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At least 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Tuning the electronic structure of SrTiO{sub 3}/SrFeO{sub 3−x} superlattices via composition and vacancy control

Using density functional theory-based calculations, we explore the effects of oxygen vacancies and epitaxial layering on the atomic, magnetic, and electronic structure of (SrTiO{sub 3}){sub n}(SrFeO{sub 3−x}){sub 1} superlattices. While structures without oxygen vacancies (x = 0) possess small or non-existent band gaps and ferromagnetic ordering in their iron layers, those with large vacancy concentrations (x = 0.5) have much larger gaps and antiferromagnetic ordering. Though the computed gaps depend numerically on the delicate energetic balance of vacancy ordering and on the value of Hubbard U{sub eff} used in the calculations, we demonstrate that changes in layering can tune the band gaps of these superlattices below that of SrTiO{sub 3} (3.2 eV) by raising their valence band maxima. This suggests the possibility that these superlattices could absorb in the solar spectrum, and could serve as water-splitting photocatalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Experimental and first principle studies on electronic structure of BaTiO{sub 3}

We have carried out photoemission experiments to obtain valence band spectra of various crystallographic symmetries of BaTiO{sub 3} system which arise as a function of temperature. We also present results of a detailed first principle study of these symmetries of BaTiO{sub 3} using generalized gradient approximation for the exchange-correlation potential. Here we present theoretical results of density of states obtained from DFT based simulations to compare with the experimental valence band spectra. Further, we also perform calculations using post density functional approaches like GGA + U method as well as non-local hybrid exchange-correlation potentials like PBE0, B3LYP, HSE in order to understand the extent of effect of correlation on band gaps of different available crystallographic symmetries (5 in number) of BaTiO{sub 3}.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The effect of Bi composition on the properties of InP{sub 1−x}Bi{sub x} grown by liquid phase epitaxy

InP{sub 1−x}Bi{sub x} epilayers (x ≥ 1.2%) on InP (001) are grown reproducibly by liquid phase epitaxy with conventional solution baking in a H{sub 2} environment. The Bi composition and surface morphology of the grown layers are studied by secondary ion mass spectroscopy and atomic force microscopy, respectively. High-resolution x-ray diffraction is used to characterize the lattice parameters and the crystalline quality of the layers. 10 K photoluminescence measurements indicate three clearly resolved peaks in undoped InP layers with band-to-band transition at 1.42 eV which is redshifted with Bi incorporation in the layer with a maximum band gap reduction of 50 meV/% Bi. The effect is attributed to the interaction between the valence band edge and Bi-related defect states as is explained here by valence-band anticrossing model. Room temperature Hall measurements indicate that the mobility of the layer is not significantly affected for Bi concentration up to 1.2%.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Highly correlated configuration interaction calculations on water with large orbital bases

A priori selected configuration interaction (SCI) with truncation energy error [C. F. Bunge, J. Chem. Phys. 125, 014107 (2006)] and CI by parts [C. F. Bunge and R. Carbó-Dorca, J. Chem. Phys. 125, 014108 (2006)] are used to approximate the total nonrelativistic electronic ground state energy of water at fixed experimental geometry with CI up to sextuple excitations. Correlation-consistent polarized core-valence basis sets (cc-pCVnZ) up to sextuple zeta and augmented correlation-consistent polarized core-valence basis sets (aug-cc-pCVnZ) up to quintuple zeta quality are employed. Truncation energy errors range between less than 1 μhartree, and 100 μhartree for the largest orbital set. Coupled cluster CCSD and CCSD(T) calculations are also obtained for comparison. Our best upper bound, −76.4343 hartree, obtained by SCI with up to sextuple excitations with a cc-pCV6Z basis recovers more than 98.8% of the correlation energy of the system, and it is only about 3 kcal/mol above the “experimental” value. Despite that the present energy upper bounds are far below all previous ones, comparatively large dispersion errors in the determination of the extrapolated energies to the complete basis set do not allow to determine a reliable estimation of the full CI energy with an accuracy better than 0.6 mhartree (0.4 kcal/mol)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Band alignment at interfaces of amorphous Al{sub 2}O{sub 3} with Ge{sub 1−x}Sn{sub x}- and strained Ge-based channels

Spectroscopy of internal photoemission of electrons from Ge and Ge{sub 1−x}Sn{sub x} (x ≤ 0.08) alloys into amorphous Al{sub 2}O{sub 3} is used to evaluate the energy of the semiconductor valence band top. It is found that in Ge and Ge{sub 1−x}Sn{sub x} the valence bands are aligned within the measurement accuracy (±0.05 eV) irrespective of the strain imposed on the semiconductor or by the kind of passivating inter-layer applied between the semiconductor and alumina. This indicates that the Ge{sub 1−x}Sn{sub x}-stressor approach may be useful for strain engineering in p-channel Ge metal-oxide-semiconductor transistors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Surface and electronic structure of epitaxial PtLuSb (001) thin films

The surface and electronic structure of single crystal thin films of PtLuSb (001) grown by molecular beam epitaxy were studied. Scanning tunneling spectroscopy (STS), photoemission spectroscopy, and temperature dependent Hall measurements of PtLuSb thin films are consistent with a zero-gap semiconductor or semi-metal. STS and photoemission measurements show a decrease in density of states approaching the Fermi level for both valence and conduction bands as well as a slight shift of the Fermi level position into the valence band. Temperature dependent Hall measurements also corroborate the Fermi level position by measurement of p-type carriers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Spectroscopy of Mn atoms isolated in solid {sup 4}He

We present an experimental study of the laser-induced luminescence spectra of Mn atoms in solid helium matrices. We observe transitions of the valence electron and of inner-shell electrons. We find that the Mn-He interaction perturbs the inner-shell transitions to a lesser extent than the valence-electron transitions. The observed lineshapes of the inner-shell transitions of Mn are similar to those of an inner-shell transition in Ba studied earlier. At the same time, they are more strongly perturbed than the corresponding transitions in Au and Cu under the same conditions. We suggest a qualitative explanation of these observations based on the atomic bubble model. Our results also suggest that the inner-shell transitions of Mn in solid He are more strongly perturbed than the same lines of Mn isolated in solid Ar or Kr matrices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Atomic and electronic structures of lattice mismatched Cu 2 O/TiO 2 interfaces

Heterojunction interfaces between metal oxides are often highly lattice mismatched. The atomic and electronic structures of such interfaces, however, are not well understood. Here, we have synthesized Cu 2 O/TiO 2 heterojunction thin films with 13% lattice mismatch and studied the interface via experimental methods and large-scale density function theory calculations of supercells containing 1300 atoms. We find that an interface of epitaxial quality is formed via a coincidence site lattice of 8 Cu 2 O unit cells matching 9 TiO 2 unit cells. Calculations reveal the existence of a dislocation core of the O sublattices at the interface and a random arrangement of one layer of interfacial Cu atoms. The interfacial electronic structure is found to be mostly determined by the interfacial Cu distribution, rather than by the O dislocation core. The conduction band minimum and valence band maximum states are spatially separated, and there is no strongly localized state near the core.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Investigation of A-site La substituted BaTi{sub 0.96}Mn{sub 0.04}O{sub 3} ceramics: Searching for ferromagnetic origin

Ba{sub 1-x}La{sub x}Ti{sub 0.96}Mn{sub 0.04}O{sub 3} ceramics (x = 0, 3%, 7%) were prepared by a modified Pechini method and the structure, morphology, magnetic and electric properties have been investigated. X-ray diffraction analysis reveals La{sup 3+} ions could suppress the formation of hexagonal phase effectively. The cell parameter c decreases firstly and then increases with the increase of La content, which indicates that La ions have been incorporated into the lattice of BaTi{sub 0.96}Mn{sub 0.04}O{sub 3}, and that Mn ions transform from high valence to low valence. The magnetization, polarization and leakage currents are also influenced by La doping greatly. Detailed analysis of magnetic variation with structural change attributes the room temperature ferromagnetism to double exchange interactions between Mn{sup 3+} and Mn{sup 4+} ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Rates of exponential decay in systems of discrete energy levels by Stieltjes imaging

An isolated bound state coupled to a continuum shows an exponential decay of its survival probability. Rates of the exponential decay occurring due to the bound-continuum coupling can be recovered from discretized continuum (L{sup 2}) calculations using a computational technique known as Stieltjes-Chebyshev moment theory or Stieltjes imaging. At the same time, some genuinely discrete level systems, e.g., Bixon-Jortner model, also show an exponential (or approximately exponential) decay of the initially populated level before the onset of quantum revivals. Here, we demonstrate numerically that Stieltjes imaging can be used for calculation of the rates of the exponential decay in such discrete level systems. We apply the Stieltjes imaging technique to the approximately exponential decay of inner-valence vacancies in trans-butadiene in order to show that the breakdown of the molecular orbital picture of ionization in the inner valence region can be physically interpreted as an energy-forbidden Coster-Kronig transition.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Fermi level pinning in Fe-doped PbTe under pressure

We synthesize an iron-doped PbTe single-crystal ingot and investigate the phase and the elemental composition as well as galvanomagnetic properties in weak magnetic fields (4.2 K≤T≤300 K, B ≤ 0.07 T) of Pb{sub 1−y}Fe{sub y}Te alloys upon varying the iron content, at atmospheric pressure and under hydrostatic compression up to 10 kilobars. We find an increase of iron concentration along the length of the ingot and the appearance of microscopic inclusions enriched with iron in the heavily doped samples. Lightly doped alloys are characterized by the p-type metal conductivity. An increase of the iron impurity content leads to a decrease in the free hole concentration, a stabilization of galvanomagnetic parameters, indicating the pinning of the Fermi energy by the iron resonant impurity level lying under the bottom of the valence band, and to the p-n inversion of the conductivity type. Under pressure, the free hole concentration in the sample, in which the stabilization of galvanomagnetic parameters takes place, increases by approximately a factor of four due to the flow of electrons from the valence band to the iron-induced resonant level. Using the two-band Kane and the six-band Dimmock dispersion relations, the pressure dependence of the Fermi energy is calculated. The model of the electronic structure rearrangement of Pb{sub 1−y}Fe{sub y}Te under pressure is proposed. The energy position and the pressure coefficient of the resonant iron impurity level are determined.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Surface structures of In-Pd intermetallic compounds. I. Experimental study of In thin films on Pd(111) and alloy formation

A combination of experimental methods was used to study the structure of In thin films deposited on the Pd(111) surface and the alloying behavior. X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and scanning tunneling microscopy results indicate that surface alloying takes place at room temperature. Below 2 monolayer equivalents (MLEs), the LEED patterns show the formation of three rotational domains of InPd(110) of poor structural quality on top of the Pd(111) substrate. Both core-levels and valence band XPS spectra show that the surface alloy does not yet exhibit the electronic structure characteristic of the 1:1 intermetallic compound under these conditions. Annealing the 1 MLE thin film up to 690 K yields to a transition from a multilayer InPd near-surface intermetallic phase to a monolayer-like surface alloy exhibiting a well ordered (√(3)×√(3)) R30{sup ∘} superstructure and an estimated composition close to In{sub 2}Pd{sub 3}. Annealing above 690 K leads to further In depletion and a (1 × 1) pattern is recovered. The (√(3)×√(3)) R30{sup ∘} superstructure is not observed for thicker films. Successive annealing of the 2 MLE thin film leads the progressive disappearance of the InPd diffraction spots till a sharp (1 × 1) pattern is recovered above 690 K. In the high coverage regime (from 4 to 35 MLE), the formation of three rotational domains of a bcc-In{sub 7}Pd{sub 3} compound with (110) orientation is observed. This In-rich phase probably grows on top of interfacial InPd(110) domains and is metastable. It transforms into a pure InPd(110) near-surface intermetallic phase in a temperature range between 500 and 600 K depending on the initial coverage. At this stage, the surface alloy exhibits core-level chemical shifts and valence band (VB) spectra identical to those of the 1:1 InPd intermetallic compound and resembling Cu-like density of states. Annealing at higher temperatures yields to a decrease of the In concentration in the near-surface region to about 20 at.% and a (1 × 1) LEED pattern is recovered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Band alignment of InN/6H-SiC heterojunction determined by x-ray photoelectron spectroscopy

The valence band offset (VBO) of InN/6H-SiC heterojunction has been directly measured by x-ray photoelectron spectroscopy. The VBO is determined to be −0.10 ± 0.23 eV and the conduction band offset is deduced to be −2.47 ± 0.23 eV, indicating that the heterojunction has a type-II band alignment. The accurate determination of the valence and conduction band offsets is important for applications and analysis of InN/6H-SiC optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Reflection High-Energy Electron Diffraction Beam-Induced Structural and Property Changes on WO3 Thin Films

Reduction of transition metal oxides can greatly change their physical and chemical properties. Using deposition of WO3 as a case study, we demonstrate that reflection high-energy electron diffraction (RHEED), a surface-sensitive tool widely used to monitor thin-film deposition processes, can significantly affect the cation valence and physical properties of the films through electron-beam induced sample reduction. The RHEED beam is found to increase film smoothness during epitaxial growth of WO3, as well as change the electronic properties of the film through preferential removal of surface oxygen.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Experimental indication for band gap widening of chalcopyrite solar cell absorbers after potassium fluoride treatment

The implementation of potassium fluoride treatments as a doping and surface modification procedure in chalcopyrite absorber preparation has recently gained much interest since it led to new record efficiencies for this kind of solar cells. In the present work, Cu(In,Ga)Se{sub 2} absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se{sub 2} absorber surface as a result of a post deposition treatment with KF (KF PDT). In particular, by comparing standard X-ray photoelectron spectroscopy and synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), we are able to confirm a strong Cu depletion in the absorbers after the KF PDT which is limited to the very near surface region. As a result of the Cu depletion, we find a change of the valence band structure and a shift of the valence band onset by approximately 0.4 eV to lower binding energies which is tentatively explained by a band gap widening as expected for Cu deficient compounds. The KF PDT increased the open circuit voltage by 60–70 mV compared to the untreated absorbers, while the fill factor deteriorated.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Predicted roles of defects on band offsets and energetics at CIGS (Cu(In,Ga)Se 2 /CdS) solar cell interfaces and implications for improving performance

The laboratory performance of CIGS (Cu(In,Ga)Se 2 ) based solar cells (20.8% efficiency) makes them promising candidate photovoltaic devices. However, there remains little understanding of how defects at the CIGS/CdS interface affect the band offsets and interfacial energies, and hence the performance of manufactured devices. To determine these relationships, we use density functional theory with the B3PW91 hybrid functional that we validate to provide very accurate descriptions of the band gaps and band offsets. This confirms the weak dependence of band offsets on surface orientation observed experimentally. We predict that the conduction band offset (CBO) of perfect CuInSe2/CdS interface is large, 0.79 eV, which would dramatically degrade performance. Moreover we show that band gap widening induced by Ga adjusts only the valence band offset, and we find that Cd impurities do not significantly affect the CBO. Thus we show that Cu vacancies at the interface play the key role in enabling the tunability of CBO. We predict that Na further improves the CBO through electrostatically elevating the valence levels to decrease the CBO, explaining the observed essential role of Na for high performance. Moreover we find that K leads to a dramatic decrease in the CBO to 0.05 eV, much better than Na. We suggest that the efficiency of CIGS devices might be improved substantially by tuning the ratio of Na to K, with the improved phase stability of Na balancing phase instability from K. All these defects reduce interfacial stability slightly, but not significantly.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Probing bismuth ferrite nanoparticles by hard x-ray photoemission: Anomalous occurrence of metallic bismuth

We have investigated bismuth ferrite nanoparticles (∼75 nm and ∼155 nm) synthesized by a chemical method, using soft X-ray (1253.6 eV) and hard X-ray (3500, 5500, and 7500 eV) photoelectron spectroscopy. This provided an evidence for the variation of chemical state of bismuth in crystalline, phase pure nanoparticles. X-ray photoelectron spectroscopy analysis using Mg Kα (1253.6 eV) source showed that iron and bismuth were present in both Fe{sup 3+} and Bi{sup 3+} valence states as expected for bismuth ferrite. However, hard X-ray photoelectron spectroscopy analysis of the bismuth ferrite nanoparticles using variable photon energies unexpectedly showed the presence of Bi{sup 0} valence state below the surface region, indicating that bismuth ferrite nanoparticles are chemically inhomogeneous in the radial direction. Consistently, small-angle X-ray scattering reveals a core-shell structure for these radial inhomogeneous nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

The effect of polarity and surface states on the Fermi level at III-nitride surfaces

Surface states and their influence on the Fermi level at the surface of GaN and AlN are studied using x-ray photoelectron spectroscopy (XPS). The effect of polarity on surface electronic properties was studied. Accurate modeling of the valence band edge and comparison with XPS data revealed the presence of donor surface states at 1.4 eV and acceptor states at energies > 2.7 eV from the valence band in GaN. Al polar AlN showed acceptor states at energies > 3.3 eV. Density of acceptor surface states was estimated to be between 10(13) and 10(14) eV(-1) cm(-2) in both GaN and AlN. The shift in charge neutrality levels and barrier heights due to polarity and the density of surface states on AlN and GaN were estimated from XPS measurements. Theoretical modeling and comparison with XPS data implied full compensation of spontaneous polarization charge by charged surface states. Barrier height measurements also reveal a dependence on polarity with phi(metal-polar)>phi(non-polar)>phi(nitrogen-polar) suggesting that the N-polar surface is the most suitable for Ohmic contacts. (C) 2014 AIP Publishing LLC.

Reddy, P↗