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At least 1,261 records · Page 70
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DOE OSTI2014

Magnetization-steps in Y₂CoMnO₆ double perovskite: The role of antisite disorder

Antisite disorder is observed to have significant impact on the magnetic properties of the double perovskite Y²CoMnO₆ which has been recently identified as a multiferroic. A paramagnetic-ferromagnetic phase transition occurs in this material at T c ≈ 75 K. At 2 K, it displays a strong ferromagnetic hysteresis with a significant coercive field of H c ≈ 15 kOe. Sharp steps are observed in the hysteresis curves recorded below 8 K. In the temperature range 2 K ≤ T ≤ 5 K, the hysteresis loops are anomalous as the virgin curve lies outside the main loop. The field-cooling conditions as well as the rate of field-sweep are found to influence the steps. Quantitative analysis of the neutron diffraction data shows that at room temperature, Y₂CoMnO₆ consists of 62% of monoclinic P2₁/n with nearly 70% antisite disorder and 38% Pnma. The bond valence sums indicate the presence of other valence states for Co and Mn which arise from disorder. We explain the origin of steps by using a model for pinning of magnetization at the antiphase boundaries created by antisite disorder. The steps in magnetization closely resemble the martensitic transformations found in intermetallics and display first-order characteristics as revealed in the Arrott's plots.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Successes and failures of Hubbard-corrected density functional theory: The case of Mg doped LiCoO{sub 2}

We have evaluated the successes and failures of the Hubbard-corrected density functional theory approach to study Mg doping of LiCoO{sub 2}. We computed the effect of the U parameter on the energetic, geometric, and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO{sub 2}. We find that formation of impurity states results in changes on the valency of Co in LiCoO{sub 2}. Variation of the Co U shifts the energy of the impurity state, resulting in energetic, geometric, and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO{sub 2}.

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

Nanoscale dynamics and aging of fibrous peptide-based gels

Solutions of the aromatic dipeptide derivative molecule fluorenylmethoxycarbonyl-diphenylalanine (Fmoc-FF) in dimethyl sulfoxide produce fibrous gels when mixed with water. We study the evolution of density fluctuations of this three-component system using X-ray photon correlation spectroscopy (XPCS) and compare these results to the macroscopic rheology of the gels and optical observations of the microstructure evolution. At the investigated scattering angles, the intensity autocorrelation functions do not follow behavior expected for simple diffusion of individual Fmoc-FF molecules localized within cages of nearest neighbors. Instead, the dynamics are associated with density fluctuations on length scales of ∼10–100 nm arising from disaggregation and reformation of fibers, leading to an increasingly uniform network. This process is correlated with the growth of the elastic modulus, which saturates at long times. Autocorrelation functions and relaxation times acquired from XPCS measurements are consistent with relaxation rates of structures at dynamic equilibrium. This study provides further support to the concept of exploring peptide-based gelators as valence-limited patchy particles capable of forming equilibrium gels.

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

Experimental determination of band offsets of NiO-based thin film heterojunctions

The energy band diagrams of NiO-based solar cell structures that use various n-type oxide semiconductors such as ZnO, Mg{sub 0.3}Zn{sub 0.7}O, Zn{sub 0.5}Sn{sub 0.5}O, In{sub 2}O{sub 3}:Sn (ITO), SnO{sub 2}, and TiO{sub 2} were evaluated by photoelectron yield spectroscopy. The valence band discontinuities were estimated to be 1.6 eV for ZnO/NiO and Mg{sub 0.3}Zn{sub 0.7}O/NiO, 1.7 eV for Zn{sub 0.5}Sn{sub 0.5}O/NiO and ITO/NiO, and 1.8 eV for SnO{sub 2}/NiO and TiO{sub 2}/NiO heterojunctions. By using the valence band discontinuity values and corresponding energy bandgaps of the layers, energy band diagrams were developed. Judging from the band diagram, an appropriate solar cell consisting of p-type NiO and n-type ZnO layers was deposited on ITO, and a slight but noticeable photovoltaic effect was obtained with an open circuit voltage (V{sub oc}) of 0.96 V, short circuit current density (J{sub sc}) of 2.2 μA/cm{sup 2}, and fill factor of 0.44.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

The electronic structure of vanadium monochloride cation (VCl{sup +}): Tackling the complexities of transition metal species

Six electronic states (X {sup 4}Σ{sup −}, A {sup 4}Π, B {sup 4}Δ, {sup 2}Φ, {sup 2}Δ, {sup 2}Σ{sup +}) of the vanadium monochloride cation (VCl{sup +}) are described using large basis set coupled cluster theory. For the two lowest quartet states (X {sup 4}Σ{sup −} and A {sup 4}Π), a focal point analysis (FPA) approach was used that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through pentuple (CCSDTQP) excitations. FPA adiabatic excitation energies (T{sub 0}) and spectroscopic constants (r{sub e}, r{sub 0}, B{sub e}, B{sub 0}, D{sup ¯}{sub e}, H{sub e}, ω{sub e}, v{sub 0}, α{sub e}, ω{sub e}x{sub e}) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, and spin-orbit coupling. Due to the delicate interplay between dynamical and static electronic correlation, single reference coupled cluster theory is able to provide the correct ground electronic state (X {sup 4}Σ{sup −}), while multireference configuration interaction theory cannot. Perturbations from the first- and second-order spin orbit coupling of low-lying states with quartet spin multiplicity reveal an immensely complex rotational spectrum relative to the isovalent species VO, VS, and TiCl. Computational data on the doublet manifold suggest that the lowest-lying doublet state ({sup 2}Γ) has a T{sub e} of ∼11 200 cm{sup −1}. Overall, this study shows that laboratory and theoretical rotational spectroscopists must work more closely in tandem to better understand the bonding and structure of molecules containing transition metals.

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

Ab initio study of point defects in PbSe and PbTe: Bulk and nanowire

First principles investigations, within the spin-polarized density functional theory, are performed to study energetic stability and electronic properties of point defects (vacancies and antisites) in PbSe and PbTe: bulk and nanowire (NW). Our results show that the energetic stability of these defects is ruled by relaxation process. These defects have lower formation energies in the nanowire structures as compared to the bulk, being more stable in the surface of the NWs. We also show that in the bulk system only one charge state is stable, otherwise, due to the larger band gaps, more than one charge state may be stable in the NWs. In addition, we have investigated how the presence of intrinsic defects affects the electronic properties of bulk and NW systems. Vacancies give rise to new electronic states near to the edges of the valence and conduction bands while the energetic position of the electronic states from antisites depends on the charge state, being localized inside the band gap or near the edges of the valence or conduction bands. We discuss how these changes in the electronic properties due to intrinsic defects may affect the thermoelectric properties of PbSe and PbTe NWs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Electron and hole photoemission detection for band offset determination of tunnel field-effect transistor heterojunctions

We report experimental methods to ascertain a complete energy band alignment of a broken-gap tunnel field-effect transistor based on an InAs/GaSb hetero-junction. By using graphene as an optically transparent electrode, both the electron and hole barrier heights at the InAs/GaSb interface can be quantified. For a Al{sub 2}O{sub 3}/InAs/GaSb layer structure, the barrier height from the top of the InAs and GaSb valence bands to the bottom of the Al{sub 2}O{sub 3} conduction band is inferred from electron emission whereas hole emissions reveal the barrier height from the top of the Al{sub 2}O{sub 3} valence band to the bottom of the InAs and GaSb conduction bands. Subsequently, the offset parameter at the broken gap InAs/GaSb interface is extracted and thus can be used to facilitate the development of predicted models of electron quantum tunneling efficiency and transistor performance.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Intervalence charge transfer luminescence: Interplay between anomalous and 5d − 4f emissions in Yb-doped fluorite-type crystals

In this paper, we report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorite-type crystals associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. By means of embedded cluster, wave function theory ab initio calculations, we show that the widely studied, very broad band, anomalous emission of Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. The IVCT luminescence is very efficiently excited by a two-photon upconversion mechanism where each photon provokes the same strong 4f{sup 14}–1A{sub 1g}→ 4f{sup 13}({sup 2}F{sub 7/2})5de{sub g}–1T{sub 1u} absorption in the Yb{sup 2+} part of the pair: the first one, from the pair ground state; the second one, from an excited state of the pair whose Yb{sup 3+} moiety is in the higher 4f{sup 13}({sup 2}F{sub 5/2}) multiplet. The Yb{sup 2+}–Yb{sup 3+} → Yb{sup 3+}–Yb{sup 2+} IVCT emission consists of an Yb{sup 2+} 5de{sub g} → Yb{sup 3+} 4f{sub 7/2} charge transfer accompanied by a 4f{sub 7/2} → 4f{sub 5/2} deexcitation within the Yb{sup 2+} 4f{sup 13} subshell: [{sup 2}F{sub 5/2}5de{sub g},{sup 2}F{sub 7/2}] → [{sup 2}F{sub 7/2},4f{sup 14}]. The IVCT vertical transition leaves the oxidized and reduced moieties of the pair after electron transfer very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are subtracted from the normal emission. The IVCT energy diagrams resulting from the quantum mechanical calculations explain the different luminescent properties of Yb-doped CaF{sub 2}, SrF{sub 2}, BaF{sub 2}, and SrCl{sub 2}: the presence of IVCT luminescence in Yb-doped CaF{sub 2} and SrF{sub 2}; its coexistence with regular 5d-4f emission in SrF{sub 2}; its absence in BaF{sub 2} and SrCl{sub 2}; the quenching of all emissions in BaF{sub 2}; and the presence of additional 5d–4f emissions in SrCl{sub 2} which are absent in SrF{sub 2}. They also allow to interpret and reproduce recent experiments on transient photoluminescence enhancement in Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, the appearance of Yb{sup 2+} 4f–5d absorption bands in the excitation spectra of the IR Yb{sup 3+} emission in partly reduced CaF{sub 2}:Yb{sup 3+} samples, and to identify the broadband observed in the excitation spectrum of the so far called anomalous emission of SrF{sub 2}:Yb{sup 2+} as an IVCT absorption, which corresponds to an Yb{sup 2+} 4f{sub 5/2} → Yb{sup 3+} 4f{sub 7/2} electron transfer.

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

Electronic structure of C and N co-doped TiO{sub 2}: A combined hard x-ray photoemission spectroscopy and density functional theory study

We have studied the electronic structure of C and N co-doped TiO{sub 2} using hard x-ray photoelectron spectroscopy and first-principles density functional theory calculations. Our results reveal overlap of the 2p states of O, N, and C in the system which shifts the valence band maximum towards the Fermi level. Combined with optical data we show that co-doping is an effective route for band gap reduction in TiO{sub 2}. Comparison of the measured valence band with theoretical photoemission density of states reveals the possibility of C on Ti and N on O site.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Strain and localization effects in InGaAs(N) quantum wells: Tuning the magnetic response

We investigated effects of localization and strain on the optical and magneto-optical properties of diluted nitrogen III–V quantum wells theoretically and experimentally. High-resolution x-ray diffraction, photoluminescence (PL), and magneto-PL measurements under high magnetic fields up to 15 T were performed at low temperatures. Bir-Pikus Hamiltonian formalism was used to study the influence of strain, confinement, and localization effects. The circularly polarized magneto-PL was interpreted considering localization aspects in the valence band ground state. An anomalous behavior of the electron-hole pair magnetic shift was observed at low magnetic fields, ascribed to the increase in the exciton reduced mass due to the negative effective mass of the valence band ground state.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Terahertz magneto-optical spectroscopy of a two-dimensional hole gas

Two-dimensional hole gases (2DHGs) have attracted recent attention for their unique quantum physics and potential applications in areas including spintronics and quantum computing. However, their properties remain relatively unexplored, motivating the use of different techniques to study them. We then used terahertz magneto-optical spectroscopy to investigate the cyclotron resonance frequency in a high mobility 2DHG, revealing a nonlinear dependence on the applied magnetic field. This is shown to be due to the complex non-parabolic valence band structure of the 2DHG, as verified by multiband Landau level calculations. We also found that impurity scattering dominates cyclotron resonance decay in the 2DHG, in contrast with the dominance of superradiant damping in two-dimensional electron gases. Our results shed light on the properties of 2DHGs, motivating further studies of these unique 2D nanosystems.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electronic structure and optical properties of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} solid-solution thin films

We have examined the effect of V doping on the electronic and optical properties of epitaxial hematite (α-Fe{sub 2}O{sub 3}) thin films, by employing several characterization techniques and computational modeling. The conductivity of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} (0 ≤ x ≤ ∼0.5) is enhanced by several orders of magnitude as x is increased, as evidenced by electrical resistivity measurements and x-ray photoelectron spectroscopy core-level and valence-band spectra. Optical absorption shows a reduction in the direct band gap by as much as 0.64 eV for x = 0.53 (E{sub g} = 1.46 eV) relative to that of α-Fe{sub 2}O{sub 3} (E{sub g} = 2.10 eV). Detailed understanding of the character of the optical transitions in the alloys is achieved using first-principles calculations of the ground and excited states. These calculations reveal that V doping results in occupied V 3d orbitals hybridized with Fe orbitals and located at approximately mid-gap in α-Fe{sub 2}O{sub 3}. The lowest energy transitions involve charge transfer from occupied V 3d to unoccupied Fe 3d* orbitals. With a low band gap and high conductivity, α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} is a promising material for photovoltaic and photoelectrochemical applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Determination of band offsets at the Al:ZnO/Cu{sub 2}SnS{sub 3} interface using X-ray photoelectron spectroscopy

The Al:ZnO/Cu{sub 2}SnS{sub 3} semiconductor heterojunction was fabricated. The structural and optical properties of the semiconductor materials were studied. The band offset at the Al:ZnO/Cu{sub 2}SnS{sub 3} heterojunction was studied using X-ray photoelectron spectroscopy technique. From the measurement of the core level energies and valence band maximum of the constituent elements, the valence band offset was calculated to be −1.1 ± 0.24 eV and the conduction band offset was 0.9 ± 0.34 eV. The band alignment at the heterojunction was found to be of type-I. The study of Al:ZnO/Cu{sub 2}SnS{sub 3} heterojunction is useful for solar cell applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Excited-state dynamics of furan studied by sub-20-fs time-resolved photoelectron imaging using 159-nm pulses

The excited-state dynamics of furan were studied by time-resolved photoelectron imaging using a sub-20-fs deep UV (198 nm) and vacuum UV (159 nm) light source. The 198- and 159-nm pulses produce photoionization signals in both pump-probe and probe-pump pulse sequences. When the 198-nm pulse precedes the 159-nm pulse, it creates the {sup 1}A{sub 2}(3s) Rydberg and {sup 1}B{sub 2}(ππ{sup ∗}) valence states, and the former decays exponentially with a time constant of about 20 fs whereas the latter exhibits more complex wave-packet dynamics. When the 159-nm pulse precedes the 198-nm pulse, a wave packet is created on the {sup 1}A{sub 1}(ππ{sup ∗}) valence state, which rapidly disappears from the observation window owing to structural deformation. The 159-nm photoexcitation also creates the 3s and 3p{sub x,y} Rydberg states non-adiabatically.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Solid-base loaded WO{sub 3} photocatalyst for decomposition of harmful organics under visible light irradiation

Composite of NaBiO{sub 3}-loaded WO{sub 3} with a mixing ratio of 10:100 was prepared for photocatalytic harmful-organic-contaminant decomposition. The composite properties were measured using X-ray diffraction, ultraviolet-visible spectrophotometer (UV-Vis), and valence band-X-ray photoelectron spectroscope (VB-XPS). The results exhibited that the potentials for top of the valence band and bottom of conduction band for NaBiO{sub 3} can be estimated, respectively, as +2.5 V and -0.1 to 0 V. Furthermore, WO{sub 3}, NaBiO{sub 3}, and the composite showed IPA oxidation properties under visible-light irradiation. Results show that the composite exhibited much higher photocatalytic activity about 2-propanol (IPA) decomposition into CO{sub 2} than individual WO{sub 3} or NaBiO{sub 3} because of charge separation promotion and the base effect of NaBiO{sub 3}.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Defect-induced bandgap narrowing in low-k dielectrics

In this work, core-level X-ray photoelectron spectroscopy was utilized to determine the surface bandgap for various porous and non-porous low-k a-SiCOH dielectrics before and after ion sputtering. By examining the onset of inelastic energy loss in O 1s core-level spectra, the gap narrowing was universally found in Ar{sup +} ion sputtered low-k dielectrics. The reduction of the bandgap ranges from 1.3 to 2.2 eV depending on the film composition. We show that the bandgap narrowing in these low-k dielectrics is caused by development of the valence-band tail as evidenced by the presence of additional electronic states above the valence-band maximum. Electron-spin-resonance measurements were made on a-SiCOH films to gain atomic insight into the nature of the sputtering-induced defects and reveal formation of carbon-related defects as the most probable origin of the gap states.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Metal-ligand delocalization and spin density in the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} molecules: Some insights from wave function theory

The aim of this paper is to unravel the physical phenomena involved in the calculation of the spin density of the CuCl{sub 2} and [CuCl{sub 4}]{sup 2−} systems using wave function methods. Various types of wave functions are used here, both variational and perturbative, to analyse the effects impacting the spin density. It is found that the spin density on the chlorine ligands strongly depends on the mixing between two types of valence bond structures. It is demonstrated that the main difficulties found in most of the previous studies based on wave function methods come from the fact that each valence bond structure requires a different set of molecular orbitals and that using a unique set of molecular orbitals in a variational procedure leads to the removal of one of them from the wave function. Starting from these results, a method to compute the spin density at a reasonable computational cost is proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A fresh look at the photoelectron spectrum of bromobenzene: A third-order non-Dyson electron propagator study

The valence-shell ionization spectrum of bromobenzene, as a representative halogen substituted aromatic, was studied using the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator. This method, also referred to as IP-ADC(3), was implemented as a part of the Q-Chem program and enables large-scale calculations of the ionization spectra, where the computational effort scales as n{sup 5} with respect to the number of molecular orbitals n. The IP-ADC(3) scheme is ideally suited for investigating low-lying ionization transitions, so fresh insight could be gained into the cationic state manifold of bromobenzene. In particular, the present IP-ADC(3) calculations with the cc-pVTZ basis reveal a whole class of low-lying low-intensity two-hole-one-particle (2h-1p) doublet and quartet states, which are relevant to various photoionization processes. The good qualitative agreement between the theoretical spectral profile for the valence-shell ionization transitions generated with the smaller cc-pVDZ basis set and the experimental photoelectron spectrum measured at a photon energy of 80 eV on the PLÉIADES beamline at the Soleil synchrotron radiation source allowed all the main features to be assigned. Some theoretical aspects of the ionization energy calculations concerning the use of various approximation schemes and basis sets are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗