everson S; Miwa, R H

2017-02-22

Based on first-principles calculations, we investigate (i) the energetic stability and electronic properties of single-layer phosphorene (SLP) adsorbed on an amorphous SiO 2 surface (SLP/a-SiO 2 ), and (ii) the further incorporation of water molecules at the phosphorene/a-SiO 2 interface. In (i), we find that the phosphorene sheet binds to a-SiO 2 through van der Waals interactions, even in the presence of oxygen vacancies on the surface. The SLP/a-SiO 2 system presents a type-I band alignment, with the valence (conduction) band maximum (minimum) of the phosphorene lying within the energy gap of the a-SiO 2 substrate. The structure and the surface-potential corrugations promote the formation of electron-rich and electron-poor regions on the phosphorene sheet and at the SLP/a-SiO 2 interface. Such charge density puddles are strengthened by the presence of oxygen vacancies in a-SiO 2 . In (ii), because of the amorphous structure of the surface, we consider a number of plausible geometries for H 2 O embedded in the SLP/a-SiO 2 interface. There is an energetic preference for the formation of hydroxyl (OH) groups on the a-SiO 2 surface. Meanwhile, in the presence of oxygenated water or interstitial oxygen in the phosphorene sheet, we observe the formation of metastable OH bonded to the phosphorene, and the formation of energetically stable P-O-Si chemical bonds at the SLP/a-SiO 2 interface. Further x-ray absorption spectra simulations are performed, which aim to provide additional structural/electronic information on the oxygen atoms forming hydroxyl groups or P-O-Si chemical bonds at the interface region.

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

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

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Stable room-temperature ferromagnetic phase at the FeRh(100) surface

DOE PAGES

Pressacco, Federico; Uhlir, Vojtech; Gatti, Matteo; ...

2016-03-03

Interfaces and low dimensionality are sources of strong modifications of electronic, structural, and magnetic properties of materials. FeRh alloys are an excellent example because of the first-order phase transition taking place at ~400 K from an antiferromagnetic phase at room temperature to a high temperature ferromagnetic one. It is accompanied by a resistance change and volume expansion of about 1%. We have investigated the electronic and magnetic properties of FeRh(100) epitaxially grown on MgO by combining spectroscopies characterized by different probing depths, namely X-ray magnetic circular dichroism and photoelectron spectroscopy. Furthermore, we find that the symmetry breaking induced at themore » Rh-terminated surface stabilizes a surface ferromagnetic layer involving five planes of Fe and Rh atoms in the nominally antiferromagnetic phase at room temperature. First-principles calculations provide a microscopic description of the structural relaxation and the electron spin-density distribution that support the experimental findings.« less

Sea spray aerosol structure and composition using cryogenic transmission electron microscopy

DOE PAGES

Patterson, Joseph P.; Collins, Douglas B.; Michaud, Jennifer M.; ...

2016-01-15

The surface properties of atmospheric aerosol particles largely control their impact on climate by affecting their ability to uptake water, react heterogeneously, and nucleate ice in clouds. However, in the vacuum of a conventional electron microscope, the native surface structure often undergoes chemical rearrangement resulting in surfaces that are quite different from their atmospheric configurations. Herein, we report the development of a cryo-TEM approach where sea spray aerosol particles are flash frozen in their native state and then probed by electron microscopy. This unique approach allows for the detection of not only mixed salts, but also soft materials including wholemore » hydrated bacteria, diatoms, virus particles, marine vesicles, as well as gel networks within hydrated salt droplets. As a result, we anticipate this method will open up a new avenue of analysis for aerosol particles, not only for ocean-derived aerosols, but for those produced from other sources where there is interest in the transfer of organic or biological species from the biosphere to the atmosphere.« less

Local electrical properties of n-AlInAs/i-GaInAs electron channel structures characterized by the probe-electron-beam-induced current technique.

PubMed

Watanabe, Kentaro; Nokuo, Takeshi; Chen, Jun; Sekiguchi, Takashi

2014-04-01

We developed a probe-electron-beam-induced current (probe-EBIC) technique to investigate the electrical properties of n-Al(0.48)In(0.52)As/i-Ga(0.30)In(0.70)As electron channel structures for a high-electron-mobility transistor, grown on a lattice-matched InP substrate and lattice-mismatched GaAs (001) and Si (001) substrates. EBIC imaging of planar surfaces at low magnifications revealed misfit dislocations originating from the AlInAs-graded buffer layer. The cross-sections of GaInAs channel structures on an InP substrate were studied by high-magnification EBIC imaging as well as cathodoluminescence (CL) spectroscopy. EBIC imaging showed that the structure is nearly defect-free and the carrier depletion zone extends from the channel toward the i-AlInAs buffer layer.

Surface effects of vapour-liquid-solid driven Bi surface droplets formed during molecular-beam-epitaxy of GaAsBi

PubMed Central

Steele, J. A.; Lewis, R. A.; Horvat, J.; Nancarrow, M. J. B.; Henini, M.; Fan, D.; Mazur, Y. I.; Schmidbauer, M.; Ware, M. E.; Yu, S.-Q.; Salamo, G. J.

2016-01-01

Herein we investigate a (001)-oriented GaAs1−xBix/GaAs structure possessing Bi surface droplets capable of catalysing the formation of nanostructures during Bi-rich growth, through the vapour-liquid-solid mechanism. Specifically, self-aligned “nanotracks” are found to exist trailing the Bi droplets on the sample surface. Through cross-sectional high-resolution transmission electron microscopy the nanotracks are revealed to in fact be elevated above surface by the formation of a subsurface planar nanowire, a structure initiated mid-way through the molecular-beam-epitaxy growth and embedded into the epilayer, via epitaxial overgrowth. Electron microscopy studies also yield the morphological, structural, and chemical properties of the nanostructures. Through a combination of Bi determination methods the compositional profile of the film is shown to be graded and inhomogeneous. Furthermore, the coherent and pure zincblende phase property of the film is detailed. Optical characterisation of features on the sample surface is carried out using polarised micro-Raman and micro-photoluminescence spectroscopies. The important light producing properties of the surface nanostructures are investigated through pump intensity-dependent micro-PL measurements, whereby relatively large local inhomogeneities are revealed to exist on the epitaxial surface for important optical parameters. We conclude that such surface effects must be considered when designing and fabricating optical devices based on GaAsBi alloys. PMID:27377213

Electron transport in ethanol & methanol absorbed defected graphene

NASA Astrophysics Data System (ADS)

Dandeliya, Sushmita; Srivastava, Anurag

2018-05-01

In the present paper, the sensitivity of ethanol and methanol molecules on surface of single vacancy defected graphene has been investigated using density functional theory (DFT). The changes in structural and electronic properties before and after adsorption of ethanol and methanol were analyzed and the obtained results show high adsorption energy and charge transfer. High adsorption happens at the active site with monovacancy defect on graphene surface. Present work confirms that the defected graphene increases the surface reactivity towards ethanol and methanol molecules. The presence of molecules near the active site affects the electronic and transport properties of defected graphene which makes it a promising choice for designing methanol and ethanol sensor.

Study of electronic and magnetic properties of h-BN on Ni surfaces: A DFT approach

NASA Astrophysics Data System (ADS)

Sahoo, M. R.; Sahu, S.; Kushwaha, A. K.; Nayak, S.

2018-04-01

Hexagonal boron nitride (h-BN) is a promising material for implementation in spintronics due to large band gap, low spin-orbit coupling, and a small lattice mismatch to graphene and close-packedsurfaces of fcc-Ni(111). Electronic and magnetic properties of single layer hexagonal Boron Nitride (h-BN) on Ni (111) surface have been studied with density functional calculation. Since lattice constants of nickel surfaces are very close to that of h-BN, nickel acts as a good substrate. We found that the interaction between 2Pz - 3dz2 orbitals leads to change in electronic band structure as well as density of states which results spin polarization in h-BN.

Structural, optical and compositional stability of MoS2 multi-layer flakes under high dose electron beam irradiation

NASA Astrophysics Data System (ADS)

Rotunno, E.; Fabbri, F.; Cinquanta, E.; Kaplan, D.; Longo, M.; Lazzarini, L.; Molle, A.; Swaminathan, V.; Salviati, G.

2016-06-01

MoS2 multi-layer flakes, exfoliated from geological molybdenite, have been exposed to high dose electron irradiation showing clear evidence of crystal lattice and stoichiometry modifications. A massive surface sulfur depletion is induced together with the consequent formation of molybdenum nanoislands. It is found that a nanometric amorphous carbon layer, unwillingly deposited during the transmission electron microscope experiments, prevents the formation of the nanoislands. In the absence of the carbon layer, the formation of molybdenum grains proceeds both on the top and bottom surfaces of the flake. If carbon is present on both the surfaces then the formation of Mo grains is completely prevented.

Electron beam induced damage in ITO coated Kapton. [Indium Tin Oxide

NASA Technical Reports Server (NTRS)

Krainsky, I.; Gordon, W. L.; Hoffman, R. W.

1981-01-01

Data for the stability of thin conductive indium tin oxide films on 0.003 inch thick Kapton substrates during exposure of the surface to electron beams are reported. The electron beam energy was 3 keV and the diameter was about 0.8 mm. Thermal effects and surface modifications are considered. For primary current greater than 0.6 microamperes, an obvious dark discoloration with diameter approximately that of the beam was produced. The structure of the discolored region was studied with the scanning electron microscope, and the findings are stated. Surface modifications were explored by AES, obtaining spectra and secondary emission coefficient as a function of time for different beam intensities. In all cases beam exposure results in a decrease of the secondary yield but because of thermal effects this change, as well as composition changes, cannot be directly interpreted in terms of electron beam dosage.

Rotatable spin-polarized electron source for inverse-photoemission experiments

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

Stolwijk, S. D., E-mail: Sebastian.Stolwijk@wwu.de; Wortelen, H.; Schmidt, A. B.

2014-01-15

We present a ROtatable Spin-polarized Electron source (ROSE) for the use in spin- and angle-resolved inverse-photoemission (SR-IPE) experiments. A key feature of the ROSE is a variable direction of the transversal electron beam polarization. As a result, the inverse-photoemission experiment becomes sensitive to two orthogonal in-plane polarization directions, and, for nonnormal electron incidence, to the out-of-plane polarization component. We characterize the ROSE and test its performance on the basis of SR-IPE experiments. Measurements on magnetized Ni films on W(110) serve as a reference to demonstrate the variable spin sensitivity. Moreover, investigations of the unoccupied spin-dependent surface electronic structure of Tl/Si(111)more » highlight the capability to analyze complex phenomena like spin rotations in momentum space. Essentially, the ROSE opens the way to further studies on complex spin-dependent effects in the field of surface magnetism and spin-orbit interaction at surfaces.« less

Electronic structures and superconductivity in LuTE2Si2 phases (TE = d-electron transition metal)

NASA Astrophysics Data System (ADS)

Samsel-Czekała, M.; Chajewski, G.; Wiśniewski, P.; Romanova, T.; Hackemer, A.; Gorzelniak, R.; Pikul, A. P.; Kaczorowski, D.

2018-05-01

In the course of our search for unconventional superconductors amidst the 1:2:2 phases, we have re-investigated the LuTE2Si2 compounds with TE = Fe, Co, Ni, Ru, Pd and Pt. In this paper, we present the results of our fully relativistic ab initio calculations of the band structures, performed using the full-potential local-orbital code. The theoretical data are supplemented by the results of low-temperature electrical transport and specific heat measurements performed down to 0.35 K. All the materials studied but LuPt2Si2 crystallize with the body-centered tetragonal ThCr2Si2-type structure (space group I4/mmm). Their Fermi surfaces exhibit a three-dimensional multi-band character. In turn, the Pt-bearing compound adopts the primitive tetragonal CaBe2Ge2-type structure (space group P4/nmm), and its Fermi surface consists of predominantly quasi-two-dimensional sheets. Bulk superconductivity was found only in LuPd2Si2 and LuPt2Si2 (independent of the structure type and dimensionality of the Fermi surface). The key superconducting characteristics indicate a fully-gapped BCS type character. Though the electronic structure of LuFe2Si2 closely resembles that of the unconventional superconductor YFe2Ge2, this Lu-based silicide exhibits neither superconductivity nor spin fluctuations at least down to 0.35 K.

Surface modification of steels and magnesium alloy by high current pulsed electron beam

NASA Astrophysics Data System (ADS)

Hao, Shengzhi; Gao, Bo; Wu, Aimin; Zou, Jianxin; Qin, Ying; Dong, Chuang; An, Jian; Guan, Qingfeng

2005-11-01

High current pulsed electron beam (HCPEB) is now developing as a useful tool for surface modification of materials. When concentrated electron flux transferring its energy into a very thin surface layer within a short pulse time, superfast processes such as heating, melting, evaporation and consequent solidification, as well as dynamic stress induced may impart the surface layer with improved physico-chemical and mechanical properties. This paper presents our research work on surface modification of steels and magnesium alloy with HCPEB of working parameters as electron energy 27 keV, pulse duration ∼1 μs and energy density ∼2.2 J/cm2 per pulse. Investigations performed on carbon steel T8, mold steel D2 and magnesium alloy AZ91HP have shown that the most pronounced changes of phase-structure state and properties occurring in the near-surface layers, while the thickness of the modified layer with improved microhardness (several hundreds of micrometers) is significantly greater than that of the heat-affected zone. The formation mechanisms of surface cratering and non-stationary hardening effect in depth are discussed based on the elucidation of non-equilibrium temperature filed and different kinds of stresses formed during pulsed electron beam melting treatment. After the pulsed electron beam treatments, samples show significant improvements in measurements of wear and corrosion resistance.

Fermi surfaces of the pyrite-type cubic AuSb2 compared with split Fermi surfaces of the ullmannite-type cubic chiral NiSbS and PdBiSe

NASA Astrophysics Data System (ADS)

Nishimura, K.; Kakihana, M.; Nakamura, A.; Aoki, D.; Harima, H.; Hedo, M.; Nakama, T.; Ōnuki, Y.

2018-05-01

We grew high-quality single crystals of AuSb2 with the pyrite (FeS2)-type cubic structure by the Bridgman method and studied the Fermi surface properties by the de Haas-van Alphen (dHvA) experiment and the full potential LAPW band calculation. The Fermi surfaces of AuSb2 are found to be similar to those of NiSbS and PdBiSe with the ullmannite (NiSbS)-type cubic chiral structure because the crystal structures are similar each other and the number of valence electrons is the same between two different compounds. Note that each Fermi surface splits into two Fermi surfaces in NiSbS and PdBiSe, reflecting the non-centrosymmetric crystal structure.

Electron-emission-induced cooling of boundary region in fusion devices

NASA Astrophysics Data System (ADS)

Mishra, Sanjay K.; Avinash, K.; Kaw, Predhiman; Kaw

2014-12-01

In this brief communication we have explored whether the electron emission from the boundary region surfaces (or from additional fine structured dust particles/droplets of some benign material put purposely in the area surrounding the surfaces) can act as an efficient cooling mechanism for boundary region surfaces/dust electrons and hence the lattice. In order to estimate the contribution of this cooling process a simple kinetic model based on charge flux balance and associated energetics has been established. Along with some additional sophistication like suitable choice of material and modification in the work function via surface coating, the estimates show that it is possible to keep the temperature of the plate/particles well within the critical limit, i.e. melting/sublimation point for the desired regime of incident heat flux.

Fabrication of anodic aluminium oxide templates on curved surfaces.

PubMed

Yin, Aijun; Guico, Rodney S; Xu, Jimmy

2007-01-24

Aluminium anodization provides a simple and inexpensive way to obtain nanoporous templates with uniform and controllable pore diameters and periods over a wide range. Moreover, one of the interesting possibilities afforded by the anodization process is that the anodization can take place on arbitrary surfaces, such as curved surfaces, which has not yet been well studied or applied in nanofabrication. In this paper, we characterize the anodization of Al films on silicon substrates with a curved top surface. The structures of the resultant anodic aluminium oxide (AAO) films are examined by scanning electron microscopy. Unique features including cessation, bending, and branching of pore channels are observed in the curved area. Possible growth mechanisms are proposed, which can also contribute to the understanding of the self-organization mechanism in the formation of porous AAO membranes. The new structures may open new opportunities in optical, electronic and electrochemical applications.

Growth and characterization of epitaxial silver indium diselenide

NASA Astrophysics Data System (ADS)

Pena Martin, Pamela

Photovoltaics (solar cells) are a key player in the renewable energy frontier, and will become increasingly important as their cost per watt continues to drop, especially if fossil fuel costs increase. One particularly promising photovoltaic technology is based on chalcopyrite-structure semiconductors. Within the chalcopyrite compounds the highest efficiency thin film solar cell absorber material to date is Cu(In,Ga)Se2 (CIGS). While current efficiency records are over 21% for single-junction cells, there is still room for improvement. Replacing some of the Cu with Ag has been shown to be beneficial in CIGS devices. However, the Ag- containing chalcopyrites are still relatively unknown in terms of their growth mechanism, energetics, and surface atomic and electronic properties. These are best inferred through study of epitaxial films, yet they have little mention in literature and have not been the subject of a detailed study. This work describes the growth of epitaxial AgInSe2 (AIS) on GaAs substrates, studying the morphology, structure, and surface properties to understand how growth takes place. It also seeks to experimentally determine the surface electronic and atomic structure at the atomic scale to gain insight into the part of the material that forms the heterojunction that collects photon energy in the device. Finally, this work seeks to compare and contrast these findings with what is known about CIGS to determine where similarities and, more importantly, the differences may lie. This study has found that single phase tetragonal AIS can be epitaxially grown on GaAs, as illustrated by x-ray diffraction (XRD), transmission electron microscope (TEM), and surface morphology data. Like CIGS, the close packed polar (112) planes have the lowest energy. The morphology points to a difference in step dynamics, leading to less faceted, straight edged island shapes compared to CIGS. Epitaxial temperature as a function of growth direction shows a different trend in AIS than in CIGS. Interdiffusion of the group III elements across the substrate interface was found to result in an epitaxial intermixed layer between the film and substrate in some cases, which may help mediate the lattice mismatch. At the atomic scale, scanning tunneling microscopy (STM) was used to observe details of the surface morphology, which indicated growth of the (112)A orientation of AIS by a screw dislocation mechanism (other surfaces were not examined by STM but are expected to show similar results). The surface atomic structure was directly imaged for the first time, revealing an arrangement similar to that expected from a bulk terminated surface. The electronic structure shows a gap in surface electronic states with a width comparable to bulk AIS, n-type conduction, and a tail of states near the valence band edge that decay well into the gap. The conduction and valence bands show fluctuations as a function of position on the surface, with greater magnitude in the valence band. The fluctuations in both bands are less than those observed on the surface of CIS by STM. It seems to indicate a reduction in band tails, both in magnitude and spacial extent, in AIS compared to CIS, likely tied to a reduction in point defect concentration at the surface.

Converting topological insulators into topological metals within the tetradymite family

NASA Astrophysics Data System (ADS)

Chen, K.-W.; Aryal, N.; Dai, J.; Graf, D.; Zhang, S.; Das, S.; Le Fèvre, P.; Bertran, F.; Yukawa, R.; Horiba, K.; Kumigashira, H.; Frantzeskakis, E.; Fortuna, F.; Balicas, L.; Santander-Syro, A. F.; Manousakis, E.; Baumbach, R. E.

2018-04-01

We report the electronic band structures and concomitant Fermi surfaces for a family of exfoliable tetradymite compounds with the formula T2C h2P n , obtained as a modification to the well-known topological insulator binaries Bi2(Se,Te ) 3 by replacing one chalcogen (C h ) with a pnictogen (P n ) and Bi with the tetravalent transition metals T = Ti, Zr, or Hf. This imbalances the electron count and results in layered metals characterized by relatively high carrier mobilities and bulk two-dimensional Fermi surfaces whose topography is well-described by first-principles calculations. Intriguingly, slab electronic structure calculations predict Dirac-like surface states. In contrast to Bi2Se3 , where the surface Dirac bands are at the Γ point, for (Zr,Hf ) 2Te2 (P,As) there are Dirac cones of strong topological character around both the Γ ¯ and M ¯ points, which are above and below the Fermi energy, respectively. For Ti2Te2P , the surface state is predicted to exist only around the M ¯ point. In agreement with these predictions, the surface states that are located below the Fermi energy are observed by angle-resolved photoemission spectroscopy measurements, revealing that they coexist with the bulk metallic state. Thus this family of materials provides a foundation upon which to develop novel phenomena that exploit both the bulk and surface states (e.g., topological superconductivity).

Size and shape dependence of CO adsorption sites on sapphire supported Fe microcrystals

NASA Technical Reports Server (NTRS)

Papageorgopoulos, C.; Heinemann, K.

1985-01-01

The surface structure and stoichiometry of alumina substrates, as well as the size, growth characteristics, and shape of Fe deposits on sapphire substrates have been investigated by low energy electron diffraction (LEED), Auger electron spectroscopy, electron energy loss spectroscopy, and X-ray photoemission spectroscopy (XPS), as well as work function measurements, in conjunction with transition electron microscopy observations. The substrates used in this work were the following: (1) new, clean Al2O3; (2) same surface amorphized by Ar ion bombardment; (3) same surface regenerated by 650 C annealing; (4) amorphous alumina films on Ta slab; and (5) polycrystal alumina films, obtained by heating amorphous films to 600 C. Substrate cleaning was found to be most effective in producing a reproducible surface upon oxygen RF plasma treatment. The Fe nucleation and growth process was found to depend strongly on the type of substrate surface and deposition conditions. Ar ion bombardment under beam flooding, and subsequent annealing at 650 C was found an effective means to restore the original Al2O3 (1102) surface for renewed Fe deposition.

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.

Plasmon Excitations of Multi-layer Graphene on a Conducting Substrate

PubMed Central

Gumbs, Godfrey; Iurov, Andrii; Wu, Jhao-Ying; Lin, M. F.; Fekete, Paula

2016-01-01

We predict the existence of low-frequency nonlocal plasmons at the vacuum-surface interface of a superlattice of N graphene layers interacting with conducting substrate. We derive a dispersion function that incorporates the polarization function of both the graphene monolayers and the semi-infinite electron liquid at whose surface the electrons scatter specularly. We find a surface plasmon-polariton that is not damped by particle-hole excitations or the bulk modes and which separates below the continuum mini-band of bulk plasmon modes. The surface plasmon frequency of the hybrid structure always lies below , the surface plasmon frequency of the conducting substrate. The intensity of this mode depends on the distance of the graphene layers from the conductor’s surface, the energy band gap between valence and conduction bands of graphene monolayer and, most importantly, on the number of two-dimensional layers. For a sufficiently large number of layers the hybrid structure has no surface plasmon. The existence of plasmons with different dispersion relations indicates that quasiparticles with different group velocity may coexist for various ranges of wavelengths determined by the number of layers in the superlattice. PMID:26883086

The Electronic Structure and Secondary Pyroelectric Properties of Lithium Tetraborate

PubMed Central

Adamiv, Volodymyr.T.; Burak, Yaroslav.V.; Wooten, David. J.; McClory, John; Petrosky, James; Ketsman, Ihor; Xiao, Jie; Losovyj, Yaroslav B.; Dowben, Peter A.

2010-01-01

We review the pyroelectric properties and electronic structure of Li2B4O7(110) and Li2B4O7(100) surfaces. There is evidence for a pyroelectric current along the [110] direction of stoichiometric Li2B4O7 so that the pyroelectric coefficient is nonzero but roughly 103 smaller than along the [001] direction of spontaneous polarization. Abrupt decreases in the pyroelectric coefficient along the [110] direction can be correlated with anomalies in the elastic stiffness C33D contributing to the concept that the pyroelectric coefficient is not simply a vector but has qualities of a tensor, as expected. The time dependent surface photovoltaic charging suggests that surface charging is dependent on crystal orientation and doping, as well as temperature. PMID:28883341

Collaborative research in tunneling and field emission pumped surface wave local oscillators and amplifiers for infrared and submillimeter wavelengths under director's discretionary fund

NASA Technical Reports Server (NTRS)

Gustafson, T. K.

1982-01-01

Progress is reported in work towards the development of surface wave sources for the infrared and sub-millimeter portion of the spectrum to be based upon electron pumping by tunneling electrons in metal-barrier-metal or metal-barrier-semiconductor devices. Tunneling phenomena and the coupling of radiation to tunnel junctions were studied. The propagation characteristics of surface electro-magnetic modes in metal-insulator-p(++) semiconductor structures as a function of frequency were calculated. A model for the gain process based upon Tucker's formalism was developed and used to estimate what low frequency gain might be expected from such structures. The question of gain was addressed from a more fundamental viewpoint using the method of Lasher and Stern.

Use of a tissue sectioner to expose internal structures of biological samples for scanning electron microscopy.

PubMed

Brown, M F; Brotzman, H G; Kinden, D A

1976-09-01

A procedure yielding sections of unembedded biological samples for observation by scanning electron microscopy is described. Sections of samples, fixed and hardened in OsO4, were obtained in quantity with a tissue sectioner. Subsequent treatments to osmium-coat cut surfaces were employed prior to critical point drying. The procedure yields cleanly cut surfaces through cells and cytoplasmic organelles which are retained in their normal position. Sections of apple leaf and mouse kidney are illustrated. Sections can be readily cut in a desired plane with less structural damage than is typically encountered by other sectioning or dissection techniques.

Asymmetric band gaps in a Rashba film system

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

Carbone, C.; Moras, P.; Sheverdyaeva, P. M.

The joint effect of exchange and Rashba spin-orbit interactions is examined on the surface and quantum well states of Ag 2 Bi -terminated Ag films grown on ferromagnetic Fe(110). The system displays a particular combination of time-reversal and translational symmetry breaking that strongly influences its electronic structure. Angle-resolved photoemission reveals asymmetric band-gap openings, due to spin-selective hybridization between Rashba-split surface states and exchange-split quantum well states. This results in an unequal number of states along positive and negative reciprocal space directions. We suggest that the peculiar asymmetry of the discovered electronic structure can have significant influence on spin-polarized transport properties.