Calculation of photoelectron spectra of molybdenum and tungsten complexes using Green's functions methods.

PubMed

Bayse, Craig A; Ortwine, Kristine N

2007-08-16

Green's functions calculations are presented for several complexes of molybdenum and tungsten, two metals that are similar structurally but display subtle, but significant, differences in electronic structure. Outer valence Green's functions IPs for M(CO)6, M(Me)6, MH6, [MCl4O](-), and [MO4](-) (M = Mo, W) are generally within +/-0.2 eV of available experimental photoelectron spectra. The calculations show that electrons in M-L bonding orbitals are ejected at lower energies for Mo while the detachment energy for electrons in d orbitals varies with metal and complex. For the metal carbonyls, the quasiparticle picture assumed in OVGF breaks down for the inner valence pi CO molecular orbitals due to the coupling of two-hole-one-particle charge transfer states to the one-hole states. Incorporation of the 2h1p states through a Tamm-Dancoff approximation calculation accurately represents the band due to detachment from these molecular orbitals. Though the ordering of IPs for Green's functions methods and DFT Koopmans' theorem IPs is similar for the highest IPs for most compounds considered, the breakdown of the quasiparticle picture for the metal carbonyls suggests that scaling of the latter values may result in a fortuitous or incorrect assignment of experimental VDEs.

Application of Koopmans' theorem for density functional theory to full valence-band photoemission spectroscopy modeling.

PubMed

Li, Tsung-Lung; Lu, Wen-Cai

2015-10-05

In this work, Koopmans' theorem for Kohn-Sham density functional theory (KS-DFT) is applied to the photoemission spectra (PES) modeling over the entire valence-band. To examine the validity of this application, a PES modeling scheme is developed to facilitate a full valence-band comparison of theoretical PES spectra with experiments. The PES model incorporates the variations of electron ionization cross-sections over atomic orbitals and a linear dispersion of spectral broadening widths. KS-DFT simulations of pristine rubrene (5,6,11,12-tetraphenyltetracene) and potassium-rubrene complex are performed, and the simulation results are used as the input to the PES models. Two conclusions are reached. First, decompositions of the theoretical total spectra show that the dissociated electron of the potassium mainly remains on the backbone and has little effect on the electronic structures of phenyl side groups. This and other electronic-structure results deduced from the spectral decompositions have been qualitatively obtained with the anionic approximation to potassium-rubrene complexes. The qualitative validity of the anionic approximation is thus verified. Second, comparison of the theoretical PES with the experiments shows that the full-scale simulations combined with the PES modeling methods greatly enhance the agreement on spectral shapes over the anionic approximation. This agreement of the theoretical PES spectra with the experiments over the full valence-band can be regarded, to some extent, as a collective validation of the application of Koopmans' theorem for KS-DFT to valence-band PES, at least, for this hydrocarbon and its alkali-adsorbed complex. Copyright © 2015 Elsevier B.V. All rights reserved.

X-ray photoelectron study of Si+ ion implanted polymers

NASA Astrophysics Data System (ADS)

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

2010-11-01

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

Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers.

PubMed

Garcia, Gustavo A; Nahon, Laurent; Harding, Chris J; Powis, Ivan

2008-03-28

Photoionization of the chiral molecule glycidol has been investigated in the valence region. Photoelectron circular dichroism (PECD) curves have been obtained at various photon energies by using circularly polarized VUV synchrotron radiation and a velocity map imaging technique to record angle-resolved photoelectron spectra (PES). The measured chiral asymmetries vary dramatically with the photon energy as well as with the ionized orbital, improving the effective orbital resolution of the PECD spectrum with respect to the PES. Typical asymmetry factors of 5% are observed, but the peak values measured range up to 15%. The experimental results are interpreted by continuum multiple scattering (CMS-Xalpha) calculations for several thermally accessible glycidol conformers. We find that a nearly quantitative agreement between theory and experiments can be achieved for the ionization of several molecular orbitals. Owing to the sensitivity of PECD to molecular conformation this allows us to identify the dominant conformer. The influence of intramolecular hydrogen bond orbital polarization is found to play a small yet significant role in determining the chiral asymmetry in the electron angular distributions.

Band alignment of 2D WS2/HfO2 interfaces from x-ray photoelectron spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Zhu, H. L.; Zhou, C. J.; Tang, B. S.; Yang, W. F.; Chai, J. W.; Tay, W. L.; Gong, H.; Pan, J. S.; Zou, W. D.; Wang, S. J.; Chi, D. Z.

2018-04-01

We report on the growth of two-dimensional (2D) WS2 on high-k HfO2/Si substrates by reactive sputtering deposition. Raman, x-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy characterizations indicate that the 2D WS2 layers exhibit high-quality crystallinity and exact stoichiometry. Through high-resolution XPS valence spectra, we find a type I alignment at the interface of monolayer WS2/HfO2 with a valence band offset (VBO) of 1.95 eV and a conduction band offset (CBO) of 1.57 eV. The VBO and CBO are also found to increase up to 2.24 eV and 2.09 eV, respectively, with increasing WS2 layers. This is consistent with the results obtained from our first-principles calculations. Our theoretical calculations reveal that the remarkable splitting and shift of the W 5 d z 2 orbital originating from interlayer orbital coupling in thicker WS2 films induce a reduction of its bandgap, leading to an increase in both the VBO and CBO. This observation can be attributed to the asymmetric splitting at different high symmetric k-points caused by the interlayer orbital coupling.

Symmetry adapted cluster-configuration interaction calculation of the photoelectron spectra of famous biological active steroids

NASA Astrophysics Data System (ADS)

Abyar, Fatemeh; Farrokhpour, Hossein

2014-11-01

The photoelectron spectra of some famous steroids, important in biology, were calculated in the gas phase. The selected steroids were 5α-androstane-3,11,17-trione, 4-androstane-3,11,17-trione, cortisol, cortisone, corticosterone, dexamethasone, estradiol and cholesterol. The calculations were performed employing symmetry-adapted cluster/configuration interaction (SAC-CI) method using the 6-311++G(2df,pd) basis set. The population ratios of conformers of each steroid were calculated and used for simulating the photoelectron spectrum of steroid. It was found that more than one conformer contribute to the photoelectron spectra of some steroids. To confirm the calculated photoelectron spectra, they compared with their corresponding experimental spectra. There were no experimental gas phase Hesbnd I photoelectron spectra for some of the steroids of this work in the literature and their calculated spectra can show a part of intrinsic characteristics of this molecules in the gas phase. The canonical molecular orbitals involved in the ionization of each steroid were calculated at the HF/6-311++g(d,p) level of theory. The spectral bands of each steroid were assigned by natural bonding orbital (NBO) calculations. Knowing the electronic structures of steroids helps us to understand their biological activities and find which sites of steroid become active when a modification is performing under a biological pathway.

Valence change detection in memristive oxide based heterostructure cells by hard X-ray photoelectron emission spectroscopy

NASA Astrophysics Data System (ADS)

Kindsmüller, A.; Schmitz, C.; Wiemann, C.; Skaja, K.; Wouters, D. J.; Waser, R.; Schneider, C. M.; Dittmann, R.

2018-04-01

The switching mechanism of valence change resistive memory devices is widely accepted to be an ionic movement of oxygen vacancies resulting in a valence change of the metal cations. However, direct experimental proofs of valence changes in memristive devices are scarce. In this work, we have employed hard X-ray photoelectron emission microscopy (PEEM) to probe local valence changes in Pt/ZrOx/Ta memristive devices. The use of hard X-ray radiation increases the information depth, thus providing chemical information from buried layers. By extracting X-ray photoelectron spectra from different locations in the PEEM images, we show that zirconia in the active device area is reduced compared to a neighbouring region, confirming the valence change in the ZrOx film during electroforming. Furthermore, we succeeded in measuring the Ta 4f spectrum for two different resistance states on the same device. In both states, as well as outside the device region, the Ta electrode is composed of different suboxides without any metallic contribution, hinting to the formation of TaOx during the deposition of the Ta thin film. We observed a reduction of the Ta oxidation state in the low resistance state with respect to the high resistive state. This observation is contradictory to the established model, as the internal redistribution of oxygen between ZrOx and the Ta electrode during switching would lead to an oxidation of the Ta layer in the low resistance state. Instead, we have to conclude that the Ta electrode takes an active part in the switching process in our devices and that oxygen is released and reincorporated in the ZrOx/TaOx bilayer during switching. This is confirmed by the degradation of the high resistance state during endurance measurements under vacuum.

X-ray spectra and electronic structure of the Ca3Ga2Ge3О12 compound

NASA Astrophysics Data System (ADS)

Shcherba, I. D.; Kostyk, L. V.; Noga, H.; Bekenov, L. V.; Uskokovich, D.; Jatsyk, B. M.

2017-09-01

The band structure of Ca3Ga2Ge3О12 with the garnet structure has been determined for the first time by X-ray emission and photoelectron spectroscopy. It has been established that the bottom of the valence band is formed by Ge d states, which are not dominant in the chemical bonding. Strong hybridization of oxygen 2s states with 4p states of Ga and Ge revealed by the presence of an extra structure in the X-ray emission spectra has been found. The middle of the valence band has been demonstrated to be occupied by d states of Ga, while Ga and Ge 4рstates with a considerable admixture of oxygen 2p states form the top of the valence band.

Direct Visualization of Valence Electron Motion Using Strong-Field Photoelectron Holography

NASA Astrophysics Data System (ADS)

He, Mingrui; Li, Yang; Zhou, Yueming; Li, Min; Cao, Wei; Lu, Peixiang

2018-03-01

Watching the valence electron move in molecules on its intrinsic timescale has been one of the central goals of attosecond science and it requires measurements with subatomic spatial and attosecond temporal resolutions. The time-resolved photoelectron holography in strong-field tunneling ionization holds the promise to access this realm. However, it remains to be a challenging task hitherto. Here we reveal how the information of valence electron motion is encoded in the hologram of the photoelectron momentum distribution (PEMD) and develop a novel approach of retrieval. As a demonstration, applying it to the PEMDs obtained by solving the time-dependent Schrödinger equation for the prototypical molecule H2+ , the attosecond charge migration is directly visualized with picometer spatial and attosecond temporal resolutions. Our method represents a general approach for monitoring attosecond charge migration in more complex polyatomic and biological molecules, which is one of the central tasks in the newly emerging attosecond chemistry.

Direct Visualization of Valence Electron Motion Using Strong-Field Photoelectron Holography.

PubMed

He, Mingrui; Li, Yang; Zhou, Yueming; Li, Min; Cao, Wei; Lu, Peixiang

2018-03-30

Watching the valence electron move in molecules on its intrinsic timescale has been one of the central goals of attosecond science and it requires measurements with subatomic spatial and attosecond temporal resolutions. The time-resolved photoelectron holography in strong-field tunneling ionization holds the promise to access this realm. However, it remains to be a challenging task hitherto. Here we reveal how the information of valence electron motion is encoded in the hologram of the photoelectron momentum distribution (PEMD) and develop a novel approach of retrieval. As a demonstration, applying it to the PEMDs obtained by solving the time-dependent Schrödinger equation for the prototypical molecule H_{2}^{+}, the attosecond charge migration is directly visualized with picometer spatial and attosecond temporal resolutions. Our method represents a general approach for monitoring attosecond charge migration in more complex polyatomic and biological molecules, which is one of the central tasks in the newly emerging attosecond chemistry.

Electronic structure of rare-earth chromium antimonides RECrSb{sub 3} (RE=La-Nd, Sm, Gd-Dy, Yb) by X-ray photoelectron spectroscopy

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

Crerar, Shane J.; Mar, Arthur, E-mail: arthur.mar@ualberta.ca; Grosvenor, Andrew P.

The electronic structure of the ternary rare-earth chromium antimonides RECrSb{sub 3} (RE=La-Nd, Sm, Gd-Dy, Yb) has been examined by high-resolution X-ray photoelectron spectroscopy (XPS) for the first time. The RE 3d or 4d core-line spectra are substantially complicated by the presence of satellite peaks but their general resemblance to those of RE{sub 2}O{sub 3} tends to support the presence of trivalent RE atoms in RECrSb{sub 3}. However, the Yb 4d spectrum of YbCrSb{sub 3} also shows peaks that are characteristic of divalent ytterbium. The Cr 2p core-line spectra exhibit asymmetric lineshapes and little change in binding energy (BE) relative tomore » Cr metal, providing strong evidence for electronic delocalization. The Sb 3d core-line spectra reveal slightly negative BE shifts relative to elemental antimony, supporting the presence of anionic Sb species in RECrSb{sub 3}. The experimental valence band spectrum of LaCrSb{sub 3} matches well with the calculated density of states, and it can be fitted to component peaks belonging to individual atoms to yield an average formulation that agrees well with expectations ('La{sup 3+}Cr{sup 3+}(Sb{sup 2-}){sub 3}'). On progressing from LaCrSb{sub 3} to NdCrSb{sub 3}, the 4f-band in the valence band spectra grows in intensity and shifts to higher BE. The valence band spectrum for YbCrSb{sub 3} also supports the presence of divalent ytterbium. - Graphical Abstract: In their valence band spectra, the 4f-band intensifies and shifts to higher BE on progressing from LaCrSb{sub 3} to NdCrSb{sub 3}. Highlights: Black-Right-Pointing-Pointer High-resolution core-line and valence band XPS spectra were measured for RECrSb{sub 3}. Black-Right-Pointing-Pointer Divalent Yb is present in YbCrSb{sub 3}, in contrast to trivalent RE in other members. Black-Right-Pointing-Pointer Asymmetric Cr 2p spectral lineshape confirms delocalization of Cr valence electrons. Black-Right-Pointing-Pointer Small negative Sb 3d BE shifts support

Evaluation of band alignment of α-Ga2O3/α-(Al x Ga1‑ x )2O3 heterostructures by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Uchida, Takayuki; Jinno, Riena; Takemoto, Shu; Kaneko, Kentaro; Fujita, Shizuo

2018-04-01

The band alignment at an α-Ga2O3/α-(Al x Ga1‑ x )2O3 heterointerface, with different Al compositions (x), grown on a c-plane sapphire substrate was evaluated by X-ray photoelectron spectroscopy. The experimental results show that the heterointerface has the type-I band discontinuity with the valence band offsets of 0.090, 0.12, and 0.14 eV, and the conduction band offsets of 0.34, 0.79, and 1.87 eV, for x values of 0.1, 0.4, and 0.8, respectively. The small band offset for the valence band is attributed to the fact that the valence band of oxides is constituted by the localized O 2p level, which is dominated by the nature of oxygen atoms. The type-I band discontinuity is desirable for a variety of heterostructure devices.

Quantum chemical study of conformational fingerprints in the photoelectron spectra and (e, 2e) electron momentum distributions of n-hexane.

PubMed

Morini, F; Knippenberg, S; Deleuze, M S; Hajgató, B

2010-04-01

The main purpose of the present work is to simulate from many-body quantum mechanical calculations the results of experimental studies of the valence electronic structure of n-hexane employing photoelectron spectroscopy (PES) and electron momentum spectroscopy (EMS). This study is based on calculations of the valence ionization spectra and spherically averaged (e, 2e) electron momentum distributions for each known conformer by means of one-particle Green's function [1p-GF] theory along with the third-order algebraic diagrammatic construction [ADC(3)] scheme and using Kohn-Sham orbitals derived from DFT calculations employing the Becke 3-parameters Lee-Yang-Parr (B3LYP) functional as approximations to Dyson orbitals. A first thermostatistical analysis of these spectra and momentum distributions employs recent estimations at the W1h level of conformational energy differences, by Gruzman et al. [J. Phys. Chem. A 2009, 113, 11974], and of correspondingly obtained conformer weights using MP2 geometrical, vibrational, and rotational data in thermostatistical calculations of partition functions beyond the level of the rigid rotor-harmonic oscillator approximation. Comparison is made with the results of a focal point analysis of these energy differences using this time B3LYP geometries and the corresponding vibrational and rotational partition functions in the thermostatistical analysis. Large differences are observed between these two thermochemical models, especially because of strong variations in the contributions of hindered rotations to relative entropies. In contrast, the individual ionization spectra or momentum profiles are almost insensitive to the employed geometry. This study confirms the great sensitivity of valence ionization bands and (e, 2e) momentum distributions on the molecular conformation and sheds further light on spectral fingerprints of through-space methylenic hyperconjugation, in both PES and EMS experiments.

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

NASA Astrophysics Data System (ADS)

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

2015-07-01

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

Band alignment at the Cu2ZnSn(SxSe1-x)4/CdS interface

NASA Astrophysics Data System (ADS)

Haight, Richard; Barkhouse, Aaron; Gunawan, Oki; Shin, Byungha; Copel, Matt; Hopstaken, Marinus; Mitzi, David B.

2011-06-01

Energy band alignments between CdS and Cu2ZnSn(SxSe1-x)4 (CZTSSe) grown via solution-based and vacuum-based deposition routes were studied as a function of the [S]/[S+Se] ratio with femtosecond laser ultraviolet photoelectron spectroscopy, photoluminescence, medium energy ion scattering, and secondary ion mass spectrometry. Band bending in the underlying CZTSSe layer was measured via pump/probe photovoltage shifts of the photoelectron spectra and offsets were determined with photoemission under flat band conditions. Increasing the S content of the CZTSSe films produces a valence edge shift to higher binding energy and increases the CZTSSe band gap. In all cases, the CdS conduction band offsets were spikes.

Interpretation of the photoelectron spectra of FeS(2)(-) by a multiconfiguration computational approach.

PubMed

Clima, Sergiu; Hendrickx, Marc F A

2007-11-01

The ground states of FeS(2) and FeS(2)(-), and several low-lying excited electronic states of FeS(2) that are responsible for the FeS(2)(-) photoelectron spectrum, are calculated. At the B3LYP level an open, quasi-linear [SFeS](-) conformation is found as the most stable structure, which is confirmed at the ab initio CASPT2 computational level. Both the neutral and the anionic unsaturated complexes possess high-spin electronic ground states. For the first time a complete assignment of the photoelectron spectrum of FeS(2)(-) is proposed. The lowest energy band in this spectrum is ascribed to an electron detachment from the two highest-lying 3dpi antibonding orbitals (with respect to the iron-sulfur bonding) of iron. The next-lowest experimental band corresponds to an electron removal from nonbonding, nearly pure sulfur orbitals. The two highest bands in the spectra are assigned as electron detachments from pi and sigma bonding mainly sulfur orbitals.

Accurate quasiparticle calculation of x-ray photoelectron spectra of solids

NASA Astrophysics Data System (ADS)

Aoki, Tsubasa; Ohno, Kaoru

2018-05-01

It has been highly desired to provide an accurate and reliable method to calculate core electron binding energies (CEBEs) of crystals and to understand the final state screening effect on a core hole in high resolution x-ray photoelectron spectroscopy (XPS), because the ΔSCF method cannot be simply used for bulk systems. We propose to use the quasiparticle calculation based on many-body perturbation theory for this problem. In this study, CEBEs of band-gapped crystals, silicon, diamond, β-SiC, BN, and AlP, are investigated by means of the GW approximation (GWA) using the full ω integration and compared with the preexisting XPS data. The screening effect on a deep core hole is also investigated in detail by evaluating the relaxation energy (RE) from the core and valence contributions separately. Calculated results show that not only the valence electrons but also the core electrons have an important contribution to the RE, and the GWA have a tendency to underestimate CEBEs due to the excess RE. This underestimation can be improved by introducing the self-screening correction to the GWA. The resulting C1s, B1s, N1s, Si2p, and Al2p CEBEs are in excellent agreement with the experiments within 1 eV absolute error range. The present self-screening corrected GW approach has the capability to achieve the highly accurate prediction of CEBEs without any empirical parameter for band-gapped crystals, and provide a more reliable theoretical approach than the conventional ΔSCF-DFT method.

Accurate quasiparticle calculation of x-ray photoelectron spectra of solids.

PubMed

Aoki, Tsubasa; Ohno, Kaoru

2018-05-31

It has been highly desired to provide an accurate and reliable method to calculate core electron binding energies (CEBEs) of crystals and to understand the final state screening effect on a core hole in high resolution x-ray photoelectron spectroscopy (XPS), because the ΔSCF method cannot be simply used for bulk systems. We propose to use the quasiparticle calculation based on many-body perturbation theory for this problem. In this study, CEBEs of band-gapped crystals, silicon, diamond, β-SiC, BN, and AlP, are investigated by means of the GW approximation (GWA) using the full ω integration and compared with the preexisting XPS data. The screening effect on a deep core hole is also investigated in detail by evaluating the relaxation energy (RE) from the core and valence contributions separately. Calculated results show that not only the valence electrons but also the core electrons have an important contribution to the RE, and the GWA have a tendency to underestimate CEBEs due to the excess RE. This underestimation can be improved by introducing the self-screening correction to the GWA. The resulting C1s, B1s, N1s, Si2p, and Al2p CEBEs are in excellent agreement with the experiments within 1 eV absolute error range. The present self-screening corrected GW approach has the capability to achieve the highly accurate prediction of CEBEs without any empirical parameter for band-gapped crystals, and provide a more reliable theoretical approach than the conventional ΔSCF-DFT method.

Core Levels, Band Alignments, and Valence-Band States in CuSbS 2 for Solar Cell Applications

DOE PAGES

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.; ...

2017-11-10

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

Core Levels, Band Alignments, and Valence-Band States in CuSbS2 for Solar Cell Applications.

PubMed

Whittles, Thomas J; Veal, Tim D; Savory, Christopher N; Welch, Adam W; de Souza Lucas, Francisco Willian; Gibbon, James T; Birkett, Max; Potter, Richard J; Scanlon, David O; Zakutayev, Andriy; Dhanak, Vinod R

2017-12-06

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga (1-x) Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.

Effects of surface condition on the work function and valence-band position of ZnSnN2

NASA Astrophysics Data System (ADS)

Shing, Amanda M.; Tolstova, Yulia; Lewis, Nathan S.; Atwater, Harry A.

2017-12-01

ZnSnN2 is an emerging wide band gap earth-abundant semiconductor with potential applications in photonic devices such as solar cells, LEDs, and optical sensors. We report the characterization by ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy of reactively radio-frequency sputtered II-IV-nitride ZnSnN2 thin films. For samples transferred in high vacuum, the ZnSnN2 surface work function was 4.0 ± 0.1 eV below the vacuum level, with a valence-band onset of 1.2 ± 0.1 eV below the Fermi level. The resulting band diagram indicates that the degenerate bulk Fermi level position in ZnSnN2 shifts to mid-gap at the surface due to band bending that results from equilibration with delocalized surface states within the gap. Brief (< 10 s) exposures to air, a nitrogen-plasma treatment, or argon-ion sputtering caused significant chemical changes at the surface, both in surface composition and interfacial energetics. The relative band positioning of the n-type semiconductor against standard redox potentials indicated that ZnSnN2 has an appropriate energy band alignment for use as a photoanode to effect the oxygen-evolution reaction.

Vibrationally resolved photoelectron spectra of lower diamondoids: A time-dependent approach

NASA Astrophysics Data System (ADS)

Xiong, Tao; Włodarczyk, Radosław; Gallandi, Lukas; Körzdörfer, Thomas; Saalfrank, Peter

2018-01-01

Vibrationally resolved lowest-energy bands of the photoelectron spectra (PES) of adamantane, diamantane, and urotropine were simulated by a time-dependent correlation function approach within the harmonic approximation. Geometries and normal modes for neutral and cationic molecules were obtained from B3LYP hybrid density functional theory (DFT). It is shown that the simulated spectra reproduce the experimentally observed vibrational finestructure (or its absence) quite well. Origins of the finestructure are discussed and related to recurrences of autocorrelation functions and dominant vibrations. Remaining quantitative and qualitative errors of the DFT-derived PES spectra refer to (i) an overall redshift by ˜0.5 eV and (ii) the absence of satellites in the high-energy region of the spectra. The former error is shown to be due to the neglect of many-body corrections to ordinary Kohn-Sham methods, while the latter has been argued to be due to electron-nuclear couplings beyond the Born-Oppenheimer approximation [Gali et al., Nat. Commun. 7, 11327 (2016)].

Intramolecular interactions of L-phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules.

PubMed

Ganesan, Aravindhan; Wang, Feng; Falzon, Chantal

2011-02-01

Intramolecular interactions between fragments of L-phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L-phenylalanine, benzene and L-alanine are studied using density functional theory methods. While fully resolved experimental PES of L-phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e(1g) and 1a(2u) orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L-phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14-20 eV, rather than outside of this region. This study presents a competent orbital based fragments-in-molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D-PDF technique. Copyright © 2010 Wiley Periodicals, Inc.

Valence-band electronic structure evolution of graphene oxide upon thermal annealing for optoelectronics

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

Yamaguchi, Hisato; Ogawa, Shuichi; Watanabe, Daiki

We report valence band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. Degree of oxygen functionalization was controlled by annealing temperatures, and an electronic structure evolution was monitored using real-time ultraviolet photoelectron spectroscopy. We observed a drastic increase in density of states around the Fermi level upon thermal annealing at ~600 °C. The result indicates that while there is an apparent band gap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of band gap closure was correlated with electrical, chemical, and structural properties to determine a setmore » of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ~500 °C leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to as-synthesized counterpart.« less

Valence-band electronic structure evolution of graphene oxide upon thermal annealing for optoelectronics

DOE PAGES

Yamaguchi, Hisato; Ogawa, Shuichi; Watanabe, Daiki; ...

2016-09-01

We report valence band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. Degree of oxygen functionalization was controlled by annealing temperatures, and an electronic structure evolution was monitored using real-time ultraviolet photoelectron spectroscopy. We observed a drastic increase in density of states around the Fermi level upon thermal annealing at ~600 °C. The result indicates that while there is an apparent band gap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of band gap closure was correlated with electrical, chemical, and structural properties to determine a setmore » of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ~500 °C leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to as-synthesized counterpart.« less

X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

NASA Technical Reports Server (NTRS)

Vasquez, R. P.; Gupta, A.; Kussmaul, A.

1991-01-01

Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

X-ray photoelectron spectroscopy investigations of band offsets in Ga0.02Zn0.98O/ZnO heterojunction for UV photodetectors

NASA Astrophysics Data System (ADS)

Singh, Karmvir; Rawal, Ishpal; Punia, Rajesh; Dhar, Rakesh

2017-10-01

Here, we report the valence and conduction band offset measurements in pure ZnO and the Ga0.02Zn0.98O/ZnO heterojunction by X-Ray photoelectron spectroscopy studies for UV photodetector applications. For detailed investigations on the band offsets and UV photodetection behavior of Ga0.02Zn0.98O/ZnO heterostructures, thin films of pristine ZnO, Ga-doped ZnO (Ga0.02Zn0.98O), and heterostructures of Ga-doped ZnO with ZnO (Ga0.02Zn0.98O/ZnO) were deposited using a pulsed laser deposition technique. The deposited thin films were characterized by X-ray diffraction, atomic force microscopy, and UV-Vis spectroscopy. X-ray photoelectron spectroscopy studies were carried out on all the thin films for the investigation of valence and conduction band offsets. The valence band was found to be shifted by 0.28 eV, while the conduction band has a shifting of -0.272 eV in the Ga0.02Zn0.98O/ZnO heterojunction as compared to pristine ZnO thin films. All the three samples were analyzed for photoconduction behavior under UVA light of the intensity of 3.3 mW/cm2, and it was observed that the photoresponse of pristine ZnO (19.75%) was found to increase with 2 wt. % doping of Ga (22.62%) and heterostructured thin films (29.10%). The mechanism of UV photodetection in the deposited samples has been discussed in detail, and the interaction of chemisorbed oxygen on the ZnO surface with holes generated by UV light exposure has been the observed mechanism for the change in electrical conductivity responsible for UV photoresponse on the present deposited ZnO films.

Valence-band structure of organic radical p-CF3PNN investigated by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Anzai, Hiroaki; Takakura, Ryosuke; Ono, Yusuke; Ishihara, Suzuna; Sato, Hitoshi; Namatame, Hirofumi; Taniguchi, Masaki; Matsui, Toshiyuki; Noguchi, Satoru; Hosokoshi, Yuko

2018-05-01

We study the electronic structure of p-trifluoromethylphenyl nitronyl nitroxide (p-CF3PNN), which forms a one-dimensional alternating antiferromagnetic chain of molecules, using angle-resolved photoemission spectroscopy. A singly occupied molecular orbital (SOMO) is observed clearly at ∼ 2 eV in the valence-band spectra. The small band gap and the overlap between the SOMO orbitals in the NO groups are associated with the antiferromagnetic interaction between neighboring spins.

Valence-band-edge shift due to doping in p + GaAs

NASA Astrophysics Data System (ADS)

Silberman, J. A.; de Lyon, T. J.; Woodall, J. M.

1991-05-01

Accurate knowledge of the shifts in valence- and conduction-band edges due to heavy doping effects is crucial in modeling GaAs device structures that utilize heavily doped layers. X-ray photoemission spectroscopy was used to deduce the shift in the valence-band-edge induced by carbon (p type) doping to a carrier density of 1×1020 cm-3 based on a determination of the bulk binding energy of the Ga and As core levels in this material. Analysis of the data indicates that the shift of the valence-band maximum into the gap and the penetration of the Fermi level into the valence bands exactly compensate at this degenerate carrier concentration, to give ΔEv =0.12±0.05 eV.

Valence band offsets of Sc x Ga1-x N/AlN and Sc x Ga1-x N/GaN heterojunctions

NASA Astrophysics Data System (ADS)

Tsui, H. C. L.; Goff, L. E.; Palgrave, R. G.; Beere, H. E.; Farrer, I.; Ritchie, D. A.; Moram, M. A.

2016-07-01

The valence band offsets of Sc x Ga1-x N/AlN heterojunctions were measured by x-ray photoelectron spectroscopy (XPS) and were found to increase from 0.42 eV to 0.95 eV as the Sc content x increased from 0 to 0.15. The increase in valence band offset with increasing x is attributed to the corresponding increase in spontaneous polarization of the wurtzite structure. The Sc x Ga1-x N/AlN heterojunction is type I, similar to other III-nitride-based heterojunctions. The data also indicate that a type II staggered heterojunction, which can enhance spatial charge separation, could be formed if Sc x Ga1-x N is grown on GaN.

Plasmon satellites in valence-band photoemission spectroscopy. Ab initio study of the photon-energy dependence in semiconductors

NASA Astrophysics Data System (ADS)

Guzzo, M.; Kas, J. J.; Sottile, F.; Silly, M. G.; Sirotti, F.; Rehr, J. J.; Reining, L.

2012-09-01

We present experimental data and theoretical results for valence-band satellites in semiconductors, using the prototypical example of bulk silicon. In a previous publication we introduced a new approach that allows us to describe satellites in valence photoemission spectroscopy, in good agreement with experiment. Here we give more details; we show how the the spectra change with photon energy, and how the theory explains this behaviour. We also describe how we include several effects which are important to obtain a correct comparison between theory and experiment, such as secondary electrons and photon cross sections. In particular the inclusion of extrinsic losses and their dependence on the photon energy are key to the description of the energy dependence of spectra.

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.

Vibrationally high-resolved electronic spectra of MCl2 (M=C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2(.).

PubMed

Ran, Yibin; Pang, Min; Shen, Wei; Li, Ming; He, Rongxing

2016-10-05

We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M=C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group. Copyright © 2016 Elsevier B.V. All rights reserved.

Doping induced modifications in the electronic structure and magnetism of ZnO films: Valence band and conduction band studies

NASA Astrophysics Data System (ADS)

Katba, Savan; Jethva, Sadaf; Udeshi, Malay; Trivedi, Priyanka; Vagadia, Megha; Shukla, D. K.; Choudhary, R. J.; Phase, D. M.; Kuberkar, D. G.

2017-11-01

The electronic structure of Pulsed Laser Deposited (PLD) ZnO, Zn0.95Fe0.05O (ZFO), Zn0.98Al0.02O (ZAO) and Zn0.93Fe0.05Al0.02O (ZFAO) films were investigated by Photoelectron spectroscopy and X-ray absorption spectroscopy. X-ray diffraction and ϕ-scan measurements show epitaxial c-directional growth of the films. Temperature dependent magnetization and M-H loop measurements show the presence of room temperature magnetic ordering in all the films. Fittings of Fe 2p XPS and Fe L3,2 -edge XAS of ZFO and ZFAO films show the presence of Fe, in both, Fe+2 and Fe+3 states in tetrahedral symmetry. Valence band spectra in resonance mode show resonance photon energy at 56 eV showing the presence of Fe2+ state (∼2 eV) near the Fermi level. A significant effect of Fe and Al doping on the spectral shape of O K-edge XAS was observed. Results of the Spectroscopic studies reveal that, ferromagnetism in the films is due to the contribution of oxygen deficiency which increases the number of charge carriers that take part in the exchange interaction. Al co-doping with Fe (in ZFAO) results in the enhancement of saturation magnetization by increase in the carrier-mediated ferromagnetic exchange interaction.

Band alignment of TiO{sub 2}/FTO interface determined by X-ray photoelectron spectroscopy: Effect of annealing

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

Fan, Haibo, E-mail: hbfan@nwu.edu.cn, E-mail: liusz@snnu.edu.cn; School of Physics, Northwest University, Xi’an 710069; Yang, Zhou

2016-01-15

The energy band alignment between pulsed-laser-deposited TiO{sub 2} and FTO was firstly characterized using high-resolution X-ray photoelectron spectroscopy. A valence band offset (VBO) of 0.61 eV and a conduction band offset (CBO) of 0.29 eV were obtained across the TiO{sub 2}/FTO heterointerface. With annealing process, the VBO and CBO across the heterointerface were found to be -0.16 eV and 1.06 eV, respectively, with the alignment transforming from type-I to type-II. The difference in the band alignment is believed to be dominated by the core level down-shift of the FTO substrate, which is a result of the oxidation of Sn. Current-voltagemore » test has verified that the band alignment has a significant effect on the current transport of the heterojunction.« less

Renner-Teller effects in the photoelectron spectra of CNC, CCN, and HCCN.

PubMed

Coudert, Laurent H; Gans, Bérenger; Garcia, Gustavo A; Loison, Jean-Christophe

2018-02-07

The line intensity of photoelectron spectra when either the neutral or cationic species display a Renner-Teller coupling is derived and applied to the modeling of the photoelectron spectra of CNC, CCN, and HCCN. The rovibronic energy levels of these three radicals and of their cations are investigated starting from ab initio results. A model treating simultaneously the bending mode and the overall rotation is developed to deal with the quasilinearity problem in CNC + , CCN + , and HCCN and accounts for the large amplitude nature of their bending mode. This model is extended to treat the Renner-Teller coupling in CNC, CCN, and HCCN + . Based on the derived photoelectron line intensity, the photoelectron spectra of all three molecules are calculated and compared to the experimental ones.

Electronic structure of the dilute magnetic semiconductor G a1 -xM nxP from hard x-ray photoelectron spectroscopy and angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Keqi, A.; Gehlmann, M.; Conti, G.; Nemšák, S.; Rattanachata, A.; Minár, J.; Plucinski, L.; Rault, J. E.; Rueff, J. P.; Scarpulla, M.; Hategan, M.; Pálsson, G. K.; Conlon, C.; Eiteneer, D.; Saw, A. Y.; Gray, A. X.; Kobayashi, K.; Ueda, S.; Dubon, O. D.; Schneider, C. M.; Fadley, C. S.

2018-04-01

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) G a0.98M n0.02P and compared it to that of an undoped GaP reference sample, using hard x-ray photoelectron spectroscopy (HXPS) and hard x-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between G a0.98M n0.02P and GaP in both angle-resolved and angle-integrated valence spectra. The G a0.98M n0.02P bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host GaP crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations and a prior HARPES study of G a0.97M n0.03As and GaAs [Gray et al., Nat. Mater. 11, 957 (2012), 10.1038/nmat3450], demonstrating the strong similarity between these two materials. The Mn 2 p and 3 s core-level spectra also reveal an essentially identical state in doping both GaAs and GaP.

Selectivity in Ketenimine Cycloadditions. Photoelectron Hel Spectra of Ketenimines

NASA Astrophysics Data System (ADS)

Bernardi, Fernando; Bottoni, Andrea; Ballaglia, Arturo; Distefano, Giuseppe; Dondoni, Alessandro

1980-05-01

The first few bands in the photoelectron (Hel) spectra of ketenimines R1R2C-C=NR3(R1,R2=H, CH3, C5H6, CH2=CH; R3=alkyl or aryl group) are assigned to the corresponding molecular orbitals. The assignment is based on SCF-MO calculations made at three different levels (CNDO/2, ab-initio STO-3C and 4-31G) coupled with perturbational molecular orbital analyses. The π-orbitals of the unsaturated substituents are found to interact with one of the two perpendicular π-electron systems of the>C=C=N- residue, the critical factor being the position of attack of the substituent. The relevance of these results on the site selectivity observed in cycloaddition reactions of these species is discussed.

Spectroscopy of the simplest Criegee intermediate CH2OO: simulation of the first bands in its electronic and photoelectron spectra.

PubMed

Lee, Edmond P F; Mok, Daniel K W; Shallcross, Dudley E; Percival, Carl J; Osborn, David L; Taatjes, Craig A; Dyke, John M

2012-09-24

CH(2)OO, the simplest Criegee intermediate, and ozone are isoelectronic. They both play very important roles in atmospheric chemistry. Whilst extensive experimental studies have been made on ozone, there were no direct gas-phase studies on CH(2)OO until very recently when its photoionization spectrum was recorded and kinetics studies were made of some reactions of CH(2)OO with a number of molecules of atmospheric importance, using photoionization mass spectrometry to monitor CH(2)OO. In order to encourage more direct studies on CH(2)OO and other Criegee intermediates, the electronic and photoelectron spectra of CH(2)OO have been simulated using high level electronic structure calculations and Franck-Condon factor calculations, and the results are presented here. Adiabatic and vertical excitation energies of CH(2)OO were calculated with TDDFT, EOM-CCSD, and CASSCF methods. Also, DFT, QCISD and CASSCF calculations were performed on neutral and low-lying ionic states, with single energy calculations being carried out at higher levels to obtain more reliable ionization energies. The results show that the most intense band in the electronic spectrum of CH(2) OO corresponds to the B(1)A' ← X(1)A' absorption. It is a broad band in the region 250-450 nm showing extensive structure in vibrational modes involving O-O stretching and C-O-O bending. Evidence is presented to show that the electronic absorption spectrum of CH(2)OO has probably been recorded in earlier work, albeit at low resolution. We suggest that CH(2)OO was prepared in this earlier work from the reaction of CH(2)I with O(2) and that the assignment of the observed spectrum solely to CH(2)IOO is incorrect. The low ionization energy region of the photoelectron spectrum of CH(2)OO consists of two overlapping vibrationally structured bands corresponding to one-electron ionizations from the highest two occupied molecular orbitals of the neutral molecule. In each case, the adiabatic component is the most intense

Photoelectron spectra of carbonyls. Propellenes and propellanones

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

Dougherty, D.; Bloomfield, J.J.; Newkome, G.R.

1976-09-23

The HeI photoelectron spectra (UPS) of a number of unsaturated (4.4.2)propellanes and (4.4.2)propellane-dione derivatives are presented. The interpretation of the UPS data is based on through-space and through-bond interaction models and on CNDO/s computations. An analysis of the photoelectron spectra of (4.4.2)propella-3,8-diene-11,12-dione (1), (4.4.2)propell-3-ene-11,12-dione (2), (4.4.2)propellane-11,12-dione (3), (4.4.2)propella-3,8-dien-11-one (4), and (4.4.2) propella-3,8-diene (5) involves the assignment of n/sub +/, n/sub -/, ..pi../sub +/, ..pi../sub -/, and sigma/sub square/ (i.e., cyclobutane sigma) ionization events. The analysis of the data for 5, (4.4.2)propella-3,8,11-triene (6), (4.4.2)propella-3,11-diene (7), and (4.4.2)propell-11-ene (8) leads to the conclusion that the photoelectron spectrum of 6 should be reassigned.more » The /sup 1/GAMMA/sub n..pi..*/ reverse arrow /sup 1/GAMMA/sub 1/ absorption spectra of 1,2, and 3 have been investigated as a function of temperature. The low energy of this transition in 1 is attributed to a high degree of CO/CO coplanarity, the high energy of this transition in 3 is attributed to CO/CO noncoplanarity, and the isomerism evident in 2 is attributed to multiple minima of the potential energy along the CO/CO dihedral angle coordinate of the ground state.« less

Valence Band Control of Metal Silicide Films via Stoichiometry.

PubMed

Streller, Frank; Qi, Yubo; Yang, Jing; Mangolini, Filippo; Rappe, Andrew M; Carpick, Robert W

2016-07-07

The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties.

Valence-band states in Bi2(Ca,Sr,La)3Cu2O8

NASA Astrophysics Data System (ADS)

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

1989-09-01

We have used photoemission spectroscopy to examine the symmetry of the occupied states of the valence band for the La-doped superconductor Bi2(Ca,Sr,La)3Cu2O8. While the oxygen states near the bottom of the 7-eV wide valence band exhibit predominantly O 2pz symmetry, the states at the top of the valence band extending to the Fermi level are found to have primarily O 2px and O 2py character. We have also examined anomalous intensity enhancements in the valence-band features for photon energies near 18 eV. These enhancements, which occur at photon energies ranging from 15.8 to 18.0 eV for the different valence-band features, are not consistent with either simple final-state effects or direct O 2s transitions to unoccupied O 2p states.

X-Ray Photoelectron Spectroscopic Characterization of Iron Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Radu, T.; Iacovita, C.; Benea, D.; Turcu, R.

2017-05-01

We report X-ray photoelectron spectroscopy (XPS) results on iron oxide magnetic nanoparticle (Fe3O4) synthesized using solvothermal reduction in the presence of polyethylene glycol. The magnetite obtained was employed as precursor for the synthesis of γ-Fe2O3 (by oxygen dissociation) which in turn was transformed into α-Fe2O3. We confirmed the magnetite, maghemite and hematite structure by Fourier Transformed Spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis of the XPS core level and valence band (VB) photoemission spectra for all investigated samples is discussed in terms of the degree of iron oxidation. This is of fundamental importance to better understand the electronic structure of the obtained iron oxide nanoparticles in order to control and improve their quality for specific biomedical applications. Moreover, theoretical band structure calculations are performed for magnetite and the separate contributions of Fe in tetragonal and octahedral environment are shown.

Photoelectron spectroscopy study on Li substituted NiO using PES beamline installed on Indus-1

NASA Astrophysics Data System (ADS)

Banerjee, A.; Chaudhari, S. M.; Phase, D. M.; Dasannacharya, B. A.

2003-01-01

Photoelectron spectroscopy beamline based on a toroidal grating monochromator (TGM) is recently commissioned on Indus-1 storage ring. It has been used to carry out valence band photoemission study of Li substituted NiO. In this paper initially a brief description of the beamline components and the experimental station for angle integrated photoemission experiment is presented. The later part of this paper is devoted to studies carried out on Li xNi 1- xO with x=0.0, 0.35 and 0.5 samples. Thin pellets of polycrystalline samples were used for the measurements reported here. Valence band spectra recorded on polycrystalline Li xNi 1- xO samples show drastic changes in various features as compared to that of pure NiO. The prominent changes are: (i) change in the relative contributions of Ni-3d and O-2p emissions, (ii) change in the peak position of Ni-3d from the top of the valance band of NiO and (iii) no noticeable change in the Ni satellite peak. These results are evaluated in terms of earlier findings in pure and low Li doped NiO.

Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Gladen, R. W.; Joglekar, P. V.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DEAC02-98CH10886.

Measurement of the low energy spectral contribution in coincidence with valence band (VB) energy levels of Ag(100) using VB-VB coincidence spectroscopy

NASA Astrophysics Data System (ADS)

Joglekar, P. V.; Gladen, R.; Lim, Z. H.; Shastry, K.; Hulbert, S. L.; Weiss, A. H.

2015-03-01

A set of coincidence measurements were obtained for the study and measurement of the electron contribution arising from the inter-valence band (VB) transitions along with the inelastically scattered VB electron contribution. These Auger-unrelated contributions arise in the Auger spectrum (Ag 4p NVV) obtained using Auger Photoelectron Coincidence Spectroscopy (APECS). The measured Auger-unrelated contribution can be eliminated from Auger spectrum to obtain the spectrum related to Auger. In our VB-VB coincidence measurement, a photon beam of energy 180eV was used to probe the Ag(100) sample. The coincidence spectrum was obtained using two Cylindrical Mirror Analyzers (CMA's). The scan CMA measured the low energy electron contribution in the energy range 0-70eV in coincidence with VB electrons measured by the fixed CMA. In this talk, we present the data obtained for VB-VB coincidence at the valence band energy of 171eV along with the coincidence measurements in the energy range of 4p core and valence band. NSF DMR 0907679, NSF Award Number: 1213727. Use of the National Synchrotron Light Source, Brookhaven National Laboratory, was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Valence and conduction band offsets of β-Ga2O3/AlN heterojunction

NASA Astrophysics Data System (ADS)

Sun, Haiding; Torres Castanedo, C. G.; Liu, Kaikai; Li, Kuang-Hui; Guo, Wenzhe; Lin, Ronghui; Liu, Xinwei; Li, Jingtao; Li, Xiaohang

2017-10-01

Both β-Ga2O3 and wurtzite AlN have wide bandgaps of 4.5-4.9 and 6.1 eV, respectively. We calculated the in-plane lattice mismatch between the (-201) plane of β-Ga2O3 and the (0002) plane of AlN, which was found to be 2.4%. This is the smallest mismatch between β-Ga2O3 and binary III-nitrides which is beneficial for the formation of a high quality β-Ga2O3/AlN heterojunction. However, the valence and conduction band offsets (VBO and CBO) at the β-Ga2O3/AlN heterojunction have not yet been identified. In this study, a very thin (less than 2 nm) β-Ga2O3 layer was deposited on an AlN/sapphire template to form the heterojunction by pulsed laser deposition. High-resolution X-ray photoelectron spectroscopy revealed the core-level (CL) binding energies of Ga 3d and Al 2p with respect to the valence band maximum in individual β-Ga2O3 and AlN layers, respectively. The separation between Ga 3d and Al 2p CLs at the β-Ga2O3/AlN interface was also measured. Eventually, the VBO was found to be -0.55 ± 0.05 eV. Consequently, a staggered-gap (type II) heterojunction with a CBO of -1.75 ± 0.05 eV was determined. The identification of the band alignment of the β-Ga2O3/AlN heterojunction could facilitate the design of optical and electronic devices based on these and related alloys.

Location of the valence band maximum in the band structure of anisotropic 1 T'-ReSe2

NASA Astrophysics Data System (ADS)

Eickholt, P.; Noky, J.; Schwier, E. F.; Shimada, K.; Miyamoto, K.; Okuda, T.; Datzer, C.; Drüppel, M.; Krüger, P.; Rohlfing, M.; Donath, M.

2018-04-01

Transition-metal dichalcogenides (TMDCs) are a focus of current research due to their fascinating optical and electronic properties with possible technical applications. ReSe2 is an interesting material of the TMDC family, with unique anisotropic properties originating from its distorted 1 T structure (1 T '). To develop a fundamental understanding of the optical and electric properties, we studied the underlying electronic structure with angle-resolved photoemission (ARPES) as well as band-structure calculations within the density functional theory (DFT)-local density approximation (LDA) and GdW approximations. We identified the Γ ¯M¯1 direction, which is perpendicular to the a axis, as a distinct direction in k space with the smallest bandwidth of the highest valence band. Using photon-energy-dependent ARPES, two valence band maxima are identified within experimental limits of about 50 meV: one at the high-symmetry point Z , and a second one at a non-high-symmetry point in the Brillouin zone. Thus, the position in k space of the global valence band maximum is undecided experimentally. Theoretically, an indirect band gap is predicted on a DFT-LDA level, while quasiparticle corrections lead to a direct band gap at the Z point.

Spectroscopic study of hafnium silicate alloys prepared by RPECVD: Comparisons between conduction/valence band offset energies and optical band gaps

NASA Astrophysics Data System (ADS)

Hong, Joon Goo

Aggressive scaling of devices has continued to improve MOSFET transistor performance. As lateral device dimensions continue to decrease, gate oxide thickness must be scaled down. As one of the promising high k alternative gate oxide materials, HfO2 and its silicates were investigated to understand their direct tunneling behavior by studying band offset energies with spectroscopy and electrical characterization. Local bonding change of remote plasma deposited (HfO2)x(SiO 2)1-x alloys were characterized by Fourier transform infrared (FTIR) spectroscopy, x-ray photoelectron spectroscopy (XPS), and Auger electron spectroscopy (AES) as a function of alloy composition, x. Two different precursors with Hf Nitrato and Hf-tert-butoxide were tested to have amorphous deposition. Film composition was determined off-line by Rutherford backscattering spectroscopy (RBS) and these results were calibrated with on-line AES. As deposited Hf-silicate alloys were characterized by off-line XPS and AES for their chemical shifts interpreting with a partial charge transfer model as well as coordination changes. Sigmoidal dependence of valence band offset energies was observed. Hf 5d* state is fixed at the bottom of the conduction band and located at 1.3 +/- 0.2 eV above the top of the Si conduction band as a conduction band offset by x-ray absorption spectroscopy (XAS). Optical band gap energy changes were observed with vacuum ultra violet spectroscopic ellipsometry (VUVSE) to verify compositional dependence of conduction and valence band offset energy changes. 1 nm EOT normalized tunneling current with Wentzel-Kramer-Brillouin (WKB) simulation based on the band offset study and Franz two band model showed the minimum at the intermediate composition matching with the experimental data. Non-linear trend in tunneling current was observed because the increases in physical thickness were mitigated by reductions in band offset energies and effective mass for tunneling. C-V curves were compared

Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation

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

Stephansen, Anne B.; King, Sarah B.; Li, Wei-Li

2015-09-14

Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison withmore » calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.« less

Evolution of optical properties and band structure from amorphous to crystalline Ga2O3 films

NASA Astrophysics Data System (ADS)

Zhang, Fabi; Li, Haiou; Cui, Yi-Tao; Li, Guo-Ling; Guo, Qixin

2018-04-01

The optical properties and band structure evolution from amorphous to crystalline Ga2O3 films was investigated in this work. Amorphous and crystalline Ga2O3 films were obtained by changing the growth substrate temperatures of pulsed laser deposition and the crystallinity increase with the rising of substrate temperature. The bandgap value and ultraviolet emission intensity of the films increase with the rising of crystallinity as observed by means of spectrophotometer and cathodoluminescence spectroscopy. Abrupt bandgap value and CL emission variations were observed when amorphous to crystalline transition took place. X-ray photoelectron spectroscopy core level spectra reveal that more oxygen vacancies and disorders exist in amorphous Ga2O3 film grown at lower substrate temperature. The valence band spectra of hard X-ray photoelectron spectroscopy present the main contribution from Ga 4sp for crystalline film deposited at substrate temperature of 500 oC, while extra subgap states has been observed in amorphous film deposited at 300 oC. The oxygen vacancy and the extra subgap density of states are suggested to be the parts of origin of bandgap and CL spectra variations. The experimental data above yields a realistic picture of optical properties and band structure variation for the amorphous to crystalline transition of Ga2O3 films.

Band alignment of ZnO/multilayer MoS{sub 2} interface determined by x-ray photoelectron spectroscopy

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

Liu, Xinke, E-mail: xkliu@szu.edu.cn, E-mail: liuwj@szu.edu.cn; He, Jiazhu; Chen, Le

2016-08-15

The energy band alignment between ZnO and multilayer (ML)-MoS{sub 2} was characterized using high-resolution x-ray photoelectron spectroscopy. The ZnO film was deposited using an atomic layer deposition tool, and ML-MoS{sub 2} was grown by chemical vapor deposition. A valence band offset (VBO) of 3.32 eV and a conduction band offset (CBO) of 1.12 eV were obtained for the ZnO/ML-MoS{sub 2} interface without any treatment. With CHF{sub 3} plasma treatment, a VBO and a CBO across the ZnO/ML-MoS{sub 2} interface were found to be 3.54 eV and 1.34 eV, respectively. With the CHF{sub 3} plasma treatment, the band alignment of the ZnO/ML-MoS{sub 2} interface hasmore » been changed from type II or staggered band alignment to type III or misaligned one, which favors the electron-hole pair separation. The band alignment difference is believed to be dominated by the down-shift in the core level of Zn 2p or the interface dipoles, which is caused by the interfacial layer rich in F.« less

Identification of metal s states in Sn-doped anatase by polarisation dependent hard X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Regoutz, A.; Oropeza, F. E.; Poll, C. G.; Payne, D. J.; Palgrave, R. G.; Panaccione, G.; Borgatti, F.; Agrestini, S.; Utsumi, Y.; Tsuei, K. D.; Liao, Y. F.; Watson, G. W.; Egdell, R. G.

2016-03-01

The contributions of Sn 5s and Ti 4s states to the valence band electronic structure of Sn-doped anatase have been identified by hard X-ray photoelectron spectroscopy. The metal s state intensity is strongly enhanced relative to that of O 2p states at high photon energies due to matrix element effects when electrons are detected parallel to the direction of the polarisation vector of the synchrotron beam, but becomes negligible in the perpendicular direction. The experimental spectra in both polarisations are in good agreement with cross section and asymmetry parameter weighted partial densities of states derived from density functional theory calculations.

Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization

NASA Astrophysics Data System (ADS)

Karpenko, A.; Iablonskyi, D.; Urpelainen, S.; Kettunen, J. A.; Cao, W.; Huttula, M.; Aksela, H.

2014-05-01

The inner-valence region of alkali bromide XBr (X=Li, Na, K, Rb) vapours has been studied experimentally by means of synchrotron radiation excited photoelectron spectroscopy. Experimental spectra were analyzed by comparing them with available theoretical results and previous experiments. Ionic character of alkali bromides is seen to change in the inner-valence region with increasing atomic number of the alkali atom. A mechanism involving mixing between Br 4s and Rb 4p orbitals has been suggested to account for the fine structure observed in inner-valence ionization region of RbBr.

Effects of the carrier concentration on polarity determination in Ga-doped ZnO films by hard x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Song, Huaping; Makino, Hisao; Kobata, Masaaki; Nomoto, Junichi; Kobayashi, Keisuke; Yamamoto, Tetsuya

2018-03-01

Core level (CL) and valence band (VB) spectra of heavily Ga-doped ZnO (GZO) films with carrier concentrations (Ne) ranging from 1.8 × 1020 to 1.0 × 1021 cm-3 were measured by high-resolution Al Kα (hν = 1486.6 eV) x-ray photoelectron spectroscopy (XPS) and Cr Kα (hν = 5414.7 eV) hard x-ray photoelectron spectroscopy (HAXPES). The CL spectra of the GZO films measured by XPS had little dependence on Ne. In contrast, clear differences in asymmetric broadening were observed in the HAXPES spectra owing to the large probing depth. The asymmetry in the Zn 2p3/2 and O 1s HAXPES spectra is mainly attributed to the energy loss of the conduction electron plasmon caused by the high Ne of the GZO films. Similar asymmetry was also observed in the VB spectra of these GZO films. It was found that such asymmetry plays a crucial role in the determination of crystal polarity. With increasing Ne, the intensity of the sub-peak at a binding energy Eb of about 5 eV in the VB spectrum decreased and the sub-peak became indistinguishable. We clarified the limitation of the criterion using the sub-peak and proposed an alternative method for polarity determination.

Electronic structure of lanthanide scandates

NASA Astrophysics Data System (ADS)

Mizzi, Christopher A.; Koirala, Pratik; Marks, Laurence D.

2018-02-01

X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and density functional theory calculations were used to study the electronic structure of three lanthanide scandates: GdSc O3,TbSc O3 , and DySc O3 . X-ray photoelectron spectra simulated from first-principles calculations using a combination of on-site hybrid and GGA +U methods were found to be in good agreement with experimental x-ray photoelectron spectra. The hybrid method was used to model the ground state electronic structure and the GGA +U method accounted for the shift of valence state energies due to photoelectron emission via a Slater-Janak transition state approach. From these results, the lanthanide scandate valence bands were determined to be composed of Ln 4 f ,O 2 p , and Sc 3 d states, in agreement with previous work. However, contrary to previous work the minority Ln 4 f states were found to be located closer to, and in some cases at, the valence band maximum. This suggests that minority Ln 4 f electrons may play a larger role in lanthanide scandate properties than previously thought.

Determination of a natural valence-band offset - The case of HgTe and CdTe

NASA Technical Reports Server (NTRS)

Shih, C. K.; Spicer, W. E.

1987-01-01

A method to determine a natural valence-band offset (NVBO), i.e., the change in the valence-band maximum energy which is intrinsic to the bulk band structures of semiconductors is proposed. The HgTe-CdTe system is used as an example in which it is found that the valence-band maximum of HgTe lies 0.35 + or - 0.06 eV above that of CdTe. The NVBO of 0.35 eV is in good agreement with the X-ray photoemission spectroscopy measurement of the heterojunction offset. The procedure to determine the NVBO between semiconductors, and its implication on the heterojunction band lineup and the electronic structures of semiconductor alloys, are discussed.

Electronic structure of germanium selenide investigated using ultra-violet photo-electron spectroscopy

NASA Astrophysics Data System (ADS)

Mishra, P.; Lohani, H.; Kundu, A. K.; Patel, R.; Solanki, G. K.; Menon, Krishnakumar S. R.; Sekhar, B. R.

2015-07-01

The valence band electronic structure of GeSe single crystals has been investigated using angle resolved photoemission spectroscopy (ARPES) and x-ray photoelectron spectroscopy. The experimentally observed bands from ARPES, match qualitatively with our LDA-based band structure calculations along the Γ-Z, Γ-Y and Γ-T symmetry directions. The valence band maximum occurs nearly midway along the Γ-Z direction, at a binding energy of -0.5 eV, substantiating the indirect band gap of GeSe. Non-dispersive features associated with surface states and indirect transitions have been observed. The difference in hybridization of Se and Ge 4p orbitals leads to the variation of dispersion along the three symmetry directions. The predominance of the Se 4pz orbitals, evidenced from theoretical calculations, may be the cause for highly dispersive bands along the Γ-T direction. Detailed electronic structure analysis reveals the significance of the cation-anion 4p orbitals hybridization in the valence band dispersion of IV-VI semiconductors. This is the first comprehensive report of the electronic structure of a GeSe single crystal using ARPES in conjugation with theoretical band structure analysis.

Use of valence band Auger electron spectroscopy to study thin film growth: oxide and diamond-like carbon films

NASA Astrophysics Data System (ADS)

Steffen, H. J.

1994-12-01

It is demonstrated how Auger line shape analysis with factor analysis (FA), least-squares fitting and even simple peak height measurements may provide detailed information about the composition, different chemical states and also defect concentration or crystal order. Advantage is taken of the capability of Auger electron spectroscopy to give valence band structure information with high surface sensitivity and the special aspect of FA to identify and discriminate quantitatively unknown chemical species. Valence band spectra obtained from Ni, Fe, Cr and NiFe40Cr20 during oxygen exposure at room temperature reveal the oxidation process in the initial stage of the thin layer formation. Furthermore, the carbon chemical states that were formed during low energy C(+) and Ne(+) ion irradiation of graphite are delineated and the evolution of an amorphous network with sp3 bonds is disclosed. The analysis represents a unique method to quantify the fraction of sp3-hybridized carbon in diamond-like materials.

Correlations Between Variations in Solar EUV and Soft X-Ray Irradiance and Photoelectron Energy Spectra Observed on Mars and Earth

NASA Technical Reports Server (NTRS)

Peterson, W. K.; Brain, D. A.; Mitchell, D. L.; Bailey, S. M.; Chamberlin, P. C.

2013-01-01

Solar extreme ultraviolet (EUV; 10-120 nm) and soft X-ray (XUV; 0-10 nm) radiation are major heat sources for the Mars thermosphere as well as the primary source of ionization that creates the ionosphere. In investigations of Mars thermospheric chemistry and dynamics, solar irradiance models are used to account for variations in this radiation. Because of limited proxies, irradiance models do a poor job of tracking the significant variations in irradiance intensity in the EUV and XUV ranges over solar rotation time scales when the Mars-Sun-Earth angle is large. Recent results from Earth observations show that variations in photoelectron energy spectra are useful monitors of EUV and XUV irradiance variability. Here we investigate photoelectron energy spectra observed by the Mars Global Surveyor (MGS) Electron Reflectometer (ER) and the FAST satellite during the interval in 2005 when Earth, Mars, and the Sun were aligned. The Earth photoelectron data in selected bands correlate well with calculations based on 1 nm resolution observations above 27 nm supplemented by broadband observations and a solar model in the 0-27 nm range. At Mars, we find that instrumental and orbital limitations to the identifications of photoelectron energy spectra in MGS/ER data preclude their use as a monitor of solar EUV and XUV variability. However, observations with higher temporal and energy resolution obtained at lower altitudes on Mars might allow the separation of the solar wind and ionospheric components of electron energy spectra so that they could be used as reliable monitors of variations in solar EUV and XUV irradiance than the time shifted, Earth-based, F(10.7) index currently used.

Correlations between variations in solar EUV and soft X-ray irradiance and photoelectron energy spectra observed on Mars and Earth

NASA Astrophysics Data System (ADS)

Peterson, W. K.; Brain, D. A.; Mitchell, D. L.; Bailey, S. M.; Chamberlin, P. C.

2013-11-01

extreme ultraviolet (EUV; 10-120 nm) and soft X-ray (XUV; 0-10 nm) radiation are major heat sources for the Mars thermosphere as well as the primary source of ionization that creates the ionosphere. In investigations of Mars thermospheric chemistry and dynamics, solar irradiance models are used to account for variations in this radiation. Because of limited proxies, irradiance models do a poor job of tracking the significant variations in irradiance intensity in the EUV and XUV ranges over solar rotation time scales when the Mars-Sun-Earth angle is large. Recent results from Earth observations show that variations in photoelectron energy spectra are useful monitors of EUV and XUV irradiance variability. Here we investigate photoelectron energy spectra observed by the Mars Global Surveyor (MGS) Electron Reflectometer (ER) and the FAST satellite during the interval in 2005 when Earth, Mars, and the Sun were aligned. The Earth photoelectron data in selected bands correlate well with calculations based on 1 nm resolution observations above 27 nm supplemented by broadband observations and a solar model in the 0-27 nm range. At Mars, we find that instrumental and orbital limitations to the identifications of photoelectron energy spectra in MGS/ER data preclude their use as a monitor of solar EUV and XUV variability. However, observations with higher temporal and energy resolution obtained at lower altitudes on Mars might allow the separation of the solar wind and ionospheric components of electron energy spectra so that they could be used as reliable monitors of variations in solar EUV and XUV irradiance than the time shifted, Earth-based, F10.7 index currently used.

Nature of the valence band states in Bi2(Ca, Sr, La)3Cu2O8

NASA Astrophysics Data System (ADS)

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

1990-01-01

We have used photoemission spectroscopy to examine the symmetry of the occupied states of the valence band for the La doped superconductor Bi2(Ca, Sr, La)3Cu2O8. While the oxygen states near the bottom of the 7 eV wide valence band exhibit predominantly O 2pz symmetry, the states at the top of the valence band extending to the Fermi level are found to have primarily O 2px and O 2py character. We have also examined anomalous intensity enhancements in the valence band feature for photon energies near 18 eV. These enhancements, which occur at photon energies ranging from 15.8 to 18.0 eV for the different valence band features, are not consistent with either simple final state effects or direct O2s transitions to unoccupied O2p states.

Band-like transport in highly crystalline graphene films from defective graphene oxides.

PubMed

Negishi, R; Akabori, M; Ito, T; Watanabe, Y; Kobayashi, Y

2016-07-01

The electrical transport property of the reduced graphene oxide (rGO) thin-films synthesized from defective GO through thermal treatment in a reactive ethanol environment at high temperature above 1000 °C shows a band-like transport with small thermal activation energy (Ea~10 meV) that occurs during high carrier mobility (~210 cm(2)/Vs). Electrical and structural analysis using X-ray absorption fine structure, the valence band photo-electron, Raman spectra and transmission electron microscopy indicate that a high temperature process above 1000 °C in the ethanol environment leads to an extraordinary expansion of the conjugated π-electron system in rGO due to the efficient restoration of the graphitic structure. We reveal that Ea decreases with the increasing density of states near the Fermi level due to the expansion of the conjugated π-electron system in the rGO. This means that Ea corresponds to the energy gap between the top of the valence band and the bottom of the conduction band. The origin of the band-like transport can be explained by the carriers, which are more easily excited into the conduction band due to the decreasing energy gap with the expansion of the conjugated π-electron system in the rGO.

Band-like transport in highly crystalline graphene films from defective graphene oxides

NASA Astrophysics Data System (ADS)

Negishi, R.; Akabori, M.; Ito, T.; Watanabe, Y.; Kobayashi, Y.

2016-07-01

The electrical transport property of the reduced graphene oxide (rGO) thin-films synthesized from defective GO through thermal treatment in a reactive ethanol environment at high temperature above 1000 °C shows a band-like transport with small thermal activation energy (Ea~10 meV) that occurs during high carrier mobility (~210 cm2/Vs). Electrical and structural analysis using X-ray absorption fine structure, the valence band photo-electron, Raman spectra and transmission electron microscopy indicate that a high temperature process above 1000 °C in the ethanol environment leads to an extraordinary expansion of the conjugated π-electron system in rGO due to the efficient restoration of the graphitic structure. We reveal that Ea decreases with the increasing density of states near the Fermi level due to the expansion of the conjugated π-electron system in the rGO. This means that Ea corresponds to the energy gap between the top of the valence band and the bottom of the conduction band. The origin of the band-like transport can be explained by the carriers, which are more easily excited into the conduction band due to the decreasing energy gap with the expansion of the conjugated π-electron system in the rGO.

Electronic structure and optical properties of Cs2HgI4: Experimental study and band-structure DFT calculations

NASA Astrophysics Data System (ADS)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Shkumat, P. N.; Myronchuk, G. L.; Khvyshchun, M.; Fedorchuk, A. O.; Parasyuk, O. V.; Khyzhun, O. Y.

2015-04-01

High-quality single crystal of cesium mercury tetraiodide, Cs2HgI4, has been synthesized by the vertical Bridgman-Stockbarger method and its crystal structure has been refined. In addition, electronic structure and optical properties of Cs2HgI4 have been studied. For the crystal under study, X-ray photoelectron core-level and valence-band spectra for pristine and Ar+-ion irradiated surfaces have been measured. The present X-ray photoelectron spectroscopy (XPS) results indicate that the Cs2HgI4 single crystal surface is very sensitive with respect to Ar+ ion-irradiation. In particular, Ar+ bombardment of the single crystal surface alters the elemental stoichiometry of the Cs2HgI4 surface. To elucidate peculiarities of the energy distribution of the electronic states within the valence-band and conduction-band regions of the Cs2HgI4 compound, we have performed first-principles band-structure calculations based on density functional theory (DFT) as incorporated in the WIEN2k package. Total and partial densities of states for Cs2HgI4 have been calculated. The DFT calculations reveal that the I p states make the major contributions in the upper portion of the valence band, while the Hg d, Cs p and I s states are the dominant contributors in its lower portion. Temperature dependence of the light absorption coefficient and specific electrical conductivity has been explored for Cs2HgI4 in the temperature range of 77-300 K. Main optical characteristics of the Cs2HgI4 compound have been elucidated by the first-principles calculations.

Photoelectron energy-loss study of the Bi2CaSr2Cu2O8 superconductor

NASA Astrophysics Data System (ADS)

Shen, Z.-X.; Lindberg, P. A. P.; Dessau, D. S.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Bozovic, I.; Kapitulnik, A.

1989-03-01

Using energy-loss spectroscopy of photoelectrons from a single crystal of Bi2CaSr2Cu2O8, we show that the electronic structure of the near-surface region is the same as that of the bulk. Utilizing the fact that photoelectrons of different elements are excited at different locations in the unit cell, we identify the energy-loss features as due to valence plasmon excitations, and one-electron excitations by comparing the photoelectron energy-loss spectra of the different elements.

On Valence-Band Splitting in Layered MoS2.

PubMed

Zhang, Youwei; Li, Hui; Wang, Haomin; Liu, Ran; Zhang, Shi-Li; Qiu, Zhi-Jun

2015-08-25

As a representative two-dimensional semiconducting transition-metal dichalcogenide (TMD), the electronic structure in layered MoS2 is a collective result of quantum confinement, interlayer interaction, and crystal symmetry. A prominent energy splitting in the valence band gives rise to many intriguing electronic, optical, and magnetic phenomena. Despite numerous studies, an experimental determination of valence-band splitting in few-layer MoS2 is still lacking. Here, we show how the valence-band maximum (VBM) splits for one to five layers of MoS2. Interlayer coupling is found to contribute significantly to phonon energy but weakly to VBM splitting in bilayers, due to a small interlayer hopping energy for holes. Hence, spin-orbit coupling is still predominant in the splitting. A temperature-independent VBM splitting, known for single-layer MoS2, is, thus, observed for bilayers. However, a Bose-Einstein type of temperature dependence of VBM splitting prevails in three to five layers of MoS2. In such few-layer MoS2, interlayer coupling is enhanced with a reduced interlayer distance, but thermal expansion upon temperature increase tends to decouple adjacent layers and therefore decreases the splitting energy. Our findings that shed light on the distinctive behaviors about VBM splitting in layered MoS2 may apply to other hexagonal TMDs as well. They will also be helpful in extending our understanding of the TMD electronic structure for potential applications in electronics and optoelectronics.

Electronic structure of ZrX2 (X = Se, Te)

NASA Astrophysics Data System (ADS)

Shkvarin, A. S.; Merentsov, A. I.; Shkvarina, E. G.; Yarmoshenko, Yu. M.; Píš, I.; Nappini, S.; Titov, A. N.

2018-03-01

The electronic structure of the ZrX2 (X = Se, Te) compounds has been studied using photoelectron, resonant photoelectron and X-ray absorption spectroscopy, theoretical calculations of the X-ray absorption spectra, and density of electronic states. It was found that the absorption spectra and valence band spectra are influenced by the chalcogen type. The results of the multiplet calculation of the Zr4+ atom show that the change in the splitting in the crystal field, which is described by the 10Dq parameter, is due to the change in the ratio of covalent and ionic contributions to the chemical bond. The resonance band near the Fermi level in the valence band spectra is observed for ZrTe2 in the Zr 3p-4d resonant excitation mode. The extent of photon energy indicates the charge localization on the Zr atom. Similar resonance band for ZrSe2 is absent; it indicates the presence of a gap at the Fermi level.

Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

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

Patanen, M.; Benkoula, S.; Nicolas, C.

2015-09-28

Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface.

Band offsets and growth mode of molecular beam epitaxy grown MgO (111) on GaN (0002) by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Craft, H. S.; Collazo, R.; Losego, M. D.; Mita, S.; Sitar, Z.; Maria, J.-P.

2007-10-01

MgO is a proposed dielectric for use as a tunneling barrier in devices integrating GaN and ferroelectric oxides. In this study, we present data regarding the growth mode and band offsets of MgO grown epitaxially on GaN (0002) surfaces using molecular beam epitaxy. Using in situ x-ray photoelectron spectroscopy (XPS) and molecular beam epitaxy, we determine, from sequential growth experiments, that the growth of MgO proceeds via the Volmer-Weber (three-dimensional) mode, and full coalescence of the film does not occur until approximately 12nm of MgO has been deposited. The observation of a three-dimensional growth mode is in agreement with previously published data. For the valence band offset, we find a value of 1.2±0.2eV, which corresponds to a 3.2eV conduction band offset. XPS measurements suggest a chemically abrupt interface and no effect on band lineup due to the slow coalescence behavior.

Ar 3p photoelectron sideband spectra in two-color XUV + NIR laser fields

NASA Astrophysics Data System (ADS)

Minemoto, Shinichirou; Shimada, Hiroyuki; Komatsu, Kazma; Komatsubara, Wataru; Majima, Takuya; Mizuno, Tomoya; Owada, Shigeki; Sakai, Hirofumi; Togashi, Tadashi; Yoshida, Shintaro; Yabashi, Makina; Yagishita, Akira

2018-04-01

We performed photoelectron spectroscopy using femtosecond XUV pulses from a free-electron laser and femtosecond near-infrared pulses from a synchronized laser, and succeeded in measuring Ar 3p photoelectron sideband spectra due to the two-color above-threshold ionization. In our calculations of the first-order time-dependent perturbation theoretical model based on the strong field approximation, the photoelectron sideband spectra and their angular distributions are well reproduced by considering the timing jitter between the XUV and the NIR pulses, showing that the timing jitter in our experiments was distributed over the width of {1.0}+0.4-0.2 ps. The present approach can be used as a method to evaluate the timing jitter inevitable in FEL experiments.

On the analysis of photo-electron spectra

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

Gao, C.-Z., E-mail: gao@irsamc.ups-tlse.fr; CNRS, LPT; Dinh, P.M.

2015-09-15

We analyze Photo-Electron Spectra (PES) for a variety of excitation mechanisms from a simple mono-frequency laser pulse to involved combination of pulses as used, e.g., in attosecond experiments. In the case of simple pulses, the peaks in PES reflect the occupied single-particle levels in combination with the given laser frequency. This usual, simple rule may badly fail in the case of excitation pulses with mixed frequencies and if resonant modes of the system are significantly excited. We thus develop an extension of the usual rule to cover all possible excitation scenarios, including mixed frequencies in the attosecond regime. We find thatmore » the spectral distributions of dipole, monopole and quadrupole power for the given excitation taken together and properly shifted by the single-particle energies provide a pertinent picture of the PES in all situations. This leads to the derivation of a generalized relation allowing to understand photo-electron yields even in complex experimental setups.« less

Valence and ionic lowest-lying electronic states of ethyl formate as studied by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy, and ab initio calculations

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

Śmiałek, M. A., E-mail: smialek@pg.gda.pl; Łabuda, M.; Guthmuller, J.

2014-09-14

The highest resolution vacuum ultraviolet photoabsorption spectrum of ethyl formate, C{sub 2}H{sub 5}OCHO, yet reported is presented over the wavelength range 115.0–275.5 nm (10.75–4.5 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of ethyl formate and are compared with a newly recorded He(I) photoelectron spectrum (from 10.1 to 16.1 eV). Newmore » vibrational structure is observed in the first photoelectron band. The photoabsorption cross sections have been used to calculate the photolysis lifetime of ethyl formate in the upper stratosphere (20–50 km)« less

Modeling of LMM-MVV Auger-Auger Coincidence Spectra From Solids

NASA Astrophysics Data System (ADS)

Sundaramoorthy, R.; Weiss, A. H.; Hulbert, S. L.; Bartynski, R. A.

2006-03-01

Atoms that are highly excited due to the presence of a hole in an inner shell often relax via an Auger transition. This auto-ionizing process results in a final state with two or more holes from an Auger cascade. We present results of the direct measurements of the second and third Auger decays in this sequence. We have measured the Mn MVV Auger spectra from a single-crystal sample of MnO in time coincidence with Auger electrons emitted from prior Mn LMM Auger decays and find these to be much wider than the MVV spectrum measured in time coincidence with M core photoelectron emission. We present a model which attributes the increased energy width of the MVV transitions that follow LMM decays to the rearrangement of ``not so innocent'' bystander hole(s) in the valence band. The energetics of the Auger cascade process are modeled mathematically in terms of correlation integral(s) and convolution integral(s) over the valence band density of states. Comparisons with recent Auger-Auger coincidence studies of Ag and Pd will be made. Acknowledgements: Welch Foundation, NSF DMR98-12628, NSF DMR98-01681, and DOE DE-AC02-98CH10886.

Electronic structure and optical properties of noncentrosymmetric LiGaSe2: Experimental measurements and DFT band structure calculations

NASA Astrophysics Data System (ADS)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Ananchenko, L. N.; Isaenko, L. I.; Yelisseyev, A. P.; Khyzhun, O. Y.

2017-04-01

We report on measurements of X-ray photoelectron (XP) spectra for pristine and Ar+ ion-irradiated surfaces of LiGaSe2 single crystal grown by Bridgman-Stockbarger method. Electronic structure of the LiGaSe2 compound is studied from a theoretical and experimental viewpoint. In particular, total and partial densities of states of LiGaSe2 are investigated by density functional theory (DFT) calculations employing the augmented plane wave + local orbitals (APW + lo) method and they are verified by data of X-ray spectroscopy measurements. The DFT calculations indicate that the main contributors to the valence band of LiGaSe2 are the Se 4p states, which contribute mainly at the top and in the upper portion of the valence band, with also essential contributions of these states in the lower portion of the band. Other substantial contributions to the valence band of LiGaSe2 emerge from the Ga 4s and Ga 4p states contributing mainly at the lower ant upper portions of the valence band, respectively. With respect to the conduction band, the calculations indicate that its bottom is composed mainly from contributions of the unoccupied Ga s and Se p states. The present calculations are confirmed experimentally when comparing the XP valence-band spectrum of the LiGaS2 single crystal on a common energy scale with the X-ray emission bands representing the energy distribution of the Ga 4p and Se 4p states. Measurements of the fundamental absorption edges at room temperature reveal that bandgap value, Eg, of LiGaSe2 is equal to 3.47 eV and the Eg value increases up to 3.66 eV when decreasing temperature to 80 K. The main optical characteristics of the LiGaSe2 compound are clarified by the DFT calculations.

Conduction band offset at GeO{sub 2}/Ge interface determined by internal photoemission and charge-corrected x-ray photoelectron spectroscopies

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

Zhang, W. F.; Nishimula, T.; Nagashio, K.

2013-03-11

We report a consistent conduction band offset (CBO) at a GeO{sub 2}/Ge interface determined by internal photoemission spectroscopy (IPE) and charge-corrected X-ray photoelectron spectroscopy (XPS). IPE results showed that the CBO value was larger than 1.5 eV irrespective of metal electrode and substrate type variance, while an accurate determination of valence band offset (VBO) by XPS requires a careful correction of differential charging phenomena. The VBO value was determined to be 3.60 {+-} 0.2 eV by XPS after charge correction, thus yielding a CBO (1.60 {+-} 0.2 eV) in excellent agreement with the IPE results. Such a large CBO (>1.5more » eV) confirmed here is promising in terms of using GeO{sub 2} as a potential passivation layer for future Ge-based scaled CMOS devices.« less

Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions

NASA Astrophysics Data System (ADS)

Weichman, Marissa L.; Neumark, Daniel M.

2018-04-01

Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1-2 cm‑1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques

PubMed Central

Limaye, Mukta V.; Chen, S. C.; Lee, C. Y.; Chen, L. Y.; Singh, Shashi B.; Shao, Y. C.; Wang, Y. F.; Hsieh, S. H.; Hsueh, H. C.; Chiou, J. W.; Chen, C. H.; Jang, L. Y.; Cheng, C. L.; Pong, W. F.; Hu, Y. F.

2015-01-01

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S2− (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S2− species, but significantly increases the concentration of larger S clusters [polysulfides (Sn2−, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples. PMID:26098075

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.

Photoelectron spectra and biological activity of cinnamic acid derivatives revisited

NASA Astrophysics Data System (ADS)

Novak, Igor; Klasinc, Leo; McGlynn, Sean P.

2018-01-01

The electronic structures of several derivatives of cinnamic acid have been studied by UV photoelectron spectroscopy (UPS) and Green's function quantum chemical calculations. The spectra reveal the presence of dimers in the gas phase for p-coumaric and ferulic acids. The electronic structure analysis has been related to the biological properties of these compounds through the analysis of some structure-activity relationships (SAR).

Core level line shapes and surface band structures of Sn/Ge(111) and Sn/Si(111)

NASA Astrophysics Data System (ADS)

Uhrberg, Roger

2001-03-01

We have performed a comparative study of Sn/Ge(111) and the closely related Sn/Si(111) system, using photoelectron spectroscopy (PES) and low energy electron diffraction (LEED). In similarity with the results from the Sn/Ge(111) surface, the Sn 4d spectra from Sn/Si(111) exhibit two major components and the valence band spectra show two surface state bands at both room temperature (RT) and 70 K. These features, which have been associated with the low temperature 3x3 phase in the case of Sn/Ge(111), are not expected for the rt3xrt3 RT surfaces. In contrast to Sn/Ge(111), we do not observe any transition to a 3x3 phase in LEED for Sn/Si(111) at temperatures down to 70 K (the lowest temperature in this study). Despite the absence of a 3x3 phase for Sn/Si(111) the core-level and the valence band data are very similar to those of Sn/Ge(111). The Sn 4d spectra show, however, one interesting difference. The intensity ratio of the two Sn 4d components is reversed for the Sn/Si(111) surface compared the Ge counterpart. This and the other PES results will be discussed in terms of the two different types of 3x3 periodicities that have been reported to be induced by substitutional defects on the Sn/Ge(111) surface [1]. [1] A.V. Melechko et al., Phys. Rev. B61, 2235 (2000)

Electronic structure and optical properties of Cs2HgCl4: DFT calculations and X-ray photoelectron spectroscopy measurements

NASA Astrophysics Data System (ADS)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

2016-10-01

A high-quality single crystal of cesium mercury tetrabromide, Cs2HgCl4, was synthesized by using the vertical Bridgman-Stockbarger method and its electronic structure was studied from both experimental and theoretical viewpoints. In particular, X-ray photoelectron spectra were measured for both pristine and Ar+ ion-bombarded Cs2HgCl4 single crystal surfaces. The present XPS measurements indicate that the Cs2HgCl4 single crystal surface is sensitive with respect to Ar+ ion-bombardment: such a treatment changes substantially its elemental stoichiometry. With the aim of exploring total and partial densities of states within the valence band and conduction band regions of the Cs2HgCl4 compound, band-structure calculations based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method as incorporated within the WIEN2k package are performed. The calculations indicate that the Cl 3p states are the principal contributors in the upper portion of the valence band, while the Hg 5d and Cs 5p states dominate in its lower portion. In addition, the calculations allow for concluding that the unoccupied Cl p and Hg s states are the main contributors to the bottom of the conduction band. Furthermore, main optical characteristics of Cs2HgCl4, namely dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity, are elucidated based on the DFT calculations.

Assessment of electron propagator methods for the simulation of vibrationally-resolved valence and core photoionization spectra

PubMed Central

Baiardi, A.; Paoloni, L.; Barone, V.; Zakrzewski, V.G.; Ortiz, J.V.

2017-01-01

The analysis of photoelectron spectra is usually facilitated by quantum mechanical simulations. Due to the recent improvement of experimental techniques, the resolution of experimental spectra is rapidly increasing, and the inclusion of vibrational effects is usually mandatory to obtain a reliable reproduction of the spectra. With the aim of defining a robust computational protocol, a general time-independent formulation to compute different kinds of vibrationally-resolved electronic spectra has been generalized to support also photoelectron spectroscopy. The electronic structure data underlying the simulation are computed using different electron propagator approaches. In addition to the more standard approaches, a new and robust implementation of the second-order self-energy approximation of the electron propagator based on a transition operator reference (TOEP2) is presented. To validate our implementation, a series of molecules has been used as test cases. The result of the simulations shows that, for ultraviolet photoionization spectra, the more accurate non-diagonal approaches are needed to obtain a reliable reproduction of vertical ionization energies, but diagonal approaches are sufficient for energy gradients and pole strengths. For X-ray photoelectron spectroscopy, the TOEP2 approach, besides being more efficient, is also the most accurate in the reproduction of both vertical ionization energies and vibrationally-resolved bandshapes. PMID:28521087

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations.

PubMed

Zhang, Ning; Chen, Chen; Mei, Zongwei; Liu, Xiaohe; Qu, Xiaolei; Li, Yunxiang; Li, Siqi; Qi, Weihong; Zhang, Yuanjian; Ye, Jinhua; Roy, Vellaisamy A L; Ma, Renzhi

2016-04-27

Exploring surface-exposed highly active crystal facets for photocatalytic oxidations is promising in utilizing monoclinic WO3 semiconductor. However, the previously reported highly active facets for monoclinic WO3 were mainly toward enhancing photocatalytic reductions. Here we report that the WO3 with {100} facet orientation and tuned surface electronic band structure can effectively enhance photocatalytic oxidation properties. The {100} faceted WO3 single crystals are synthesized via a facile hydrothermal method. The UV-visible diffuse reflectance, X-ray photoelectron spectroscopy valence band spectra, and photoelectrochemical measurements suggest that the {100} faceted WO3 has a much higher energy level of valence band maximum compared with the normal WO3 crystals without preferred orientation of the crystal face. The density functional theory calculations reveal that the shift of O 2p and W 5d states in {100} face induce a unique band structure. In comparison with the normal WO3, the {100} faceted WO3 exhibits an O2 evolution rate about 5.1 times in water splitting, and also shows an acetone evolution rate of 4.2 times as well as CO2 evolution rate of 3.8 times in gaseous degradation of 2-propanol. This study demonstrates an efficient crystal face engineering route to tune the surface electronic band structure for enhanced photocatalytic oxidations.

Photoelectron spectra and biological activity of cinnamic acid derivatives revisited.

PubMed

Novak, Igor; Klasinc, Leo; McGlynn, Sean P

2018-01-15

The electronic structures of several derivatives of cinnamic acid have been studied by UV photoelectron spectroscopy (UPS) and Green's function quantum chemical calculations. The spectra reveal the presence of dimers in the gas phase for p-coumaric and ferulic acids. The electronic structure analysis has been related to the biological properties of these compounds through the analysis of some structure-activity relationships (SAR). Copyright © 2017 Elsevier B.V. All rights reserved.

Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions.

PubMed

Lebech, M; Houver, J C; Raseev, G; dos Santos, A S; Dowek, D; Lucchese, Robert R

2012-03-07

Experimental and theoretical results for molecular-frame photoemission are presented for inner-valence shell photoionization of the CO molecule induced by linearly and circularly polarized light. The experimental recoil frame photoelectron angular distributions (RFPADs) obtained from dissociative photoionization measurements where the velocities of the ionic fragment and photoelectron were detected in coincidence, are compared to RFPADs computed using the multichannel Schwinger configuration interaction method. The formalism for including a finite lifetime of the predissociative ion state is presented for the case of general elliptically polarized light, to obtain the RFPAD rather than the molecular frame photoelectron angular distribution (MFPAD), which would be obtained with the assumption of instantaneous dissociation. We have considered photoionization of CO for the photon energies of 26.0 eV, 29.5 eV, and 32.5 eV. A comparison of experimental and theoretical RFPADs allows us to identify the ionic states detected in the experimental studies. In addition to previously identified states, we found evidence for the 2 (2)Δ state with an ionization potential of 25.3 eV and (2)Σ(+) states with ionization potentials near 32.5 eV. A comparison of the experimental and theoretical RFPADs permits us to estimate predissociative lifetimes of 0.25-1 ps for some of the ion states. Consideration of the MFPADs of a series of (2)Π ion states indicates the importance of inter-channel coupling at low photoelectron kinetic energy and the limitations of a single-channel analysis based on the corresponding Dyson orbitals. © 2012 American Institute of Physics

Intrinsic transmission magnetic circular dichroism spectra of GaMnAs

NASA Astrophysics Data System (ADS)

Terada, Hiroshi; Ohya, Shinobu; Tanaka, Masaaki

2018-03-01

Transmission magnetic circular dichroism (MCD) spectroscopy has been widely used to reveal the spin-dependent band structure of ferromagnetic semiconductors. In these previous studies, some band pictures have been proposed from the spectral shapes observed in transmission MCD; however, extrinsic signals originating from optical interference have not been appropriately considered. In this study, we calculate the MCD spectra taking into account the optical interference of the layered structure of samples and show that the spectral shape of MCD is strongly influenced by optical interference. To correctly understand the transmission MCD, we also calculate the intrinsic MCD spectra of GaMnAs that are not influenced by the optical interference. The spectral shape of the intrinsic MCD can be explained by the characteristic band structure of GaMnAs, that is, the spin-polarized valence band and the impurity band existing above the valence band top.

Probability of Two-Step Photoexcitation of Electron from Valence Band to Conduction Band through Doping Level in TiO2.

PubMed

Nishikawa, Masami; Shiroishi, Wataru; Honghao, Hou; Suizu, Hiroshi; Nagai, Hideyuki; Saito, Nobuo

2017-08-17

For an Ir-doped TiO 2 (Ir:TiO 2 ) photocatalyst, we examined the most dominant electron-transfer path for the visible-light-driven photocatalytic performance. The Ir:TiO 2 photocatalyst showed a much higher photocatalytic activity under visible-light irradiation than nondoped TiO 2 after grafting with the cocatalyst of Fe 3+ . For the Ir:TiO 2 photocatalyst, the two-step photoexcitation of an electron from the valence band to the conduction band through the Ir doping level occurred upon visible-light irradiation, as observed by electron spin resonance spectroscopy. The two-step photoexcitation through the doping level was found to be a more stable process with a lower recombination rate of hole-electron pairs than the two-step photoexcitation process through an oxygen vacancy. Once electrons are photoexcited to the conduction band by the two-step excitation, the electrons can easily transfer to the surface because the conduction band is a continuous electron path, whereas the electrons photoexcited at only the doping level could not easily transfer to the surface because of the discontinuity of this path. The observed two-step photoexcitation from the valence band to the conduction band through the doping level significantly contributes to the enhancement of the photocatalytic performance.

Spin orbit and tetragonal crystalline field interaction in the valence band of CuInSe2-related ordered vacancy compound CuIn7Se12

NASA Astrophysics Data System (ADS)

Reena Philip, Rachel; Pradeep, B.; Shripathi, T.

2005-04-01

Thin films of the off-tie-line ordered vacancy compound CuIn7Se12 were deposited on optically flat glass substrates by multi-source co-evaporation method. The preliminary structural, compositional and morphological characterizations were done using X-ray diffraction, energy dispersive X-ray analysis and atomic force microscopy. The X-ray diffraction data were further analysed applying the Nelson-Riley method and CTB plus = experiment rule, respectively, for lattice constants (a = 5.746 Å and c = 11.78 Å) and bond length estimations (RCu-Se = 2.465 Å and RIn-Se = 2.554 Å). A detailed analysis of the optical absorption spectra of the compound, which exhibited a three-fold optical absorption structure in the fundamental gap region, yielded three characteristic direct energy gaps at 1.37, 1.48(7) and 1.72(8) eV indicative of valence band splitting, which were evaluated using Hopfield's quasi-cubic model. The 0.04 eV increase in spin-orbit splitting parameter of the compound (0.27 eV) compared to that of CuInSe2 (0.23 eV) is found to be suggestive of the smaller contribution of Cu d orbitals to hybridization (determined by the linear hybridization model) in this Cu-deficient compound. Spectral response spectra exhibit, in addition to a maximum around 1.34 ± 0.03 eV, two other defect transition peaks near 1.07 and 0.85 eV. The binding energies of Cu, In and Se in the compound were determined using X-ray photoelectron spectroscopy.

AgI alloying in SnTe boosts the thermoelectric performance via simultaneous valence band convergence and carrier concentration optimization

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

Banik, Ananya; Biswas, Kanishka, E-mail: kanishka@jncasr.ac.in

SnTe, a Pb-free analogue of PbTe, was earlier assumed to be a poor thermoelectric material due to excess p-type carrier concentration and large energy separation between light and heavy hole valence bands. Here, we report the enhancement of the thermoelectric performance of p-type SnTe by Ag and I co-doping. AgI (1–6 mol%) alloying in SnTe modulates its electronic structure by increasing the band gap of SnTe, which results in decrease in the energy separation between its light and heavy hole valence bands, thereby giving rise to valence band convergence. Additionally, iodine doping in the Te sublattice of SnTe decreases themore » excess p-type carrier concentration. Due to significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands, significant enhancement in Seebeck coefficient was achieved at the temperature range of 600–900 K for Sn{sub 1−x}Ag{sub x}Te{sub 1−x}I{sub x} samples. A maximum thermoelectric figure of merit, zT, of ~1.05 was achieved at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Graphical abstract: Significant decrease in hole concentration and reduction of the energy separation between light and heavy hole valence bands resulted in a maximum thermoelectric figure of merit, zT, of ~1.05 at 860 K in high quality crystalline ingot of p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}. - Highlights: • AgI alloying in SnTe increases the principle band gap. • Hole concentration reduction and valence band convergence enhances thermopower of SnTe-AgI. • A maximum zT of ~1.05 was achieved at 860 K in p-type Sn{sub 0.95}Ag{sub 0.05}Te{sub 0.95}I{sub 0.05}.« less

The localized effect of the Bi level on the valence band in the dilute bismuth GaBixAs1-x alloy

NASA Astrophysics Data System (ADS)

Zhao, Chuan-Zhen; Zhu, Min-Min; Wang, Jun; Wang, Sha-Sha; Lu, Ke-Qing

2018-05-01

The research on the temperature dependence of the band gap energy of the dilute bismuth GaBixAs1-x alloy has been done. It is found that its temperature insensitiveness is due to the enhanced localized character of the valence band state and the small decrease of the temperature coefficient for the conduction band minimum (CBM). The enhanced localized character of the valence band state is the main factor. In order to describe the localized effect of the Bi levels on the valence band, the localized energy is introduced into the Varshni's equation. It is found that the effect of the localized Bi level on the valence band becomes strong with increasing Bi content. In addition, it is found that the pressure dependence of the band gap energy of GaBixAs1-x does not seem to be influenced by the localized Bi levels. It is due to two factors. One is that the pressure dependence of the band gap energy is mainly determined by the D CBM of GaBixAs1-x. The D CBM of GaBixAs1-x is not influenced by the localized Bi levels. The other is that the small variation of the pressure coefficient for the D valence band maximum (VBM) state of GaBixAs1-x can be cancelled by the variation of the pressure coefficient for the D CBM state of GaBixAs1-x.

Exchange-mediated anisotropy of (ga,mn)as valence-band probed by resonant tunneling spectroscopy.

PubMed

Elsen, M; Jaffrès, H; Mattana, R; Tran, M; George, J-M; Miard, A; Lemaître, A

2007-09-21

We report on experiments and theory of resonant tunneling anisotropic magnetoresistance (TAMR) in AlAs/GaAs/AlAs quantum wells (QW) contacted by a (Ga,Mn)As ferromagnetic electrode. Such resonance effects manifest themselves by bias-dependent oscillations of the TAMR signal correlated to the successive positions of heavy (HH) and light (LH) quantized hole energy levels in GaAs QW. We have modeled the experimental data by calculating the spin-dependent resonant tunneling transmission in the frame of the 6 x 6 valence-band k.p theory. The calculations emphasize the opposite contributions of the (Ga,Mn)As HH and LH subbands near the Gamma point, unraveling the anatomy of the diluted magnetic semiconductor valence band.

Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej; Li, Xiang; Bowen, Kit H

2008-08-07

The photoelectron spectrum (PES) of the uracil anion is reported and discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of the anions of various tautomers of uracil. The PES peak maximum is found at an electron binding energy of 2.4 eV, and the width of the main feature suggests that the parent anions are in a valence rather than a dipole-bound state. The canonical tautomer as well as four tautomers that result from proton transfer from an NH group to a C atom were investigated computationally. At the Hartree-Fock and second-order Moller-Plesset perturbation theory levels, the adiabatic electron affinity (AEA) and the VDE have been converged to the limit of a complete basis set to within +/-1 meV. Post-MP2 electron-correlation effects have been determined at the coupled-cluster level of theory including single, double, and noniterative triple excitations. The quantum chemical calculations suggest that the most stable valence anion of uracil is the anion of a tautomer that results from a proton transfer from N1H to C5. It is characterized by an AEA of 135 meV and a VDE of 1.38 eV. The peak maximum is as much as 1 eV larger, however, and the photoelectron intensity is only very weak at 1.38 eV. The PES does not lend support either to the valence anion of the canonical tautomer, which is the second most stable anion, and whose VDE is computed at about 0.60 eV. Agreement between the peak maximum and the computed VDE is only found for the third most stable tautomer, which shows an AEA of approximately -0.1 eV and a VDE of 2.58 eV. This tautomer results from a proton transfer from N3H to C5. The results illustrate that the characteristics of biomolecular anions are highly dependent on their tautomeric form. If indeed the third most stable anion is observed in the experiment, then it remains an open question why and how this species is formed under the given conditions.

Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

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

Bradforth, Stephen Edmund

1992-11-01

The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound {yields} bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN -, NCO - and NCS -. Transition state photoelectron spectra are presented for the following systems Br + HI, Clmore » + HI, F + HI, F + CH 30H,F + C 2H 5OH,F + OH and F + H 2. A time dependent framework for the simulation and interpretation of the bound → free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH → O( 3P, 1D) + HF and F + H 2. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H 2 system, comparisons with three-dimensional quantum calculations are made.« less

Direct determination of exciton wavefunction amplitudes by the momentum-resolved photo-electron emission experiment

NASA Astrophysics Data System (ADS)

Ohnishi, Hiromasa; Tomita, Norikazu; Nasu, Keiichiro

2018-03-01

We study conceptional problems of a photo-electron emission (PEE) process from a free exciton in insulating crystals. In this PEE process, only the electron constituting the exciton is suddenly emitted out of the crystal, while the hole constituting the exciton is still left inside and forced to be recoiled back to its original valence band. This recoil on the hole is surely reflected in the spectrum of the PEE with a statistical distribution along the momentum-energy curve of the valence band. This distribution is nothing but the square of the exciton wavefunction amplitude, since it shows how the electron and the hole are originally bound together. Thus, the momentum-resolved PEE can directly determine the exciton wavefunction. These problems are clarified, taking the Γ and the saddle point excitons in GaAs, as typical examples. New PEE experiments are also suggested.

Electronic structure of the La 1 + xBa 2 - xCu 3O 7 + δ system studied by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lindberg, P. A. P.; Shen, Z.-X.; Hwang, J.; Shih, C. K.; Lindau, I.; Spicer, W. E.; Mitzi, D. B.; Kapitulnik, A.

1989-01-01

Photoemission experiments utilizing synchrotron radiation have been carried out on the high temperature superconductor La 1.075Ba 1.925Cu 3O 7.0. The valence band spectra show similar spectral features as those of YBa 2Cu 3O 6.9, even though large differences in relative peak intensities are observed. Oxygen-related states are identified by scanning the photon energy through the O2 s → O2 p absorption edge. The stability of the sample surface, and changes in the valence band spectra after annealing in ultrahigh vacuum are also briefly discussed.

Spectroscopic evidence for temperature dependent relative movement of light and heavy hole valence bands of PbQ (Q=Te,Se,S)

NASA Astrophysics Data System (ADS)

Chatterjee, Utpal; Zhao, Junjing; Kanatzidis, Mercouri; Malliakas, Christos

We have conducted temperature dependent Angle Resolved Photoemission Spectroscopy (ARPES) studies of the electronic structures of PbTe, PbSe and PbS. Our ARPES measurements provide direct evidences for the light hole upper valence bands (UVBs) and the so-called heavy hole lower valence bands (LVBs), and an unusual temperature dependent relative movement between their band maxima leading to a monotonic decrease in the energy separation between LVBs and UVBs with increase in temperature. This enables convergence of these valence bands and consequently an effective increase in the valley degeneracy in PbQ at higher temperatures, which has long been believed to be the driving factor behind their extraordinary thermoelectric performance.

The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy

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

Lüder, Johann; Sanyal, Biplab; Eriksson, Olle

In this paper, we provide detailed insights into the electronic structure of the gas phase biphenylene molecule through core and valence spectroscopy. By comparing results of X-ray Photoelectron Spectroscopy (XPS) measurements with ΔSCF core-hole calculations in the framework of Density Functional Theory (DFT), we could decompose the characteristic contributions to the total spectra and assign them to non-equivalent carbon atoms. As a difference with similar molecules like biphenyl and naphthalene, an influence of the localized orbitals on the relative XPS shifts was found. The valence spectrum probed by photoelectron spectroscopy at a photon energy of 50 eV in conjunction withmore » hybrid DFT calculations revealed the effects of the localization on the electronic states. Using the transition potential approach to simulate the X-ray absorption spectroscopy measurements, similar contributions from the non-equivalent carbon atoms were determined from the total spectrum, for which the slightly shifted individual components can explain the observed asymmetric features.« less

Finding the hidden valence band of N  =  7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Senkovskiy, Boris V.; Usachov, Dmitry Yu; Fedorov, Alexander V.; Haberer, Danny; Ehlen, Niels; Fischer, Felix R.; Grüneis, Alexander

2018-07-01

To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass () of armchair graphene nanoribbons with a width of N  =  7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report   ≈0.2 and  ≈0.4 of the free electron mass (m e ), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 m e , a charge carrier velocity in the linear part of the band of 0.63  ×  106 m s‑1 and an energy separation of only  ≈60 meV to the second sub-band. Our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.

Imprints of the Molecular Electronic Structure in the Photoelectron Spectra of Strong-Field Ionized Asymmetric Triatomic Model Molecules

NASA Astrophysics Data System (ADS)

Paul, Matthias; Yue, Lun; Gräfe, Stefanie

2018-06-01

We examine the circular dichroism in the angular distribution of photoelectrons of triatomic model systems ionized by strong-field ionization. Following our recent work on this effect [Paul, Yue, and Gräfe, J. Mod. Opt. 64, 1104 (2017), 10.1080/09500340.2017.1299883], we demonstrate how the symmetry and electronic structure of the system is imprinted into the photoelectron momentum distribution. We use classical trajectories to reveal the origin of the threefolded pattern in the photoelectron momentum distribution, and show how an asymmetric nuclear configuration of the triatomic system effects the photoelectron spectra.

Role of surface energy on the morphology and optical properties of GaP micro & nano structures grown on polar and non-polar substrates

NASA Astrophysics Data System (ADS)

Roychowdhury, R.; Kumar, Shailendra; Wadikar, A.; Mukherjee, C.; Rajiv, K.; Sharma, T. K.; Dixit, V. K.

2017-10-01

Role of surface energy on the morphology, crystalline quality, electronic structure and optical properties of GaP layer grown on Si (001), Si (111), Ge (111) and GaAs (001) is investigated. GaP layers are grown on four different substrates under identical growth kinetics by metal organic vapour phase epitaxy. The atomic force microscopy images show that GaP layer completely covers the surface of GaAs substrate. On the other hand, the surfaces of Si (001), Si (111), Ge (111) substrates are partially covered with crystallographically morphed GaP island type micro and nano-structures. Origin of these crystallographically morphed GaP island is explained by the theoretical calculation of surface energy of the layer and corresponding substrates respectively. The nature of GaP island type micro and nano-structures and layers are single crystalline with existence of rotational twins on Si and Ge (111) substrates which is confirmed by the phi, omega and omega/2theta scans of high resolution x-ray diffraction. The electronic valence band offsets between the GaP and substrates have been determined from the valence band spectra of ultraviolet photoelectron spectroscopy. The valence electron plasmon of GaP are investigated by studying the energy values of Ga (3d) core level along with loss peaks in the energy dependent photoelectron spectra. The peak observed within the range of 3-6 eV from the Ga (3d) core level in the photoelectron spectra are associated to inter band transitions as their energy values are estimated from the pseudo dielectric function by the spectroscopic ellipsometry.

Polarization Dependent Bulk-sensitive Valence Band Photoemission Spectroscopy and Density Functional Theory Calculations: Part I. 3d Transition Metals

NASA Astrophysics Data System (ADS)

Ueda, Shigenori; Hamada, Ikutaro

2017-12-01

The X-ray polarization dependent valence band HAXPES spectra of 3d transition metals (TMs) of Ti-Zn were measured to investigate the orbital resolved electronic structures by utilizing that the fact the photoionization cross-section of the atomic orbitals strongly depends on the experimental geometry. We have calculated the HAXPES spectra, which correspond to the cross-section weighted densities of states (CSW-DOSs), where the DOSs were obtained by the density functional theory calculations, and we have determined the relative photoionization cross-sections of the 4s and 4p orbitals to the 3d orbital in the 3d TMs. The experimentally obtained bulk-sensitive 3d and 4s DOSs were good agreement with the calculated DOSs in Ti, V, Cr, and Cu. In contrast, the deviations between the experimental and calculated 3d DOSs for Mn, Fe, Co, Ni were found, suggesting that the electron correlation plays an important role in the electronic structures for these materials.

Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

DOE PAGES

Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda; ...

2016-12-06

Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that

Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

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

Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda

Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that

Surface studies of novel oxide-free biocompatible coatings on metals

NASA Astrophysics Data System (ADS)

GAO, FENG

The valence band and core-level X-ray Photoelectron Spectroscopy (XPS) was used to probe biocompatible films formed on the surface of metals. The key to the successful adhesion of these biocompatible films is shown to be the initial formation of a thin, oxide free, etidronate film on the metal. It was not found possible to prepare the biocompatible films directly on the metal surfaces. These films formed on metals may find application in medical implants. The biocompatible films were exposed to air, water and sodium chloride for corrosion studies. The thin hydroxyapatite and etidronate film on the metal show differential charging effects that caused a doubling of the peaks in some core level spectra. This shows the coating has some electric properties such as dielectric or piezoelectric characters. This coating may have application in the insulating materials of electronic circuits or dielectric/ piezoelectric layer in bio-sensors. Experiment and calculation method of X-ray Photoelectron Spectroscopy is one powerful technology in surface and interface analysis. The valence band spectra proved especially valuable in the identification of the surface chemistry of the films, and these spectra were interpreted by comparing the experimental spectra with spectra calculated using band structure calculations which showed good agreement with experiment. The calculated spectrum could also be used to compare with the difference of experiment spectra for the investigation of the interface layers.

Spectroscopic evidence for temperature-dependent convergence of light- and heavy-hole valence bands of PbQ (Q = Te, Se, S)

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

Zhao, J.; Malliakas, C. D.; Wijayaratne, K.

2017-01-01

We have conducted a temperature- dependent angle-resolved photoemission spectroscopy (ARPES) study of the electronic structures of PbTe, PbSe and PbS. Our ARPES data provide direct evidence for the light-hole upper valence bands (UVBs) and hitherto undetected heavy-hole lower valence bands (LVBs) in these materials. An unusual temperature-dependent relative movement between these bands leads to a monotonic decrease in the energy separation between their maxima with increasing temperature, which is known as band convergence and has long been believed to be the driving factor behind extraordinary thermoelectric performances of these compounds at elevated temperatures.

Spectroscopic evidence for temperature-dependent convergence of light- and heavy-hole valence bands of PbQ (Q = Te, Se, S)

NASA Astrophysics Data System (ADS)

Zhao, J.; Malliakas, C. D.; Wijayaratne, K.; Karlapati, V.; Appathurai, N.; Chung, D. Y.; Rosenkranz, S.; Kanatzidis, M. G.; Chatterjee, U.

2017-01-01

We have conducted a temperature-dependent angle-resolved photoemission spectroscopy (ARPES) study of the electronic structures of PbTe, PbSe and PbS. Our ARPES data provide direct evidence for the light-hole upper valence bands (UVBs) and hitherto undetected heavy-hole lower valence bands (LVBs) in these materials. An unusual temperature-dependent relative movement between these bands leads to a monotonic decrease in the energy separation between their maxima with increasing temperature, which is known as band convergence and has long been believed to be the driving factor behind extraordinary thermoelectric performances of these compounds at elevated temperatures.

A low-temperature study of manganese-induced ferromagnetism and valence band convergence in tin telluride

DOE PAGES

Chi, Hang; Tan, Gangjian; Kanatzidis, Mercouri G.; ...

2016-05-02

In this study, SnTe is renowned for its promise in advancing energy-related technologies based on thermoelectricity and for its topological crystalline insulator character. Here, we demonstrate that each Mn atom introduces ~4 μ B (Bohr magneton) of magnetic moment to Sn 1–xMn xTe. The Curie temperatureTC reaches ~14K for x = 0.12, as observed in the field dependent hysteresis of magnetization and the anomalous Hall effect. In accordance with a modified two-band electronic Kane model, the light L-valence-band and the heavy Σ-valence-band gradually converge in energy with increasing Mn concentration, leading to a decreasing ordinary Hall coefficient R H andmore » a favorably enhanced Seebeck coefficient S at the same time. With the thermal conductivityκ lowered chiefly via point defects associated with the incorporation of Mn, the strategy of Mn doping also bodes well for efficient thermoelectric applications at elevated temperatures.« less

Energy band alignment of antiferroelectric (Pb,La)(Zr,Sn,Ti)O3

NASA Astrophysics Data System (ADS)

Klein, Andreas; Lohaus, Christian; Reiser, Patrick; Dimesso, Lucangelo; Wang, Xiucai; Yang, Tongqing

2017-06-01

The energy band alignment of antiferroelectric (Pb,La)(Zr,Sn,Ti)O3 is studied with photoelectron spectroscopy using interfaces with high work function RuO2 and low work function Sn-doped In2O3 (ITO). It is demonstrated how spectral deconvolution can be used to determine absolute Schottky barrier heights for insulating materials with a high accuracy. Using this approach it is found that the valence band maximum energy of (Pb,La)(Zr,Sn,Ti)O3 is found to be comparable to that of Pb- and Bi-containing ferroelectric materials, which is ∼1 eV higher than that of BaTiO3. The results provide additional evidence for the occupation of the 6s orbitals as origin of the higher valence band maximum, which is directly related to the electrical properties of such compounds. The results also verify that the energy band alignment determined by photoelectron spectroscopy of as-deposited electrodes is not influenced by polarisation. The electronic structure of (Pb,La)(Zr,Sn,Ti)O3 should enable doping of the material without strongly modifying its insulating properties, which is crucial for high energy density capacitors. Moreover, the position of the energy bands should result in a great freedom of selecting electrode materials in terms of avoiding charge injection.

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

Bisti, F.; Stroppa, A.; Picozzi, S.

The electronic structure of Croconic Acid in the condensed phase has been studied by comparing core level and valence band x-ray photoelectron spectroscopy experiments and first principles density functional theory calculations using the Heyd-Scuseria-Ernzerhof screened hybrid functional and the GW approximation. By exploring the photoemission spectra for different deposition thicknesses, we show how the formation of the hydrogen bond network modifies the O 1s core level lineshape. Moreover, the valence band can be explained only if the intermolecular interactions are taken into account in the theoretical approach.

Investigation on the interfacial chemical state and band alignment for the sputtering-deposited CaF2/p-GaN heterojunction by angle-resolved X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Kexiong; Liao, Meiyong; Sumiya, Masatomo; Koide, Yasuo; Sang, Liwen

2016-11-01

The interfacial chemical state and the band alignment of the sputtering-deposited CaF2/p-GaN hetero-structure were investigated by angle-resolved X-ray photoelectron spectroscopy. The dependence of Ga 3p core-level positions on the collection angles proves that the downward band bending of p-GaN is reduced from 1.51 to 0.85 eV after the deposition of CaF2, which may be due to the reduction of Mg-Ga-O-related interface states by the oxygen-free deposition of CaF2. The band gap of sputtering-deposited CaF2 is estimated to be about 7.97 eV with a potential gradient of 0.48 eV obtained by the variation of the Ca 2p3/2 position on different collection angles. By taking into account the p-GaN surface band bending and potential gradient in the CaF2 layer, large valence and conduction band offsets of 2.66 ± 0.20 and 1.92 ± 0.20 eV between CaF2 and p-GaN are obtained. These results indicate that CaF2 is a promising gate dielectric layer on the p-GaN for the application of metal-insulator-semiconductor devices.

Influence of LaSiOx passivation interlayer on band alignment between PEALD-Al2O3 and 4H-SiC determined by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Qian; Cheng, Xinhong; Zheng, Li; Shen, Lingyan; Zhang, Dongliang; Gu, Ziyue; Qian, Ru; Cao, Duo; Yu, Yuehui

2018-01-01

The influence of lanthanum silicate (LaSiOx) passivation interlayer on the band alignment between plasma enhanced atomic layer deposition (PEALD)-Al2O3 films and 4H-SiC was investigated by high resolution X-ray photoelectron spectroscopy (XPS). An ultrathin in situ LaSiOx interfacial passivation layer (IPL) was introduced between the Al2O3 gate dielectric and the 4H-SiC substrate to enhance the interfacial characteristics. The valence band offset (VBO) and corresponding conduction band offset (CBO) for the Al2O3/4H-SiC interface without any passivation were extracted to be 2.16 eV and 1.49 eV, respectively. With a LaSiOx IPL, a VBO of 1.79 eV and a CBO of 1.86 eV could be obtained across the Al2O3/4H-SiC interface. The difference in the band alignments was dominated by the band bending or band shift in the 4H-SiC substrate as a result of different interfacial layers (ILs) formed at the interface. This understanding of the physical details of the band alignment could be a good foundation for Al2O3/LaSiOx/4H-SiC heterojunctions applied in the 4H-SiC metal-oxide-semiconductor field effect transistors (MOSFETs).

Modified band alignment effect in ZnO/Cu2O heterojunction solar cells via Cs2O buffer insertion

NASA Astrophysics Data System (ADS)

Eom, Kiryung; Lee, Dongyoon; Kim, Seunghwan; Seo, Hyungtak

2018-02-01

The effects of a complex buffer layer of cesium oxide (Cs2O) on the photocurrent response in oxide heterojunction solar cells (HSCs) were investigated. A p-n junction oxide HSC was fabricated using p-type copper (I) oxide (Cu2O) and n-type zinc oxide (ZnO); the buffer layer was inserted between the Cu2O and fluorine-doped tin oxide (FTO). Ultraviolet-visible (UV-vis) and x-ray and ultraviolet photoelectron spectroscopy analyses were performed to characterize the electronic band structures of cells, both with and without this buffer layer. In conjunction with the measured band electronic structures, the significantly improved visible-range photocurrent spectra of the buffer-inserted HSC were analyzed in-depth. As a result, the 1 sun power conversion efficiency was increased by about three times by the insertion of buffer layer. The physicochemical origin of the photocurrent enhancement was mainly ascribed to the increased photocarrier density in the buffer layer and modified valence band offset to promote the effective hole transfer at the interface to FTO on the band-alignment model.

Polarization-dependent X-ray photoemission spectroscopy for High-Tc cuprate superconductors

NASA Astrophysics Data System (ADS)

Yamagami, Kohei; Kanai, Yuina; Naimen, Sho; Fujiwara, Hidenori; Kiss, Takayuki; Tanaka, Arata; Higashiya, Atsushi; Imada, Shin; Kadono, Toshiharu; Tamasaku, Kenji; Muro, Takayuki; Yabashi, Makina; Ishikawa, Tetsuya; Eisaki, Hiroshi; Miyasaka, Shigeki; Tajima, Setsuko; Sekiyama, Akira

2018-05-01

We have performed photon energy (hν) and linear polarization dependent X-ray photoemission for optimal doped Pb-Bi2Sr2CaCu2O8+δ (Bi2212) to investigate the ground Cu 3d orbital symmetry. We identified that the bulk Cu 3d components in valence-band spectra develop with decreasing hν from 7900 eV to 460 eV. Moreover, the photoelectron intensity ratio of the valence-band spectra measured at hν = 460 eV has shown that the Cu 3dx2-y2 orbital contributions are dominant near the Fermi level (EF). Meanwhile, we revealed that the bulk Cu 2p3/2 core-level spectra without the Bi 4s component is detected at hν = 1550 eV compared with hν and linear-polarization-dependent spectra.

Theoretical study on the anion photoelectron spectra of Ln(COT)2- including the spin-orbit effects

NASA Astrophysics Data System (ADS)

Nakajo, Erika; Yabushita, Satoshi

2017-06-01

The multiplet level splittings for both anion and neutral sandwich complexes Ln(COT)2 (Ln = Ce-Yb, COT = 1,3,5,7-cyclooctatetraene) were calculated with spin-orbit interactions to analyze their anion photoelectron spectra. The theoretically simulated spectra obtained with these energies and the pole strengths are generally consistent with the experimental spectra for the X peak. The magnitudes of the energy splittings, relative peak intensities, and their Ln dependence are reproduced. In comparison to our previous calculations, the inclusion of spin-orbit interactions with the SO-MCQDPT2 method makes the simulated spectra more consistent with the results of the experiment.

The valence and Rydberg states of difluoromethane: A combined experimental vacuum ultraviolet spectrum absorption and theoretical study by ab initio configuration interaction and density functional computations

NASA Astrophysics Data System (ADS)

Palmer, Michael H.; Vrønning Hoffmann, Søren; Jones, Nykola C.; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare

2018-06-01

two states, which are only active in absorption. The nature of the two states, 11B1 and 21B1, is fundamentally different, but both are complex owing to the presence of FC and HT effects occurring in different ways. The two most intense bands, close to 12.5 and 15.5 eV, contain valence states as expected; the onset of the 15.5 eV band shows a set of vibrational peaks, but the vibration frequency does not correspond to any of the photoelectron spectral (PES) structure and is clearly valence in nature. The routine use of PES footprints to detect Rydberg states in VUV spectra is shown to be inadequate. The combined effects of FC and HT in the VUV spectral bands lead to additional vibrations when compared with the PES.

X-ray photoelectron spectrum and electronic properties of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4): LDA, GGA, and EV-GGA.

PubMed

Reshak, Ali Hussain; Khenata, R; Kityk, I V; Plucinski, K J; Auluck, S

2009-04-30

An all electron full potential linearized augmented plane wave method has been applied for a theoretical study of the band structure, density of states, and electron charge density of a noncentrosymmetric chalcopyrite compound HgGa(2)S(4) using three different approximations for the exchange correlation potential. Our calculations show that the valence band maximum (VBM) and conduction band minimum (CBM) are located at Gamma resulting in a direct energy gap of about 2.0, 2.2, and 2.8 eV for local density approximation (LDA), generalized gradient approximation (GGA), and Engel-Vosko (EVGGA) compared to the experimental value of 2.84 eV. We notice that EVGGA shows excellent agreement with the experimental data. This agreement is attributed to the fact that the Engel-Vosko GGA formalism optimizes the corresponding potential for band structure calculations. We make a detailed comparison of the density of states deduced from the X-ray photoelectron spectra with our calculations. We find that there is a strong covalent bond between the Hg and S atoms and Ga and S atoms. The Hg-Hg, Ga-Ga, and S-S bonds are found to be weaker than the Hg-S and Ga-S bonds showing that a covalent bond exists between Hg and S atoms and Ga and S atoms.

Valence-band offsets in strained SiGeSn/Si layers with different tin contents

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

Bloshkin, A. A., E-mail: bloshkin@isp.nsc.ru; Yakimov, A. I.; Timofeev, V. A.

Admittance spectroscopy is used to study hole states in Si{sub 0.7–y}Ge{sub 0.3}Sn{sub y}/Si quantum wells in the tin content range y = 0.04–0.1. It is found that the hole binding energy increases with tin content. The hole size-quantization energies in structures containing a pseudomorphic Si{sub 0.7–y}Ge{sub 0.3}Sn{sub y} layer in the Si matrix are determined using the 6-band kp method. The valence-band offset at the Si{sub 0.7–y}Ge{sub 0.3}Sn{sub y} heterointerface is determined by combining the numerical calculation results and experimental data. It is found that the dependence of the experimental values of the valence-band offsets between pseudomorphic Si{sub 0.7–y}Ge{sub 0.3}Sn{submore » y} layers and Si on the tin content is described by the expression ΔE{sub V}{sup exp} = (0.21 ± 0.01) + (3.35 ± 7.8 × 10{sup –4})y eV.« less

Band alignment of atomic layer deposited MgO/Zn0.8Al0.2O heterointerface determined by charge corrected X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Yan, Baojun; Liu, Shulin; Yang, Yuzhen; Heng, Yuekun

2016-05-01

Pure magnesium (MgO) and zinc oxide doped with aluminum oxide (Zn0.8Al0.2O) were prepared via atomic layer deposition. We have studied the structure and band gap of bulk Zn0.8Al0.2O material by X-ray diffractometer (XRD) and Tauc method, and the band offsets and alignment of atomic layer deposited MgO/Zn0.8Al0.2O heterointerface were investigated systematically using X-ray photoelectron spectroscopy (XPS) in this study. Different methodologies, such as neutralizing electron gun, the use of C 1s peak recalibration and zero charging method, were applied to recover the actual position of the core levels in insulator materials which were easily influenced by differential charging phenomena. Schematic band alignment diagram, valence band offset (ΔEV) and conduction band offset (ΔEC) for the interface of the MgO/Zn0.8Al0.2O heterostructure have been constructed. An accurate value of ΔEV = 0.72 ± 0.11 eV was obtained from various combinations of core levels of heterojunction with varied MgO thickness. Given the experimental band gaps of 7.83 eV for MgO and 5.29 eV for Zn0.8Al0.2O, a type-II heterojunction with a ΔEC of 3.26 ± 0.11 eV was found. Band offsets and alignment studies of these heterojunctions are important for gaining deep consideration to the design of various optoelectronic devices based on such heterointerface.

Band offsets in ITO/Ga2O3 heterostructures

NASA Astrophysics Data System (ADS)

Carey, Patrick H.; Ren, F.; Hays, David C.; Gila, B. P.; Pearton, S. J.; Jang, Soohwan; Kuramata, Akito

2017-11-01

The valence band offsets in rf-sputtered Indium Tin Oxide (ITO)/single crystal β-Ga2O3 (ITO/Ga2O3) heterostructures were measured with X-Ray Photoelectron Spectroscopy using the Kraut method. The bandgaps of the component materials in the heterostructure were determined by Reflection Electron Energy Loss Spectroscopy as 4.6 eV for Ga2O3 and 3.5 eV for ITO. The valence band offset was determined to be -0.78 ± 0.30 eV, while the conduction band offset was determined to be -0.32 ± 0.13 eV. The ITO/Ga2O3 system has a nested gap (type I) alignment. The use of a thin layer of ITO between a metal and the Ga2O3 is an attractive approach for reducing contact resistance on Ga2O3-based power electronic devices and solar-blind photodetectors.

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2.

PubMed

Perevalov, T V; Islamov, D R; Gritsenko, V A; Prosvirin, I P

2018-05-11

The electronic structure of oxygen-deficient Hf 0.5 Zr 0.5 O 2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf 0.5 Zr 0.5 O 2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf 0.5 Zr 0.5 O 2 : an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf 0.5 Zr 0.5 O 2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Electronic structure of stoichiometric and oxygen-deficient ferroelectric Hf0.5Zr0.5O2

NASA Astrophysics Data System (ADS)

Perevalov, T. V.; Islamov, D. R.; Gritsenko, V. A.; Prosvirin, I. P.

2018-05-01

The electronic structure of oxygen-deficient Hf0.5Zr0.5O2 in the non-centrosymmetric orthorhombic (ferroelectric) phase was investigated by means of x-ray photoelectron spectroscopy and first-principle density functional theory calculations. It was established that a peak in the photoelectron spectra observed at an energy above the valence band top of ferroelectric Hf0.5Zr0.5O2 in ion-etched samples was due to oxygen vacancies. A method for evaluating the oxygen vacancies concentration in the material from the comparison of experimental and theoretical photoelectron spectra of the valence band is proposed. It is found that oxygen polyvacancies are not formed in ferroelectric Hf0.5Zr0.5O2: an energy-favorable spatial arrangement of several oxygen vacancies in the crystal corresponds to the configuration formed by noninteracting vacancies distant from each other. The oxygen vacancies in five charged states were simulated. The electron levels in the bandgap caused by charged oxygen vacancies indicate that any type of oxygen vacancies in ferroelectric Hf0.5Zr0.5O2 can capture both electrons and holes, i.e. can act as an amphoteric localization center for charge carriers.

Observations of silicate reststrahlen bands in lunar infrared spectra

NASA Technical Reports Server (NTRS)

Potter, A. E., Jr.; Morgan, T. H.

1982-01-01

Thermal emission spectra of three lunar sites (Apollo 11, Descartes Formation, and Tycho central peak) are measured in the 8-14 micron spectral range. Transmission and instrument effects are accounted for by forming ratios of the Descartes and Tycho spectra to the Apollo 11 spectrum. The ratio spectra are compared with ratios of published laboratory spectra of returned lunar samples and also with ratio spectra calculated using the Aronson-Emslie (1975) model. The comparisons show pyroxene bands in the Descartes ratio spectrum and plagioclase bands in the Tycho ratio spectrum. The Tycho spectrum is found to be consistent with the existence of fine plagioclase dust (approximately 1 micron) at the rock surface and a higher-than-usual sodium content of the plagioclase.

Naval Surface Warfare Center Dahlgren Division Technical Digest. Advanced Materials Technology

DTIC Science & Technology

1993-09-01

of Prins1 2’h3 ated TL glow curve plus a contribution from and Novakov ,12 these peaks are interpreted to the phototransfer process. arise from the... Novakov , T., "X-ray Photoelectron Spectra cist in the Radiation and Molecular Orbital Interpretation of the Valence Dosimetry Group. Since Band

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

NASA Astrophysics Data System (ADS)

Pistor, P.; Greiner, D.; Kaufmann, C. A.; Brunken, S.; Gorgoi, M.; Steigert, A.; Calvet, W.; Lauermann, I.; Klenk, R.; Unold, T.; Lux-Steiner, M.-C.

2014-08-01

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)Se2 absorbers have been evaporated on alkali containing Mo/soda-lime glass substrates. We report on compositional and electronic changes of the Cu(In,Ga)Se2 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.

Increased photoelectron transmission in High-pressure photoelectron spectrometers using "swift acceleration"

NASA Astrophysics Data System (ADS)

Edwards, Mårten O. M.; Karlsson, Patrik G.; Eriksson, Susanna K.; Hahlin, Maria; Siegbahn, Hans; Rensmo, Håkan; Kahk, Juhan M.; Villar-Garcia, Ignacio J.; Payne, David J.; Åhlund, John

2015-06-01

A new operation mode of a HPXPS (high-pressure X-ray photoelectron spectroscopy) analyzer is evaluated on a HPXPS system fitted with an Al Kα X-ray source. A variety of metal foil samples (gold, silver and copper) were measured in different sample gas environments (N2 and H2O), and a front aperture diameter of 0.8 mm. The new design concept is based upon "swiftly" accelerating the photoelectrons to kinetic energies of several keV after they pass the analyzer front aperture. Compared to the standard mode, in which the front section between the two first apertures is field-free, this gives a wider angular collection and a lower tendency for electron losses in collisions with gas molecules within the analyzer. With the swift-acceleration mode we attain, depending on the experimental conditions, up to about 3 times higher peak intensities in vacuum and about 10 to 20 times higher peak intensities in the 6-9 mbar regime, depending on kinetic energy. These experimental findings agree well with simulated transmission functions for the analyzer. The new mode of operation enables faster data acquisition than the standard mode of operation, particularly valuable in a home laboratory environment. Further demonstrations of performance are highlighted by measurements of the valence band structure in dye-sensitized solar cell photoelectrodes under a 2 mbar H2O atmosphere, a molecularly modified surface of interest in photoelectrochemical devices.

Investigations on surface chemical analysis using X-ray photoelectron spectroscopy and optical properties of Dy3+-doped LiNa3P2O7 phosphor

NASA Astrophysics Data System (ADS)

Munirathnam, K.; Dillip, G. R.; Chaurasia, Shivanand; Joo, S. W.; Deva Prasad Raju, B.; John Sushma, N.

2016-08-01

Near white-light emitting LiNa3P2O7:Dy3+ phosphors were prepared by a conventional solid-state reaction method. The orthorhombic crystal structure of the phosphors was confirmed using X-ray diffraction (XRD), and the valence states of the surface elements were determined from the binding energies of Li 1s, O 1s, Na 1s, P 2p, and Dy 3d by X-ray photoelectron spectroscopy (XPS). Attenuated total reflectance (ATR) - Fourier transform infrared (FT-IR) spectroscopy was employed to identify the pyrophosphate groups in the phosphors. Diffuse reflectance spectra (DRS) show the absorption bands of the Dy3+ ions in the host material. Intense blue (481 nm) and yellow (575 nm) emissions were obtained at an excitation wavelength of 351 nm and are attributed to the 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions, respectively. The combination of these two intense bands generates light emission in the near-white region of the chromaticity diagram.

Identification of Cr valence states in Cr and Nd co-doped Lu3Al5O12 laser ceramics

NASA Astrophysics Data System (ADS)

Zhang, Pande; Jiang, Benxue; Fan, Jintai; Mao, Xiaojian; Zhang, Long

2017-09-01

Cr and Nd co-doped laser ceramics, as the potential gain materials in inertial confinement fusion (ICF), have been widely investigated. And the study on valence states of chromium ions is important. The effects of sintering additives and annealing atmosphere on the valence state of chromium were studied in detail, and the results shown that the Cr valence states were demonstrated to be Cr2+ and Cr3+ ions in HIP-sintered Cr(0.2 at.%), Nd(0.8 at.%): LuAG laser ceramics. And the intensity of the near-infrared absorption band caused by Cr2+ ions was attenuated with the decreasing SiO2 concentration and increasing MgO amount. The near-infrared absorption could be eliminated by annealing in air. And the transformation of valence states of Cr ions in the Cr,Nd:LuAG ceramics were also confirmed by electron paramagnetic resonance and X-ray photoelectron spectroscopy.

Photoelectron spectroscopy study of the electronic structures at CoPc/Bi(111) interface

NASA Astrophysics Data System (ADS)

Sun, Haoliang; Liang, Zhaofeng; Shen, Kongchao; Hu, Jinbang; Ji, Gengwu; Li, Zheshen; Li, Haiyang; Zhu, Zhiyuan; Li, Jiong; Gao, Xingyu; Han, Huang; Jiang, Zheng; Song, Fei

2017-07-01

Self-assembly of functional molecules on solid substrate has been recognized as an appealing approach for the fabrication of diverse nanostructures for nanoelectronics. Herein, we investigate the growth of cobalt phthalocyanine (CoPc) on a Bi(111) surface with focus on the interface electronic structures utilizing photoelectron spectroscopy. While charge transfer from bismuth substrate to the molecule results in the emergence of an interface component in the Co 3p core level at lower binding energy, core-levels associated to the molecular ligand (C 1s and N 1s) are less influenced by the adsorption. In addition, density functional theory (DFT) calculations also support the empirical inference that the molecule-substrate interaction mainly involves the out-of-plane empty Co 3d orbital and bismuth states. Finally, valence band spectra demonstrate the molecule-substrate interaction is induced by interface charge transfer, agreeing well with core level measurements. Charge transfer is shown to be mainly from the underlying bismuth substrate to the empty states located at the central Co atom in the CoPc molecules. This report may provide a fundamental basis to the on-surface engineering of interfaces for molecular devices and spintronics.

Bulk electronic structure of non-centrosymmetric EuTGe 3 (T=Co, Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

DOE PAGES

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemys?aw; ...

2018-03-15

Non-centrosymmetric EuTGe 3 ( T = Co, Ni, Rh, and Ir) possesses magnetic Eu 2+ ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge 3 ( T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3d core-level spectrum confirms the robust Eu 2+ valence state against the transition-metal substitutionmore » with a small contribution from Eu 3+ . The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2p spectrum shifts to higher binding energy upon cha nging the transition metal from 3d to 4d to 5d elements, hinting at a change in the Ge- T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.« less

Bulk electronic structure of non-centrosymmetric EuTGe 3 (T=Co, Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

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

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemys?aw

Non-centrosymmetric EuTGe 3 ( T = Co, Ni, Rh, and Ir) possesses magnetic Eu 2+ ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge 3 ( T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3d core-level spectrum confirms the robust Eu 2+ valence state against the transition-metal substitutionmore » with a small contribution from Eu 3+ . The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2p spectrum shifts to higher binding energy upon cha nging the transition metal from 3d to 4d to 5d elements, hinting at a change in the Ge- T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.« less

Laser-produced lithium plasma as a narrow-band extended ultraviolet radiation source for photoelectron spectroscopy.

PubMed

Schriever, G; Mager, S; Naweed, A; Engel, A; Bergmann, K; Lebert, R

1998-03-01

Extended ultraviolet (EUV) emission characteristics of a laser-produced lithium plasma are determined with regard to the requirements of x-ray photoelectron spectroscopy. The main features of interest are spectral distribution, photon flux, bandwidth, source size, and emission duration. Laser-produced lithium plasmas are characterized as emitters of intense narrow-band EUV radiation. It can be estimated that the lithium Lyman-alpha line emission in combination with an ellipsoidal silicon/molybdenum multilayer mirror is a suitable EUV source for an x-ray photoelectron spectroscopy microscope with a 50-meV energy resolution and a 10-mum lateral resolution.

Structures of cycloserine and 2-oxazolidinone probed by X-ray photoelectron spectroscopy: theory and experiment.

PubMed

Ahmed, Marawan; Wang, Feng; Acres, Robert G; Prince, Kevin C

2014-05-22

The electronic structures and properties of 2-oxazolidinone and the related compound cycloserine (CS) have been investigated using theoretical calculations and core and valence photoelectron spectroscopy. Isomerization of the central oxazolidine heterocycle and the addition of an amino group yield cycloserine. Theory correctly predicts the C, N, and O 1s core spectra, and additionally, we report theoretical natural bond orbital (NBO) charges. The valence ionization energies are also in agreement with theory and previous measurements. Although the lowest binding energy part of the spectra of the two compounds shows superficial similarities, further analysis of the charge densities of the frontier orbitals indicates substantial reorganization of the wave functions as a result of isomerization. The highest occupied molecular orbital (HOMO) of CS shows leading carbonyl π character with contributions from other heavy (non-H) atoms in the molecule, while the HOMO of 2-oxazolidinone (OX2) has leading nitrogen, carbon, and oxygen pπ characters. The present study further theoretically predicts bond resonance effects of the compounds, evidence for which is provided by our experimental measurements and published crystallographic data.

Valence shell threshold photoelectron spectroscopy of the CHxCN (x = 0-2) and CNC radicals.

PubMed

Garcia, Gustavo A; Krüger, Julia; Gans, Bérenger; Falvo, Cyril; Coudert, Laurent H; Loison, Jean-Christophe

2017-07-07

We present the photoelectron spectroscopy of four radical species, CH x CN (x = 0-2) and CNC, formed in a microwave discharge flow-tube reactor by consecutive H abstractions from CH 3 CN (CH x CN + F → CH x-1 CN + HF (x = 1-3)). The spectra were obtained combining tunable vacuum ultraviolet synchrotron radiation with double imaging electron/ion coincidence techniques, which yielded mass-selected threshold photoelectron spectra. The results obtained for H 2 CCN complement existing ones while for the other radicals the data represent the first observation of their (single-photon) ionizing transitions. In the case of H 2 CCN, Franck-Condon calculations have been performed in order to assign the vibrational structure of the X + 1 A 1 ←X 2 B 1 ionizing transition. A similar treatment for the HCCN, CCN, and CNC radicals appeared to be more complicated mainly because a Renner-Teller effect strongly affects the vibrational levels of the ground electronic state of the HCCN + , CCN, and CNC species. Nevertheless, the first adiabatic ionization energies of these radicals are reported and compared to our ab initio calculated values, leading to new values for enthalpies of formation (Δ f H 298 0 (HCCN + (X 2 A ' ))=1517±12kJmol -1 ,Δ f H 298 0 (CCN(X 2 Π))=682±13kJmol -1 , and Δ f H 298 0 (CNC(X 2 Πg))=676±12kJmol -1 ), which are of fundamental importance for astrochemistry.

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual

Band bending at the heterointerface of GaAs/InAs core/shell nanowires monitored by synchrotron X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Khanbabaee, B.; Bussone, G.; Knutsson, J. V.; Geijselaers, I.; Pryor, C. E.; Rieger, T.; Demarina, N.; Grützmacher, D.; Lepsa, M. I.; Timm, R.; Pietsch, U.

2016-10-01

Unique electronic properties of semiconductor heterostructured nanowires make them useful for future nano-electronic devices. Here, we present a study of the band bending effect at the heterointerface of GaAs/InAs core/shell nanowires by means of synchrotron based X-ray photoelectron spectroscopy. Different Ga, In, and As core-levels of the nanowire constituents have been monitored prior to and after cleaning from native oxides. The cleaning process mainly affected the As-oxides and was accompanied by an energy shift of the core-level spectra towards lower binding energy, suggesting that the As-oxides turn the nanowire surfaces to n-type. After cleaning, both As and Ga core-levels revealed an energy shift of about -0.3 eV for core/shell compared to core reference nanowires. With respect to depth dependence and in agreement with calculated strain distribution and electron quantum confinement, the observed energy shift is interpreted by band bending of core-levels at the heterointerface between the GaAs nanowire core and the InAs shell.

Ab Initio Determinations of Photoelectron Spectra Including Vibronic Features: An Upper-Level Undergraduate Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Lord, Richard L.; Davis, Lisa; Millam, Evan L.; Brown, Eric; Offerman, Chad; Wray, Paul; Green, Susan M. E.

2008-01-01

We present a first-principles determination of the photoelectron spectra of water and hypochlorous acid as a laboratory exercise accessible to students in an undergraduate physical chemistry course. This paper demonstrates the robustness and user-friendliness of software developed for the Franck-Condon factor calculation. While the calculator is…

First determination of the valence band dispersion of CH3NH3PbI3 hybrid organic-inorganic perovskite

NASA Astrophysics Data System (ADS)

Lee, Min-I.; Barragán, Ana; Nair, Maya N.; Jacques, Vincent L. R.; Le Bolloc'h, David; Fertey, Pierre; Jemli, Khaoula; Lédée, Ferdinand; Trippé-Allard, Gaëlle; Deleporte, Emmanuelle; Taleb-Ibrahimi, Amina; Tejeda, Antonio

2017-07-01

The family of hybrid organic-inorganic halide perovskites is in the limelight because of their recently discovered high photovoltaic efficiency. These materials combine photovoltaic energy conversion efficiencies exceeding 22% and low-temperature and low-cost processing in solution; a breakthrough in the panorama of renewable energy. Solar cell operation relies on the excitation of the valence band electrons to the conduction band by solar photons. One factor strongly impacting the absorption efficiency is the band dispersion. The band dispersion has been extensively studied theoretically, but no experimental information was available. Herein, we present the first experimental determination of the valence band dispersion of methylammonium lead halide in the tetragonal phase. Our results pave the way for contrasting the electronic hopping or the electron effective masses in different theories by comparing to our experimental bands. We also show a significant broadening of the electronic states, promoting relaxed conditions for photon absorption, and demonstrate that the tetragonal structure associated to the octahedra network distortion below 50 °C induces only a minor modification of the electronic bands, with respect to the cubic phase at high temperature, thus minimizing the impact of the cubic-tetragonal transition on solar cell efficiencies.

Surface and bulk electronic structures of unintentionally and Mg-doped In0.7Ga0.3N epilayer by hard X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Imura, Masataka; Tsuda, Shunsuke; Takeda, Hiroyuki; Nagata, Takahiro; Banal, Ryan G.; Yoshikawa, Hideki; Yang, AnLi; Yamashita, Yoshiyuki; Kobayashi, Keisuke; Koide, Yasuo; Yamaguchi, Tomohiro; Kaneko, Masamitsu; Uematsu, Nao; Wang, Ke; Araki, Tsutomu; Nanishi, Yasushi

2018-03-01

The surface and bulk electronic structures of In0.7Ga0.3N epilayers are investigated by angle-resolved hard X-ray photoelectron spectroscopy (HX-PES) combined with soft X-PES. The unintentionally and Mg-doped In0.7Ga0.3N (u-In0.7Ga0.3N and In0.7Ga0.3N:Mg, respectively) epilayers are grown by radio-frequency plasma-assisted molecular beam epitaxy. Here three samples with different Mg concentrations ([Mg] = 0, 7 × 1019, and 4 × 1020 cm-3) are chosen for comparison. It is found that a large downward energy band bending exists in all samples due to the formation of a surface electron accumulation (SEA) layer. For u-In0.7Ga0.3N epilayer, band bending as large as 0.8 ± 0.05 eV occurs from bulk to surface. Judged from the valence band spectral edge and numerical analysis of energy band with a surface quantum well, the valence band maximum (VBM) with respect to Fermi energy (EF) level in the bulk is determined to be 1.22 ± 0.05 eV. In contrast, for In0.7Ga0.3N:Mg epilayers, the band bending increases and the VBM only in the bulk tends to shift toward the EF level owing to the Mg acceptor doping. Hence, the energy band is considered to exhibit a downward bending structure due to the coexistence of the n+ SEA layer and Mg-doped p layer formed in the bulk. When [Mg] changes from 7 × 1019 to 4 × 1020 cm-3, the peak split occurs in HX-PES spectra under the bulk sensitive condition. This result indicates that the energy band forms an anomalous downward bending structure with a singular point due to the generation of a thin depleted region at the n+ p interface. For In0.7Ga0.3N:Mg epilayers, the VBM in the bulk is assumed to be slightly lower than EF level within 0.1 eV.

Bulk electronic structure of non-centrosymmetric Eu T Ge3 (T =Co , Ni, Rh, Ir) studied by hard x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Utsumi, Yuki; Kasinathan, Deepa; Swatek, Przemysław; Bednarchuk, Oleksandr; Kaczorowski, Dariusz; Ablett, James M.; Rueff, Jean-Pascal

2018-03-01

Non-centrosymmetric Eu T Ge3 (T = Co, Ni, Rh, and Ir) possesses magnetic Eu2 + ions, and antiferromagnetic ordering appears at low temperatures. Transition-metal substitution leads to changes in the unit-cell volume and in the magnetic ordering. However, the magnetic ordering temperature does not scale with the volume change, and the Eu valence is expected to remain divalent. Here we study the bulk electronic structure of non-centrosymmetric Eu T Ge3 (T = Co, Ni, Rh, and Ir) by hard x-ray photoelectron spectroscopy. The Eu 3 d core-level spectrum confirms the robust Eu2 + valence state against the transition-metal substitution with a small contribution from Eu3 +. The estimated Eu mean valence is around 2.1 in these compounds, as confirmed by multiplet calculations. In contrast, the Ge 2 p spectrum shifts to higher binding energy upon changing the transition metal from 3 d to 4 d to 5 d elements, hinting at a change in the Ge-T bonding strength. The valence bands of the different compounds are found to be well reproduced by ab initio band structure calculations.

Band Offsets at the Interface between Crystalline and Amorphous Silicon from First Principles

NASA Astrophysics Data System (ADS)

Jarolimek, K.; Hazrati, E.; de Groot, R. A.; de Wijs, G. A.

2017-07-01

The band offsets between crystalline and hydrogenated amorphous silicon (a -Si ∶H ) are key parameters governing the charge transport in modern silicon heterojunction solar cells. They are an important input for macroscopic simulators that are used to further optimize the solar cell. Past experimental studies, using x-ray photoelectron spectroscopy (XPS) and capacitance-voltage measurements, have yielded conflicting results on the band offset. Here, we present a computational study on the band offsets. It is based on atomistic models and density-functional theory (DFT). The amorphous part of the interface is obtained by relatively long DFT first-principles molecular-dynamics runs at an elevated temperature on 30 statistically independent samples. In order to obtain a realistic conduction-band position the electronic structure of the interface is calculated with a hybrid functional. We find a slight asymmetry in the band offsets, where the offset in the valence band (0.29 eV) is larger than in the conduction band (0.17 eV). Our results are in agreement with the latest XPS measurements that report a valence-band offset of 0.3 eV [M. Liebhaber et al., Appl. Phys. Lett. 106, 031601 (2015), 10.1063/1.4906195].

Determination of the absolute carrier-envelope phase by angle-resolved photoelectron spectra of Ar by intense circularly polarized few-cycle pulses

NASA Astrophysics Data System (ADS)

Fukahori, Shinichi; Ando, Toshiaki; Miura, Shun; Kanya, Reika; Yamanouchi, Kaoru; Rathje, Tim; Paulus, Gerhard G.

2017-05-01

The angle-resolved photoelectron spectra of Ar are recorded using intense circularly polarized near-infrared few-cycle laser pulses, and the effect of the depletion of Ar atoms by the ionization and the effect of the Coulombic potential are examined by the classical trajectory Monte Carlo simulations. On the basis of the comparison between the experimental and theoretical photoelectron spectra, a procedure for estimating the absolute carrier-envelope phase (CEP) of the few-cycle laser pulses interacting with atoms and molecules is proposed. It is confirmed that the absolute CEP can securely be estimated without any numerical calculations once the angular distribution of the yield of photoelectrons having the kinetic energy larger than 30 eV is measured with the peak laser intensity in the range between 1 ×1014 and 5 ×1014W /c m2 .

Band alignment and interfacial chemical structure of the HfLaO/InGaZnO4 heterojunction investigated by x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Qian, Ling-Xuan; Wu, Ze-Han; Zhang, Yi-Yu; Liu, Yuan; Song, Jia-Qi; Liu, Xing-Zhao; Li, Yan-Rong

2017-04-01

Amorphous InGaZnO4 thin film transistors (a-IGZO TFTs) with HfLaO gate dielectrics have been widely demonstrated to possess extremely excellent electrical characteristics, and thus show great potential for applications in various next-generation electronic products. Nevertheless, the in-depth understanding of HfLaO/IGZO interfacial features is still lacking, which makes further device optimization lack clear guidance. In this work, the band alignment and interfacial chemical structure of a sputtering-prepared HfLaO/IGZO heterojunction was investigated through x-ray photoelectron spectroscopy. The valence and conduction band offsets (ΔE v and ΔE c) at the interface were determined to be 0.57 eV and 1.48 eV, respectively. The relatively large ΔE v is mainly attributed to the formation of the interfacial layer (IL) and thus the upward band bending from IGZO to the surface of HfLaO. Furthermore, it was found that the oxygen vacancies on the surface of IGZO were significantly suppressed upon the deposition of HfLaO, which not only explained the previously reported ultrahigh performance of a-IGZO/HfLaO TFTs to some extent, but also additionally validated the formation of the IL. Our findings have successfully revealed the importance of ILs in modifying the band alignment and interfacial trap states of HfLaO/IGZO heterojunctions, thus suggesting a potential route to further optimizing a-IGZO/HfLaO TFTs so as to satisfy the requirements of next-generation technologies.

On the Widths of Bands in the Infrared Spectra of Oxyanions.

PubMed

Griffiths, Peter R; Eastman Fries, Brandy; Weakley, Andrew T

2018-01-01

It is well known that the antisymmetric stretching (ν 3 ) band in the mid-infrared spectra of oxyanion salts is usually very broad, whereas all the other fundamental bands are narrow. In this paper, we propose that the underlying cause of the increased width is the effect of the very high absorption index of this band for samples prepared with a range of particle sizes. When oxyanion salts are ground, the diameter of the resulting particles usually varies from less than 100 nm to about 2 µm. While the peak absorbance of the ν 3 band of the smaller particles (diameter < 200 nm) is less than 1, that of the larger particles can be as high as 6. We show that the average transmittance of these particles leads to a significant band broadening, especially when there are small voids in the resulting sample. Although the effect is always seen in the spectra of alkali halide disks and mineral oil mulls, it is also seen in diffuse reflection and attenuated total reflection (ATR) spectra. Because the depth of penetration of infrared radiation below 1500 cm -1 is less than 1 µm for ATR spectra measured with a germanium internal reflection element (IRE), the width of the ν 3 band is lower than that of ATR spectra measured with an IRE of lower refractive index such as diamond on zinc selenide.

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

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

Pistor, P., E-mail: paul.pistor@physik.uni-halle.de; Greiner, D.; Kaufmann, C. A.

2014-08-11

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 depletionmore » 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.« less

Synchrotron radiation based cross-sectional scanning photoelectron microscopy and spectroscopy of n-ZnO:Al/p-GaN:Mg heterojunction

NASA Astrophysics Data System (ADS)

Lee, Kai-Hsuan; Chang, Ping-Chuan; Chen, Tse-Pu; Chang, Sheng-Po; Shiu, Hung-Wei; Chang, Lo-Yueh; Chen, Chia-Hao; Chang, Shoou-Jinn

2013-02-01

Al-doped ZnO (AZO) deposited by radio frequency co-sputtering is formed on epitaxial Mg-doped GaN template at room temperature to achieve n-AZO/p-GaN heterojunction. Alignment of AZO and GaN bands is investigated using synchrotron radiation based cross-sectional scanning photoelectron microscopy and spectroscopy on the nonpolar side-facet of a vertically c-axis aligned heterostructure. It shows type-II band configuration with valence band offset of 1.63 ± 0.1 eV and conduction band offset of 1.61 ± 0.1 eV, respectively. Rectification behavior is clearly observed, with a ratio of forward-to-reverse current up to six orders of magnitude when the bias is applied across the p-n junction.

Synchrotron radiation based cross-sectional scanning photoelectron microscopy and spectroscopy of n-ZnO:Al/p-GaN:Mg heterojunction

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

Lee, Kai-Hsuan; Chen, Chia-Hao; Chang, Ping-Chuan

2013-02-18

Al-doped ZnO (AZO) deposited by radio frequency co-sputtering is formed on epitaxial Mg-doped GaN template at room temperature to achieve n-AZO/p-GaN heterojunction. Alignment of AZO and GaN bands is investigated using synchrotron radiation based cross-sectional scanning photoelectron microscopy and spectroscopy on the nonpolar side-facet of a vertically c-axis aligned heterostructure. It shows type-II band configuration with valence band offset of 1.63 {+-} 0.1 eV and conduction band offset of 1.61 {+-} 0.1 eV, respectively. Rectification behavior is clearly observed, with a ratio of forward-to-reverse current up to six orders of magnitude when the bias is applied across the p-n junction.

Local Bonding Analysis of the Valence and Conduction Band Features of TiO2

DTIC Science & Technology

2007-01-01

valence and conduction band features of TiO2 L. Fleming, C. C. Fulton, G. Lucovsky, J. E. Rowe, M. D. Ulrich, J. Luning W911NF-04-D-0003 Dept of...J. Luning , L. F. Edge, J. L. Whitten, R. J. Nemanich, H. Ade, D. G. Schlom, V. V. Afanase’v, A. Stesmans, S. Zollner, D. Triyoso, and B. R. Rogers

Oxidation and deprotonation of synthetic Fe{sup II}-Fe{sup III} (oxy)hydroxycarbonate Green Rust: An X-ray photoelectron study

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

Mullet, M.; Guillemin, Y.; Ruby, C.

X-ray photoelectron spectroscopy (XPS) was used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rusts (GRs). GRs with variable composition, i.e. Fe{sup II}{sub 6(1-x)}Fe{sup III}{sub 6x}O{sub 12}H{sub 2(7-3x)} CO{sub 3}.3H{sub 2}O where the Fe{sup III} molar fraction of the positively charged hydroxide sheets, x=[Fe(III)]/[Fe(total)] belongs to [1/3, 1], were synthesised under an inert atmosphere. The broadened Fe(2p{sub 3/2}) spectra were fitted using Gupta and Sen multiplets peaks and additional satellite and surface features. The [Fe(III)]/[Fe(total)] surface atomic ratios closely agree with the x ratios expected from the bulk composition, which gives amore » high degree of confidence on the validity of the proposed fitting procedure. The valence band spectra are also reported and show dependencies on iron speciation. The O(1s) spectra revealed the presence of O{sup 2-}, OH{sup -} species and adsorbed water. The hydroxyl component decreases with increasing x values, i.e. with the amount of ferric iron, while the oxide component increases. This study provides direct spectroscopic evidence of the deprotonation of hydroxyl groups that occurs simultaneously with the oxidation of ferrous iron within the GR structure. - Graphical abstract: X-ray photoelectron spectroscopy (XPS) is used to investigate chemical bonding and distribution of iron and oxygen species at the surface of Green Rust (GR) compounds. First spectroscopic evidence of the deprotonation of hydroxyls groups occurring simultaneously to the oxidation of Fe(II) into Fe(III) species is provided.« less

Electronic Structures of Purple Bronze KMo6O17 Studied by X-Ray Photoemission Spectra

NASA Astrophysics Data System (ADS)

Qin, Xiaokui; Wei, Junyin; Shi, Jing; Tian, Mingliang; Chen, Hong; Tian, Decheng

X-ray photoemission spectroscopy study has been performed for the purple bronze KMo6O17. The structures of conduction band and valence band are analogous to the results of ultraviolet photoemission spectra and are also consistent with the model of Travaglini et al., but the gap between conduction and valence band is insignificant. The shape of asymmetric and broadening line of O-1s is due to unresolved contributions from the many inequivalent oxygen sites in this crystal structure. Mo 3d core-level spectrum reveals that there are two kinds of valence states of Molybdenum (Mo+5 and Mo+6). The calculated average valence state is about +5.6, which is consistent with the expectation value from the composition of this material. The tail of Mo-3d spectrum toward higher binding energy is the consequence of the excitation of electron-hole pairs with singularity index of 0.21.

Experimental study of the valence band of Bi 2 Se 3

DOE PAGES

Gao, Yi-Bin; He, Bin; Parker, David; ...

2014-09-26

The valence band of Bi 2Se 3 is investigated with Shubnikov - de Haas measurements, galvanomagnetic and thermoelectric transport. At low hole concentration, the hole Fermi surface is closed and box-like, but at higher concentrations it develops tube-like extensions that are open. The experimentally determined density-of-states effective mass is lighter than density-functional theory calculations predict; while we cannot give a definitive explanation for this, we suspect that the theory may lack sufficient precision to compute room-temperature transport properties, such as the Seebeck coefficient, in solids in which there are Van der Waals interlayer bonds.

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Synthesis, structural, electronic and linear electro-optical features of new quaternary Ag2Ga2SiS6 compound

NASA Astrophysics Data System (ADS)

Piasecki, M.; Myronchuk, G. L.; Parasyuk, O. V.; Khyzhun, O. Y.; Fedorchuk, A. O.; Pavlyuk, V. V.; Kozer, V. R.; Sachanyuk, V. P.; El-Naggar, A. M.; Albassam, A. A.; Jedryka, J.; Kityk, I. V.

2017-02-01

For the first time phase equilibria and phase diagram of the AgGaS2-SiS2 system were successfully explored by differential thermal and X-ray phase analysis methods. Crystal structure of low-temperature (LT) modification of Ag2Ga2SiS6 (LT- Ag2Ga2SiS6) was studied by X-ray powder method and it belongs to tetragonal space group I-42d, with unit cell parameters a=5.7164(4) Å, c=9.8023(7) Å, V=320.32(7) Å3. Additional details regarding the crystal structure exploration are available at the web page Fachinformationszentrum Karlsruhe. X-ray photoelectron core-level and valence-band spectra were measured for pristine LT- Ag2Ga2SiS6 crystal surface. In addition, the X-ray photoelectron valence-band spectrum of LT-Ag2Ga2SiS6 was matched on a common energy scale with the X-ray emission S Kβ1,3 and Ga Kβ2 bands, which give information on the energy distribution of the S 3p and Ga 4p states, respectively. The presented X-ray spectroscopy results indicate that the valence S p and Ga p atomic states contribute mainly to the upper and central parts of the valence band of LT-Ag2Ga2SiS6, respectively, with a less significant contribution also to other valence-band regions. Band gap energy was estimated by measuring the quantum energy in the spectral range of the fundamental absorption. We have found that energy gap Eg is equal to 2.35 eV at 300 K. LT-Ag2Ga2SiS6 is a photosensitive material and reveals two spectral maxima on the curve of spectral photoconductivity spectra at λmax1 =590 nm and λmax2 =860 nm. Additionally, linear electro-optical effect of LT-Ag2Ga2SiS6 for the wavelengths of a cw He-Ne laser at 1150 nm was explored.

Calculation of density of states of transition metals: From bulk sample to nanocluster

NASA Astrophysics Data System (ADS)

Krasavin, Andrey V.; Borisyuk, Petr V.; Vasiliev, Oleg S.; Zhumagulov, Yaroslav V.; Kashurnikov, Vladimir A.; Kurelchuk, Uliana N.; Lebedinskii, Yuriy Yu.

2018-03-01

A technique is presented of restoring the electronic density of states of the valence band from data of X-ray photoelectron spectroscopy (XPS). The originality of the technique consists in using a stochastic procedure to solve an integral equation relating the density of states and the experimental X-ray photoelectron spectra via the broadening function. To obtain the broadening function, only the XPS spectra of the core levels are needed. The results are presented for bulk sample of gold and tungsten and nanoclusters of tantalum; the possibility of using the results to determine the density of states of low-dimensional structures, including ensembles of metal nanoclusters, is demonstrated.

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.

Influence of leaching on surface composition, microstructure, and valence band of single grain icosahedral Al-Cu-Fe quasicrystal

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

Lowe, M.; McGrath, R.; Sharma, H. R.

The use of quasicrystals as precursors to catalysts for the steam reforming of methanol is potentially one of the most important applications of these new materials. To develop application as a technology requires a detailed understanding of the microscopic behavior of the catalyst. Here, we report the effect of leaching treatments on the surface microstructure, chemical composition, and valence band of the icosahedral (i-) Al-Cu-Fe quasicrystal in an attempt to prepare a model catalyst. The high symmetry fivefold surface of a single grain i-Al-Cu-Fe quasicrystal was leached with NaOH solution for varying times, and the resulting surface was characterized bymore » x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The leaching treatments preferentially remove Al producing a capping layer consisting of Fe and Cu oxides. The subsurface layer contains elemental Fe and Cu in addition to the oxides. The quasicrystalline bulk structure beneath remains unchanged. The subsurface gradually becomes Fe{sub 3}O{sub 4} rich with increasing leaching time. The surface after leaching exhibits micron sized dodecahedral cavities due to preferential leaching along the fivefold axis. Nanoparticles of the transition metals and their oxides are precipitated on the surface after leaching. The size of the nanoparticles is estimated by high resolution transmission microscopy to be 5-20 nm, which is in agreement with the AFM results. Selected area electron diffraction (SAED) confirms the crystalline nature of the nanoparticles. SAED further reveals the formation of an interface between the high atomic density lattice planes of nanoparticles and the quasicrystal. These results provide an important insight into the preparation of model catalysts of nanoparticles for steam reforming of methanol.« less

Broadening of effective photonic band gaps in biological chiral structures: From intrinsic narrow band gaps to broad band reflection spectra

NASA Astrophysics Data System (ADS)

Vargas, W. E.; Hernández-Jiménez, M.; Libby, E.; Azofeifa, D. E.; Solis, Á.; Barboza-Aguilar, C.

2015-09-01

Under normal illumination with non-polarized light, reflection spectra of the cuticle of golden-like and red Chrysina aurigans scarabs show a structured broad band of left-handed circularly polarized light. The polarization of the reflected light is attributed to a Bouligand-type left-handed chiral structure found through the scarab's cuticle. By considering these twisted structures as one-dimensional photonic crystals, a novel approach is developed from the dispersion relation of circularly polarized electromagnetic waves traveling through chiral media, to show how the broad band characterizing these spectra arises from an intrinsic narrow photonic band gap whose spectral position moves through visible and near-infrared wavelengths.

Synthesis, Structural, Thermal, and Electronic Properties of Palmierite-Related Double Molybdate α-Cs2Pb(MoO4)2.

PubMed

Solodovnikov, Sergey F; Atuchin, Victor V; Solodovnikova, Zoya A; Khyzhun, Oleg Y; Danylenko, Mykola I; Pishchur, Denis P; Plyusnin, Pavel E; Pugachev, Alexey M; Gavrilova, Tatiana A; Yelisseyev, Alexander P; Reshak, Ali H; Alahmed, Zeyad A; Habubi, Nadir F

2017-03-20

Cs 2 Pb(MoO 4 ) 2 crystals were prepared by crystallization from their own melt, and the crystal structure has been studied in detail. At 296 K, the molybdate crystallizes in the low-temperature α-form and has a monoclinic palmierite-related superstructure (space group C2/m, a = 2.13755(13) nm, b = 1.23123(8) nm, c = 1.68024(10) nm, β = 115.037(2)°, Z = 16) possessing the largest unit cell volume, 4.0066(4) nm 3 , among lead-containing palmierites. The compound undergoes a distortive phase transition at 635 K and incongruently melts at 943 K. The electronic structure of α-Cs 2 Pb(MoO 4 ) 2 was explored by using X-ray emission spectroscopy (XES) and X-ray photoelectron spectroscopy methods. For α-Cs 2 Pb(MoO 4 ) 2 , the photoelectron core-level and valence-band spectra and the XES band representing the energy distribution of Mo 4d and O 2p states were recorded. Our results allow one to conclude that the Mo 4d and O 2p states contribute mainly to the central part and at the top of the valence band, respectively, with also significant contributions throughout the whole valence-band region of the molybdate under consideration.

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group's Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN.

PubMed

Rodríguez Pirani, Lucas S; Della Védova, Carlos O; Geronés, Mariana; Romano, Rosana M; Cavasso-Filho, Reinaldo; Ge, Maofa; Ma, Chunping; Erben, Mauricio F

2017-12-07

Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CCl 3 SCN and CCl 2 FSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CCl 3 SCN and CCl 2 FSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CX 3 SCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX 3 group is observed. Irradiation of CCl 3 SCN and CCl 2 FSCN with photons in the valence energy regions leads to the formation of CCl 2 X + and CClXSCN + ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

Direct observation of strain-induced orbital valence band splitting in HfSe2 by sodium intercalation

NASA Astrophysics Data System (ADS)

Eknapakul, T.; Fongkaew, I.; Siriroj, S.; Jindata, W.; Chaiyachad, S.; Mo, S.-K.; Thakur, S.; Petaccia, L.; Takagi, H.; Limpijumnong, S.; Meevasana, W.

2018-05-01

By using angle-resolved photoemission spectroscopy (ARPES), the variation of the electronic structure of HfSe2 has been studied as a function of sodium intercalation. We observe how this drives a band splitting of the p -orbital valence bands and a simultaneous reduction of the indirect band gap by values of up to 400 and 280 meV, respectively. Our calculations indicate that such behavior is driven by the band deformation potential, which is a result of our observed strain induced by sodium intercalation. The applied uniaxial strain calculations based on density functional theory agree strongly with the experimental ARPES data. These findings should assist in studying the physical relationship between intercalation and strain, as well as for large-scale two-dimensional straintronics.

The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

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

Vasilatou, K.; Michaud, J. M.; Baykusheva, D.

2014-08-14

The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra ofmore » deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.« less

Evidence of mixed valence states in U M2Al 3 ( M = Ni, Pd) studied by X-ray photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Fujimori, Shin-ichi; Saito, Yasuharu; Sato, Noriaki; Komatsubara, Takemi; Suzuki, Shoji; Sato, Shigeru; Ishii, Takehiko

1998-01-01

We have measured the XPS valence band and core-level spectra of U M2Al 3 ( M = Ni and Pd). The results are compared with those of reference materials, dilute alloy U 0.1La 0.9Pd 2Al 3 and itinerant 5 f compound URh 3. The similarity of the core-level spectra between UPd 2Al 3 and U 0.1La 0.9Pd 2Al 3 suggests that their core-level spectra are governed by the interaction between U 5 f and ligand states of neighboring palladium and aluminum sites, with negligible contributions from neighboring uranium states. A complex satellite structure, observed in the core-level spectra of U M2Al 3, suggests that the uranium atoms are in the strong mixed valence states with 5 f2(U 4+) and 5 f3(U 3+).

High Power Factor and Enhanced Thermoelectric Performance of SnTe-AgInTe2: Synergistic Effect of Resonance Level and Valence Band Convergence.

PubMed

Banik, Ananya; Shenoy, U Sandhya; Saha, Sujoy; Waghmare, Umesh V; Biswas, Kanishka

2016-10-05

Understanding the basis of electronic transport and developing ideas to improve thermoelectric power factor are essential for production of efficient thermoelectric materials. Here, we report a significantly large thermoelectric power factor of ∼31.4 μW/cm·K 2 at 856 K in Ag and In co-doped SnTe (i.e., SnAg x In x Te 1+2x ). This is the highest power factor so far reported for SnTe-based material, which arises from the synergistic effects of Ag and In on the electronic structure and the improved electrical transport properties of SnTe. In and Ag play different but complementary roles in modifying the valence band structure of SnTe. In-doping introduces resonance levels inside the valence bands, leading to a significant improvement in the Seebeck coefficient at room temperature. On the other hand, Ag-doping reduces the energy separation between light- and heavy-hole valence bands by widening the principal band gap, which also results in an improved Seebeck coefficient. Additionally, Ag-doping in SnTe enhances the p-type carrier mobility. Co-doping of In and Ag in SnTe yields synergistically enhanced Seebeck coefficient and power factor over a broad temperature range because of the synergy of the introduction of resonance states and convergence of valence bands, which have been confirmed by first-principles density functional theory-based electronic structure calculations. As a consequence, we have achieved an improved thermoelectric figure of merit, zT ≈ 1, in SnAg 0.025 In 0.025 Te 1.05 at 856 K.

Outer-valence Electron Spectra of Prototypical Aromatic Heterocycles from an Optimally Tuned Range-Separated Hybrid Functional

PubMed Central

2014-01-01

Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. Phys. Rev. Lett.2012, 109, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within ∼0.1–0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception found—a high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost. PMID:24839410

Band Offset Measurements in Atomic-Layer-Deposited Al2O3/Zn0.8Al0.2O Heterojunction Studied by X-ray Photoelectron Spectroscopy.

PubMed

Yan, Baojun; Liu, Shulin; Heng, Yuekun; Yang, Yuzhen; Yu, Yang; Wen, Kaile

2017-12-01

Pure aluminum oxide (Al 2 O 3 ) and zinc aluminum oxide (Zn x Al 1-x O) thin films were deposited by atomic layer deposition (ALD). The microstructure and optical band gaps (E g ) of the Zn x Al 1-x O (0.2 ≤ x ≤ 1) films were studied by X-ray diffractometer and Tauc method. The band offsets and alignment of atomic-layer-deposited Al 2 O 3 /Zn 0.8 Al 0.2 O heterojunction were investigated in detail using charge-corrected X-ray photoelectron spectroscopy. In this work, different methodologies were adopted to recover the actual position of the core levels in insulator materials which were easily affected by differential charging phenomena. Valence band offset (ΔE V ) and conduction band offset (ΔE C ) for the interface of the Al 2 O 3 /Zn 0.8 Al 0.2 O heterojunction have been constructed. An accurate value of ΔE V  = 0.82 ± 0.12 eV was obtained from various combinations of core levels of heterojunction with varied Al 2 O 3 thickness. Given the experimental E g of 6.8 eV for Al 2 O 3 and 5.29 eV for Zn 0.8 Al 0.2 O, a type-I heterojunction with a ΔE C of 0.69 ± 0.12 eV was found. The precise determination of the band alignment of Al 2 O 3 /Zn 0.8 Al 0.2 O heterojunction is of particular importance for gaining insight to the design of various electronic devices based on such heterointerface.

Elucidating the electronic structure of supported gold nanoparticles and its relevance to catalysis by means of hard X-ray photoelectron spectroscopy

DOE PAGES

Reinecke, Benjamin N.; Kuhl, Kendra P.; Ogasawara, Hirohito; ...

2015-12-31

We report on the electronic structure of Au (gold) nanoparticles supported onto TiO 2 with a goal of elucidating the most important effects that contribute to their high catalytic activity. We synthesize and characterize with high resolution transmission electron microscopy (HRTEM) 3.4, 5.3, and 9.5 nm diameter TiO 2-supported Au nanoparticles with nearly spherical shape and measure their valence band using Au 5d subshell sensitive hard X-ray photoelectron spectroscopy (HAXPES) conducted at Spring-8. Based on density functional theory (DFT) calculations of various Au surface structures, we interpret the observed changes in the Au 5d valence band structure as a functionmore » of size in terms of an increasing percentage of Au atoms at corners/edges for decreasing particle size. Finally, this work elucidates how Au coordination number impacts the electronic structure of Au nanoparticles, ultimately giving rise to their well-known catalytic activity.« less

Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2 -xSex system

NASA Astrophysics Data System (ADS)

Mizuguchi, Y.; Paris, E.; Wakita, T.; Jinno, G.; Puri, A.; Terashima, K.; Joseph, B.; Miura, O.; Yokoya, T.; Saini, N. L.

2017-02-01

We have studied the effect of Se substitution on Eu valence in a layered Eu0.5La0.5FBiS2 -xSex superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu L3-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting Eu2 + and Eu3 +. The average Eu valence decreases sharply from ˜2.3 for x =0.0 to ˜2.1 for x =0.4 . Consistently, Eu 3 d XPS shows a clear decrease in the average valence by Se substitution. Bi 4 f XPS indicates that effective charge carriers in the BiCh2 (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in Eu0.5La0.5FBiS2 -xSex is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

Site-specific intermolecular valence-band dispersion in α-phase crystalline films of cobalt phthalocyanine studied by angle-resolved photoemission spectroscopy

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

Yamane, Hiroyuki; Kosugi, Nobuhiro; The Graduate University for Advanced Studies, Okazaki 444-8585

2014-12-14

The valence band structure of α-phase crystalline films of cobalt phthalocyanine (CoPc) grown on Au(111) is investigated by using angle-resolved photoemission spectroscopy (ARPES) with synchrotron radiation. The photo-induced change in the ARPES peaks is noticed in shape and energy of the highest occupied molecular orbital (HOMO, C 2p) and HOMO-1 (Co 3d) of CoPc, and is misleading the interpretation of the electronic properties of CoPc films. From the damage-free normal-emission ARPES measurement, the clear valence-band dispersion has been first observed, showing that orbital-specific behaviors are attributable to the interplay of the intermolecular π-π and π-d interactions. The HOMO band dispersionmore » of 0.1 eV gives the lower limit of the hole mobility for α-CoPc of 28.9 cm{sup 2} V{sup −1} s{sup −1} at 15 K. The non-dispersive character of the split HOMO-1 bands indicates that the localization of the spin state is a possible origin of the antiferromagnetism.« less

Excitonic and band-band transitions of Cu2ZnSiS4 determined from reflectivity spectra

NASA Astrophysics Data System (ADS)

Guc, M.; Levcenko, S.; Dermenji, L.; Gurieva, G.; Schorr, S.; Syrbu, N. N.; Arushanov, E.

2014-07-01

Exciton spectra of Cu2ZnSiS4 single crystals are investigated by reflection spectroscopy at 10 and 300 K for light polarized perpendicular (E⊥c) and parallel (E∥c) to the optical axis. The parameters of the excitons and dielectric constant are determined. The free carriers effective masses have been estimated. The room temperature reflectivity spectra at photon energies higher than the fundamental band gap in the polarization Е⊥с and E∥с were measured and related to the electronic band structure of Cu2ZnSiS4.

Nitrogen-Induced Perturbation of the Valence Band States in GaP1-xNx Alloys

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

Dudiy, S. V.; Zunger, A.; Felici, M.

2006-01-01

The effects of diluted nitrogen impurities on the valence- and conduction-band states of GaP{sub 1-x}N{sub x} have been predicted and measured experimentally. The calculation uses state-of-the-art atomistic modeling: we use large supercells with screened pseudopotentials and consider several random realizations of the nitrogen configurations. These calculations agree with photoluminescence excitation (PLE) measurements performed for nitrogen concentrations x up to 0.035 and photon energies up to 1 eV above the GaP optical-absorption edge, as well as with published ellipsometry data. In particular, a predicted nitrogen-induced buildup of the L character near the valence- and conduction-band edges accounts for the surprising broad-absorptionmore » plateau observed in PLE between the X{sub 1c} and the {Lambda}{sub 1c} critical points of GaP. Moreover, theory accounts quantitatively for the downward bowing of the indirect conduction-band edge and for the upward bowing of the direct transition with increasing nitrogen concentration. We review some of the controversies in the literature regarding the shifts in the conduction band with composition, and conclude that measured results at ultralow N concentration cannot be used to judge behavior at a higher concentration. In particular, we find that at the high concentrations of nitrogen studied here ({approx}1%) the conduction-band edge (CBE) is a hybridized state made from the original GaP X{sub 1c} band-edge state plus all cluster states. In this limit, the CBE plunges down in energy as the N concentration increases, in quantitative agreement with the measurements reported here. However, at ultralow nitrogen concentrations (<0.1%), the CBE is the nearly unperturbed host X{sub 1c}, which does not sense the nitrogen cluster levels. Thus, this state does not move energetically as nitrogen is added and stays pinned in energy, in agreement with experimental results.« less

NLTE ANALYSIS OF HIGH-RESOLUTION H -BAND SPECTRA. I. NEUTRAL SILICON

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

Zhang, Junbo; Shi, Jianrong; Liu, Chao

We investigated the reliability of our silicon atomic model and the influence of non-local thermodynamical equilibrium (NLTE) on the formation of neutral silicon (Si i) lines in the near-infrared (near-IR) H -band. We derived the differential Si abundances for 13 sample stars with high-resolution H -band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE), as well as from optical spectra, both under local thermodynamical equilibrium (LTE) and NLTE conditions. We found that the differences between the Si abundances derived from the H -band and from optical lines for the same stars are less than 0.1 dex when themore » NLTE effects are included, and that NLTE reduces the line-to-line scatter in the H -band spectra for most sample stars. These results suggest that our Si atomic model is appropriate for studying the formation of H -band Si lines. Our calculations show that the NLTE corrections of the Si i H -band lines are negative, i.e., the final Si abundances will be overestimated in LTE. The corrections for strong lines depend on surface gravity, and tend to be larger for giants, reaching ∼−0.2 dex in our sample, and up to ∼−0.4 dex in extreme cases of APOGEE targets. Thus, the NLTE effects should be included in deriving silicon abundances from H -band Si i lines, especially for the cases where only strong lines are available.« less

Interplay of Coulomb interactions and disorder in three-dimensional quadratic band crossings without time-reversal symmetry and with unequal masses for conduction and valence bands

NASA Astrophysics Data System (ADS)

Mandal, Ipsita; Nandkishore, Rahul M.

2018-03-01

Coulomb interactions famously drive three-dimensional quadratic band crossing semimetals into a non-Fermi liquid phase of matter. In a previous work [Nandkishore and Parameswaran, Phys. Rev. B 95, 205106 (2017), 10.1103/PhysRevB.95.205106], the effect of disorder on this non-Fermi liquid phase was investigated, assuming that the band structure was isotropic, assuming that the conduction and valence bands had the same band mass, and assuming that the disorder preserved exact time-reversal symmetry and statistical isotropy. It was shown that the non-Fermi liquid fixed point is unstable to disorder and that a runaway flow to strong disorder occurs. In this paper, we extend that analysis by relaxing the assumption of time-reversal symmetry and allowing the electron and hole masses to differ (but continuing to assume isotropy of the low energy band structure). We first incorporate time-reversal symmetry breaking disorder and demonstrate that there do not appear any new fixed points. Moreover, while the system continues to flow to strong disorder, time-reversal-symmetry-breaking disorder grows asymptotically more slowly than time-reversal-symmetry-preserving disorder, which we therefore expect should dominate the strong-coupling phase. We then allow for unequal electron and hole masses. We show that whereas asymmetry in the two masses is irrelevant in the clean system, it is relevant in the presence of disorder, such that the `effective masses' of the conduction and valence bands should become sharply distinct in the low-energy limit. We calculate the RG flow equations for the disordered interacting system with unequal band masses and demonstrate that the problem exhibits a runaway flow to strong disorder. Along the runaway flow, time-reversal-symmetry-preserving disorder grows asymptotically more rapidly than both time-reversal-symmetry-breaking disorder and the Coulomb interaction.

Hard X-ray photoelectron spectroscopy of Li{sub x}Ni{sub 1−x}O epitaxial thin films with a high lithium content

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

Kumara, L. S. R., E-mail: KUMARA.Rosantha@nims.go.jp; Yang, Anli; Sakata, Osami, E-mail: SAKATA.Osami@nims.go.jp

2014-07-28

The core-level and valence-band electronic structures of Li{sub x}Ni{sub 1−x}O epitaxial thin films with x = 0, 0.27, and 0.48 were studied by hard X-ray photoelectron spectroscopy. A double peak structure, consisting of a main peak and a shoulder peak, and a satellite structure were observed in the Ni 2p{sub 3/2} core-level spectra. The intensity ratio of the shoulder to main peak in this double peak structure increased with increasing lithium content in Li{sub x}Ni{sub 1−x}O. This lithium doping dependence of the Ni 2p{sub 3/2} core-level spectra was investigated using an extended cluster model, which included the Zhang–Rice (ZR) doubletmore » bound states arising from a competition between O 2p – Ni 3d hybridization and the Ni on-site Coulomb interaction. The results indicated that the change in the intensity ratio in the main peak is because of a reduction in the ZR doublet bound states from lithium substitutions. This strongly suggests that holes compensating Li doping in Li{sub x}Ni{sub 1−x}O are of primarily ZR character.« less

Band bending at ferroelectric surfaces and interfaces investigated by x-ray photoelectron spectroscopy

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

Apostol, Nicoleta Georgiana, E-mail: nicoleta.apostol@infim.ro

2014-11-24

This work reports on the use of X-ray photoelectron spectroscopy to quantify band bending at ferroelectric free surfaces and at their interfaces with metals. Surfaces exhibiting out-of-plane ferroelectric polarization are characterized by a band bending, due to the formation of a dipole layer at the surface, composed by the uncompensated polarization charges (due to ionic displacement) and to the depolarization charge sheet of opposite sign, composed by mobile charge carriers, which migrate near surface, owing to the depolarization electric field. To this surface band bending due to out-of-plane polarization states, metal-semiconductor Schottky barriers must be considered additionally when ferroelectrics aremore » covered by metal layers. It is found that the net band bending is not always an algebraic sum of the two effects discussed above, since sometimes the metal is able to provide additional charge carriers, which are able to fully compensate the surface charge of the ferroelectric, up to the vanishing of the ferroelectric band bending. The two cases which will be discussed in more detail are Au and Cu deposited by molecular beam epitaxy on PbZr{sub 0.2}Ti{sub 0.8}O{sub 3}(001) single crystal thin layers, prepared by pulsed laser deposition. Gold forms unconnected nanoparticles, and their effect on the band bending is the apparition of a Schottky band bending additional to the band bending due to the out-of-plane polarization. Copper, starting with a given thickness, forms continuous metal layers connected to the ground of the system, and provide electrons in sufficient quantity to compensate the band bending due to the out-of-plane polarization.« less

Photoelectron spectroscopy of the 6-azauracil anion.

PubMed

Chen, Jing; Buonaugurio, Angela; Dolgounitcheva, Olga; Zakrzewski, V G; Bowen, Kit H; Ortiz, J V

2013-02-14

We report the photoelectron spectrum of the 6-azauracil anion. The spectrum is dominated by a broad band exhibiting a maximum at an electron binding energy (EBE) of 1.2 eV. This spectral pattern is indicative of a valence anion. Our calculations were carried out using ab initio electron propagator and other many-body methods. Comparison of the anion and corresponding neutral of 6-azauracil with those of uracil shows that substituting a nitrogen atom for C-H at the C6 position of uracil gives rise to significant changes in the electronic structure of 6-azauracil versus that of uracil. The adiabatic electron affinity (AEA) of the canonical 6-azauracil tautomer is substantially larger than that of canonical uracil. Among the five tautomeric, 6-azauracil anions studied computationally, the canonical structure was found to be the most stable. The vertical detachment energies (VDE) of the canonical, valence-bound anion of 6-azauracil and its closest "very-rare" tautomer have been calculated. Electron propagator calculations on the canonical anion yield a VDE value that is in close agreement with the experimentally determined VDE value of 1.2 eV. The AEA value of 6-azauracil, assessed at the CCSD(T) level of theory to be 0.5 eV, corresponds with the EBE value of the onset of the experimental spectrum.

Photonic band gap spectra in Octonacci metamaterial quasicrystals

NASA Astrophysics Data System (ADS)

Brandão, E. R.; Vasconcelos, M. S.; Albuquerque, E. L.; Fulco, U. L.

2017-02-01

In this work we study theoretically the photonic band gap spectra for a one-dimensional quasicrystal made up of SiO2 (layer A) and a metamaterial (layer B) organized following the Octonacci sequence, where its nth-stage Sn is given by the inflation rule Sn =Sn - 1Sn - 2Sn - 1 for n ≥ 3 , with initial conditions S1 = A and S2 = B . The metamaterial is characterized by a frequency dependent electric permittivity ε(ω) and magnetic permeability μ(ω) . The polariton dispersion relation is obtained analytically by employing a theoretical calculation based on a transfer-matrix approach. A quantitative analysis of the spectra is then discussed, stressing the distribution of the allowed photonic band widths for high generations of the Octonacci structure, which depict a self-similar scaling property behavior, with a power law depending on the common in-plane wavevector kx .

Valence-band structure of the ferromagnetic semiconductor GaMnAs studied by spin-dependent resonant tunneling spectroscopy.

PubMed

Ohya, Shinobu; Muneta, Iriya; Hai, Pham Nam; Tanaka, Masaaki

2010-04-23

The valence-band structure and the Fermi level (E(F)) position of ferromagnetic-semiconductor GaMnAs are quantitatively investigated by electrically detecting the resonant tunneling levels of a GaMnAs quantum well (QW) in double-barrier heterostructures. The resonant level from the heavy-hole first state is clearly observed in the metallic GaMnAs QW, indicating that holes have a high coherency and that E(F) exists in the band gap. Clear enhancement of tunnel magnetoresistance induced by resonant tunneling is demonstrated in these double-barrier heterostructures.

Slow photoelectron imaging spectroscopy of CCO- and CCS-.

PubMed

Garand, Etienne; Yacovitch, Tara I; Neumark, Daniel M

2008-08-21

High-resolution photodetachment spectra of CCO(-) and CCS(-) using slow photoelectron velocity-map imaging spectroscopy are reported. Well-resolved transitions to the neutral X (3)Sigma(-), a (1)Delta, b (1)Sigma(+), and A (3)Pi states are seen for both species. The electron affinities of CCO and CCS are determined to be 2.3107+/-0.0006 and 2.7475+/-0.0006 eV, respectively, and precise term energies for the a (1)Delta, b (1)Sigma(+), and A (3)Pi excited states are also determined. The two low-lying singlet states of CCS are observed for the first time, as are several vibronic transitions within the four bands. Analysis of hot bands finds the spin-orbit orbit splitting in the X (2)Pi ground state of CCO(-) and CCS(-) to be 61 and 195 cm(-1), respectively.

Revisiting the origin of satellites in core-level photoemission of transparent conducting oxides: The case of n -doped SnO2

NASA Astrophysics Data System (ADS)

Borgatti, Francesco; Berger, J. A.; Céolin, Denis; Zhou, Jianqiang Sky; Kas, Joshua J.; Guzzo, Matteo; McConville, C. F.; Offi, Francesco; Panaccione, Giancarlo; Regoutz, Anna; Payne, David J.; Rueff, Jean-Pascal; Bierwagen, Oliver; White, Mark E.; Speck, James S.; Gatti, Matteo; Egdell, Russell G.

2018-04-01

The longstanding problem of interpretation of satellite structures in core-level photoemission spectra of metallic systems with a low density of conduction electrons is addressed using the specific example of Sb-doped SnO2. Comparison of ab initio many-body calculations with experimental hard x-ray photoemission spectra of the Sn 4 d states shows that strong satellites are produced by coupling of the Sn core hole to the plasma oscillations of the free electrons introduced by doping. Within the same theoretical framework, spectral changes of the valence band spectra are also related to dynamical screening effects. These results demonstrate that, for the interpretation of electron correlation features in the core-level photoelectron spectra of such narrow-band materials, going beyond the homogeneous electron gas electron-plasmon coupling model is essential.

Study of space charge layer in silver bromide microcrystals by means of ultraviolet photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Inami, Yoshiyasu

2000-09-01

Ultraviolet photoelectron spectroscopy has been successfully used to measure the heights of the tops of the valence bands of the surfaces of AgBr layers on Ag substrates for the verification of the space charge layer model. According to this model, the positive space charge layer (composed of negative charges with excess negative kink sites on the surface and corresponding positive charges with interstitial silver ions in the interior) is formed in silver halides, causing the difference in the electronic energy levels between their surface and interior. The depression of the positive space charge layer of AgBr caused by such adsorbates as photographic stabilizers and antifoggants was estimated from the decrease in the ionic conductivity of cubic AgBr microcrystals by the adsorbates. It was confirmed by the decrease in the heights of the tops of the valence bands of the surfaces of AgBr layers caused by the adsorbates in the presence of thin gelatin membranes on their surfaces. This result provided the explanation for the fact that the adsorbates increased the number of the microcrystals which formed latent image centers on the surface and decreased the number of the microcrystals, which formed latent image centers in the interior.

Electron Phonon Coupling versus Photoelectron Energy Loss at the Origin of Replica Bands in Photoemission of FeSe on SrTiO3

NASA Astrophysics Data System (ADS)

Li, Fengmiao; Sawatzky, George A.

2018-06-01

The recent observation of replica bands in single-layer FeSe /SrTiO3 by angle-resolved photoemission spectroscopy (ARPES) has triggered intense discussions concerning the potential influence of the FeSe electrons coupling with substrate phonons on the superconducting transition temperature. Here we provide strong evidence that the replica bands observed in the single-layer FeSe /SrTiO3 system and several other cases are largely due to the energy loss processes of the escaping photoelectron, resulted from the well-known strong coupling of external propagating electrons to Fuchs-Kliewer surface phonons in ionic materials in general. The photoelectron energy loss in ARPES on single-layer FeSe /SrTiO3 is calculated using the demonstrated successful semiclassical dielectric theory in describing low energy electron energy loss spectroscopy of ionic insulators. Our result shows that the observed replica bands are mostly a result of extrinsic photoelectron energy loss and not a result of the electron phonon interaction of the Fe d electrons with the substrate phonons. The strong enhancement of the superconducting transition temperature in these monolayers remains an open question.

Band bending at magnetic Ni/Ge(001) interface investigated by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Bocîrnea, Amelia Elena; Tănase, Liviu Cristian; Costescu, Ruxandra Maria; Apostol, Nicoleta Georgiana; Teodorescu, Cristian Mihail

2017-12-01

We report the molecular beam epitaxy growth of Ni on a clean Ge(001) surface with an intermediate NiGe layer forming at the interface at room temperature. The crystallinity of the substrate is lost after the deposition of more than 2 Ni monolayers. The Schottky barrier formation is investigated by X-ray photoelectron spectroscopy. The method allows us to infer a 0.39-0.45 eV band bending at the interface between the compound and Ge(001). Magneto-optical Kerr effect measurements were conclusive in detecting the ferromagnetic ordering of Ni outermost layers.

Temperature-dependent optical band gap of the metastable zinc-blende structure [beta]-GaN

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

Ramirez-Flores, G.; Navarro-Contreras, H.; Lastras-Martinez, A.

1994-09-15

The temperature-dependent (10--300 K) optical band gap [ital E][sub 0]([ital T]) of the epitaxial metastable zinc-blende-structure [beta]-GaN(001)4[times]1 has been determined by modulated photoreflectance and used to interpret low-temperature photoluminescence spectra. [ital E][sub 0] in [beta]-GaN was found to vary from 3.302[plus minus]0.004 eV at 10 K to 3.231[plus minus]0.008 eV at 300 K with a temperature dependence given by [ital E][sub 0]([ital T]) =3.302--6.697[times]10[sup [minus]4][ital T][sup 2]/([ital T]+600) eV. The spin-orbit splitting [Delta][sub 0] in the valence band was determined to be 17[plus minus]1 meV. The oscillations in the photoreflectance spectra were very sharp with a broadening parameter [Gamma] ofmore » only 10 meV at 10 K. The dominant transition observed in temperature-dependent photoluminescence was attributed to radiative recombination between a shallow donor, at [congruent]11 meV below the conduction-band edge and the valence band.« less

Conduction- and Valence-Band Energies in Bulk InAs(1-x)Sb(x) and Type II InAs(1-x) Sb(x)/InAs Strained-Layer Superlattices

DTIC Science & Technology

2013-03-08

tions in the studied SLS structures . The fit of the dependence of the valence- band energy of unstrained InAs1!xSbx on the composition x with a... band . STRUCTURES Bulk InAsSb epilayers on metamorphic buffers and InAsSb/InAs strained-layer superlattices (SLS) were grown on GaSb substrates by solid...meV in InAs and Ev = 0 meV in InSb. For InAsSb with 22.5% Sb grown on GaSb , an unstrained valence- band energy of Ev = !457 meV was obtained. For the

Absolute band structure determination on naturally occurring rutile with complex chemistry: Implications for mineral photocatalysis on both Earth and Mars

NASA Astrophysics Data System (ADS)

Li, Yan; Xu, Xiaoming; Li, Yanzhang; Ding, Cong; Wu, Jing; Lu, Anhuai; Ding, Hongrui; Qin, Shan; Wang, Changqiu

2018-05-01

Rutile is the most common and stable form of TiO2 that ubiquitously existing on Earth and other terrestrial planets like Mars. Semiconducting mineral such as rutile-based photoredox reactions have been considered to play important roles in geological times. However, due to the inherent complexity in chemistry, the precision determination on band structure of natural rutile and the theoretical explanation on its solar-driven photochemistry have been hardly seen yet. Considering the multiple minor and trace elements in natural rutile, we firstly obtained the single-crystal crystallography, mineralogical composition and defects characteristic of the rutile sample by using both powder and single crystal X-ray diffraction, electron microprobe analysis and X-ray photoelectron spectroscopy. Then, the band gap was accurately determined by synchrotron-based O K-edge X-ray absorption and emission spectra, which was firstly applied to natural rutile due to its robustness on compositions and defects. The absolute band edges of the rutile sample was calculated by considering the electronegativity of the atoms, band gap and point of zero charge. Besides, after detecting the defect energy levels by photoluminescence spectra, we drew the schematic band structure of natural rutile. The band gap (2.7 eV) of natural rutile was narrower than that of synthetic rutile (3.0 eV), and the conduction and valence band edges of natural rutile at pH = pHPZC were determined to be -0.04 V and 2.66 V (vs. NHE), respectively. The defect energy levels located at nearly the middle position of the forbidden band. Further, we used theoretical calculations to verify the isomorphous substitution of Fe and V for Ti gave rise to the distortion of TiO6 octahedron and created vacancy defects in natural rutile. Based on density functional theory, the narrowed band gap was interpreted to the contribution of Fe-3d and V-3d orbits, and the defect energy state was formed by hybridization of O-2p and Fe/V/Ti-3d

Electronic structure of the heavy-fermion caged compound Ce 3 Pd 20 X 6 ( X = Si, Ge ) studied by density functional theory and photoelectron spectroscopy

DOE PAGES

Yamaoka, Hitoshi; Schwier, Eike F.; Arita, Masashi; ...

2015-03-30

The electronic structure of Ce₃Pd₂₀X₆ (X = Si, Ge) has been studied using detailed density functional theory (DFT) calculations and high-resolution photoelectron spectroscopy (PES) measurements. The orbital decomposition of the electronic structure by DFT calculations indicates that Ce atoms at the (8c) site surrounded by 16 Pd atoms have a more localized nature and a tendency to be magnetic. Ce atoms in the (4a) site surrounded by 12 Pd and 6 X atoms, on the other, show only a negligible magnetic moment. In the photoemission valence-band spectra we observe a strong f⁰ (Ce⁴⁺) component with a small fraction of f¹more » (Ce³⁺) component. The spectral weight of f¹ component near the Fermi level Ce₃Pd₂₀Si₆ is stronger than that for Ce₃Pd₂₀Ge₆ at the 4d-4f resonance, suggesting stronger c-f hybridization in the former. This may hint to the origin of the large electronic specific coefficient of Ce₃Pd₂₀Si₆ compared to Ce₃Pd₂₀Ge₆.« less

Electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations of ethyl acetate

NASA Astrophysics Data System (ADS)

Śmialek, Malgorzata A.; Łabuda, Marta; Guthmuller, Julien; Hubin-Franskin, Marie-Jeanne; Delwiche, Jacques; Hoffmann, Søren Vrønning; Jones, Nykola C.; Mason, Nigel J.; Limão-Vieira, Paulo

2016-06-01

The high-resolution vacuum ultraviolet photoabsorption spectrum of ethyl acetate, C4H8O2, is presented over the energy range 4.5-10.7 eV (275.5-116.0 nm). Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Also, the photoabsorption cross sections have been used to calculate the photolysis lifetime of this ester in the upper stratosphere (20-50 km). Calculations have also been carried out to determine the ionisation energies and fine structure of the lowest ionic state of ethyl acetate and are compared with a newly recorded photoelectron spectrum (from 9.5 to 16.7 eV). Vibrational structure is observed in the first photoelectron band of this molecule for the first time.

Valence-band offsets of CoTiSb/In0.53Ga0.47As and CoTiSb/In0.52Al0.48As heterojunctions

NASA Astrophysics Data System (ADS)

Harrington, S. D.; Sharan, A.; Rice, A. D.; Logan, J. A.; McFadden, A. P.; Pendharkar, M.; Pennachio, D. J.; Wilson, N. S.; Gui, Z.; Janotti, A.; Palmstrøm, C. J.

2017-08-01

The valence-band offsets, ΔEv, between semiconducting half-Heusler compound CoTiSb and lattice-matched III-V In0.53Ga0.47As and In0.52Al0.48As heterojunction interfaces have been measured using X-ray photoemission spectroscopy (XPS). These interfaces were formed using molecular beam epitaxy and transferred in situ for XPS measurements. Valence-band offsets of 0.30 eV and 0.58 eV were measured for CoTiSb/In0.53Ga0.47As and CoTiSb/In0.52Al0.48As, respectively. By combining these measurements with previously reported XPS ΔEv (In0.53Ga0.47As/In0.52Al0.48As) data, the results suggest that band offset transitivity is satisfied. In addition, the film growth order of the interface between CoTiSb and In0.53Ga0.47As is explored and does not seem to affect the band offsets. Finally, the band alignments of CoTiSb with GaAs, AlAs, and InAs are calculated using the density function theory with the HSE06 hybrid functional and applied to predict the band alignment of CoTiSb with In0.53Ga0.47As and In0.52Al0.48As. Good agreement is found between the calculated valence-band offsets and those determined from XPS.

Valence-band offsets of CoTiSb/In 0.53Ga 0.47As and CoTiSb/In 0.52Al 0.48As heterojunctions

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

Harrington, S. D.; Sharan, A.; Rice, A. D.

2017-08-11

The valence-band offsets, ΔE v, between semiconducting half-Heusler compound CoTiSb and lattice-matched III-V In 0.53Ga 0.47As and In 0.52Al 0.48As heterojunction interfaces have been measured using X-ray photoemission spectroscopy (XPS). These interfaces were formed using molecular beam epitaxy and transferred in situ for XPS measurements. Valence-band offsets of 0.30 eV and 0.58 eV were measured for CoTiSb/In 0.53Ga 0.47As and CoTiSb/In 0.52Al 0.48As, respectively. By combining these measurements with previously reported XPS ΔE v (In 0.53Ga 0.47As/In 0.52Al 0.48As) data, the results suggest that band offset transitivity is satisfied. In addition, the film growth order of the interface between CoTiSbmore » and In 0.53Ga 0.47As is explored and does not seem to affect the band offsets. Finally, the band alignments of CoTiSb with GaAs, AlAs, and InAs are calculated using the density function theory with the HSE06 hybrid functional and applied to predict the band alignment of CoTiSb with In 0.53Ga 0.47As and In 0.52Al 0.48As. As a result, good agreement is found between the calculated valence-band offsets and those determined from XPS.« less

Calculation of the X-Ray emission K and L 2,3 bands of metallic magnesium and aluminum with allowance for multielectron effects

NASA Astrophysics Data System (ADS)

Ovcharenko, R. E.; Tupitsyn, I. I.; Savinov, E. P.; Voloshina, E. N.; Dedkov, Yu. S.; Shulakov, A. S.

2014-01-01

A procedure is proposed to calculate the shape of the characteristic X-ray emission bands of metals with allowance for multielectron effects. The effects of the dynamic screening of a core vacancy by conduction electrons and the Auger effect in the valence band are taken into account. The dynamic screening of a core vacancy, which is known to be called the MND (Mahan-Nozeieres-De Dominics) effect, is taken into account by an ab initio band calculation of crystals using the PAW (projected augmented waves) method. The Auger effect is taken into account by a semiempirical method using the approximation of a quadratic dependence of the level width in the valence band on the difference between the level energy and the Fermi energy. The proposed calculation procedure is used to describe the X-ray emission K and L 2,3 bands of metallic magnesium and aluminum crystals. The calculated spectra agree well with the experimental bands both near the Fermi level and in the low-energy part of the spectra in all cases.

Quantitative determination of band distortions in diamond attenuated total reflectance infrared spectra.

PubMed

Boulet-Audet, Maxime; Buffeteau, Thierry; Boudreault, Simon; Daugey, Nicolas; Pézolet, Michel

2010-06-24

Due to its unmatched hardness and chemical inertia, diamond offers many advantages over other materials for extreme conditions and routine analysis by attenuated total reflection (ATR) infrared spectroscopy. Its low refractive index can offer up to a 6-fold absorbance increase compared to germanium. Unfortunately, it also results for strong bands in spectral distortions compared to transmission experiments. The aim of this paper is to present a methodological approach to determine quantitatively the degree of the spectral distortions in ATR spectra. This approach requires the determination of the optical constants (refractive index and extinction coefficient) of the investigated sample. As a typical example, the optical constants of the fibroin protein of the silk worm Bombyx mori have been determined from the polarized ATR spectra obtained using both diamond and germanium internal reflection elements. The positions found for the amide I band by germanium and diamond ATR are respectively 6 and 17 cm(-1) lower than the true value dtermined from the k(nu) spectrum, which is calculated to be 1659 cm(-1). To determine quantitatively the effect of relevant parameters such as the film thickness and the protein concentration, various spectral simulations have also been performed. The use of a thinner film probed by light polarized in the plane of incidence and diluting the protein sample can help in obtaining ATR spectra that are closer to their transmittance counterparts. To extend this study to any system, the ATR distortion amplitude has been evaluated using spectral simulations performed for bands of various intensities and widths. From these simulations, a simple empirical relationship has been found to estimate the band shift from the experimental band height and width that could be of practical use for ATR users. This paper shows that the determination of optical constants provides an efficient way to recover the true spectrum shape and band frequencies of

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.

Comparative study on Ga1-xZnxN1-yOy oxynitride synthesized by different techniques for application in photocatalytic hydrogen production

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Baskar, K.; Singh, Shubra

2017-06-01

Hydrogen evolution by overall water splitting has emerged as a potential method for green energy generation due to the introduction of highly efficient photocatalysts active under visible region of spectra. In the present work, we focus on a comparative study of the properties of Ga1-xZnxN1-yOy oxynitride samples synthesized by two techniques and their effect on the sample properties. The samples were prepared by both traditional nitridation technique and solution combustion method. Room temperature photoluminescence studies revealed the introduction of additional energy levels above the valence band which in turns broadens the valence band and subsequently reduces the band gap. The band gap narrowing was further confirmed using diffuse reflectance spectroscopy and Valence band X-ray photoelectron spectroscopy (VB-XPS). It was also realized from VB XPS that the reduction of band gap in both the samples was due to upshift of valence band without affecting the conduction band. The presence of disorder activated modes in the samples was examined using temperature dependent Raman spectroscopy. In this work we corroborate the theoretical prediction reported by Al-Jassim et. al that the bandgap narrowing mechanism in ZnO rich solid solution and GaN rich solid solution is asymmetric and a significant bandgap reduction could be observed for ZnO rich solid solution than GaN rich.

Visible sub-band gap photoelectron emission from nitrogen doped and undoped polycrystalline diamond films

NASA Astrophysics Data System (ADS)

Elfimchev, S.; Chandran, M.; Akhvlediani, R.; Hoffman, A.

2017-07-01

In this study the origin of visible sub-band gap photoelectron emission (PEE) from polycrystalline diamond films is investigated. The PEE yields as a function of temperature were studied in the wavelengths range of 360-520 nm. Based on the comparison of electron emission yields from diamond films deposited on silicon and molybdenum substrates, with different thicknesses and nitrogen doping levels, we suggested that photoelectrons are generated from nitrogen related centers in diamond. Our results show that diamond film thickness and substrate material have no significant influence on the PEE yield. We found that nanocrystalline diamond films have low electron emission yields, compared to microcrystalline diamond, due to the presence of high amount of defects in the former, which trap excited electrons before escaping into the vacuum. However, the low PEE yield of nanocrystalline diamond films was found to increase with temperature. The phenomenon was explained by the trap assisted photon enhanced thermionic emission (ta-PETE) model. According to the ta-PETE model, photoelectrons are trapped by shallow traps, followed by thermal excitation at elevated temperatures and escape into the vacuum. Activation energies of trap levels were estimated for undoped nanocrystalline, undoped microcrystalline and N-doped diamond films using the Richardson-Dushman equation, which gives 0.13, 0.39 and 0.04 eV, respectively. Such low activation energy of trap levels makes the ta-PETE process very effective at elevated temperatures.

Occupied and unoccupied electronic structures of an L-cysteine film studied by core-absorption and resonant photoelectron spectroscopies

NASA Astrophysics Data System (ADS)

Kamada, M.; Hideshima, T.; Azuma, J.; Yamamoto, I.; Imamura, M.; Takahashi, K.

2016-04-01

Unoccupied and occupied electronic structures of an L-cysteine film have been studied by absorption and resonant photoelectron spectroscopies. Core absorptions at S-L, C-K, N-K, and O-K levels indicate that the lower unoccupied states are predominantly composed of oxygen-2p, carbon-2p, and sulfur-4s+3d orbitals, while higher unoccupied states may be attributed dominantly to nitrogen-np (n ≥ 3), oxygen-np (n ≥ 3), and sulfur-ns+md (n ≥ 4, m ≥ 3) orbitals. Resonant photoelectron spectra at S-L23 and O-K levels indicate that the highest occupied state is originated from sulfur-3sp orbitals, while oxygen-2sp orbitals contribute to the deeper valence states. The delocalization lifetimes of the oxygen-1s and sulfur-2p excited states are estimated from a core-hole clock method to be about 9 ± 1 and 125 ± 25 fs, respectively.

Occupied and unoccupied electronic structures of an L-cysteine film studied by core-absorption and resonant photoelectron spectroscopies

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

Kamada, M., E-mail: kamada@cc.saga-u.ac.jp; Hideshima, T.; Azuma, J.

2016-04-15

Unoccupied and occupied electronic structures of an L-cysteine film have been studied by absorption and resonant photoelectron spectroscopies. Core absorptions at S-L, C-K, N-K, and O-K levels indicate that the lower unoccupied states are predominantly composed of oxygen-2p, carbon-2p, and sulfur-4s+3d orbitals, while higher unoccupied states may be attributed dominantly to nitrogen-np (n ≥ 3), oxygen-np (n ≥ 3), and sulfur-ns+md (n ≥ 4,  m ≥ 3) orbitals. Resonant photoelectron spectra at S-L{sub 23} and O-K levels indicate that the highest occupied state is originated from sulfur-3sp orbitals, while oxygen-2sp orbitals contribute to the deeper valence states. The delocalization lifetimesmore » of the oxygen-1s and sulfur-2p excited states are estimated from a core-hole clock method to be about 9 ± 1 and 125 ± 25 fs, respectively.« less

High Pressure Oxygen A-Band Spectra

NASA Astrophysics Data System (ADS)

Drouin, Brian; Sung, Keeyoon; Yu, Shanshan; Lunny, Elizabeth M.; Bui, Thinh Quoc; Okumura, Mitchio; Rupasinghe, Priyanka; Bray, Caitlin; Long, David A.; Hodges, Joseph; Robichaud, David; Benner, D. Chris; Devi, V. Malathy; Hoo, Jiajun

2015-06-01

Composition measurements from remote sensing platforms require knowledge of air mass to better than the desired precision of the composition. Oxygen spectra allow determination of air mass since the mixing ratio of oxygen is fixed. The OCO-2 mission is currently retrieving carbon dioxide concentration using the oxygen A-band for air mass normalization. The 0.25% accuracy desired for the carbon dioxide concentration has pushed the state-of-the-art for oxygen spectroscopy. To produce atmospheric pressure A-band cross-sections with this accuracy requires a sophisticated line-shape model (Galatry or Speed-Dependent) with line mixing (LM) and collision induced absorption (CIA). Models of each of these phenomena exist, but an integrated self-consistent model must be developed to ensure accuracy. This presentation will describe the ongoing effort to parameterize these phenomena on a representative data set created from complementary experimental techniques. The techniques include Fourier transform spectroscopy (FTS), photo-acoustic spectroscopy (PAS) and cavity ring-down spectroscopy (CRDS). CRDS data allow long-pathlength measurements with absolute intensities, providing lineshape information as well as LM and CIA, however the subtleties of the lineshape are diminished in the saturated line-centers. Conversely, the short paths and large dynamic range of the PAS data allow the full lineshape to be discerned, but with an arbitrary intensity axis. Finally, the FTS data provides intermediate paths and consistency across a broad pressure range. These spectra are all modeled with the Labfit software using first the spectral line database HITRAN, and then model values are adjusted and fitted for better agreement with the data.

Real-time observation of intramolecular proton transfer in the electronic ground state of chloromalonaldehyde: an ab initio study of time-resolved photoelectron spectra.

PubMed

do N Varella, Márcio T; Arasaki, Yasuki; Ushiyama, Hiroshi; Takatsuka, Kazuo; Wang, Kwanghsi; McKoy, Vincent

2007-02-07

The authors report on studies of time-resolved photoelectron spectra of intramolecular proton transfer in the ground state of chloromalonaldehyde, employing ab initio photoionization matrix elements and effective potential surfaces of reduced dimensionality, wherein the couplings of proton motion to the other molecular vibrational modes are embedded by averaging over classical trajectories. In the simulations, population is transferred from the vibrational ground state to vibrationally hot wave packets by pumping to an excited electronic state and dumping with a time-delayed pulse. These pump-dump-probe simulations demonstrate that the time-resolved photoelectron spectra track proton transfer in the electronic ground state well and, furthermore, that the geometry dependence of the matrix elements enhances the tracking compared with signals obtained with the Condon approximation. Photoelectron kinetic energy distributions arising from wave packets localized in different basins are also distinguishable and could be understood, as expected, on the basis of the strength of the optical couplings in different regions of the ground state potential surface and the Franck-Condon overlaps of the ground state wave packets with the vibrational eigenstates of the ion potential surface.

Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

NASA Astrophysics Data System (ADS)

Sugiura, Chikara

1991-08-01

The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

Valence electronic properties of porphyrin derivatives.

PubMed

Stenuit, G; Castellarin-Cudia, C; Plekan, O; Feyer, V; Prince, K C; Goldoni, A; Umari, P

2010-09-28

We present a combined experimental and theoretical investigation of the valence electronic structure of porphyrin-derived molecules. The valence photoemission spectra of the free-base tetraphenylporphyrin and of the octaethylporphyrin molecule were measured using synchrotron radiation and compared with theoretical spectra calculated using the GW method and the density-functional method within the generalized gradient approximation. Only the GW results could reproduce the experimental data. We found that the contribution to the orbital energies due to electronic correlations has the same linear behavior in both molecules, with larger deviations in the vicinity of the HOMO level. This shows the importance of adequate treatment of electronic correlations in these organic systems.

Isobutyl acetate: electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations

NASA Astrophysics Data System (ADS)

Śmiałek, Malgorzata A.; Łabuda, Marta; Hubin-Franskin, Marie-Jeanne; Delwiche, Jacques; Hoffmann, Søren Vrønning; Jones, Nykola C.; Mason, Nigel J.; Limão-Vieira, Paulo

2017-05-01

The high-resolution vacuum ultraviolet photoabsorption spectrum of isobutyl acetate, C6H12O2, is presented here and was measured over the energy range 4.3-10.8 eV (290-115 nm). Valence and Rydberg transitions with their associated vibronic series have been observed in the photoabsorption spectrum and are assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. The measured photoabsorption cross sections have been used to calculate the photolysis lifetime of this ester in the Earth's upper atmosphere (20-50 km). Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of isobutyl acetate and are compared with a photoelectron spectrum (from 9.5 to 16.7 eV), recorded for the first time. Vibrational structure is observed in the first photoelectron band of this molecule. Contribution to the Topical Issue: "Dynamics of Systems at the Nanoscale", edited by Andrey Solov'yov and Andrei Korol.

Theoretical Analysis of Photoelectron Spectra of Pure and Mixed Metal Clusters: Disentangling Size, Structure, and Composition Effects

DOE PAGES

Acioli, Paulo H.; Jellinek, Julius

2017-07-14

A theoretical/computational description and analysis of the spectra of electron binding energies of Al 12 -, Al 13 - and Al 12Ni- clusters, which differ in size and/or composition by a single atom yet possess strikingly different measured photoelectron spectra, is presented. It is shown that the measured spectra can not only be reproduced computationally with quantitative fidelity – this is achieved through a combination of state-of-the-art density functional theory with a highly accurate scheme for conversion of the Kohn-Sham eigenenergies into electron binding energies – but also explained in terms of the effects of size, structure/symmetry and composition. Furthermore,more » a new methodology is developed and applied that provides for disentanglement and differential assignment of the separate roles played by size, structure/symmetry and composition in defining the observed differences in the measured spectra. The methodology is general and applicable to any finite system, homogeneous or heterogeneous. Finally, we project that in combination with advances in synthesis techniques this methodology will become an indispensable computation-based aid in the design of controlled synthesis protocols for manufacture of nanosystems and nanodevices with precisely desired electronic and other characteristics.« less

Theoretical Analysis of Photoelectron Spectra of Pure and Mixed Metal Clusters: Disentangling Size, Structure, and Composition Effects

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

Acioli, Paulo H.; Jellinek, Julius

A theoretical/computational description and analysis of the spectra of electron binding energies of Al 12 -, Al 13 - and Al 12Ni- clusters, which differ in size and/or composition by a single atom yet possess strikingly different measured photoelectron spectra, is presented. It is shown that the measured spectra can not only be reproduced computationally with quantitative fidelity – this is achieved through a combination of state-of-the-art density functional theory with a highly accurate scheme for conversion of the Kohn-Sham eigenenergies into electron binding energies – but also explained in terms of the effects of size, structure/symmetry and composition. Furthermore,more » a new methodology is developed and applied that provides for disentanglement and differential assignment of the separate roles played by size, structure/symmetry and composition in defining the observed differences in the measured spectra. The methodology is general and applicable to any finite system, homogeneous or heterogeneous. Finally, we project that in combination with advances in synthesis techniques this methodology will become an indispensable computation-based aid in the design of controlled synthesis protocols for manufacture of nanosystems and nanodevices with precisely desired electronic and other characteristics.« less

Electronic structure and optical properties of LiGa0.5In0.5Se2 single crystal, a nonlinear optical mid-IR material

NASA Astrophysics Data System (ADS)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, Tuan V.; Isaenko, L. I.; Yelisseyev, A. P.; Khyzhun, O. Y.

2018-06-01

Measurements of X-ray photoelectron core-level and valence-band spectra for pristine and irradiated with Ar+ ions surfaces of LiGa0.5In0.5Se2 single crystal, novel nonlinear optical mid-IR selenide grown by a modified vertical Bridgman-Stockbarger technique, are reported. Electronic structure of LiGa0.5In0.5Se2 is elucidated from theoretical and experimental points of view. Notably, total and partial densities of states (DOSs) of the LiGa0.5In0.5Se2 compound are calculated based on density functional theory (DFT) using the augmented plane wave + local orbitals (APW + lo) method. In accordance with the DFT calculations, the principal contributors to the valence band are the Se 4p states, making the main input at the top and in the upper part of the band, while its bottom is dominated by contributions of the valence s states associated with Ga and In atoms. The theoretical total DOS curve peculiarities are found to be in excellent agreement with the shape of the X-ray photoelectron valence-band spectrum of the LiGa0.5In0.5Se2 single crystal. The bottom of the conduction band of LiGa0.5In0.5Se2 is formed mainly by contributions of the unoccupied Ga 4s and In 5s states in almost equal proportion, with somewhat smaller contributions of the unoccupied Se 4p states as well. Our calculations indicate that the LiGa0.5In0.5Se2 compound is a direct gap semiconductor. The principal optical constants of LiGa0.5In0.5Se2 are calculated in the present work.

NLTE ANALYSIS OF HIGH-RESOLUTION H -BAND SPECTRA. II. NEUTRAL MAGNESIUM

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

Zhang, Junbo; Shi, Jianrong; Liu, Chao

Aiming at testing the validity of our magnesium atomic model and investigating the effects of non-local thermodynamical equilibrium (NLTE) on the formation of the H -band neutral magnesium lines, we derive the differential Mg abundances from selected transitions for 13 stars either adopting or relaxing the assumption of local thermodynamical equilibrium (LTE). Our analysis is based on high-resolution and high signal-to-noise ratio H -band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) and optical spectra from several instruments. The absolute differences between the Mg abundances derived from the two wavelength bands are always less than 0.1 dex inmore » the NLTE analysis, while they are slightly larger for the LTE case. This suggests that our Mg atomic model is appropriate for investigating the NLTE formation of the H -band Mg lines. The NLTE corrections for the Mg i H -band lines are sensitive to the surface gravity, becoming larger for smaller log g values, and strong lines are more susceptible to departures from LTE. For cool giants, NLTE corrections tend to be negative, and for the strong line at 15765 Å they reach −0.14 dex in our sample, and up to −0.22 dex for other APOGEE stars. Our results suggest that it is important to include NLTE corrections in determining Mg abundances from the H -band Mg i transitions, especially when strong lines are used.« less

C-H Hot Bands in the Near-IR Emission Spectra of Leonids

NASA Technical Reports Server (NTRS)

Freund, F. T.; Scoville, J.; Holm, R.; Seelemann, R.; Freund, M. M.

2002-01-01

The reported infrared (IR) emission spectra from 1999 Leonid fireballs show a 3.4 micron C-H emission band and unidentified bands at longer wavelengths. Upon atmospheric entry, the Leonid meteorites were flash-heated to temperatures around 2400K, which would destroy any organics on the surface of the meteorite grains. We propose that the nu(sub )CH emission band in the Leonid emission spectra arises from matrix-embedded C(sub n)-H-O entities that are protected from instant pyrolysis. Our model is based on IR absorption nu(sub )CH bands, which we observed in laboratory-grown MgO and natural olivine single crystals, where they arise from C(sub n)-H-O units imbedded in the mineral matrix, indicative of aliphatic -CH2- and -CH3 organics. Instead of being pyrolyzed, the C(sub n)-H-O entities in the Leonid trails become vibrationally excited to higher levels n = 1, 2, 3 etc. During de-excitation they emit at 3.4 microns, due to the (0 => 1) transition, and at longer wavelengths, due to hot bands. As a first step toward verifying this hypothesis we measured the C-H vibrational manifold of hexane (C6H14). The calculated positions of the (2 => l ) , (3 => 2), and possibly (4 => 3) hot bands agree with the Leonid emission bands at 3.5, 3.8 and 4.l microns.

Electronic and spin structure of the wide-band-gap topological insulator: Nearly stoichiometric Bi2Te2S

NASA Astrophysics Data System (ADS)

Annese, E.; Okuda, T.; Schwier, E. F.; Iwasawa, H.; Shimada, K.; Natamane, M.; Taniguchi, M.; Rusinov, I. P.; Eremeev, S. V.; Kokh, K. A.; Golyashov, V. A.; Tereshchenko, O. E.; Chulkov, E. V.; Kimura, A.

2018-05-01

We have grown the phase-homogeneous ternary compound with composition Bi2Te1.85S1.15 very close to the stoichiometric Bi2Te2S . The measurements performed with spin- and angle-resolved photoelectron spectroscopy as well as density functional theory and G W calculations revealed a wide-band-gap three-dimensional topological insulator phase. The surface electronic spectrum is characterized by the topological surface state (TSS) with Dirac point located above the valence band and Fermi level lying in the band gap. TSS band dispersion and constant energy contour manifest a weak warping effect near the Fermi level along with in-plane and out-of-plane spin polarization along the Γ ¯-K ¯ line. We identified four additional states at deeper binding energies with high in-plane spin polarization.

Direct work function measurement by gas phase photoelectron spectroscopy and its application on PbS nanoparticles.

PubMed

Axnanda, Stephanus; Scheele, Marcus; Crumlin, Ethan; Mao, Baohua; Chang, Rui; Rani, Sana; Faiz, Mohamed; Wang, Suidong; Alivisatos, A Paul; Liu, Zhi

2013-01-01

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Exploration of faint absorption bands in the reflectance spectra of the asteroids by method of optimal smoothing: Vestoids

NASA Astrophysics Data System (ADS)

Shestopalov, D. I.; McFadden, L. A.; Golubeva, L. F.

2007-04-01

An optimization method of smoothing noisy spectra was developed to investigate faint absorption bands in the visual spectral region of reflectance spectra of asteroids and the compositional information derived from their analysis. The smoothing algorithm is called "optimal" because the algorithm determines the best running box size to separate weak absorption bands from the noise. The method is tested for its sensitivity to identifying false features in the smoothed spectrum, and its correctness of forecasting real absorption bands was tested with artificial spectra simulating asteroid reflectance spectra. After validating the method we optimally smoothed 22 vestoid spectra from SMASS1 [Xu, Sh., Binzel, R.P., Burbine, T.H., Bus, S.J., 1995. Icarus 115, 1-35]. We show that the resulting bands are not telluric features. Interpretation of the absorption bands in the asteroid spectra was based on the spectral properties of both terrestrial and meteorite pyroxenes. The bands located near 480, 505, 530, and 550 nm we assigned to spin-forbidden crystal field bands of ferrous iron, whereas the bands near 570, 600, and 650 nm are attributed to the crystal field bands of trivalent chromium and/or ferric iron in low-calcium pyroxenes on the asteroids' surface. While not measured by microprobe analysis, Fe 3+ site occupancy can be measured with Mössbauer spectroscopy, and is seen in trace amounts in pyroxenes. We believe that trace amounts of Fe 3+ on vestoid surfaces may be due to oxidation from impacts by icy bodies. If that is the case, they should be ubiquitous in the asteroid belt wherever pyroxene absorptions are found. Pyroxene composition of four asteroids of our set is determined from the band position of absorptions at 505 and 1000 nm, implying that there can be orthopyroxenes in all range of ferruginosity on the vestoid surfaces. For the present we cannot unambiguously interpret of the faint absorption bands that are seen in the spectra of 4005 Dyagilev, 4038

High temperature and low pressure chemical vapor deposition of silicon nitride on AlGaN: Band offsets and passivation studies

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

Reddy, Pramod; Washiyama, Shun; Kaess, Felix

2016-04-14

In this work, we employed X-ray photoelectron spectroscopy to determine the band offsets and interface Fermi level at the heterojunction formed by stoichiometric silicon nitride deposited on Al{sub x}Ga{sub 1-x}N (of varying Al composition “x”) via low pressure chemical vapor deposition. Silicon nitride is found to form a type II staggered band alignment with AlGaN for all Al compositions (0 ≤ x ≤ 1) and present an electron barrier into AlGaN even at higher Al compositions, where E{sub g}(AlGaN) > E{sub g}(Si{sub 3}N{sub 4}). Further, no band bending is observed in AlGaN for x ≤ 0.6 and a reduced band bending (by ∼1 eV in comparison to that atmore » free surface) is observed for x > 0.6. The Fermi level in silicon nitride is found to be at 3 eV with respect to its valence band, which is likely due to silicon (≡Si{sup 0/−1}) dangling bonds. The presence of band bending for x > 0.6 is seen as a likely consequence of Fermi level alignment at Si{sub 3}N{sub 4}/AlGaN hetero-interface and not due to interface states. Photoelectron spectroscopy results are corroborated by current-voltage-temperature and capacitance-voltage measurements. A shift in the interface Fermi level (before band bending at equilibrium) from the conduction band in Si{sub 3}N{sub 4}/n-GaN to the valence band in Si{sub 3}N{sub 4}/p-GaN is observed, which strongly indicates a reduction in mid-gap interface states. Hence, stoichiometric silicon nitride is found to be a feasible passivation and dielectric insulation material for AlGaN at any composition.« less

Ab initio based study of the ArO- photoelectron spectra: Selectivity of spin-orbit transitions

NASA Astrophysics Data System (ADS)

Buchachenko, A. A.; Jakowski, Jacek; Chałasiński, Grzegorz; Szczȩśniak, M. M.; Cybulski, S. M.

2000-04-01

A combined ab initio atoms-in-molecule approach was implemented to model the photoelectron spectra of the ArO- anion. The lowest adiabatic states of Σ and Π symmetry of ArO and ArO- were investigated using the fourth-order Møller-Plessett perturbation theory including bond functions. The total energies were dissected into electrostatic, exchange, induction, and dispersion components. The complex of Ar with atomic oxygen is only weakly bound, primarily by dispersion interaction. The Π state possesses a deeper minimum (Re=3.4Å,De=380μEh) than the Σ state (Re=3.8Å,De=220μEh). In contrast, the anion complex is fairly strongly bound, primarily by ion-induced dipole induction forces, and the Σ state possesses a deeper minimum at shorter interatomic distances (Re=3.02Å,De=3600μEh) than the Π state (Re=3.35Å,De=2400μEh). The Σ-Π splittings in both systems are mainly due to differences in the exchange repulsion terms. Atoms-in-molecule models were used to account for the spin-orbit interaction, and to generate adiabatic relativistic potentials and wave functions. Collisional properties, diffusion, and mobility coefficients of O and O- in Ar, and absolute total Ar+O scattering cross sections, were calculated and found to agree well with the available experimental data. The photoelectron spectra were simulated within vibronic model, and were found in excellent agreement with the experimental measurements. The bimodal electron kinetic energy distribution was shown to stem from the strong selectivity of spin-orbit transitions, which split into two dense groups, depending on the initial electronic state of the anion. The latter feature cannot be described without explicit consideration of electronic intensity factor.

Extracting the differential inverse inelastic mean free path and differential surface excitation probability of Tungsten from X-ray photoelectron spectra and electron energy loss spectra

NASA Astrophysics Data System (ADS)

Afanas'ev, V. P.; Gryazev, A. S.; Efremenko, D. S.; Kaplya, P. S.; Kuznetcova, A. V.

2017-12-01

Precise knowledge of the differential inverse inelastic mean free path (DIIMFP) and differential surface excitation probability (DSEP) of Tungsten is essential for many fields of material science. In this paper, a fitting algorithm is applied for extracting DIIMFP and DSEP from X-ray photoelectron spectra and electron energy loss spectra. The algorithm uses the partial intensity approach as a forward model, in which a spectrum is given as a weighted sum of cross-convolved DIIMFPs and DSEPs. The weights are obtained as solutions of the Riccati and Lyapunov equations derived from the invariant imbedding principle. The inversion algorithm utilizes the parametrization of DIIMFPs and DSEPs on the base of a classical Lorentz oscillator. Unknown parameters of the model are found by using the fitting procedure, which minimizes the residual between measured spectra and forward simulations. It is found that the surface layer of Tungsten contains several sublayers with corresponding Langmuir resonances. The thicknesses of these sublayers are proportional to the periods of corresponding Langmuir oscillations, as predicted by the theory of R.H. Ritchie.

Photoelectron imaging of doped helium nanodroplets

NASA Astrophysics Data System (ADS)

Neumark, Daniel

2008-03-01

Photoelectron images of helium nanodroplets doped with Kr and Ne atoms are reported. The images and resulting photoelectron spectra were obtained using tunable synchrotron radiation to ionize the droplets. Droplets were excited at 21.6 eV, corresponding to a strong droplet electronic excitation. The rare gas dopant is then ionized via a Penning excitation transfer process. The electron kinetic energy distributions reflect complex ionization and electron escape dynamics.

Site-specific recoil-induced effects on inner-shell photoionization of linear triatomic molecules: N 1 s photoelectron spectra of N2 O

NASA Astrophysics Data System (ADS)

Krivosenko, Yu. S.; Pavlychev, A. A.

2016-11-01

We investigate hard X-ray ionization of linear triatomic molecules accenting recoil-induced effects on the dynamics of molecular frame. This dynamics is studied within the two-springs and harmonic approximations. The mode-channel relationship connecting the excitations of vibrational, rotational and translational degrees of freedom with the Σ → Σ and Σ → Π photoionization channels is applied to compute the N 1s-1 photoelectron spectra of molecular N2 O for various photon energies. The distinct ionized-site- and molecular-orientation-specific changes in the vibration structure of the 1 s photoelectron lines of terminal and central nitrogen atoms are revealed and discussed.

Angle-resolved photoelectron spectroscopy of formaldehyde and methanol

NASA Astrophysics Data System (ADS)

Keller, P. R.; Taylor, J. W.; Grimm, F. A.; Carlson, Thomas A.

1984-10-01

Angle-resolved photoelectron spectroscopy was employed to obtain the angular distribution parameter, β, for the valence orbitals (IP < 21.1 eV) of formaldehyde and methanol over the 10-30 eV photon energy range using dispersed polarized synchrotron radiation as the excitation source. It was found that the energy dependence of β in the photoelectron energy range between 2 and 10 eV can be related to the molecular-orbital type from which ionization occurs. This generalized energy behavior is discussed with regard to earlier energy-dependence studies on molecules of different orbital character. Evidence is presented for the presence of resonance photoionization phenomena in formaldehyde in agreement with theoretical cross-section calculations.

Near-infrared diffuse interstellar bands in APOGEE telluric standard star spectra . Weak bands and comparisons with optical counterparts

NASA Astrophysics Data System (ADS)

Elyajouri, M.; Lallement, R.; Monreal-Ibero, A.; Capitanio, L.; Cox, N. L. J.

2017-04-01

Aims: Information on the existence and properties of diffuse interstellar bands (DIBs) outside the optical domain is still limited. Additional infra-red (IR) measurements and IR-optical correlative studies are needed to constrain DIB carriers and locate various absorbers in 3D maps of the interstellar matter. Methods: We extended our study of H-band DIBs in Apache Point Observatory Galactic Evolution Experiment (APOGEE) Telluric Standard Star (TSS) spectra. We used the strong λ15273 band to select the most and least absorbed targets. We used individual spectra of the former subsample to extract weaker DIBs, and we searched the two stacked series for differences that could indicate additional bands. High-resolution NARVAL and SOPHIE optical spectra for a subsample of 55 TSS targets were additionally recorded for NIR/optical correlative studies. Results: From the TSS spectra we extract a catalog of measurements of the poorly studied λλ15617, 15653, and 15673 DIBs in ≃300 sightlines, we obtain a first accurate determination of their rest wavelength and constrained their intrinsic width and shape. In addition, we studied the relationship between these weak bands and the strong λ15273 DIB. We provide a first or second confirmation of several other weak DIBs that have been proposed based on different instruments, and we add new constraints on their widths and locations. We finally propose two new DIB candidates. Conclusions: We compared the strength of the λ15273 absorptions with their optical counterparts λλ5780, 5797, 6196, 6283, and 6614. Using the 5797-5780 ratio as a tracer of shielding against the radiation field, we showed that the λ15273 DIB carrier is significantly more abundant in unshielded (σ-type) clouds, and it responds even more strongly than the λ5780 band carrier to the local ionizing field. Full Table 5 is available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http

Energy shift and conduction-to-valence band transition mediated by a time-dependent potential barrier in graphene

NASA Astrophysics Data System (ADS)

Chaves, Andrey; da Costa, D. R.; de Sousa, G. O.; Pereira, J. M.; Farias, G. A.

2015-09-01

We investigate the scattering of a wave packet describing low-energy electrons in graphene by a time-dependent finite-step potential barrier. Our results demonstrate that, after Klein tunneling through the barrier, the electron acquires an extra energy which depends on the rate of change of the barrier height with time. If this rate is negative, the electron loses energy and ends up as a valence band state after leaving the barrier, which effectively behaves as a positively charged quasiparticle.

Photoemission spectra and band structures of simple metals

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

Shung, K.W.; Mahan, G.D.

1988-08-15

We present a detailed calculation of the angle-resolved photoemission spectra of Na. The calculation follows a theory by Mahan, which allows for the inclusion of various bulk and surface effects. We find it important to take into account various broadening effects in order to explain the anomalous structure at E/sub F/, which was found by Jensen and Plummer in the spectra of Na. The broadening effects also help to resolve the discrepancy of the conduction-band width. Efforts are made to compare our results with new measurements of Plummer and Lyo. We discuss the ambiguity concerning the sign of the crystalmore » potential and comment on charge-density waves in the systems. We have also generalized our discussions to other simple metals like K.« less

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

NASA Astrophysics Data System (ADS)

Poklonski, N. A.; Vyrko, S. A.; Poklonskaya, O. N.; Kovalev, A. I.; Zabrodskii, A. G.

2016-06-01

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator-metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atoms with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature Tj is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature Tj, the concentration of "free" holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3Tj/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to Tj hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (-1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p-type diamond with boron atom concentrations in the

The influence of Si in Ni on the interface modification and the band alignment between Ni and alumina

NASA Astrophysics Data System (ADS)

Yoshitake, Michiko; Nemšák, Slavomír; Skála, Tomáš; Tsud, Nataliya; Matolín, Vladimír; Prince, Kevin C.

2018-06-01

The influence of a small amount of Si in a Ni single crystal on the interface formation between aluminum oxide and Ni has been investigated. The interface was formed by in-situ growth of the oxide by simultaneous supply of Al and oxygen onto Ni(1 1 1) in an ultrahigh vacuum chamber equipped with XPS apparatus. The oxide growth and the interface formation were compared between Si-containing Ni(1 1 1) and pure Ni(1 1 1). It was revealed that Si segregated on the surface of Ni and oxidized, forming an epitaxial thin alumino-silicate film. Valence band spectra demonstrated that the band offset between the oxide and Ni (energy level difference between the valence band top and the Fermi level) is different due to the oxidized Si segregation at the interface.

Simultaneous Conduction and Valence Band Quantization in Ultrashallow High-Density Doping Profiles in Semiconductors

NASA Astrophysics Data System (ADS)

Mazzola, F.; Wells, J. W.; Pakpour-Tabrizi, A. C.; Jackman, R. B.; Thiagarajan, B.; Hofmann, Ph.; Miwa, J. A.

2018-01-01

We demonstrate simultaneous quantization of conduction band (CB) and valence band (VB) states in silicon using ultrashallow, high-density, phosphorus doping profiles (so-called Si:P δ layers). We show that, in addition to the well-known quantization of CB states within the dopant plane, the confinement of VB-derived states between the subsurface P dopant layer and the Si surface gives rise to a simultaneous quantization of VB states in this narrow region. We also show that the VB quantization can be explained using a simple particle-in-a-box model, and that the number and energy separation of the quantized VB states depend on the depth of the P dopant layer beneath the Si surface. Since the quantized CB states do not show a strong dependence on the dopant depth (but rather on the dopant density), it is straightforward to exhibit control over the properties of the quantized CB and VB states independently of each other by choosing the dopant density and depth accordingly, thus offering new possibilities for engineering quantum matter.

X-ray photoelectron spectroscopy analysis for the chemical impact of solvent addition rate on electromagnetic shielding effectiveness of HCl-doped polyaniline nanopowders

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

Tantawy, Hesham Ramzy; Aston, D. Eric, E-mail: aston@uidaho.edu; Kengne, Blaise-Alexis F.

2015-11-07

An in-depth analysis of the chemical functionality in HCl-doped polyaniline (PANI) nanopowders is discussed through interpretations of x-ray photoelectron spectra. The distinctions between three PANI sample types, produced under varied synthesis conditions, are compared on the basis correlations between newly collected electron spectra for chemical analysis (or also x-ray photoelectron spectroscopy) and electromagnetic (EM) shielding effectiveness (SE) within two frequency bands (100–1500 MHz and ∼2–14 GHz). The findings are discussed with reference to previous data analysis of electrical conductivities and Raman and UV-vis spectra analyzed from replicates of the same PANI nanopowders, where only the 8–12 GHz range for SE was tested.more » They further corroborate previous results for limited-solvent conditions that enhance EM shielding. The three nanopowder types show distinctive differences in polaron, bipolaron, and polar lattice contributions. The collective findings describe the chemical connections between controlling and, most importantly, limiting the available solvent for polymerization with simultaneously doping and how it is that the newly developed solvent-limited approach for HCl-PANI nanopowders provides better shielding than traditionally solvent-rich methods by having more extended and perhaps even faster polaron delocalization than other PANI-based products. The maximum oxidation (50%) and doping (49%) levels obtained in the solvent-free nanopowders also produced the highest SE values of 37.3 ± 3.7 dB (MHz band) and 68.6 ± 4.6 dB (GHz band)« less

Interpretation of monoclinic hafnia valence electron energy-loss spectra by time-dependent density functional theory

NASA Astrophysics Data System (ADS)

Hung, L.; Guedj, C.; Bernier, N.; Blaise, P.; Olevano, V.; Sottile, F.

2016-04-01

We present the valence electron energy-loss spectrum and the dielectric function of monoclinic hafnia (m -HfO2) obtained from time-dependent density-functional theory (TDDFT) predictions and compared to energy-filtered spectroscopic imaging measurements in a high-resolution transmission-electron microscope. Fermi's golden rule density-functional theory (DFT) calculations can capture the qualitative features of the energy-loss spectrum, but we find that TDDFT, which accounts for local-field effects, provides nearly quantitative agreement with experiment. Using the DFT density of states and TDDFT dielectric functions, we characterize the excitations that result in the m -HfO2 energy-loss spectrum. The sole plasmon occurs between 13 and 16 eV, although the peaks ˜28 and above 40 eV are also due to collective excitations. We furthermore elaborate on the first-principles techniques used, their accuracy, and remaining discrepancies among spectra. More specifically, we assess the influence of Hf semicore electrons (5 p and 4 f ) on the energy-loss spectrum, and find that the inclusion of transitions from the 4 f band damps the energy-loss intensity in the region above 13 eV. We study the impact of many-body effects in a DFT framework using the adiabatic local-density approximation (ALDA) exchange-correlation kernel, as well as from a many-body perspective using "scissors operators" matched to an ab initio G W calculation to account for self-energy corrections. These results demonstrate some cancellation of errors between self-energy and excitonic effects, even for excitations from the Hf 4 f shell. We also simulate the dispersion with increasing momentum transfer for plasmon and collective excitation peaks.

Infrared band intensities of saturated hydrocarbons

NASA Technical Reports Server (NTRS)

Pinkley, L. W.; Sethna, P. P.; Williams, D.

1978-01-01

Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.

Lithium cluster anions: photoelectron spectroscopy and ab initio calculations.

PubMed

Alexandrova, Anastassia N; Boldyrev, Alexander I; Li, Xiang; Sarkas, Harry W; Hendricks, Jay H; Arnold, Susan T; Bowen, Kit H

2011-01-28

Structural and energetic properties of small, deceptively simple anionic clusters of lithium, Li(n)(-), n = 3-7, were determined using a combination of anion photoelectron spectroscopy and ab initio calculations. The most stable isomers of each of these anions, the ones most likely to contribute to the photoelectron spectra, were found using the gradient embedded genetic algorithm program. Subsequently, state-of-the-art ab initio techniques, including time-dependent density functional theory, coupled cluster, and multireference configurational interactions methods, were employed to interpret the experimental spectra.

Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

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

Bradforth, S.E.

1992-11-01

The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus

Band alignments at Ga2O3 heterojunction interfaces with Si and Ge

NASA Astrophysics Data System (ADS)

Gibbon, J. T.; Jones, L.; Roberts, J. W.; Althobaiti, M.; Chalker, P. R.; Mitrovic, Ivona Z.; Dhanak, V. R.

2018-06-01

Amorphous Ga2O3 thin films were deposited on p-type (111) and (100) surfaces of silicon and (100) germanium by atomic layer deposition (ALD). X-ray photoelectron spectroscopy (XPS) was used to investigate the band alignments at the interfaces using the Kraut Method. The valence band offsets were determined to be 3.49± 0.08 eV and 3.47± 0.08 eV with Si(111) and Si(100) respectively and 3.51eV± 0.08 eV with Ge(100). Inverse photoemission spectroscopy (IPES) was used to investigate the conduction band of a thick Ga2O3 film and the band gap of the film was determined to be 4.63±0.14 eV. The conduction band offsets were found to be 0.03 eV and 0.05eV with Si(111) and Si(100) respectively, and 0.45eV with Ge(100). The results indicate that the heterojunctions of Ga2O3 with Si(100), Si(111) and Ge(100) are all type I heterojunctions.

Band alignment of atomic layer deposited SiO2 and HfSiO4 with (\\bar{2}01) β-Ga2O3

NASA Astrophysics Data System (ADS)

Carey, Patrick H., IV; Ren, Fan; Hays, David C.; Gila, Brent P.; Pearton, Stephen J.; Jang, Soohwan; Kuramata, Akito

2017-07-01

The valence band offset at both SiO2/β-Ga2O3 and HfSiO4/β-Ga2O3 heterointerfaces was measured using X-ray photoelectron spectroscopy. Both dielectrics were deposited by atomic layer deposition (ALD) onto single-crystal β-Ga2O3. The bandgaps of the materials were determined by reflection electron energy loss spectroscopy as 4.6 eV for Ga2O3, 8.7 eV for Al2O3 and 7.0 eV for HfSiO4. The valence band offset was determined to be 1.23 ± 0.20 eV (straddling gap, type I alignment) for ALD SiO2 on β-Ga2O3 and 0.02 ± 0.003 eV (also type I alignment) for HfSiO4. The respective conduction band offsets were 2.87 ± 0.70 eV for ALD SiO2 and 2.38 ± 0.50 eV for HfSiO4, respectively.

Emission and reflection spectra from AlxGa1-xN/GaN single heterostructures

NASA Astrophysics Data System (ADS)

Reynolds, D. C.; Hoelscher, J.; Litton, C. W.; Collins, T. C.; Fitch, R.; Via, G. D.; Gillespie, J.; Crespo, A.; Jenkins, T. J.; Saxler, A.

2003-10-01

Emission and reflection spectra from AlGaN/GaN single heterostructures grown on SiC substrates were investigated. Two-dimensional electron gas (2DEG) transitions were observed in both emission and reflection. The transitions are sharp, associated with the excited state of the 2DEG, reflect the conservation of the K-selection rule, and are excitonlike. The transitions are also associated with both the A- and B-valence bands. To verify the origin of the reflection and emission spectra, the top AlGaN layer was removed by reactive ion etching. After etching, only the excitonic reflection and emission spectra associated with GaN were observed.

Ionization equilibrium at the transition from valence-band to acceptor-band migration of holes in boron-doped diamond

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

Poklonski, N. A., E-mail: poklonski@bsu.by; Vyrko, S. A.; Poklonskaya, O. N.

A quasi-classical model of ionization equilibrium in the p-type diamond between hydrogen-like acceptors (boron atoms which substitute carbon atoms in the crystal lattice) and holes in the valence band (v-band) is proposed. The model is applicable on the insulator side of the insulator–metal concentration phase transition (Mott transition) in p-Dia:B crystals. The densities of the spatial distributions of impurity atoms (acceptors and donors) and of holes in the crystal are considered to be Poissonian, and the fluctuations of their electrostatic potential energy are considered to be Gaussian. The model accounts for the decrease in thermal ionization energy of boron atomsmore » with increasing concentration, as well as for electrostatic fluctuations due to the Coulomb interaction limited to two nearest point charges (impurity ions and holes). The mobility edge of holes in the v-band is assumed to be equal to the sum of the threshold energy for diffusion percolation and the exchange energy of the holes. On the basis of the virial theorem, the temperature T{sub j} is determined, in the vicinity of which the dc band-like conductivity of holes in the v-band is approximately equal to the hopping conductivity of holes via the boron atoms. For compensation ratio (hydrogen-like donor to acceptor concentration ratio) K ≈ 0.15 and temperature T{sub j}, the concentration of “free” holes in the v-band and their jumping (turbulent) drift mobility are calculated. Dependence of the differential energy of thermal ionization of boron atoms (at the temperature 3T{sub j}/2) as a function of their concentration N is calculated. The estimates of the extrapolated into the temperature region close to T{sub j} hopping drift mobility of holes hopping from the boron atoms in the charge states (0) to the boron atoms in the charge states (−1) are given. Calculations based on the model show good agreement with electrical conductivity and Hall effect measurements for p

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

NASA Astrophysics Data System (ADS)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO2), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

Electronic structure and optical properties of noncentrosymmetric LiGaGe2Se6, a promising nonlinear optical material

NASA Astrophysics Data System (ADS)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Ananchenko, L. N.; Isaenko, L. I.; Yelisseyev, A.; Krinitsin, P. G.; Khyzhun, O. Y.

2016-11-01

X-ray photoelectron core-level and valence-band spectra are measured for pristine and Ar+ ion-bombarded surfaces of LiGaGe2Se6 single crystal grown by Bridgman-Stockbarger technique. Further, electronic structure of LiGaGe2Se6 is elucidated from both theoretical and experimental viewpoints. Density functional theory (DFT) calculations are made using the augmented plane wave +local orbitals (APW+lo) method to study total and partial densities of states in the LiGaGe2Se6 compound. The present calculations indicate that the principal contributors to the valence band are the Se 4p states: they contribute mainly at the top and in the central portion of the valence band of LiGaGe2Se6, with also their significant contributions in its lower portion. The Ge 4s and Ge 4p states are among other significant contributors to the valence band of LiGaGe2Se6, contributing mainly at the bottom and in the central portion, respectively. In addition, the calculations indicate that the bottom of the conduction band is composed mainly from the unoccupied Ge s and Se p states. The present DFT calculations are supported experimentally by comparison on a common energy scale of the X-ray emission bands representing the energy distribution of the 4p states associated with Ga, Ge and Se and the XPS valence-band spectrum of the LiGaGe2Se6 single crystal. The main optical characteristics of the LiGaGe2Se6 compound are elucidated by the first-principles calculations.

Lifetimes and energetics of the first electronically excited states of NaH2O from time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Gartmann, Thomas E.; Yoder, Bruce L.; Chasovskikh, Egor; Signorell, Ruth

2017-09-01

The energetics and lifetimes of the first electronically excited states (;3p-states;) of NaH2O and NaD2O have been measured by pump-probe (740/780 and 400 nm) photoelectron imaging. The photoelectron spectra of NaH2O show two bands at an electron kinetic energy of 0.14 and 0.38 eV, respectively. We assign the former to excitation via the two energetically close lying ;pπ-states; with flat potential curves in the intermolecular degrees of freedom, and the latter to the excitation via the ;pσ-state; characterized by significantly steeper potential curves. The relaxation of all ;p-states; follows a double exponential decay with a lifetime around 110 ps for the dominant fast component.

Understanding type Ia supernovae through their U-band spectra

NASA Astrophysics Data System (ADS)

Nordin, J.; Aldering, G.; Antilogus, P.; Aragon, C.; Bailey, S.; Baltay, C.; Barbary, K.; Bongard, S.; Boone, K.; Brinnel, V.; Buton, C.; Childress, M.; Chotard, N.; Copin, Y.; Dixon, S.; Fagrelius, P.; Feindt, U.; Fouchez, D.; Gangler, E.; Hayden, B.; Hillebrandt, W.; Kim, A.; Kowalski, M.; Kuesters, D.; Leget, P.-F.; Lombardo, S.; Lin, Q.; Pain, R.; Pecontal, E.; Pereira, R.; Perlmutter, S.; Rabinowitz, D.; Rigault, M.; Runge, K.; Rubin, D.; Saunders, C.; Smadja, G.; Sofiatti, C.; Suzuki, N.; Taubenberger, S.; Tao, C.; Thomas, R. C.; Nearby Supernova Factory

2018-06-01

Context. Observations of type Ia supernovae (SNe Ia) can be used to derive accurate cosmological distances through empirical standardization techniques. Despite this success neither the progenitors of SNe Ia nor the explosion process are fully understood. The U-band region has been less well observed for nearby SNe, due to technical challenges, but is the most readily accessible band for high-redshift SNe. Aims: Using spectrophotometry from the Nearby Supernova Factory, we study the origin and extent of U-band spectroscopic variations in SNe Ia and explore consequences for their standardization and the potential for providing new insights into the explosion process. Methods: We divide the U-band spectrum into four wavelength regions λ(uNi), λ(uTi), λ(uSi) and λ(uCa). Two of these span the Ca H&K λλ 3934, 3969 complex. We employ spectral synthesis using SYNAPPS to associate the two bluer regions with Ni/Co and Ti. Results: The flux of the uTi feature is an extremely sensitive temperature/luminosity indicator, standardizing the SN peak luminosity to 0.116 ± 0.011 mag root mean square (RMS). A traditional SALT2.4 fit on the same sample yields a 0.135 mag RMS. Standardization using uTi also reduces the difference in corrected magnitude between SNe originating from different host galaxy environments. Early U-band spectra can be used to probe the Ni+Co distribution in the ejecta, thus offering a rare window into the source of light curve power. The uCa flux further improves standardization, yielding a 0.086 ± 0.010 mag RMS without the need to include an additional intrinsic dispersion to reach χ2/dof 1. This reduction in RMS is partially driven by an improved standardization of Shallow Silicon and 91T-like SNe. All tables are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A71. Individual SN spectra shown are available at http://snfactory.lbl.gov/snf/data

An electron momentum spectroscopy and density functional theory study of the outer valence electronic structure of stella-2,6-dione

NASA Astrophysics Data System (ADS)

Nixon, K. L.; Wang, F.; Campbell, L.; Maddern, T.; Winkler, D.; Gleiter, R.; Loeb, P.; Weigold, E.; Brunger, M. J.

2003-07-01

We report on the first electron momentum spectroscopy (EMS) study into the outer valence electronic structure of the ground electronic state for the organic molecule stella-2,6-dione (C8H8O2). Experimentally measured binding-energy spectra are compared against a He(Ialpha) photoelectron spectroscopy result, while our derived momentum distributions (MDs) are compared against corresponding results from the plane wave impulse approximation (PWIA) level calculations. These computations employed density functional theory (DFT) basis states at the triple zeta valence polarization (TZVP) level, with a range of exchange-correlation (XC) functionals. A detailed comparison between the experimental and PWIA DFT-XC/TZVP calculated MDs enabled us to evaluate the accuracy of the various functionals, the Becke-Perdew (BP) XC functional being found to provide the most accurate description here. The importance of the through-bond interaction to the molecular orbitals (MOs) of stella-2,6-dione is demonstrated using the orbital imaging capability of EMS. Finally we show that the molecular geometry of this molecule, as derived from BP/TZVP, is in quite good agreement with corresponding independent experimental data.

X-ray Photoelectron Spectroscopy of High-κ Dielectrics

NASA Astrophysics Data System (ADS)

Mathew, A.; Demirkan, K.; Wang, C.-G.; Wilk, G. D.; Watson, D. G.; Opila, R. L.

2005-09-01

Photoelectron spectroscopy is a powerful technique for the analysis of gate dielectrics because it can determine the elemental composition, the chemical states, and the compositional depth profiles non-destructively. The sampling depth, determined by the escape depth of the photoelectrons, is comparable to the thickness of current gate oxides. A maximum entropy algorithm was used to convert photoelectron collection angle dependence of the spectra to compositional depth profiles. A nitrided hafnium silicate film is used to demonstrate the utility of the technique. The algorithm balances deviations from a simple assumed depth profile against a calculated depth profile that best fits the angular dependence of the photoelectron spectra. A flow chart of the program is included in this paper. The development of the profile is also shown as the program is iterated. Limitations of the technique include the electron escape depths and elemental sensitivity factors used to calculate the profile. The technique is also limited to profiles that extend to the depth of approximately twice the escape depth. These limitations restrict conclusions to comparison among a family of similar samples. Absolute conclusions about depths and concentrations must be used cautiously. Current work to improve the algorithm is also described.

Reassignment of the Iron (3) Absorption Bands in the Spectra of Mars

NASA Technical Reports Server (NTRS)

Sherman, D. M.

1985-01-01

Absorption features in the near-infrared and visible region reflectance spectra of Mars have been assigned to specific Fe (3+) crystal-field and o(2-) yields Fe(3+) charge transfer transitions. Recently, near-ultraviolet absorption spectra of iron oxides were obtained and the energies of o(2-) yields Fe(3+) charge-transfer (LMCT) transitions were determined from accurate SCF-X # alpha-SW molecular orbital calculations on (FeO6)(9-) and (FeO4)(5-) clusters. Both the theoretical and experimental results, together with existing data in the literature, show that some of the previous Fe(3+) band assignments in the spectra of Mars need to be revised. The theory of Fe(3+) spectra in minerals is discussed and applied to the spectrum of Mars.

GPI Spectra of HR8799 C, D, and E in H-K Bands with KLIP Forward Modeling

NASA Technical Reports Server (NTRS)

Greenbaum, Alexandra Z.; Pueyo, Laurent; Ruffio, Jean-Baptiste; Wang, Jason J.; De Rosa, Robert J.; Aguilar, Jonathan; Rameau, Julien; Barman, Travis; Marois, Christian; Marley, Mark S.;

A four-component Fock-space coupled cluster investigation of the HM(CO)5, (M = Mn, Re) photoelectron spectra

NASA Astrophysics Data System (ADS)

Nikoobakht, Behnam; Siebert, Max; Pernpointner, Markus

2015-11-01

In this work, we readdress the photoelectron spectra of the HM(CO)5, (M=Mn, Re) carbonyl complexes by applying four-component Fock-space coupled cluster (FSCC) methods for their calculation in order to extend earlier studies based on less demanding approaches. The final-state characterisation was based on group theoretical considerations of the contributing orbitals and allowed for an unambiguous assignment. Energy level diagrams show the effect of spin-orbit (SO) coupling starting from scalar relativistic results and for the heavy representative HRe(CO)5 nonadditivity effects of SO and electron correlation can be observed requiring a consistent treatment of both contributions.

Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires

NASA Astrophysics Data System (ADS)

Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.; Schaller, Richard D.; Gosztola, David J.; Stroscio, Michael A.; Dutta, Mitra

2018-04-01

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy ({V}{{O}}) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of {V}{{O}} defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In 2 O 3 nanowires

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

Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P.

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor–liquid–solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy (VO) defects as confirmed using Raman spectroscopy. A combination of highmore » resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of VO defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.« less

Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires.

PubMed

Mukherjee, Souvik; Sarkar, Ketaki; Wiederrecht, Gary P; Schaller, Richard D; Gosztola, David J; Stroscio, Michael A; Dutta, Mitra

2018-04-27

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In 2 O 3 ) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In 2 O 3 nanostructure based device characteristics for potential optoelectronic applications. In 2 O 3 nanowires with cubic crystal structure (c-In 2 O 3 ) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy [Formula: see text] defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of [Formula: see text] defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

Chalcogen doping at anionic site: A scheme towards more dispersive valence band in CuAlO2

NASA Astrophysics Data System (ADS)

Mazumder, Nilesh; Sen, Dipayan; Chattopadhyay, Kalyan Kumar

2013-02-01

Using first-principles calculations, we propose to enhance the dispersion of the top of valence band at high-symmetry points by selective introduction of chalcogen (Ch) impurities at oxygen site. As ab-plane hole mobility of CuAlO2 is large enough to support a band-conduction model over a polaronic one at room temperature [M. S. Lee et al. Appl. Phys. Lett. 79, 2029, (2001); J. Tate et al. Phys. Rev. B 80, 165206, (2009)], we examine its electronic and optical properties normal to c-axis. Intrinsic indirectness of energy-gap at Γ-point can be effectively removed along with substantial increase in density of states near Fermi level (EF) upon Ch addition. This can be attributed to S 2p-Cu 3d interaction just at or below EF, which should result in significantly improved carrier mobility and conductivity profile for this important p-type TCO.

Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments

NASA Astrophysics Data System (ADS)

Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

2018-02-01

Recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2-acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. The results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.

Intrinsic electrophilic properties of nucleosides: Photoelectron spectroscopy of their parent anions

NASA Astrophysics Data System (ADS)

Stokes, Sarah T.; Li, Xiang; Grubisic, Andrej; Ko, Yeon Jae; Bowen, Kit H.

2007-08-01

The nucleoside parent anions 2'-deoxythymidine-, 2'-deoxycytidine-, 2'-deoxyadenosine-, uridine-, cytidine-, adenosine-, and guanosine- were generated in a novel source, employing a combination of infrared desorption, electron photoemission, and a gas jet expansion. Once mass selected, the anion photoelectron spectrum of each of these was recorded. In the three cases in which comparisons were possible, the vertical detachment energies and likely adiabatic electron affinities extracted from these spectra agreed well with the values calculated both by Richardson et al. [J. Am. Chem. Soc. 126, 4404 (2004)] and by Li et al. [Radiat. Res. 165, 721 (2006)]. Through the combination of our experimental results and their theoretical calculations, several implications emerge. (1) With the possible exception of dG-, the parent anions of nucleosides exist, and they are stable. (2) These nucleoside anions are valence anions, and in most cases the negative charge is closely associated with the nucleobase moiety. (3) The nucleoside parent anions we have generated and studied are the negative ions of canonical, neutral nucleosides, similar to those found in DNA.

Intrinsic electrophilic properties of nucleosides: photoelectron spectroscopy of their parent anions.

PubMed

Stokes, Sarah T; Li, Xiang; Grubisic, Andrej; Ko, Yeon Jae; Bowen, Kit H

2007-08-28

The nucleoside parent anions 2(')-deoxythymidine(-), 2(')-deoxycytidine(-), 2(')-deoxyadenosine(-), uridine(-), cytidine(-), adenosine(-), and guanosine(-) were generated in a novel source, employing a combination of infrared desorption, electron photoemission, and a gas jet expansion. Once mass selected, the anion photoelectron spectrum of each of these was recorded. In the three cases in which comparisons were possible, the vertical detachment energies and likely adiabatic electron affinities extracted from these spectra agreed well with the values calculated both by Richardson et al. [J. Am. Chem. Soc. 126, 4404 (2004)] and by Li et al. [Radiat. Res. 165, 721 (2006)]. Through the combination of our experimental results and their theoretical calculations, several implications emerge. (1) With the possible exception of dG(-), the parent anions of nucleosides exist, and they are stable. (2) These nucleoside anions are valence anions, and in most cases the negative charge is closely associated with the nucleobase moiety. (3) The nucleoside parent anions we have generated and studied are the negative ions of canonical, neutral nucleosides, similar to those found in DNA.

Effect of exact Coulomb-exchange calculations on band-head spectra of odd-proton nuclei

NASA Astrophysics Data System (ADS)

Koh, Meng-Hock; Nurhafiza, Mohamad Nor

2017-10-01

Previous calculations of band-head energy spectra of odd-mass heavy nuclei in the Hartree-Fock-plus-Bardeen-Cooper-Schrieffer (HF-BCS) framework showed that the agreement with data is better for odd-neutron as compared to odd-proton nuclei. The reason for a poorer agreement with data for the latter have been ascribed to the possible usage of the Slater approximation in calculating the Coulomb-exchange term. In this work, we report the effect of exact Coulomb-exchange calculations on band-head energy spectra of two odd-proton nuclei (namely 237Np and 241Am) as compared to the results obtained using the Slater approximation. We performed self-consistent blocking calculations while taking the breaking of time-reversal symmetry at the mean-field level into account due to the unpaired nucleon. The SkM* and SIII parametrizations of the Skyrme interaction have been employed to approximate the effective nucleon-nucleon interaction while a seniority force is used for the pairing channel. Contrary to what was expected, our preliminary results show no improvement on the band-head spectra as compared to data when the Coulomb-exchange term is calculated exactly.

Auroral and photoelectron fluxes in cometary ionospheres

NASA Astrophysics Data System (ADS)

Bhardwaj, A.; Haider, S. A.; Spinghal, R. P.

1990-05-01

The analytical yield spectrum method has been used to ascertain photoelectron and auroral electron fluxes in cometary ionospheres, with a view to determining the effects of cometocentric distances, solar zenith angle, and solar minimum and maximum conditions. Auroral electron fluxes are thus calculated for monoenergetic and observed primary electron spectra; auroral electrons are found to make a larger contribution to the observed electron spectrum than EUV-generated photoelectrons. Good agreement is established with extant theoretical works.

Angularly resolved X-ray photoelectron spectroscopy investigation of PTFE after prolonged space exposure

NASA Technical Reports Server (NTRS)

Dalins, I.; Karimi, M.

1992-01-01

Monochromatized angularly resolved X-ray photoelectron spectroscopy (ARXPS) was used to study PTFE (Teflon) that had been exposed to an earth orbital environment for approximately six years. The primary interest of the research is on a very reactive component of this environment (atomic oxygen) which, because of the typical orbital velocities of a spacecraft, impinge on exposed surfaces with 5 eV energy. This presentation deals with the method of analysis, the findings as they pertain to a rather complex carbon, oxygen, and fluorine XPS peak analysis, and the character of the valence bands. An improved bias referencing method, based on ARXPS, is also demonstrated for evaluating specimen charging effects. It was found that the polymer molecule tends to resist the atomic oxygen attack by reorienting itself, so that the most electronegative CF3 groups are facing the incoming hyperthermal oxygen atoms. The implications of these findings to ground-based laboratory studies are discussed.

Theoretical Study on the Photoelectron Spectra of Ln(COT)2-: Lanthanide Dependence of the Metal-Ligand Interaction.

PubMed

Nakajo, Erika; Masuda, Tomohide; Yabushita, Satoshi

2016-12-08

We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT) 2 - (Ln = La-Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e 1g < e 1u < e 2g < e 2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e 2u symmetry. Because the magnitude of this 4f-ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

Photoelectron spectroscopy of nitromethane anion clusters

NASA Astrophysics Data System (ADS)

Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

2016-08-01

Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

Valency configuration of transition metal impurities in ZnO

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

Petit, Leon; Schulthess, Thomas C; Svane, Axel

2006-01-01

We use the self-interaction corrected local spin-density approximation to investigate the ground state valency configuration of transition metal (TM=Mn, Co) impurities in n- and p-type ZnO. We find that in pure Zn{sub 1-x}TM{sub x}O, the localized TM{sup 2+} configuration is energetically favored over the itinerant d-electron configuration of the local spin density (LSD) picture. Our calculations indicate furthermore that the (+/0) donor level is situated in the ZnO gap. Consequently, for n-type conditions, with the Fermi energy {epsilon}F close to the conduction band minimum, TM remains in the 2+ charge state, while for p-type conditions, with {epsilon}F close to themore » valence band maximum, the 3+ charge state is energetically preferred. In the latter scenario, modeled here by co-doping with N, the additional delocalized d-electron charge transfers into the entire states at the top of the valence band, and hole carriers will only exist, if the N concentration exceeds the TM impurity concentration.« less

Synthesis, characterization, and photophysical properties of a series of supramolecular mixed-valence compounds.

PubMed

Pfennig, B W; Fritchman, V A; Hayman, K A

2001-01-15

The synthesis and characterization of 10 cyano-bridged trinuclear mixed-valence compounds of the form [(NH3)5M-NC-FeII(CN)4-CN-M'(NH3)5]n+ (M = RuIII, OsIII, CrIII, or PtIV; n = 2, 3, or 4) is reported. The electronic spectra of these supramolecular compounds exhibit a single intervalent (IT) absorption band for each nondegenerate Fe-->M/M' transition. The redox potential of the Fe(II) center is shifted more positive with the addition of each coordinated metal complex, while the redox potentials of the pendant metals vary only slightly from their dinuclear counterparts. As a result, the Fe-->M IT bands are blue-shifted from those in the corresponding dinuclear mixed-valence compounds. The energies of these IT bands show a linear correlation with the ground-state thermodynamic driving force, as predicted by classical electron transfer theory. Estimates of the degree of electronic coupling (Hab) between the metal centers using a theoretical analysis of the IT band shapes indicate that most of these values are similar to those for the corresponding dinuclear species. Notable exceptions occur for the Fe-->M IT transitions in Os-Fe-M (M = Cr or Pt). The enhanced electronic coupling in these two species can be explained as a result of excited state mixing between electron transfer and/or ligand-based charge transfer states and an intensity-borrowing mechanism. Additionally, the possibility of electronic coupling between the remote metal centers in the Ru-Fe-Ru species is discussed in order to explain the observation of two closely spaced redox waves for the degenerate Ru(III) acceptors.

Modeling, Analysis, and Interpretation of Photoelectron Energy Spectra at Enceladus Observed by Cassini

NASA Astrophysics Data System (ADS)

Taylor, S. A.; Coates, A. J.; Jones, G. H.; Wellbrock, A.; Fazakerley, A. N.; Desai, R. T.; Caro-Carretero, R.; Michiko, M. W.; Schippers, P.; Waite, J. H.

2018-01-01

The Electron Spectrometer (ELS) of the Cassini Plasma Spectrometer has observed photoelectrons produced in the plume of Enceladus. These photoelectrons are observed during Enceladus encounters in the energetic particle shadow where the spacecraft is largely shielded from penetrating radiation by the moon. We present a complex electron spectrum at Enceladus including evidence of two previously unidentified electron populations at 6-10 eV and 10-16 eV. We estimate that the proportion of "hot" (>15 eV) to "cold" (<15 eV) electrons during the Enceladus flybys is ≈ 0.1-0.5%. We have constructed a model of photoelectron production in the plume and compared it with ELS Enceladus flyby data by scaling and energy shifting according to spacecraft potential. We suggest that the complex structure of the electron spectrum observed can be explained entirely by photoelectron production in the plume ionosphere.

Inter-Layer Coupling Induced Valence Band Edge Shift in Mono- to Few-Layer MoS2

PubMed Central

Trainer, Daniel J.; Putilov, Aleksei V.; Di Giorgio, Cinzia; Saari, Timo; Wang, Baokai; Wolak, Mattheus; Chandrasena, Ravini U.; Lane, Christopher; Chang, Tay-Rong; Jeng, Horng-Tay; Lin, Hsin; Kronast, Florian; Gray, Alexander X.; Xi, Xiaoxing X.; Nieminen, Jouko; Bansil, Arun; Iavarone, Maria

2017-01-01

Recent progress in the synthesis of monolayer MoS2, a two-dimensional direct band-gap semiconductor, is paving new pathways toward atomically thin electronics. Despite the large amount of literature, fundamental gaps remain in understanding electronic properties at the nanoscale. Here, we report a study of highly crystalline islands of MoS2 grown via a refined chemical vapor deposition synthesis technique. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS), photoemission electron microscopy/spectroscopy (PEEM) and μ-ARPES we investigate the electronic properties of MoS2 as a function of the number of layers at the nanoscale and show in-depth how the band gap is affected by a shift of the valence band edge as a function of the layer number. Green’s function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap reduction with increasing thickness, and the role of the interfacial Sulphur atoms is clarified. Our study, which gives new insight into the variation of electronic properties of MoS2 films with thickness bears directly on junction properties of MoS2, and thus impacts electronics application of MoS2. PMID:28084465

Inter-layer coupling induced valence band edge shift in mono- to few-layer MoS 2

DOE PAGES

Trainer, Daniel J.; Putilov, Aleksei V.; Di Giorgio, Cinzia; ...

2017-01-13

In this study, recent progress in the synthesis of monolayer MoS 2, a two-dimensional direct band-gap semiconductor, is paving new pathways toward atomically thin electronics. Despite the large amount of literature, fundamental gaps remain in understanding electronic properties at the nanoscale. Here,we report a study of highly crystalline islands of MoS 2 grown via a refined chemical vapor deposition synthesis technique. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS), photoemission electron microscopy/spectroscopy (PEEM) and μ-ARPES we investigate the electronic properties of MoS 2 as a function of the number of layers at the nanoscale and show in-depth how themore » band gap is affected by a shift of the valence band edge as a function of the layer number. Green’s function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap reduction with increasing thickness, and the role of the interfacial Sulphur atoms is clarified. Our study, which gives new insight into the variation of electronic properties of MoS 2 films with thickness bears directly on junction properties of MoS2, and thus impacts electronics application of MoS 2.« less

Band structure and visible light photocatalytic activity of multi-type nitrogen doped TiO(2) nanoparticles prepared by thermal decomposition.

PubMed

Dong, Fan; Zhao, Weirong; Wu, Zhongbiao; Guo, Sen

2009-03-15

Multi-type nitrogen doped TiO(2) nanoparticles were prepared by thermal decomposition of the mixture of titanium hydroxide and urea at 400 degrees C for 2h. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and photoluminescence (PL). The results showed that the as-prepared samples exhibited strong visible light absorption due to multi-type nitrogen doped in the form of substitutional (N-Ti-O and Ti-O-N) and interstitial (pi* character NO) states, which were 0.14 and 0.73 eV above the top of the valence band, respectively. A physical model of band structure was established to clarify the visible light photocatalytic process over the as-prepared samples. The photocatalytic activity was evaluated for the photodegradation of gaseous toluene under visible light irradiation. The activity of the sample prepared from wet titanium hydroxide and urea (TiO(2)-Nw, apparent reaction rate constant k = 0.045 min(-1)) was much higher than other samples including P25 (k = 0.0013 min(-1)). The high activity can be attributed to the results of the synergetic effects of strong visible light absorption, good crystallization, large surface hydroxyl groups, and enhanced separation of photoinduced carriers.

Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires

DOE PAGES

Vasseur, Guillaume; Fagot-Revurat, Yannick; Sicot, Muriel; ...

2016-01-04

We study the electronic structure of an ordered array of poly(para-phenylene) chains produced by surface-catalyzed dehalogenative polymerization of 1,4-dibromobenzene on copper (110). The quantization of unoccupied molecular states is measured as a function of oligomer length by scanning tunnelling spectroscopy, with Fermi level crossings observed for chains longer than ten phenyl rings. Angle-resolved photoelectron spectroscopy reveals a quasi-one-dimensional valence band as well as a direct gap of 1.15 eV, as the conduction band is partially filled through adsorption on the surface. Tight-binding modelling and ab initio density functional theory calculations lead to a full description of the organic band-structure, includingmore » the k-dispersion, the gap size and electron charge transfer mechanisms, highlighting a strong substrate-molecule interaction that drives the system into a metallic behaviour. In summary, we have fully characterized the band structure of a carbon-based conducting wire. This model system may be considered as a fingerprint of -conjugation of surface organic frameworks.« less

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Vovna, Vitaliy I.; Osmushko, Ivan S.; Fedorenko, Elena V.; Mirochnik, Anatoliy G.

2018-01-01

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

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

Yun, Dong-Jin; Chung, JaeGwan; Jung, Changhoon

The material arrangement and energy level alignment of an organic bilayer comprising of phenyl-c71-butyric-acid-methyl ester (PCBM-71) and pentacene were studied using ultraviolet photoelectron spectroscopy (UPS) and the argon gas cluster ion beam (GCIB) sputtering process. Although there is a small difference in the full width at half maximum of the carbon C 1s core level peaks and differences in the oxygen O 1s core levels of an X-ray photoemission spectroscopy spectra, these differences are insufficient to clearly distinguish between PCBM-71 and pentacene layers and to classify the interface and bulk regions. On the other hand, the valence band structures inmore » the UPS spectra contain completely distinct configurations for the PCBM-71 and pentacene layers, even when they have similar atomic compositions. According to the valence band structures of the PCBM-71/pentacene/electrodes, the highest unoccupied molecular orbital (HOMO) region of pentacene is at least 0.8 eV closer to the Fermi level than that of PCBM-71 and it does not overlap with any of the chemical states in the valence band structure of PCBM-71. Therefore, by just following the variations in the area of the HOMO region of pentacene, the interface/bulk regions of the PCBM/pentacene layers were distinctly categorized. Besides, the variation of valence band structures as a function of the Ar GCIB sputtering time fully corroborated with the surface morphologies observed in the atomic force microscope images. In summary, we believe that the novel approach, which involves UPS analysis in conjunction with Ar GCIB sputtering, can be one of the best methods to characterize the material distribution and energy level alignments of stacks of organic layers.« less

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

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

Epitaxial growth of MgO/Ga2O3 heterostructure and its band alignment studied by X-ray photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Matsuo, Norihiro; Doko, Naoki; Yasukawa, Yukiko; Saito, Hidekazu; Yuasa, Shinji

2018-07-01

We have grown an epitaxial MgO/Ga2O3 heterostructure on a MgO(001) substrate by molecular beam epitaxy. Crystallographic studies revealed the out-of-plane and in-plane crystal orientations between the MgO overlayer and the Ga2O3 layer, which were MgO(001) ∥ β-Ga2O3(001) and MgO[100] ∥ β-Ga2O3 [02\\bar{1}], respectively. The valence band offset at the MgO/β-Ga2O3 interface was determined to be 0.19 eV (type-II band alignment) by X-ray photoelectron spectroscopy, resulting in a large conduction band offset of 2.7–3.2 eV. These results indicate that MgO is a promising potential barrier for electrons in an epitaxial MgO/Ga2O3 multilayered structure.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

PubMed

Roy, Soumendra K; Jian, Tian; Lopez, Gary V; Li, Wei-Li; Su, Jing; Bross, David H; Peterson, Kirk A; Wang, Lai-Sheng; Li, Jun

2016-02-28

The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

NASA Astrophysics Data System (ADS)

Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

2016-02-01

The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

A photoelectron spectroscopic investigation of vinyl fluoride (C2H3F): the HeI, threshold and CIS photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Locht, R.; Leyh, B.; Dehareng, D.; Hottmann, K.; Baumgärtel, H.

2010-01-01

The threshold photoelectron spectrum (TPES) and the constant ion state (CIS) spectra of the individual ionic states of C2H3F have been recorded using synchrotron radiation. For comparison a well-resolved HeI photoelectron spectrum (HeI-PES) has also been measured and analysed in detail. The TPES has been measured between 9.5 eV and 35 eV photon energy. Numerous vibrational structures, reported for the first time, observed in the ground state and the six excited states of the cation are analysed. Quantum chemical calculations have been performed and provide strong support to the assignments. State-selected CIS spectra highlighted the major importance of autoionization for the production of almost all ionized states of C2H3F observed in this work.

Electronic and vibrational spectra of matrix isolated anthracene radical cations - Experimental and theoretical aspects

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin; Talbi, Dahbia; Parisel, Olivier; Ellinger, Yves

1993-01-01

The IR vibrational and visible/UV electronic absorption spectra of the anthracene cation, An(+), were studied experimentally, in argon matrices at 12 K, as well as theoretically, using ab initio calculations for the vibrational modes and enhanced semiempirical methods with configuration interaction for the electronic spectra. It was found that both approaches predicted well the observed photoelectron spectrum. The theoretical IR intensities showed some remarkable differences between neutral and ionized species (for example, the CH in-plane bending modes and CC in-plane stretching vibrations were predicted to increase by several orders of magnitude upon ionization). Likewise, estimated experimental IR intensities showed a significant increase in the cation band intensities over the neutrals. The implication of these findings for the hypothesis that polycyclic aromatic hydrocarbon cations are responsible for the unidentified IR emission bands from interstellar space is discussed.

Holographic Reconstruction of Photoelectron Diffraction and Its Circular Dichroism for Local Structure Probing

NASA Astrophysics Data System (ADS)

Matsui, Fumihiko; Matsushita, Tomohiro; Daimon, Hiroshi

2018-06-01

The local atomic structure around a specific element atom can be recorded as a photoelectron diffraction pattern. Forward focusing peaks and diffraction rings around them indicate the directions and distances from the photoelectron emitting atom to the surrounding atoms. The state-of-the-art holography reconstruction algorithm enables us to image the local atomic arrangement around the excited atom in a real space. By using circularly polarized light as an excitation source, the angular momentum transfer from the light to the photoelectron induces parallax shifts in these diffraction patterns. As a result, stereographic images of atomic arrangements are obtained. These diffraction patterns can be used as atomic-site-resolved probes for local electronic structure investigation in combination with spectroscopy techniques. Direct three-dimensional atomic structure visualization and site-specific electronic property analysis methods are reviewed. Furthermore, circular dichroism was also found in valence photoelectron and Auger electron diffraction patterns. The investigation of these new phenomena provides hints for the development of new techniques for local structure probing.

Fluorine Kα X-Ray Emission Spectra of MgF2, CaF2, SrF2 and BaF2

NASA Astrophysics Data System (ADS)

Sugiura, Chikara; Konishi, Wataru; Shoji, Shizuko; Kojima, Shinjiro

1990-11-01

The fluorine Kα emission spectra in fluorescence from a series of alkaline-earth fluorides MF2 (M=Mg, Ca, Sr and Ba) are measured with a high-resolution two-crystal vacuum spectrometer. An anomalously low intensity of the K1L1 satellite peak arising from 1s-1(2s2p)-1 initial states is observed for SrF2. The measured emission spectra are presented along with the UPS spectra of the F- 2p valence bands obtained by Poole et al. and the fluorine K absorption-edge spectra by Oizumi et al. By using these spectra, the first peak or shoulder in the fluorine K absorption-edge spectra is identified as being due to a core exciton which is formed below the bottom of the conduction band. The binding energy of the exciton is estimated to be 1.3(± 0.3), 1.1(± 0.2), 1.0(± 0.2) and 1.7(± 0.2) eV for MgF2, CaF2, SrF2 and BaF2, respectively.

Quasiparticle band structures and interface physics of SnS and GeS

NASA Astrophysics Data System (ADS)

Malone, Brad; Kaxiras, Efthimios

2013-03-01

Orthorhombic SnS and GeS are layered materials made of earth-abundant elements which have the potential to play a useful role in the massive scale up of renewable power necessary by 2050 to avoid unmanageable levels of climate change. We report on first principles calculations of the quasiparticle spectra of these two materials, predicting the type and magnitude of the fundamental band gap, a quantity which shows a strong degree of scatter in the experimental literature. Additionally, in order to evaluate the possible role of GeS as an electron-blocking layer in a SnS-based photovoltaic device, we investigate the band offsets of the interfaces between these materials along the three principle crystallographic directions. We find that while the valence-band offsets are similar along the three principle directions, the conduction-band offsets display a substantial amount of anisotropy.

Photoelectron imaging spectroscopy of MoC{sup −} and NbN{sup −} diatomic anions: A comparative study

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

Liu, Qing-Yu; Li, Zi-Yu; He, Sheng-Gui, E-mail: shengguihe@iccas.ac.cn, E-mail: chenh@iccas.ac.cn

2015-04-28

The isoeletronic diatomic MoC{sup −} and NbN{sup −} anions have been prepared by laser ablation and studied by photoelectron imaging spectroscopy combined with quantum chemistry calculations. The photoelectron spectra of NbN{sup −} can be very well assigned on the basis of literature reported optical spectroscopy of NbN. In contrast, the photoelectron spectra of MoC{sup −} are rather complex and the assignments suffered from the presence of many electronically hot bands and limited information from the reported optical spectroscopy of MoC. The electron affinities of NbN and MoC have been determined to be 1.450 ± 0.003 eV and 1.360  ±  0.003more » eV, respectively. The good resolution of the imaging spectroscopy provided a chance to resolve the Ω splittings of the X{sup 3}Σ{sup −} (Ω = 0 and 1) state of MoC and the X{sup 4}Σ{sup −} (Ω = 1/2 and 3/2) state of MoC{sup −} for the first time. The spin-orbit splittings of the X{sup 2}Δ state of NbN{sup −} and the a{sup 2}Δ state of MoC{sup −} were also determined. The similarities and differences between the electronic structures of the NbN and MoC systems were discussed.« less

Electronic-structure theory of plutonium chalcogenides

NASA Astrophysics Data System (ADS)

Shick, Alexander; Havela, Ladislav; Gouder, Thomas; Rebizant, Jean

2009-03-01

The correlated band theory methods, the around-mean-field LDA + U and dynamical LDA + HIA (Hubbard-I), are applied to investigate the electronic structure of Pu chalcogenides. The LDA + U calculations for PuX (X = S, Se, Te) provide non-magnetic ground state in agreement with the experimental data. Non-integer filling of 5 f-manifold (from approx. 5.6 in PuS to 5.7 PuTe). indicates a mixed valence ground state which combines f5 and f6 multiplets. Making use of the dynamical LDA+HIA method the photoelectron spectra are calculated in good agreement with experimental data. The three-peak feature near EF attributed to 5 f-manifold is well reproduced by LDA + HIA, and follows from mixed valence character of the ground state.

Multicolor emission from intermediate band semiconductor ZnO 1-xSe x

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

Welna, M.; Baranowski, M.; Linhart, W. M.

Photoluminescence and photomodulated reflectivity measurements of ZnOSe alloys are used to demonstrate a splitting of the valence band due to the band anticrossing interaction between localized Se states and the extended valence band states of the host ZnO matrix. A strong multiband emission associated with optical transitions from the conduction band to lower E - and upper E + valence subbands has been observed at room temperature. The composition dependence of the optical transition energies is well explained by the electronic band structure calculated using the kp method combined with the band anticrossing model. The observation of the multiband emissionmore » is possible because of relatively long recombination lifetimes. Longer than 1 ns lifetimes for holes photoexcited to the lower valence subband offer a potential of using the alloy as an intermediate band semiconductor for solar power conversion applications.« less

Multicolor emission from intermediate band semiconductor ZnO 1-xSe x

DOE PAGES

Welna, M.; Baranowski, M.; Linhart, W. M.; ...

2017-03-13

Photoluminescence and photomodulated reflectivity measurements of ZnOSe alloys are used to demonstrate a splitting of the valence band due to the band anticrossing interaction between localized Se states and the extended valence band states of the host ZnO matrix. A strong multiband emission associated with optical transitions from the conduction band to lower E - and upper E + valence subbands has been observed at room temperature. The composition dependence of the optical transition energies is well explained by the electronic band structure calculated using the kp method combined with the band anticrossing model. The observation of the multiband emissionmore » is possible because of relatively long recombination lifetimes. Longer than 1 ns lifetimes for holes photoexcited to the lower valence subband offer a potential of using the alloy as an intermediate band semiconductor for solar power conversion applications.« less

Valence Band Structure of Highly Efficient p-type Thermoelectric PbTe-PbS Alloys

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

Jaworski, C. M.; Nielsen, Mechele; Wang, Hsin

New experimental evidence is given relevant to the temperature-dependence of valence band structure of PbTe and PbTe1-xSx alloys (0.04 x 0.12), and its effect on the thermoelectric figure of merit zT. The x = 0.08 sample has zT ~ 1.55 at 773K. The magnetic field dependence of the high-temperature Hall resistivity of heavily p-type (> 1019 cm-3) Na-doped PbTe1-xSx reveals the presence of high-mobility electrons. This put in question prior analyses of the Hall coefficient and the conclusion that PbTe would be an indirect gap semiconductor at temperatures where its zT is optimal. Possible origins for these electrons are discussed:more » they can be induced by photoconductivity, or by the topology of the Fermi surface when the L and -bands merge. Negative values for the low-temperature thermopower are also observed. Our data show that PbTe continues to be a direct gap semiconductor at temperatures where the zT and S2 of p-type PbTe are optimal e.g. 700-900K. The previously suggested temperature induced rapid rise in energy of the heavy hole LVB relative to the light hole UVB is not supported by the experimental data.« less

Electronic and Photoelectron Spectroscopy of Toluene

NASA Astrophysics Data System (ADS)

Gardner, Adrian M.; Green, Alistair M.; Tame-Reyes, Victor; Wright, Timothy G.

2012-06-01

Electronic and photoelectron spectra of toluene are presented and discussed. The utilization of a recently reported scheme for assigning the normal vibrations of substituted benzenes allows these spectra to be compared to those of other molecules with unprecedented clarity. Changes in vibrational activity within a series of substituted benzene molecules will be discussed, specifically the increased rate of intramolecular vibrational energy redistribution observed in molecules where the substituent is a methyl group. A. M. Gardner and T. G. Wright, J. Chem. Phys., 135, 114305 (2011)

Temperature and pressure dependences of Sm valence in intermediate valence compound SmB6

NASA Astrophysics Data System (ADS)

Emi, N.; Mito, T.; Kawamura, N.; Mizumaki, M.; Ishimatsu, N.; Pristáš, G.; Kagayama, T.; Shimizu, K.; Osanai, Y.; Iga, F.

2018-05-01

We report the results of the X-ray absorption spectroscopy (XAS) on the intermediate valence compound SmB6. The XAS measurements were performed near the nonmagnetic-magnetic phase boundary. Mean Sm valence vSm was estimated from absorption spectra, and we found that vSm near the boundary (P ≥ 10 GPa and T ∼ 12 K) is far below a trivalent state with magnetic characteristics. Although the result is markedly different from the cases of pressure induced magnetic orders in Yb and Ce compounds, it is likely that the large deviation from the trivalent state seems to be common in some Sm compounds which possess electronic configuration between 4f5 and 4f6 with multi 4 f electrons.

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

NASA Astrophysics Data System (ADS)

Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

2004-05-01

X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2Ge 0.8Cr 0.2O 4, Ba 2Ge 0.1Cr 0.9O 4, Sr 2CrO 4, Ca 2(PO 4) x(CrO 4) 1- xCl ( x=0.25,0.5), Ca 5(CrO 4) 3Cl, CrO 3, the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3, CrF 3, Cr 2O 3, KCr(SO 4) 2 · 12H 2O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

Electronic structure and charge transport in nonstoichiometric tantalum oxide

NASA Astrophysics Data System (ADS)

Perevalov, T. V.; Gritsenko, V. A.; Gismatulin, A. A.; Voronkovskii, V. A.; Gerasimova, A. K.; Aliev, V. Sh; Prosvirin, I. A.

2018-06-01

The atomic and electronic structure of nonstoichiometric oxygen-deficient tantalum oxide TaO x<2.5 grown by ion beam sputtering deposition was studied. The TaO x film content was analyzed by x-ray photoelectron spectroscopy and by quantum-chemistry simulation. TaO x is composed of Ta2O5, metallic tantalum clusters and tantalum suboxides. A method for evaluating the stoichiometry parameter of TaO x from the comparison of experimental and theoretical photoelectron valence band spectra is proposed. The charge transport properties of TaO x were experimentally studied and the transport mechanism was quantitatively analyzed with four theoretical dielectric conductivity models. It was found that the charge transport in almost stoichiometric and nonstoichiometric tantalum oxide can be consistently described by the phonon-assisted tunneling between traps.

Decoding emotional valence from electroencephalographic rhythmic activity.

PubMed

Celikkanat, Hande; Moriya, Hiroki; Ogawa, Takeshi; Kauppi, Jukka-Pekka; Kawanabe, Motoaki; Hyvarinen, Aapo

2017-07-01

We attempt to decode emotional valence from electroencephalographic rhythmic activity in a naturalistic setting. We employ a data-driven method developed in a previous study, Spectral Linear Discriminant Analysis, to discover the relationships between the classification task and independent neuronal sources, optimally utilizing multiple frequency bands. A detailed investigation of the classifier provides insight into the neuronal sources related with emotional valence, and the individual differences of the subjects in processing emotions. Our findings show: (1) sources whose locations are similar across subjects are consistently involved in emotional responses, with the involvement of parietal sources being especially significant, and (2) even though the locations of the involved neuronal sources are consistent, subjects can display highly varying degrees of valence-related EEG activity in the sources.

Photoelectron spectrometer for attosecond spectroscopy of liquids and gases

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

Jordan, I.; Huppert, M.; Wörner, H. J., E-mail: hwoerner@ethz.ch

2015-12-15

A new apparatus for attosecond time-resolved photoelectron spectroscopy of liquids and gases is described. It combines a liquid microjet source with a magnetic-bottle photoelectron spectrometer and an actively stabilized attosecond beamline. The photoelectron spectrometer permits venting and pumping of the interaction chamber without affecting the low pressure in the flight tube. This pressure separation has been realized through a sliding skimmer plate, which effectively seals the flight tube in its closed position and functions as a differential pumping stage in its open position. A high-harmonic photon spectrometer, attached to the photoelectron spectrometer, exit port is used to acquire photon spectramore » for calibration purposes. Attosecond pulse trains have been used to record photoelectron spectra of noble gases, water in the gas and liquid states as well as solvated species. RABBIT scans demonstrate the attosecond resolution of this setup.« less

One-shot calculation of temperature-dependent optical spectra and phonon-induced band-gap renormalization

NASA Astrophysics Data System (ADS)

Zacharias, Marios; Giustino, Feliciano

2016-08-01

Recently, Zacharias et al. [Phys. Rev. Lett. 115, 177401 (2015), 10.1103/PhysRevLett.115.177401] developed an ab initio theory of temperature-dependent optical absorption spectra and band gaps in semiconductors and insulators. In that work, the zero-point renormalization and the temperature dependence were obtained by sampling the nuclear wave functions using a stochastic approach. In the present work, we show that the stochastic sampling of Zacharias et al. can be replaced by fully deterministic supercell calculations based on a single optimal configuration of the atomic positions. We demonstrate that a single calculation is able to capture the temperature-dependent band-gap renormalization including quantum nuclear effects in direct-gap and indirect-gap semiconductors, as well as phonon-assisted optical absorption in indirect-gap semiconductors. In order to demonstrate this methodology, we calculate from first principles the temperature-dependent optical absorption spectra and the renormalization of direct and indirect band gaps in silicon, diamond, and gallium arsenide, and we obtain good agreement with experiment and with previous calculations. In this work we also establish the formal connection between the Williams-Lax theory of optical transitions and the related theories of indirect absorption by Hall, Bardeen, and Blatt, and of temperature-dependent band structures by Allen and Heine. The present methodology enables systematic ab initio calculations of optical absorption spectra at finite temperature, including both direct and indirect transitions. This feature will be useful for high-throughput calculations of optical properties at finite temperature and for calculating temperature-dependent optical properties using high-level theories such as G W and Bethe-Salpeter approaches.

Photoelectron wave function in photoionization: plane wave or Coulomb wave?

PubMed

Gozem, Samer; Gunina, Anastasia O; Ichino, Takatoshi; Osborn, David L; Stanton, John F; Krylov, Anna I

2015-11-19

The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectron wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. The results suggest that accurate molecular photoionization cross sections can be computed with a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion.

Comparison of HITRAN Calculated Spectra with Laboratory Measurements of the 820, 940, 1130, and 1370 nm Water Vapor Bands

NASA Technical Reports Server (NTRS)

Giver, Lawrence P.; Pilewskie, P.; Gore, Warren J.; Freedman, R. S.; Chackerian, C., Jr.; Varanasi, P.

2001-01-01

Several groups have recently been working to improve the near-infrared spectrum of water vapor on HITRAN. The unit-conversion errors found by Giver, et al have now been corrected on the recently released HITRAN-2000. The most important aspect of this article for atmospheric absorption was increasing all the HITRAN-1996 intensities of the 940 nm band by nearly 15%. New intensity measurements of this band by Brown, et al (submitted to J. Mol. Spec.) have now been included in the latest HITRAN. However, Belmiloud, et al discuss new data in the 633-1175 nm region which they expect will substantially increase the calculated absorption of solar radiation by water vapor. They suggest the 4 bands at 725, 820, 940, and 1130 nm are all stronger than the sum of the line intensities currently on HITRAN. For the 725 and 820 nm bands, their recommended intensity increases are 10% and 15%, about the same as previously noted by Grossmann and Browell and Ponsardin and Browell. Belmiloud, et al only suggest a 6% increase for the 940 nm. band over the corrected HITRAN-1996 intensities, but a large 38% increase for the 1130 nm band. The new data discussed by Belmiloud, et al have now been published in greater detail by Schermaul, et al. The intensity increase for the 1130 nm band discussed by Belmiloud, et al is very substantial; it is important to quickly determine if the HITRAN intensity values are in error by as much as they claim. Only intensity errors for the strong lines could result in the total band intensity being in error by such a large amount. To quickly get a number of spectra of the entire near-infrared region from 650 to 1650 nm, we used the Solar Spectral Flux Radiometer with our 25-meter base path White absorption cell. This moderate resolution spectrometer is a flight instrument that has flown on the Sandia Twin Otter for the ARESE 11 experiment. The measured band profiles were then compared to calculated spectra using the latest HITRAN line intensities, convolved

Photoelectron angular distributions from rotationally resolved autoionizing states of N 2

DOE PAGES

Chartrand, A. M.; McCormack, E. F.; Jacovella, U.; ...

2017-12-08

The single-photon, photoelectron-photoion coincidence spectrum of N 2 has been recorded at high (~1.5 cm -1) resolution in the region between the N 2 + X 2Σ g +, v + = 0 and 1 ionization thresholds by using a double imaging spectrometer and intense vacuum-ultraviolet light from the Synchrotron SOLEIL. This approach provides the relative photoionization cross section, the photoelectron energy distribution, and the photoelectron angular distribution as a function of photon energy. The region of interest contains autoionizing valence states, vibrationally autoionizing Rydberg states converging to vibrationally excited levels of the N 2 + X 2Σ g +more » ground state, and electronically autoionizing states converging to the N 2 + A 2Π and B 2Σ u + states. The wavelength resolution is sufficient to resolve rotational structure in the autoionizing states, but the electron energy resolution is insufficient to resolve rotational structure in the photoion spectrum. Here, a simplified approach based on multichannel quantum defect theory is used to predict the photoelectron angular distribution parameters, β, and the results are in reasonably good agreement with experiment.« less

Determination of band offsets at GaN/single-layer MoS{sub 2} heterojunction

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

Tangi, Malleswararao; Mishra, Pawan; Ng, Tien Khee

2016-07-18

We report the band alignment parameters of the GaN/single-layer (SL) MoS{sub 2} heterostructure where the GaN thin layer is grown by molecular beam epitaxy on CVD deposited SL-MoS{sub 2}/c-sapphire. We confirm that the MoS{sub 2} is an SL by measuring the separation and position of room temperature micro-Raman E{sup 1}{sub 2g} and A{sup 1}{sub g} modes, absorbance, and micro-photoluminescence bandgap studies. This is in good agreement with HRTEM cross-sectional analysis. The determination of band offset parameters at the GaN/SL-MoS{sub 2} heterojunction is carried out by high-resolution X-ray photoelectron spectroscopy accompanying with electronic bandgap values of SL-MoS{sub 2} and GaN. Themore » valence band and conduction band offset values are, respectively, measured to be 1.86 ± 0.08 and 0.56 ± 0.1 eV with type II band alignment. The determination of these unprecedented band offset parameters opens up a way to integrate 3D group III nitride materials with 2D transition metal dichalcogenide layers for designing and modeling of their heterojunction based electronic and photonic devices.« less

Temperature-driven band inversion in Pb 0.77 Sn 0.23 Se : Optical and Hall effect studies

DOE PAGES

Anand, Naween; Buvaev, Sanal; Hebard, A. F.; ...

2014-12-23

Optical and Hall-effect measurements have been performed on single crystals of Pb₀.₇₇Sn₀.₂₃Se, a IV-VI mixed chalcogenide. The temperature dependent (10–300 K) reflectance was measured over 40–7000 cm⁻¹ (5–870 meV) with an extension to 15,500 cm⁻¹ (1.92 eV) at room temperature. The reflectance was fit to the Drude-Lorentz model using a single Drude component and several Lorentz oscillators. The optical properties at the measured temperatures were estimated via Kramers-Kronig analysis as well as by the Drude-Lorentz fit. The carriers were p-type with the carrier density determined by Hall measurements. A signature of valence intraband transition is found in the low-energy opticalmore » spectra. It is found that the valence-conduction band transition energy as well as the free carrier effective mass reach minimum values at 100 K, suggesting temperature-driven band inversion in the material. Thus, density function theory calculation for the electronic band structure also make similar predictions.« less

Electronic Band Structure Tuning of Highly-Mismatched-Alloys for Energy Conversion Applications

NASA Astrophysics Data System (ADS)

Ting, Min

Highly-mismatched alloys: ZnO1-xTe x and GaN1-xSb x are discussed within the context of finding the suitable material for a cost-effective Si-based tandem solar cell (SBTSC). SBTSC is an attractive concept for breaking through the energy conversion efficiency theoretical limit of a single junction solar cell. Combining with a material of 1.8 eV band gap, SBTSC can theoretically achieve energy conversion efficiency > 45%. ZnO and GaN are wide band gap semiconductors. Alloying Te in ZnO and alloying Sb in GaN result in large band gap reduction to < 2 eV from 3.3 eV and 3.4 eV respectively. The band gap reduction is majorly achieved by the upward shift of valence band (VB). Incorporating Te in ZnO modifies the VB of ZnO through the valence-band anticrossing (VBAC) interaction between localized Te states and ZnO VB delocalized states, which forms a Te-derived VB at 1 eV above the host VB. Similar band structure modification is resulted from alloying Sb in GaN. Zn1-xTex and GaN 1-xSbx thin films are synthesized across the whole composition range by pulsed laser deposition (PLD) and low temperature molecular beam epitaxy (LT-MBE) respectively. The electronic band edges of these alloys are measured by synchrotron X-ray absorption, emission, and the X-ray photoelectron spectroscopies. Modeling the optical absorption coefficient with the band anticrossing (BAC) model revealed that the Te and Sb defect levels to be at 0.99 eV and 1.2 eV above the VB of ZnO and GaN respectively. Electrically, Zn1-xTex is readily n-type conductive and GaN1-xSbx is strongly p-type conductive. A heterojunction device of p-type GaN 0.93Sb0.07 with n-type ZnO0.77Te0.93 upper cell (band gap at 1.8 eV) on Si bottom cell is proposed as a promising SBTSC device.

Energies of rare-earth ion states relative to host bands in optical materials from electron photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Thiel, Charles Warren

There are a vast number of applications for rare-earth-activated materials and much of today's cutting-edge optical technology and emerging innovations are enabled by their unique properties. In many of these applications, interactions between the rare-earth ion and the host material's electronic states can enhance or inhibit performance and provide mechanisms for manipulating the optical properties. Continued advances in these technologies require knowledge of the relative energies of rare-earth and crystal band states so that properties of available materials may be fully understood and new materials may be logically developed. Conventional and resonant electron photoemission techniques were used to measure 4f electron and valence band binding energies in important optical materials, including YAG, YAlO3, and LiYF4. The photoemission spectra were theoretically modeled and analyzed to accurately determine relative energies. By combining these energies with ultraviolet spectroscopy, binding energies of excited 4fN-15d and 4fN+1 states were determined. While the 4fN ground-state energies vary considerably between different trivalent ions and lie near or below the top of the valence band in optical materials, the lowest 4f N-15d states have similar energies and are near the bottom of the conduction band. As an example for YAG, the Tb3+ 4f N ground state is in the band gap at 0.7 eV above the valence band while the Lu3+ ground state is 4.7 eV below the valence band maximum; however, the lowest 4fN-15d states are 2.2 eV below the conduction band for both ions. We found that a simple model accurately describes the binding energies of the 4fN, 4fN-1 5d, and 4fN+1 states. The model's success across the entire rare-earth series indicates that measurements on two different ions in a host are sufficient to predict the energies of all rare-earth ions in that host. This information provides new insight into electron transfer transitions, luminescence quenching, and valence

Operando x-ray photoelectron emission microscopy for studying forward and reverse biased silicon p-n junctions.

PubMed

Barrett, N; Gottlob, D M; Mathieu, C; Lubin, C; Passicousset, J; Renault, O; Martinez, E

2016-05-01

Significant progress in the understanding of surfaces and interfaces of materials for new technologies requires operando studies, i.e., measurement of chemical, electronic, and magnetic properties under external stimulus (such as mechanical strain, optical illumination, or electric fields) applied in situ in order to approach real operating conditions. Electron microscopy attracts much interest, thanks to its ability to determine semiconductor doping at various scales in devices. Spectroscopic photoelectron emission microscopy (PEEM) is particularly powerful since it combines high spatial and energy resolution, allowing a comprehensive analysis of local work function, chemistry, and electronic structure using secondary, core level, and valence band electrons, respectively. Here we present the first operando spectroscopic PEEM study of a planar Si p-n junction under forward and reverse bias. The method can be used to characterize a vast range of materials at near device scales such as resistive oxides, conducting bridge memories and domain wall arrays in ferroelectrics photovoltaic devices.

Photoelectron Spectroscopy Study of Quinonimides

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

Hossain, Ekram; Deng, Shihu M.; Gozem, Samer

Structures and energetics of o-, m- and p-quinonimide anions (OC6H4N) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, andmore » it is shown that accurate predictions for the electronic structure of the para quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.« less

Energetic (above 60 eV) atmospheric photoelectrons

NASA Technical Reports Server (NTRS)

Winningham, J. D.; Decker, D. T.; Kozyra, J. U.; Nagy, A. F.; Jasperse, J. R.

1989-01-01

Data from low altitude plasma instrument (LAPI) on Dynamics Explorer 2 document a population of high-energy (up to 800 eV) atmospheric photoelectrons that has not been reported in the published literature. The source of these photoelectrons is postulated to be the soft X-ray portion of the whole sun spectrum. This conclusion is supported by sunrise-sunset characteristics that track those of the classical (below 60 eV) EUV-produced photoelectrons, and theoretical results from two models that incorporate the soft X-ray portion of the solar spectrum. The models include K-shell ionization effects and predict peaks in the photoelectron spectrum due to Auger electrons emitted from oxygen and nitrogen. The peak for nitrogen is observed as predicted, but the peak for oxygen is barely observable. Excellent quantitative agreement is achieved between theory and experiment by using reasonable adjustments to the few published soft X-ray spectra based on solar activity. The upflowing energetic photoelectrons provide a heretofore unknown source of electrons to the magnetosphere. They occur whenever and wherever the sun is up, that is, at all invariant latitudes. Their density is low, but they are steady and ubiquitous. If scattering and trapping occur on closed field lines, then photoelectrons could contribute as a significant particle source and thus represent a new facet of magnetosphere-ionosphere coupling.

Synchrotron-based valence shell photoionization of CH radical

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

Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C.; Holzmeier, F.

2016-05-28

We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg statesmore » of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.« less

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

PubMed

Schneider, M; Soshnikov, D Yu; Holland, D M P; Powis, I; Antonsson, E; Patanen, M; Nicolas, C; Miron, C; Wormit, M; Dreuw, A; Trofimov, A B

2015-10-14

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(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.

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

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

Schneider, M.; Wormit, M.; Dreuw, A.

2015-10-14

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-pVTZmore » 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.« less

Modeling Photoelectron Spectra of CuO, Cu2O, and CuO2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space.

PubMed

Orms, Natalie; Krylov, Anna I

2018-04-12

The experimental photoelectron spectra of di- and triatomic copper oxide anions have been reported previously. We present an analysis of the experimental spectra of the CuO - , Cu 2 O - , and CuO 2 - anions using equation-of-motion coupled-cluster (EOM-CC) methods. The open-shell electronic structure of each molecule demands a unique combination of EOM-CC methods to achieve an accurate and balanced representation of the multiconfigurational anionic- and neutral-state manifolds. Analysis of the Dyson orbitals associated with photodetachment from CuO - reveals the strong non-Koopmans character of the CuO states. For the lowest detachment energy, a good agreement between theoretical and experimental values is obtained with CCSD(T) (coupled-cluster with single and double excitations and perturbative account of triple excitations). The (T) correction is particularly important for Cu 2 O - . Use of a relativistic pseudopotential and matching basis set improves the quality of results in most cases. EOM-DIP-CCSD analysis of the low-lying states of CuO 2 - reveals multiple singlet and triplet anionic states near the triplet ground state, adding an extra layer of complexity to the interpretation of the experimental CuO 2 - photoelectron spectrum.

Infrared Spectra and Band Strengths of Amorphous and Crystalline N2O

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Loeffler, M. J.; Gerakines, P. A.

2017-01-01

Infrared transmission spectra from 4000 to 400 cm (exp -1), and associated band strengths and absorption coefficients, are presented for the first time for both amorphous and crystalline N2O. Changes in the spectra as a function of ice thickness and ice temperature are shown. New measurements of density, refractive index, and specific refraction are reported for amorphous and crystalline N2O. Comparisons are made to published results, and the most-likely reason for some recent disagreements in the literature is discussed. As with CO2, its isoelectronic congener, the formation of amorphous N2O is found to require greater care than the formation of amorphous solids from more-polar molecules.

Anion Photoelectron Spectroscopic Studies of NbCr(CO)_n- (n = 2,3) Heterobimetallic Carbonyl Complexes

NASA Astrophysics Data System (ADS)

Baudhuin, Melissa A.; Boopalachandran, Praveenkumar; Leopold, Doreen

2015-06-01

Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)2- and NbCr(CO)3- complexes prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities (± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr-, which have formal bond orders of 5.5 (2Δ) and 6 (1σ+), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.

Band lineup of lattice mismatched InSe/GaSe quantum well structures prepared by van der Waals epitaxy: Absence of interfacial dipoles

NASA Astrophysics Data System (ADS)

Lang, O.; Klein, A.; Pettenkofer, C.; Jaegermann, W.; Chevy, A.

1996-10-01

Epitaxial growth of the strongly lattice mismatched (6.5%) layered chalcogenides InSe and GaSe on each other is obtained with the concept of van der Waals epitaxy as proven by low-energy electron diffraction and scanning tunnel microscope. InSe/GaSe/InSe and GaSe/InSe/GaSe quantum well structures were prepared by molecular beam epitaxy and their interface properties were characterized by soft x-ray photoelectron spectroscopy. Valence and conduction band offsets are determined to be 0.1 and 0.9 eV, respectively, and do not depend on deposition sequence (commutativity). As determined from the measured work functions the interface dipole is 0.05 eV; the band lineup between the two materials is correctly predicted by the Anderson model (electron affinity rule).

Interfacial band alignment and structural properties of nanoscale TiO2 thin films for integration with epitaxial crystallographic oriented germanium

NASA Astrophysics Data System (ADS)

Jain, N.; Zhu, Y.; Maurya, D.; Varghese, R.; Priya, S.; Hudait, M. K.

2014-01-01

We have investigated the structural and band alignment properties of nanoscale titanium dioxide (TiO2) thin films deposited on epitaxial crystallographic oriented Ge layers grown on (100), (110), and (111)A GaAs substrates by molecular beam epitaxy. The TiO2 thin films deposited at low temperature by physical vapor deposition were found to be amorphous in nature, and high-resolution transmission electron microscopy confirmed a sharp heterointerface between the TiO2 thin film and the epitaxially grown Ge with no traceable interfacial layer. A comprehensive assessment on the effect of substrate orientation on the band alignment at the TiO2/Ge heterointerface is presented by utilizing x-ray photoelectron spectroscopy and spectroscopic ellipsometry. A band-gap of 3.33 ± 0.02 eV was determined for the amorphous TiO2 thin film from the Tauc plot. Irrespective of the crystallographic orientation of the epitaxial Ge layer, a sufficient valence band-offset of greater than 2 eV was obtained at the TiO2/Ge heterointerface while the corresponding conduction band-offsets for the aforementioned TiO2/Ge system were found to be smaller than 1 eV. A comparative assessment on the effect of Ge substrate orientation revealed a valence band-offset relation of ΔEV(100) > ΔEV(111) > ΔEV(110) and a conduction band-offset relation of ΔEC(110) > ΔEC(111) > ΔEC(100). These band-offset parameters are of critical importance and will provide key insight for the design and performance analysis of TiO2 for potential high-κ dielectric integration and for future metal-insulator-semiconductor contact applications with next generation of Ge based metal-oxide field-effect transistors.

Anion photoelectron spectroscopy of radicals and clusters

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

Travis, Taylor R.

1999-12-01

Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C 2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C 2H and C 4H. Other radicals studied include NCN and I 3. The author was able to observe the low-lying singlet and triplet states of NCNmore » for the first time. Measurement of the electron affinity of I 3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.« less

Angle-resolved photoelectron spectroscopy of the chloro-substituted methanes

NASA Astrophysics Data System (ADS)

Keller, P. R.; Taylor, J. W.; Carlson, Thomas A.; Grimm, F. A.

1983-09-01

The angular distribution parameter, β, was determined for the valence orbitals (IP ' 21.2 eV) of CCl 4, CHCl 3, CH 2Cl 2, and CH 3Cl in the 10-30 eV photon energy range using dispersed polarized synchrotron radiation. The energy dependence of β in the photoelectron energy range of 2 to 10 eV for the non-bonding chlorine n(Cl) orbitals of these molecules was found to be similar for all n(Cl) orbitals investigated. The energy dependence of β for the σ orbitals in these molecules was similar to that observed previously for other σ orbitals. The experimental CCl 4 results were compared with theoretical CCl 4 results obtained using the Xα multiple scattering formalism. Theory predicts the existence of two strong shape resonances in each of the valence orbitals of CCl 4. The overall agreement between experiment and theory is evaluated along with the experimental evidence concerning the verification of the predicted shape resonances.

Multiphoton Rydberg and valence dynamics of CH3Br probed by mass spectrometry and slice imaging.

PubMed

Hafliðason, Arnar; Glodic, Pavle; Koumarianou, Greta; Samartzis, Peter C; Kvaran, Ágúst

2018-06-18

The multiphoton dynamics of CH3Br were probed by Mass Resolved MultiPhoton Ionization (MR-MPI), Slice Imaging and Photoelectron Imaging in the two-photon excitation region of 66 000 to 80 000 cm-1. Slice images of the CH3+ and Br+ photoproducts of ten two-photon resonant transitions to np and nd Rydberg states of the parent molecule were recorded. CH3+ ions dominate the mass spectra. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin-orbit excited (Br*) states.

Dynamical correlation effects in a weakly correlated material: Inelastic x-ray scattering and photoemission spectra of beryllium

NASA Astrophysics Data System (ADS)

Seidu, Azimatu; Marini, Andrea; Gatti, Matteo

2018-03-01

Beryllium is a weakly correlated simple metal. Still we find that dynamical correlation effects, beyond the independent-particle picture, are necessary to successfully interpret the electronic spectra measured by inelastic x-ray scattering (IXS) and photoemission spectroscopies (PES). By combining ab initio time-dependent density-functional theory (TDDFT) and many-body Green's function theory in the G W approximation (G W A ), we calculate the dynamic structure factor, the quasiparticle (QP) properties and PES spectra of bulk Be. We show that band-structure effects (i.e., due to interaction with the crystal potential) and QP lifetimes (LT) are both needed in order to explain the origin of the measured double-peak features in the IXS spectra. A quantitative agreement with experiment is obtained only when LT are supplemented to the adiabatic local-density approximation (ALDA) of TDDFT. Besides the valence band, PES spectra display a satellite, a signature of dynamical correlation due to the coupling of QPs and plasmons, which we are able to reproduce thanks to the combination of the G W A for the self-energy with the cumulant expansion of the Green's function.

The asymptotic spectra of banded Toeplitz and quasi-Toeplitz matrices

NASA Technical Reports Server (NTRS)

Beam, Richard M.; Warming, Robert F.

1991-01-01

Toeplitz matrices occur in many mathematical, as well as, scientific and engineering investigations. This paper considers the spectra of banded Toeplitz and quasi-Toeplitz matrices with emphasis on non-normal matrices of arbitrarily large order and relatively small bandwidth. These are the type of matrices that appear in the investigation of stability and convergence of difference approximations to partial differential equations. Quasi-Toeplitz matrices are the result of non-Dirichlet boundary conditions for the difference approximations. The eigenvalue problem for a banded Toeplitz or quasi-Toeplitz matrix of large order is, in general, analytically intractable and (for non-normal matrices) numerically unreliable. An asymptotic (matrix order approaches infinity) approach partitions the eigenvalue analysis of a quasi-Toeplitz matrix into two parts, namely the analysis for the boundary condition independent spectrum and the analysis for the boundary condition dependent spectrum. The boundary condition independent spectrum is the same as the pure Toeplitz matrix spectrum. Algorithms for computing both parts of the spectrum are presented. Examples are used to demonstrate the utility of the algorithms, to present some interesting spectra, and to point out some of the numerical difficulties encountered when conventional matrix eigenvalue routines are employed for non-normal matrices of large order. The analysis for the Toeplitz spectrum also leads to a diagonal similarity transformation that improves conventional numerical eigenvalue computations. Finally, the algorithm for the asymptotic spectrum is extended to the Toeplitz generalized eigenvalue problem which occurs, for example, in the stability of Pade type difference approximations to differential equations.

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

X-ray edge spectra — a sea-boson perspective

NASA Astrophysics Data System (ADS)

Setlur, Girish S.; Meera, V.

2007-07-01

The well-studied X-ray-edge problem is revisited using the sea-boson method. This approach is contrasted with the well-known theories of Mahan, Nozières and De Dominicis (MND). The present approach does not use the sudden approximation and the holes carry a momentum label unlike in the MND theory. We focus on the case of doped semiconductors rather than metals. The problem of electrons in a partially filled conduction band and holes in the initially hole-depleted valence band is recast in the sea-boson language. The resulting hamiltonian is shown to be equivalent to the electron-phonon hamiltonian with the excitons taking on the role of electrons and intra-conduction band particle-hole excitations known as 'conductrons' taking on the role of phonons. It is shown that the excitonic pole in the computed absorption spectra is replaced by a branch cut with a simple radical leading to a broadening of the exicton line due to these many-body effects. A critical comparison is made with the MND theory as well as with relevant experiments.

Evidence for intramolecular OH⋯π hydrogen bonding in unsaturated alcohols from UV photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Kowski, Klaus; Lüttke, Wolfgang; Rademacher, Paul

2001-06-01

The gas phase He(I) photoelectron (PE) spectra of several unsaturated alcohols (1-11) have been measured and analysed with respect to intramolecular OH⋯π hydrogen bonding. Evidence for such a hydrogen bond has been detected in the spectra of 2-allylphenol (1) and 2-phenylethan-1-ol (3). 1 exists as a conformational mixture of a hydrogen bonded form 1a and an open form 1b in a composition of roughly 2:1. A strong ionization band (IPv=10.01 eV; where IPv is the vertical ionization potential) is assigned to the ethylenic Cdbnd C double bond in the major conformer (1a) and a weak band (IPv=9.72 eV) to that of the minor conformer (1b). The latter IP coincides with the corresponding ionization of allylbenzene. In the series of ω-phenylalkan-1-ols, compound 3 exhibits an unusually low nπ(O) ionization indicating hydrogen bonding between the OH group and the π electron system of the phenyl ring. The higher homologs 4 and 5 prefer 'open' conformations without such interaction. The PE spectra of alkenols such as but-3-en-1-ol (7) and pent-4-en-1-ol (8) as well as of alkynols such as but-3-yn-1-ol (10) and pent-4-yn-1-ol (11) are consistent with OH⋯π hydrogen bonded conformers. The methanol/ethylene hetero-dimer has a T-shaped structure, as indicated by B3LYP/6-311++G(d) calculations, with a binding energy of 5.65 kJ mol-1.

Energetic band structure of Zn3P2 crystals

NASA Astrophysics Data System (ADS)

Stamov, I. G.; Syrbu, N. N.; Dorogan, A. V.

2013-01-01

Optical functions n, k, ε1, ε2 and d2ε2/dE2 have been determined from experimental reflection spectra in the region of 1-10 eV. The revealed electronic transitions are localized in the Brillouin zone. The magnitude of valence band splitting caused by the spin-orbital interaction ΔSO is lower than the splitting caused by the crystal field ΔCR in the center of Brillouin zone and L and X points. The switching effects are investigated in Zn3P2 crystals. The characteristics of experimental samples with electric switching, adjustable resistors, and time relays based on Zn3P2 are presented.

Synthesis, structural, electronic and linear electro-optical features of new quaternary Ag{sub 2}Ga{sub 2}SiS{sub 6} compound

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

Piasecki, M., E-mail: m.piasecki@ajd.czest.pl; Myronchuk, G.L.; Parasyuk, O.V.

For the first time phase equilibria and phase diagram of the AgGaS{sub 2}–SiS{sub 2} system were successfully explored by differential thermal and X-ray phase analysis methods. Crystal structure of low-temperature (LT) modification of Ag{sub 2}Ga{sub 2}SiS{sub 6} (LРў- Ag{sub 2}Ga{sub 2}SiS{sub 6}) was studied by X-ray powder method and it belongs to tetragonal space group I-42d, with unit cell parameters a=5.7164(4) Å, c=9.8023(7) Å, V=320.32(7) Å{sup 3}. Additional details regarding the crystal structure exploration are available at the web page Fachinformationszentrum Karlsruhe. X-ray photoelectron core-level and valence-band spectra were measured for pristine LРў- Ag{sub 2}Ga{sub 2}SiS{sub 6} crystal surface. Inmore » addition, the X-ray photoelectron valence-band spectrum of LРў-Ag{sub 2}Ga{sub 2}SiS{sub 6} was matched on a common energy scale with the X-ray emission S Kβ{sub 1,3} and Ga Kβ{sub 2} bands, which give information on the energy distribution of the S 3p and Ga 4p states, respectively. The presented X-ray spectroscopy results indicate that the valence S p and Ga p atomic states contribute mainly to the upper and central parts of the valence band of LРў-Ag{sub 2}Ga{sub 2}SiS{sub 6}, respectively, with a less significant contribution also to other valence-band regions. Band gap energy was estimated by measuring the quantum energy in the spectral range of the fundamental absorption. We have found that energy gap Eg is equal to 2.35 eV at 300 K. LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} is a photosensitive material and reveals two spectral maxima on the curve of spectral photoconductivity spectra at λ{sub max1} =590 nm and λ{sub max2} =860 nm. Additionally, linear electro-optical effect of LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} for the wavelengths of a cw He-Ne laser at 1150 nm was explored. - Graphical abstract: Manuscript present the technology of growth and investigation of properties a new quaternary compound Ag{sub 2}Ga{sub 2}Si

Norbornane: An investigation into its valence electronic structure using electron momentum spectroscopy, and density functional and Green's function theories

NASA Astrophysics Data System (ADS)

Knippenberg, S.; Nixon, K. L.; Brunger, M. J.; Maddern, T.; Campbell, L.; Trout, N.; Wang, F.; Newell, W. R.; Deleuze, M. S.; Francois, J.-P.; Winkler, D. A.

2004-12-01

We report on the results of an exhaustive study of the valence electronic structure of norbornane (C7H12), up to binding energies of 29 eV. Experimental electron momentum spectroscopy and theoretical Green's function and density functional theory approaches were all utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among all the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-ζ quality provides the best representation of the electron momentum distributions for all of the 20 valence orbitals of norbornane. This experimentally validated quantum chemistry model was then used to extract some chemically important properties of norbornane. When these calculated properties are compared to corresponding results from other independent measurements, generally good agreement is found. Green's function calculations with the aid of the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than 22.5 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet photoemission and newly presented (e,2e) ionization spectra, except for the band associated with the 1a2-1 one-hole state, which is probably subject to rather significant vibronic coupling effects, and a band at ˜25 eV characterized by a momentum distribution of "s-type" symmetry, which Green's function calculations fail to reproduce. We note the vicinity of the vertical double ionization threshold at ˜26 eV.

Band structure calculations of CuAlO2, CuGaO2, CuInO2, and CuCrO2 by screened exchange

NASA Astrophysics Data System (ADS)

Gillen, Roland; Robertson, John

2011-07-01

We report density functional theory band structure calculations on the transparent conducting oxides CuAlO2, CuGaO2, CuInO2, and CuCrO2. The use of the hybrid functional screened-exchange local density approximation (sX-LDA) leads to considerably improved electronic properties compared to standard LDA and generalized gradient approximation (GGA) approaches. We show that the resulting electronic band gaps compare well with experimental values and previous quasiparticle calculations, and show the correct trends with respect to the atomic number of the cation (Al, Ga, In). The resulting energetic depths of Cu d and O p levels and the valence-band widths are considerable improvements compared to LDA and GGA and are in good agreement with available x-ray photoelectron spectroscopy data. Lastly, we show the calculated imaginary part of the dielectric function for all four systems.

Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)5 via a singlet pathway upon excitation at 266 nm

PubMed Central

Leitner, T.; Mazza, T.; Schröder, H.; Kunnus, K.; Schreck, S.; Radcliffe, P.; Düsterer, S.; Meyer, M.; Föhlisch, A.

2017-01-01

We prove the hitherto hypothesized sequential dissociation of Fe(CO)5 in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)4 within the temporal resolution of the experiment and further to Fe(CO)3 within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)5, Fe(CO)4, and Fe(CO)3 showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)5 complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. PMID:28595420

The production and photoelectron spectrum of thiazyl iodide. NSI

NASA Astrophysics Data System (ADS)

Allaf, A. W.; Matti, G. Y.; Suffolk, R. J.; Watts, J. D.

1989-02-01

The previously unknown molecule thiazyl iodide, NSI, has been prepared and studied by HeI photoelectron and low-resolution infrared spectroscopy. It has been produced by an on-line process using thiazyl chloride, NSCl, as precursor. The observed photoelectron spectrum has been rationalised using ab initio molecular-orbital calculations. The first ionisation energy is 10.06±0.05 eV, assigned to a largely non-bonding orbital with major components on nitrogen and iodine. Gas-phase infrared spectra yield a value for ν 1 of 1295 cm -1.

Interaction between adsorbed hydrogen and potassium on a carbon nanocone containing material as studied by photoemission

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

Yu, Xiaofeng; Raaen, Steinar, E-mail: sraaen@ntnu.no

2015-09-14

Hydrogen adsorption on a potassium doped carbon nanocone containing material was studied by photoelectron spectroscopy and work function measurement. The valence band spectra indicate that there is charge transfer from potassium to carbon. Upon deposition on carbon potassium is in its ionic state for lower doping and shows both ionic and metallic behavior at higher doping. Adsorption of hydrogen facilitates diffusion of potassium on the carbon material as seen by changes in the K{sub 2p} core level spectrum. Variations in the measured sample work function indicate that hydrogen initially adsorb on the K dopants and subsequently adsorb on the carbonmore » cone containing material.« less

Investigation of the spectral properties and magnetism of BiFeO3 by dynamical mean-field theory

NASA Astrophysics Data System (ADS)

Paul, Souvik; Iuşan, Diana; Thunström, Patrik; Kvashnin, Yaroslav O.; Hellsvik, Johan; Pereiro, Manuel; Delin, Anna; Knut, Ronny; Phuyal, Dibya; Lindblad, Andreas; Karis, Olof; Sanyal, Biplab; Eriksson, Olle

2018-03-01

Using the local density approximation plus dynamical mean-field theory (LDA+DMFT), we have computed the valence-band photoelectron spectra and magnetic excitation spectra of BiFeO3, one of the most studied multiferroics. Within the DMFT approach, the local impurity problem is tackled by the exact diagonalization solver. The solution of the impurity problem within the LDA+DMFT method for the paramagnetic and magnetically ordered phases produces result in agreement with the experimental data on electronic and magnetic structures. For comparison, we also present results obtained by the LDA +U approach which is commonly used to compute the physical properties of this compound. Our LDA+DMFT derived electronic spectra match adequately with the experimental hard x-ray photoelectron spectroscopy and resonant photoelectron spectroscopy for Fe 3 d states, whereas the LDA +U method fails to capture the general features of the measured spectra. This indicates the importance of accurately incorporating the dynamical aspect of electronic correlation among Fe 3 d orbitals to reproduce the experimental excitation spectra. Specifically, the LDA+DMFT derived density of states exhibits a significant amount of Fe 3 d states at the position of Bi lone pairs, implying that the latter are not alone in the spectral scenario. This fact might modify our interpretation about the origin of ferroelectric polarization in this material. Our study demonstrates that the combination of orbital cross sections for the constituent elements and broadening schemes for the spectral functions are crucial to explain the detailed structures of the experimental electronic spectra. Our magnetic excitation spectra computed from the LDA+DMFT result conform well with the inelastic neutron scattering data.

Determination of band structure parameters and the quasi-particle gap of CdSe quantum dots by cyclic voltammetry.

PubMed

Inamdar, Shaukatali N; Ingole, Pravin P; Haram, Santosh K

2008-12-01

Band structure parameters such as the conduction band edge, the valence band edge and the quasi-particle gap of diffusing CdSe quantum dots (Q-dots) of various sizes were determined using cyclic voltammetry. These parameters are strongly dependent on the size of the Q-dots. The results obtained from voltammetric measurements are compared to spectroscopic and theoretical data. The fit obtained to the reported calculations based on the semi-empirical pseudopotential method (SEPM)-especially in the strong size-confinement region, is the best reported so far, according to our knowledge. For the smallest CdSe Q-dots, the difference between the quasi-particle gap and the optical band gap gives the electron-hole Coulombic interaction energy (J(e1,h1)). Interband states seen in the photoluminescence spectra were verified with cyclic voltammetry measurements.

Computational and photoelectron spectroscopic study of the dipole-bound anions, indole(H2O)1,2 (.).

PubMed

Buytendyk, A M; Buonaugurio, A M; Xu, S-J; Nilles, J M; Bowen, K H; Kirnosov, N; Adamowicz, L

2016-07-14

We report our joint computational and anion photoelectron spectroscopic study of indole-water cluster anions, indole(H2O)1,2 (-). The photoelectron spectra of both cluster anions show the characteristics of dipole-bound anions, and this is confirmed by our theoretical computations. The experimentally determined vertical electron detachment (VDE) energies for indole(H2O)1 (-) and indole(H2O)2 (-) are 144 meV and 251 meV, respectively. The corresponding theoretically determined VDE values for indole(H2O)1 (-) and indole(H2O)2 (-) are 124 meV and 255 meV, respectively. The vibrational features in the photoelectron spectra of these cluster anions are assigned as the vibrations of the water molecule.

Computational and photoelectron spectroscopic study of the dipole-bound anions, indole(H2O)1,2-

NASA Astrophysics Data System (ADS)

Buytendyk, A. M.; Buonaugurio, A. M.; Xu, S.-J.; Nilles, J. M.; Bowen, K. H.; Kirnosov, N.; Adamowicz, L.

2016-07-01

We report our joint computational and anion photoelectron spectroscopic study of indole-water cluster anions, indole(H2O)1,2-. The photoelectron spectra of both cluster anions show the characteristics of dipole-bound anions, and this is confirmed by our theoretical computations. The experimentally determined vertical electron detachment (VDE) energies for indole(H2O)1- and indole(H2O)2- are 144 meV and 251 meV, respectively. The corresponding theoretically determined VDE values for indole(H2O)1- and indole(H2O)2- are 124 meV and 255 meV, respectively. The vibrational features in the photoelectron spectra of these cluster anions are assigned as the vibrations of the water molecule.

Energy band structure and electrical properties of Ga-oxide/GaN interface formed by remote oxygen plasma

NASA Astrophysics Data System (ADS)

Yamamoto, Taishi; Taoka, Noriyuki; Ohta, Akio; Truyen, Nguyen Xuan; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Makihara, Katsunori; Nakatsuka, Osamu; Shimizu, Mitsuaki; Miyazaki, Seiichi

2018-06-01

The energy band structure of a Ga-oxide/GaN structure formed by remote oxygen plasma exposure and the electrical interface properties of the GaN metal–oxide–semiconductor (MOS) capacitors with the SiO2/Ga-oxide/GaN structures with postdeposition annealing (PDA) at various temperatures have been investigated. Reflection high-energy electron diffraction and X-ray photoelectron spectroscopy clarified that the formed Ga-oxide layer is neither a single nor polycrystalline phase with high crystallinity. We found that the energy band offsets at the conduction band minimum and at the valence band maximum between the Ga-oxide layer and the GaN surface were 0.4 and 1.2 ± 0.2 eV, respectively. Furthermore, capacitance–voltage (C–V) characteristics revealed that the interface trap density (D it) is lower than the evaluation limit of Terman method without depending on the PDA temperatures, and that the SiO2/Ga-oxide stack can work as a protection layer to maintain the low D it, avoiding the significant decomposition of GaN at the high PDA temperature of 800 °C.

New quaternary thallium indium germanium selenide TlInGe2Se6: Crystal and electronic structure

NASA Astrophysics Data System (ADS)

Khyzhun, O. Y.; Parasyuk, O. V.; Tsisar, O. V.; Piskach, L. V.; Myronchuk, G. L.; Levytskyy, V. O.; Babizhetskyy, V. S.

2017-10-01

Crystal structure of a novel quaternary thallium indium germanium selenide TlInGe2Se6 was investigated by means of powder X-ray diffraction method. It was determined that the compound crystallizes in the trigonal space group R3 with the unit cell parameters a = 10.1798(2) Å, c = 9.2872(3) Å. The relationship with similar structures was discussed. The as-synthesized TlInGe2Se6 ingot was tested with X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES). In particular, the XPS valence-band and core-level spectra were recorded for initial and Ar+ ion-bombarded surfaces of the sample under consideration. The XPS data allow for statement that the TlInGe2Se6 surface is rigid with respect to Ar+ ion-bombardment. Particularly, Ar+ ion-bombardment (3.0 keV, 5 min duration, ion current density fixed at 14 μA/cm2) did not cause substantial modifications of stoichiometry in topmost surface layers. Furthermore, comparison on a common energy scale of the XES Se Kβ2 and Ge Kβ2 bands and the XPS valence-band spectrum reveals that the principal contributions of the Se 4p and Ge 4p states occur in the upper and central portions of the valence band of TlInGe2Se6, respectively, with also their substantial contributions in other portions of the band. The bandgap energy of TlInGe2Se6 at the level of αg=103 cm-1 is equal to 2.38 eV at room temperature.

Type-II quantum wells with tensile-strained GaAsSb layers for interband cascade lasers with tailored valence band mixing

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

Motyka, M.; Dyksik, M.; Ryczko, K.

Optical properties of modified type II W-shaped quantum wells have been investigated with the aim to be utilized in interband cascade lasers. The results show that introducing a tensely strained GaAsSb layer, instead of a commonly used compressively strained GaInSb, allows employing the active transition involving valence band states with a significant admixture of the light holes. Theoretical predictions of multiband k·p theory have been experimentally verified by using photoluminescence and polarization dependent photoreflectance measurements. These results open a pathway for practical realization of mid-infrared lasing devices with uncommon polarization properties including, for instance, polarization-independent midinfrared light emitters.

Isomer-specific vibronic structure of the 9-, 1-, and 2-anthracenyl radicals via slow photoelectron velocity-map imaging

PubMed Central

DeVine, Jessalyn A.; Levine, Daniel S.; Kim, Jongjin B.; Neumark, Daniel M.

2016-01-01

Polycyclic aromatic hydrocarbons, in various charge and protonation states, are key compounds relevant to combustion chemistry and astrochemistry. Here, we probe the vibrational and electronic spectroscopy of gas-phase 9-, 1-, and 2-anthracenyl radicals (C14H9) by photodetachment of the corresponding cryogenically cooled anions via slow photoelectron velocity-map imaging (cryo-SEVI). The use of a newly designed velocity-map imaging lens in combination with ion cooling yields photoelectron spectra with <2 cm−1 resolution. Isomer selection of the anions is achieved using gas-phase synthesis techniques, resulting in observation and interpretation of detailed vibronic structure of the ground and lowest excited states for the three anthracenyl radical isomers. The ground-state bands yield electron affinities and vibrational frequencies for several Franck–Condon active modes of the 9-, 1-, and 2-anthracenyl radicals; term energies of the first excited states of these species are also measured. Spectra are interpreted through comparison with ab initio quantum chemistry calculations, Franck–Condon simulations, and calculations of threshold photodetachment cross sections and anisotropies. Experimental measures of the subtle differences in energetics and relative stabilities of these radical isomers are of interest from the perspective of fundamental physical organic chemistry and aid in understanding their behavior and reactivity in interstellar and combustion environments. Additionally, spectroscopic characterization of these species in the laboratory is essential for their potential identification in astrochemical data. PMID:26792521

Photoelectron energy loss and spectral features deduced by the plasma line technique. [in topside F region

NASA Technical Reports Server (NTRS)

Abreu, V. J.; Carlson, H. C.

1977-01-01

Plasma line data gathered at the Arecibo Observatory are used to examine relative variations in topside F region differential photoelectron fluxes in the 5- to 20-eV range. A spectral feature not found in present theoretically calculated spectra is noted near 15 eV. A new approach to the interpretation of the measured spectra is taken, which allows a qualitative estimate of the relative importance of different energy loss mechanisms. The altitude variation of the observed photoelectron flux energy spectra at the higher altitudes (above 350 km) and the lower energies (less than 10 eV) agrees quantitatively with the expected variation of the spectrum.

Sample-morphology effects on x-ray photoelectron peak intensities. III. Simulated spectra of model core–shell nanoparticles

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

Powell, Cedric J., E-mail: cedric.powell@nist.gov; Chudzicki, Maksymilian; Werner, Wolfgang S. M.

2015-09-15

The National Institute of Standards and Technology database for the simulation of electron spectra for surface analysis has been used to simulate Cu 2p photoelectron spectra for four types of spherical copper–gold nanoparticles (NPs). These simulations were made to extend the work of Tougaard [J. Vac. Sci. Technol. A 14, 1415 (1996)] and of Powell et al. [J. Vac. Sci. Technol. A 31, 021402 (2013)] who performed similar simulations for four types of planar copper–gold films. The Cu 2p spectra for the NPs were compared and contrasted with analogous results for the planar films and the effects of elastic scatteringmore » were investigated. The new simulations were made for a monolayer of three types of Cu/Au core–shell NPs on a Si substrate: (1) an Au shell of variable thickness on a Cu core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm; (2) a Cu shell of variable thickness on an Au core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm; and (3) an Au shell of variable thickness on a 1 nm Cu shell on an Au core with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm. For these three morphologies, the outer-shell thickness was varied until the Cu 2p{sub 3/2} peak intensity was the same (within 2%) as that found in our previous work with planar Cu/Au morphologies. The authors also performed similar simulations for a monolayer of spherical NPs consisting of a CuAu{sub x} alloy (also on a Si substrate) with diameters of 0.5, 1.0, 2.0, 5.0, and 10.0 nm. In the latter simulations, the relative Au concentration (x) was varied to give the same Cu 2p{sub 3/2} peak intensity (within 2%) as that found previously. For each morphology, the authors performed simulations with elastic scattering switched on and off. The authors found that elastic-scattering effects were generally strong for the Cu-core/Au-shell and weak for the Au-core/Cu-shell NPs; intermediate elastic-scattering effects were found for the Au-core/Cu-shell/Au-shell NPs. The shell thicknesses required

Valence holes observed in nanodiamonds dispersed in water

NASA Astrophysics Data System (ADS)

Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F.

2015-02-01

Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed.Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed. Electronic supplementary information (ESI) available: Experimental methods, details on XAS/XES normalization and background correction procedures. See DOI: 10.1039/c4nr06639a

Study of Nb2O(y) (y = 2-5) anion and neutral clusters using anion photoelectron spectroscopy and density functional theory calculations.

PubMed

Mann, Jennifer E; Waller, Sarah E; Rothgeb, David W; Jarrold, Caroline Chick

2011-09-14

A study combining anion photoelectron spectroscopy and density functional theory calculations on the transition metal suboxide series, Nb(2)O(y)(-) (y = 2-5), is described. Photoelectron spectra of the clusters are obtained, and Franck-Condon simulations using calculated anion and neutral structures and frequencies are used to evaluate the calculations and assign transitions observed in the spectra. The spectra, several of which exhibit partially resolved vibrational structure, show an increase in electron affinity with increasing cluster oxidation state. Hole-burning experiments suggest that the photoelectron spectra of both Nb(2)O(2)(-) and Nb(2)O(3)(-) have contributions from more than one structural isomer. Reasonable agreement between experiment and computational results is found among all oxides. © 2011 American Institute of Physics

Valence structures of aromatic bioactive compounds: a combined theoretical and experimental study.

PubMed

Wickrama Arachchilage, Anoja Pushpamali; Feyer, Vitaliy; Plekan, Oksana; Iakhnenko, Marianna; Prince, Kevin C; Wang, Feng

2012-09-01

Valence electronic structures of three recently isolated aryl bioactive compounds, namely 2-phenylethanol (2PE), p-hydroxyphenylethanol (HPE) and 4-hydroxybenzaldehyde (HBA), are studied using a combined theoretical and experimental method. Density functional theory-based calculations indicate that the side chains cause electron charge redistribution and therefore influence the aromaticity of the benzene derivatives. The simulated IR spectra further reveal features induced by the side chains. Solvent effects on the IR spectra are simulated using the polarizable continuum model, which exhibits enhancement of the O-H stretch vibrations with significant red-shift of 464 cm(-1) in 2PE. A significant spectral peak splitting of 94 cm(-1) between O(4)-H and O(8)-H of HPE is revealed in an aqueous environment. Experimental measurements for valence binding energy spectra for 2PE, HPE and HBA are presented and analyzed using outer-valence Green function calculations. The experimental (predicted) first ionization energies are measured as 9.19 (8.79), 8.47 (8.27) and 8.97 (8.82) eV for 2PE, HPE and HBA, respectively. The frontier orbitals (highest occupied molecular orbitals, HOMOs, and lowest unoccupied molecular orbitals, LUMOs) have similar atomic orbital characters although the HOMO-LUMO energy gaps are quite different.

Electronic structure and fundamental absorption edges of KPb2Br5, K0.5Rb0.5Pb2Br5, and RbPb2Br5 single crystals

NASA Astrophysics Data System (ADS)

Tarasova, A. Yu.; Isaenko, L. I.; Kesler, V. G.; Pashkov, V. M.; Yelisseyev, A. P.; Denysyuk, N. M.; Khyzhun, O. Yu.

2012-05-01

X-ray photoelectron core-level and valence-band spectra for pristine and Ar+-ion irradiated (001) surfaces of KPb2Br5, K0.5Rb0.5Pb2Br5, and RbPb2Br5 single crystals grown by the Bridgman method have been measured and fundamental absorption edges of the ternary bromides have been recorded in the polarized light at 300 K and 80 K. The present X-ray photoelectron spectroscopy (XPS) results reveal high chemical stability of (001) surfaces of KxRb1-xPb2Br5 (x=0, 0.5, and 1.0) single crystals. Substitution of potassium for rubidium in KxRb1-xPb2Br5 does not cause any changes of binding energy values and shapes of the XPS constituent element core-level spectra. Measurements of the fundamental absorption edges indicate that band gap energy, Eg, increases by about 0.14 and 0.19 eV when temperature decreases from 300 K to 80 K in KPb2Br5 and RbPb2Br5, respectively. Furthermore, there is no dependence of the Eg value for KPb2Br5 upon the light polarization, whilst the band gap energy value for RbPb2Br5 is bigger by 0.03-0.05 eV in the case of E‖c compared to those in the cases of E‖a and E‖b.

Quasiparticle band offset at the (001) interface and band gaps in ultrathin superlattices of GaAs-AlAs heterojunctions

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

Zhang, S.B.; Cohen, M.L.; Louie, S.G.

1990-05-15

A newly developed first-principles quasiparticle theory is used to calculate the band offset at the (001) interface and band gaps in 1{times}1 and 2{times}2 superlattices of GaAs-AlAs heterojunctions. We find a sizable many-body contribution to the valence-band offset which is dominated by the many-body corrections to bulk GaAs and AlAs quasiparticle energies. The resultant offset {Delta}{ital E}{sub {ital v}}=0.53{plus minus}0.05 eV is in good agreement with the recent experimental values of 0.50--0.56 eV. Our calculated direct band gaps for ultrathin superlattices are also in good agreement with experiment. The {ital X}{sub 1{ital c}}-derived state at point {bar {Gamma}}, is however,more » above the {Gamma}{sub 1{ital c}}-derived state for both the 1{times}1 and 2{times}2 lattices, contrary to results obtained under the virtual-crystal approximation (a limiting case for the Kronig-Penny model) and some previous local-density-approximation (corrected) calculations. The differences are explained in terms of atomic-scale localizations and many-body effects. Oscillator strengths and the effects of disorder on the spectra are discussed.« less

Strain Dependent Electronic Structure and Band Offset Tuning at Heterointerfaces of ASnO3 (A=Ca, Sr, and Ba) and SrTiO3

PubMed Central

Baniecki, John D.; Yamazaki, Takashi; Ricinschi, Dan; Van Overmeere, Quentin; Aso, Hiroyuki; Miyata, Yusuke; Yamada, Hiroaki; Fujimura, Norifumi; Maran, Ronald; Anazawa, Toshihisa; Valanoor, Nagarajan; Imanaka, Yoshihiko

2017-01-01

The valence band (VB) electronic structure and VB alignments at heterointerfaces of strained epitaxial stannate ASnO3 (A=Ca, Sr, and Ba) thin films are characterized using in situ X-ray and ultraviolet photoelectron spectroscopies, with band gaps evaluated using spectroscopic ellipsometry. Scanning transmission electron microscopy with geometric phase analysis is used to resolve strain at atomic resolution. The VB electronic structure is strain state dependent in a manner that correlated with a directional change in Sn-O bond lengths with strain. However, VB offsets are found not to vary significantly with strain, which resulted in ascribing most of the difference in band alignment, due to a change in the band gaps with strain, to the conduction band edge. Our results reveal significant strain tuning of conduction band offsets using epitaxial buffer layers, with strain-induced offset differences as large as 0.6 eV possible for SrSnO3. Such large conduction band offset tunability through elastic strain control may provide a pathway to minimize the loss of charge confinement in 2-dimensional electron gases and enhance the performance of photoelectrochemical stannate-based devices. PMID:28195149

Determination of band alignment at two-dimensional MoS2/Si van der Waals heterojunction

NASA Astrophysics Data System (ADS)

Goel, Neeraj; Kumar, Rahul; Mishra, Monu; Gupta, Govind; Kumar, Mahesh

2018-06-01

To understand the different mechanism occurring at the MoS2-silicon interface, we have fabricated a MoS2/Si heterojunction by exfoliating MoS2 on top of the silicon substrate. Raman spectroscopy and atomic force microscopy (AFM) measurement expose the signature of few-layers in the deposited MoS2 flake. Herein, the temperature dependence of the energy barrier and carrier density at the MoS2/Si heterojunction has been extensively investigated. Furthermore, to study band alignment at the MoS2/Si interface, we have calculated a valence band offset of 0.66 ± 0.17 eV and a conduction band offset of 0.42 ± 0.17 eV using X-ray and Ultraviolet photoelectron spectroscopy. We determined a type-II band alignment at the interface which is very conducive for the transport of photoexcited carriers. As a proof-of-concept application, we extend our analysis of the photovoltaic behavior of the MoS2/Si heterojunction. This work provides not only a comparative study between MoS2/p-Si and MoS2/n-Si heterojunctions but also paves the way to engineer the properties of the interface for the future integration of MoS2 with silicon.

Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation.

PubMed

Gartmann, Thomas E; Hartweg, Sebastian; Ban, Loren; Chasovskikh, Egor; Yoder, Bruce L; Signorell, Ruth

2018-06-06

Low-energy electron scattering in water clusters (H2O)n with average cluster sizes of n < 700 is investigated by angle-resolved photoelectron spectroscopy using high harmonic radiation at photon energies of 14.0, 20.3, and 26.5 eV for ionization from the three outermost valence orbitals. The measurements probe the evolution of the photoelectron anisotropy parameter β as a function of cluster size. A remarkably steep decrease of β with increasing cluster size is observed, which for the largest clusters reaches liquid bulk values. Detailed electron scattering calculations reveal that neither gas nor condensed phase scattering can explain the cluster data. Qualitative agreement between experiment and simulations is obtained with scattering calculations that treat cluster scattering as an intermediate case between gas and condensed phase scattering.

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy.

PubMed

Goncharov, Vasiliy; Kaledin, Leonid A; Heaven, Michael C

2006-10-07

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.

Pressure and magnetic field effects on the valence transition of EuRh2Si2

NASA Astrophysics Data System (ADS)

Mitsuda, Akihiro; Kishaba, Eigo; Fujimoto, Takumi; Oyama, Kohei; Wada, Hirofumi; Mizumaki, Masaichiro; Kawamura, Naomi; Ishimatsu, Naoki

2018-05-01

We have measured the X-ray absorption spectra (XAS), electrical resistivity and magnetic susceptibility of EuRh2Si2, which undergoes a valence transition under high pressures. A sharp decrease in the Eu valence determined from the XAS was observed at around 70 K in the temperature dependence at P = 1.2-1.9 GPa. In the temperature dependence of electrical resistivity and magnetic susceptibility, we observed jumps associated with the temperature-induced valence transition under high pressures. The magnetoresistance detected a field-induced valence transition. The results are discussed from the thermodynamic point of view.

Effects of ultrashort laser pulses on angular distributions of photoionization spectra.

PubMed

Ooi, C H Raymond; Ho, W L; Bandrauk, A D

2017-07-27

We study the photoelectron spectra by intense laser pulses with arbitrary time dependence and phase within the Keldysh framework. An efficient semianalytical approach using analytical transition matrix elements for hydrogenic atoms in any initial state enables efficient and accurate computation of the photoionization probability at any observation point without saddle point approximation, providing comprehensive three dimensional photoelectron angular distribution for linear and elliptical polarizations, that reveal the intricate features and provide insights on the photoionization characteristics such as angular dispersions, shift and splitting of photoelectron peaks from the tunneling or above threshold ionization(ATI) regime to non-adiabatic(intermediate) and multiphoton ionization(MPI) regimes. This facilitates the study of the effects of various laser pulse parameters on the photoelectron spectra and their angular distributions. The photoelectron peaks occur at multiples of 2ħω for linear polarization while  odd-ordered peaks are suppressed in the direction perpendicular to the electric field. Short pulses create splitting and angular dispersion where the peaks are strongly correlated to the angles. For MPI and elliptical polarization with shorter pulses the peaks split into doublets and the first peak vanishes. The carrier envelope phase(CEP) significantly affects the ATI spectra while the Stark effect shifts the spectra of intermediate regime to higher energies due to interference.

On the origin of the low-temperature band in depolarization current spectra of poled multicomponent silicate glasses

NASA Astrophysics Data System (ADS)

Brunkov, P. N.; Kaasik, V. P.; Lipovskii, A. A.; Tagantsev, D. K.

2018-04-01

Thermally stimulated depolarization current spectra of poled silicate multicomponent glasses in the vicinity of room temperature (220-320 K) have been recorded and two bands, typical for such glasses, have been observed. It was shown that the high-temperature band (at about 290 K) is related to the relaxation of poled glass structure in the bulk, while the low-temperature band (at about 230-270 K) should be attributed to the surface phenomenon—absorption/desorption of positive species of ambient atmosphere, supposedly, water cluster ions H+(H2O)n.

Rebonding of Se to As and Ge in Ge33As12Se55 films upon thermal annealing: Evidence from x-ray photoelectron spectra investigations

NASA Astrophysics Data System (ADS)

Wang, R. P.; Choi, D. Y.; Rode, A. V.; Madden, S. J.; Luther-Davies, B.

2007-06-01

We have measured and analyzed x-ray photoelectron spectra (XPS) of as-grown and annealed Ge33As12Se55 films compared with bulk material. We found that the as-grown film contains a large number of separated Se clusters which can coalesce with As and Ge after annealing at high temperatures. In addition, both the Ge and As 3d spectra show the presence of oxides. While the Ge oxidation increases with an increasing annealing temperature, As oxidation is almost unaffected by annealing. The difference could be due to their different electro-negativities. Our results suggest that, while thermal annealing is effective to move the film toward the bond structure of bulk glass, the simultaneous surface oxidation must be suppressed in order to achieve high quality films.

The origin of 2.7 eV luminescence and 5.2 eV excitation band in hafnium oxide

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

Perevalov, T. V., E-mail: timson@isp.nsc.ru; Novosibirsk State University, 2 Pirogova St., 630090 Novosibirsk; Aliev, V. Sh.

2014-02-17

The origin of a blue luminescence band at 2.7 eV and a luminescence excitation band at 5.2 eV of hafnia has been studied in stoichiometric and non-stoichiometric hafnium oxide films. Experimental and calculated results from the first principles valence band spectra showed that the stoichiometry violation leads to the formation of the peak density of states in the band gap caused by oxygen vacancies. Cathodoluminescence in the non-stoichiometric film exhibits a band at 2.65 eV that is excited at the energy of 5.2 eV. The optical absorption spectrum calculated for the cubic phase of HfO{sub 2} with oxygen vacancies showsmore » a peak at 5.3 eV. Thus, it could be concluded that the blue luminescence band at 2.7 eV and HfO{sub x} excitation peak at 5.2 eV are due to oxygen vacancies. The thermal trap energy in hafnia was estimated.« less

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

NASA Technical Reports Server (NTRS)

Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Ramdas, A.; Su, Ching-Hua; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(x)V(1-x), alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(x),V(1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(x)Te(l-x) and ZnSe(Y)Te(1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(y)Te(1-y) alloys in the entire composition range, 0 less than or equal to y less than or equal to 1. The samples used in this study are bulk ZnSe(y)Te(1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the interaction between

Identification of the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch in stratospheric solar occultation spectra

NASA Technical Reports Server (NTRS)

Perrin, A.; Flaud, J.-M.; Camy-Peyret, C.; Goldman, A.; Rinsland, C. P.; Gunson, M. R.

1994-01-01

The spectroscopic identification for the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch at 830.4/cm is reported based on 0.01/cm resolution solar occultation spectra of the lower stratosphere recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer and a recent analysis of this band. Least-squares fits to 0.0025/cm resolution laboratory spectra in the Q branch region indicate an integrated intensity of 0.529 x 10(exp -18)/cm/mol/sq cm at 296 K for this weak band. Stratospheric HNO3 retrievals derived from the ATMOS data are consistent with this value within its estimated uncertainty of about +/- 30%. A set of spectroscopic line parameters suitable for atmospheric studies has been generated.

Early stages of plasma induced nitridation of Si (111) surface and study of interfacial band alignment

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

Shetty, Satish; Shivaprasad, S. M., E-mail: smsprasad@jncasr.ac.in

2016-02-07

We report here a systematic study of the nitridation of the Si (111) surface by nitrogen plasma exposure. The surface and interface chemical composition and surface morphology are investigated by using RHEED, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM). At the initial stage of nitridation two superstructures—“8 × 8” and “8/3 × 8/3”—form, and further nitridation leads to 1 × 1 stoichiometric silicon nitride. The interface is seen to have the Si{sup 1+} and Si{sup 3+} states of silicon bonding with nitrogen, which suggests an atomically abrupt and defect-free interface. The initial single crystalline silicon nitride layers are seen to become amorphous at higher thicknesses.more » The AFM image shows that the nitride nucleates at interfacial dislocations that are connected by sub-stoichiometric 2D-nitride layers, which agglomerate to form thick overlayers. The electrical properties of the interface yield a valence band offset that saturates at 1.9 eV and conduction band offset at 2.3 eV due to the evolution of the sub-stoichiometric interface and band bending.« less

Mapping the conduction band edge density of states of γ-In2Se3 by diffuse reflectance spectra

NASA Astrophysics Data System (ADS)

Kumar, Pradeep; Vedeshwar, Agnikumar G.

2018-03-01

It is demonstrated that the measured diffuse reflectance spectra of γ-In2Se3 can be used to map the conduction band edge density of states through Kubelka-Munk analysis. The Kubelka-Munk function derived from the measured spectra almost mimics the calculated density of states in the vicinity of conduction band edge. The calculation of density of states was carried out using first-principles approach yielding the structural, electronic, and optical properties. The calculations were carried out implementing various functionals and only modified Tran and Blaha (TB-MBJ) results tally closest with the experimental result of band gap. The electronic and optical properties were calculated using FP-LAPW + lo approach based on the Density Functional Theory formalism implementing only TB-mBJ functional. The electron and hole effective masses have been calculated as me * = 0.25 m 0 and mh * = 1.11 m 0 , respectively. The optical properties clearly indicate the anisotropic nature of γ-In2Se3.

A New Ka-Band Scanning Radar Facility: Polarimetric and Doppler Spectra Measurements of Snow Events

NASA Astrophysics Data System (ADS)

Oue, M.; Kollias, P.; Luke, E. P.; Mead, J.

2017-12-01

Polarimetric radar analyses offer the capability of identification of ice hydrometeor species as well as their spatial distributions. In addition to polarimetric parameter observations, Doppler spectra measurements offer unique insights into ice particle properties according to particle fall velocities. In particular, millimeter-wavelength radar Doppler spectra can reveal supercooled liquid cloud droplets embedded in ice precipitation clouds. A Ka-band scanning polarimetric radar, named KASPR, was installed in an observation facility at Stony Brook University, located 22 km west of the KOKX NEXRAD radar at Upton, NY. The KASPR can measure Doppler spectra and full polarimetric variables, including radar reflectivity, differential reflectivity (ZDR), differential phase (φDP), specific differential phase (KDP), correlation coefficient (ρhv), and linear depolarization ratio (LDR). The facility also includes a micro-rain radar and a microwave radiometer capable of measuring reflectivity profiles and integrated liquid water path, respectively. The instruments collected initial datasets during two snowstorm events and two snow shower events in March 2017. The radar scan strategy was a combination of PPI scans at 4 elevation angles (10, 20, 45, and 60°) and RHI scans in polarimetry mode, and zenith pointing with Doppler spectra collection. During the snowstorm events the radar observed relatively larger ZDR (1-1.5 dB) and enhanced KDP (1-2 ° km-1) at heights corresponding to a plate/dendrite crystal growth regime. The Doppler spectra showed that slower-falling particles (< 0.5 m s-1) coexisted with faster-falling particles (> 1 m s-1). The weakly increased ZDR could be produced by large, faster falling particles such as quasi-spherical aggregates, while the enhanced KDP could be produced by highly-oriented oblate, slowly-falling particles. Below 2 km altitude, measurements of dual wavelength ratio (DWR) based on Ka and S-band reflectivities from the KASPR and NEXRAD

Interface energy band alignment at the all-transparent p-n heterojunction based on NiO and BaSnO3

NASA Astrophysics Data System (ADS)

Zhang, Jiaye; Han, Shaobo; Luo, Weihuang; Xiang, Shuhuai; Zou, Jianli; Oropeza, Freddy E.; Gu, Meng; Zhang, Kelvin H. L.

2018-04-01

Transparent oxide semiconductors hold great promise for many optoelectronic devices such as transparent electronics, UV-emitting devices, and photodetectors. A p-n heterojunction is the most ubiquitous building block to realize these devices. In this work, we report the fabrication and characterization of the interface properties of a transparent heterojunction consisting of p-type NiO and n-type perovskite BaSnO3. We show that high-quality NiO thin films can be epitaxially grown on BaSnO3 with sharp interfaces because of a small lattice mismatch (˜1.3%). The diode fabricated from this heterojunction exhibits rectifying behavior with a ratio of 500. X-ray photoelectron spectroscopy reveals a type II or "staggered" band alignment with valence and conduction band offsets of 1.44 eV and 1.86 eV, respectively. Moreover, a large upward band bending potential of 0.90 eV for BaSnO3 and a downward band bending potential of 0.15 eV for NiO were observed in the interface region. Such electronic properties have important implication for optoelectronic applications as the large built-in potential provides favorable energetics for photo-generated electron-hole separation/migration.

Electronic structure of uranium overlayers on magnesium and aluminium

NASA Astrophysics Data System (ADS)

Gouder, T.

1997-06-01

We studied U overlayers on polycrystalline Mg and Al by X-ray and ultra-violet photoelectron spectroscopies (XPS and UPS, respectively), and compared the mode of growth and the evolution of the electronic structure as a function of coverage. The goal of this work was to detect localization, or at least correlation effects, in U overlayers and U substrate near surface alloys, which were expected to occur because of the reduced U 5f bandwidth in these systems. On Mg, U deposits as a pure overlayer without any interdiffusion, while on Al spontaneous interdiffusion takes place. The U 4f spectra of {U}/{Mg} show only weak correlation satellites. Nevertheless, the asymmetrical shape of the U 4f peak indicates 5f band narrowing. On Al, strong correlation satellites are observed in addition to plasmon loss features. It seems that U-substrate interactions promote correlation effects, while the reduced coordination in overlayers plays a less important role. UPS valence-band (VB) spectra of the two systems look remarkably similar. They do not show any correlation satellites. With decreasing overlayer thickness the 5f peak narrows, which is attributed to 5f band narrowing at the surface.

Levels of Valence

PubMed Central

Shuman, Vera; Sander, David; Scherer, Klaus R.

2013-01-01

The distinction between the positive and the negative is fundamental in our emotional life. In appraisal theories, in particular in the component process model of emotion (Scherer, 1984, 2010), qualitatively different types of valence are proposed based on appraisals of (un)pleasantness, goal obstructiveness/conduciveness, low or high power, self-(in)congruence, and moral badness/goodness. This multifaceted conceptualization of valence is highly compatible with the frequent observation of mixed feelings in real life. However, it seems to contradict the one-dimensional conceptualization of valence often encountered in psychological theories, and the notion of valence as a common currency used to explain choice behavior. Here, we propose a framework to integrate the seemingly disparate conceptualizations of multifaceted valence and one-dimensional valence by suggesting that valence should be conceived at different levels, micro and macro. Micro-valences correspond to qualitatively different types of evaluations, potentially resulting in mixed feelings, whereas one-dimensional macro-valence corresponds to an integrative “common currency” to compare alternatives for choices. We propose that conceptualizing levels of valence may focus research attention on the mechanisms that relate valence at one level (micro) to valence at another level (macro), leading to new hypotheses, and addressing various concerns that have been raised about the valence concept, such as the valence-emotion relation. PMID:23717292

IDENTIFICATION OF NEODYMIUM IN THE APOGEE H -BAND SPECTRA

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

Hasselquist, Sten; Holtzman, Jon; Chojnowski, Drew

2016-12-10

We present the detection of 10 lines of singly ionized neodymium (Nd ii, Z  = 60) in H -band spectra using observations from the SDSS-III Apache Point Observatory Galactic Evolution Experiment (APOGEE) survey. These lines were detected in a metal-poor ([Fe/H] ∼ −1.5), neutron-capture element-enhanced star recently discovered in the APOGEE sample. Using an optical high-resolution spectrum, we derive a Nd abundance for this star using Nd ii lines with precise, laboratory-derived gf values. This optical abundance is used to derive log( gf ) values for the H -band lines. We use these lines to rederive Nd ii abundances for two more metal-rich, s -process enhancedmore » stars observed by APOGEE and find that these lines yield consistent Nd ii abundances, confirming the Nd enhancement of these stars. We explore the region of parameter space in the APOGEE sample over which these lines can be used to measure Nd ii abundances. We find that Nd abundances can be reliably derived for ∼18% of the red giants observed by APOGEE. This will result in ∼50,000 Milky Way stars with Nd ii abundances following the conclusion of APOGEE-2, allowing for studies of neutron-capture element abundance distributions across the entire Milky Way.« less

WIDE-BAND SPECTRA OF GIANT RADIO PULSES FROM THE CRAB PULSAR

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

Mikami, Ryo; Asano, Katsuaki; Tanaka, Shuta J.

2016-12-01

We present the results of the simultaneous observation of giant radio pulses (GRPs) from the Crab pulsar at 0.3, 1.6, 2.2, 6.7, and 8.4 GHz with four telescopes in Japan. We obtain 3194 and 272 GRPs occurring at the main pulse and the interpulse phases, respectively. A few GRPs detected at both 0.3 and 8.4 GHz are the most wide-band samples ever reported. In the frequency range from 0.3 to 2.2 GHz, we find that about 70% or more of the GRP spectra are consistent with single power laws and their spectral indices are distributed from −4 to −1. Wemore » also find that a significant number of GRPs have such a hard spectral index (approximately −1) that the fluence at 0.3 GHz is below the detection limit (“dim-hard” GRPs). Stacking light curves of such dim-hard GRPs at 0.3 GHz, we detect consistent enhancement compared to the off-GRP light curve. Our samples show apparent correlations between the fluences and the spectral hardness, which indicates that more energetic GRPs tend to show softer spectra. Our comprehensive studies on the GRP spectra are useful materials to verify the GRP model of fast radio bursts in future observations.« less

Photoelectron interference fringes by super intense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Toyota, Koudai; Tolstikhin, Oleg I.; Morishita, Toru; Watanabe, Shinichi

2009-09-01

The photoelectron spectra of H- produced by circularly polarized strong high-frequency laser pulses are theoretically studied. An oscillating substructure in the above-threshold ionization (ATI) peaks is observed, which extends the validity of the earlier findings in the 1D calculations [K. Toyota et al., Phys. Rev. A 76, 043418 (2007)] and 3D calculations for linear polarization [O. I. Tolstikhin, Phys. Rev. A 77, 032712 (2008)]. Its origin is due to an interference between a pair of photoelectron wave packets created in the rising and falling part of the pulse, which appears clearly in the stabilization regime.

Isomer-specific vibronic structure of the 9-, 1-, and 2-anthracenyl radicals via slow photoelectron velocity-map imaging

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

Weichman, Marissa L.; DeVine, Jessalyn A.; Levine, Daniel S.

Polycyclic aromatic hydrocarbons, in various charge and protonation states, are key compounds relevant to combustion chemistry and astrochemistry. In this paper, we probe the vibrational and electronic spectroscopy of gas-phase 9-, 1-, and 2-anthracenyl radicals (C 14H 9) by photodetachment of the corresponding cryogenically cooled anions via slow photoelectron velocity-map imaging (cryo-SEVI). The use of a newly designed velocity-map imaging lens in combination with ion cooling yields photoelectron spectra with <2 cm -1 resolution. Isomer selection of the anions is achieved using gas-phase synthesis techniques, resulting in observation and interpretation of detailed vibronic structure of the ground and lowest excitedmore » states for the three anthracenyl radical isomers. The ground-state bands yield electron affinities and vibrational frequencies for several Franck–Condon active modes of the 9-, 1-, and 2-anthracenyl radicals; term energies of the first excited states of these species are also measured. Spectra are interpreted through comparison with ab initio quantum chemistry calculations, Franck–Condon simulations, and calculations of threshold photodetachment cross sections and anisotropies. Experimental measures of the subtle differences in energetics and relative stabilities of these radical isomers are of interest from the perspective of fundamental physical organic chemistry and aid in understanding their behavior and reactivity in interstellar and combustion environments. Finally and additionally, spectroscopic characterization of these species in the laboratory is essential for their potential identification in astrochemical data.« less

Isomer-specific vibronic structure of the 9-, 1-, and 2-anthracenyl radicals via slow photoelectron velocity-map imaging

DOE PAGES

Weichman, Marissa L.; DeVine, Jessalyn A.; Levine, Daniel S.; ...

2016-01-20

Polycyclic aromatic hydrocarbons, in various charge and protonation states, are key compounds relevant to combustion chemistry and astrochemistry. In this paper, we probe the vibrational and electronic spectroscopy of gas-phase 9-, 1-, and 2-anthracenyl radicals (C 14H 9) by photodetachment of the corresponding cryogenically cooled anions via slow photoelectron velocity-map imaging (cryo-SEVI). The use of a newly designed velocity-map imaging lens in combination with ion cooling yields photoelectron spectra with <2 cm -1 resolution. Isomer selection of the anions is achieved using gas-phase synthesis techniques, resulting in observation and interpretation of detailed vibronic structure of the ground and lowest excitedmore » states for the three anthracenyl radical isomers. The ground-state bands yield electron affinities and vibrational frequencies for several Franck–Condon active modes of the 9-, 1-, and 2-anthracenyl radicals; term energies of the first excited states of these species are also measured. Spectra are interpreted through comparison with ab initio quantum chemistry calculations, Franck–Condon simulations, and calculations of threshold photodetachment cross sections and anisotropies. Experimental measures of the subtle differences in energetics and relative stabilities of these radical isomers are of interest from the perspective of fundamental physical organic chemistry and aid in understanding their behavior and reactivity in interstellar and combustion environments. Finally and additionally, spectroscopic characterization of these species in the laboratory is essential for their potential identification in astrochemical data.« less

Effects of local field and inherent strain in reflectance anisotropy spectra of AIIIBV semiconductors with naturally oxidized surfaces

NASA Astrophysics Data System (ADS)

Berkovits, V. L.; Kosobukin, V. A.; Gordeeva, A. B.

2015-12-01

Reflectance anisotropy (RA) spectra of naturally oxidized (001) surfaces of GaAs and InAs crystals are measured for photon energies from 1.5 up to 5.5 eV. The differential high-accuracy RA spectra reveal features substantially different from those caused by either a reconstruction of clean surface or a built-in near-surface electric field. Models of atomic structure with anisotropic transition layers of excess arsenic atoms specific for GaAs(001)/oxide and InAs(001)/oxide interfaces are proposed. In conformity with these models, a general theory of reflectance anisotropy is developed for semiconductor/oxide interfaces within the Green's function technique. The theory takes into account the combined effect of local field due to interface dipoles and of intrinsic near-surface strain of the crystal. Measured RA spectra are analyzed in the model of valence-bond dipoles occupying a rectangular lattice in a multilayer medium. Comparing the measured and calculated spectra, we conclude that RA spectra of oxidized GaAs(001) and InAs(001) surfaces are simultaneously influenced by interface and near-surface anisotropies. The former is responsible for the broad-band spectral features which are associated with polarizability of the valence bonds attached to As atoms at the crystal/oxide interface. The near-surface anisotropy is due to inherent uniaxial straining the near-surface region of crystal. The effect of strain on RA spectra is experimentally and theoretically substantiated for GaAs crystal wafers undergone a uniaxial applied stress. Basically, this work results in the following. It establishes the physical nature of different levels of RA spectra observed in a majority of papers, but never analyzed. It demonstrates how the studied features of RA spectra could be applied for optical characterization of strained interfaces and atomic layers.

Pressure and temperature dependence of the Ce valence and c -f hybridization gap in Ce T2In5(T =Co ,Rh ,Ir ) heavy-fermion superconductors

NASA Astrophysics Data System (ADS)

Yamaoka, H.; Yamamoto, Y.; Schwier, E. F.; Honda, F.; Zekko, Y.; Ohta, Y.; Lin, J.-F.; Nakatake, M.; Iwasawa, H.; Arita, M.; Shimada, K.; Hiraoka, N.; Ishii, H.; Tsuei, K.-D.; Mizuki, J.

2015-12-01

Pressure- and temperature-induced changes in the Ce valence and c -f hybridization of the Ce115 superconductors have been studied systematically. Resonant x-ray-emission spectroscopy indicated that the increase of the Ce valence with pressure was significant for CeCoIn5, and moderate for CeIr (In0.925Cd0.075)5 . We found no abrupt change of the Ce valence in the Kondo regime for CeIr (In0.925Cd0.075)5 , which suggests that valence fluctuations are unlikely to mediate the superconductivity in this material. X-ray-diffraction results were consistent with the pressure-induced change in the Ce valence. High-resolution photoelectron spectroscopy revealed a temperature-dependent reduction of the spectral intensity at the Fermi level, indicating enhanced c -f hybridization on cooling.

Description of plasmon-like band in silver clusters: the importance of the long-range Hartree-Fock exchange in time-dependent density-functional theory simulations.

PubMed

Rabilloud, Franck

2014-10-14

Absorption spectra of Ag20 and Ag55(q) (q = +1, -3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.

Electronic structure of LiCoO2 thin films: A combined photoemission spectroscopy and density functional theory study

NASA Astrophysics Data System (ADS)

Ensling, David; Thissen, Andreas; Laubach, Stefan; Schmidt, Peter C.; Jaegermann, Wolfram

2010-11-01

The electronic properties of LiCoO2 have been studied by theoretical band-structure calculations (using density functional theory) and experimental methods (photoemission). Synchrotron-induced photoelectron spectroscopy, resonant photoemission spectroscopy (ResPES), and soft x-ray absorption (XAS) have been applied to investigate the electronic structure of both occupied and unoccupied states. High-quality PES spectra were obtained from stoichiometric and highly crystalline LiCoO2 thin films deposited “in situ” by rf magnetron sputtering. An experimental approach of separating oxygen- and cobalt-derived (final) states by ResPES in the valence-band region is presented. The procedure takes advantage of an antiresonant behavior of cobalt-derived states at the 3p-3d excitation threshold. Information about the unoccupied density of states has been obtained by OK XAS. The structure of the CoL absorption edge is compared to semiempirical charge-transfer multiplet calculations. The experimental results are furthermore compared with band-structure calculations considering three different exchange potentials [generalized gradient approximation (GGA), using a nonlocal Hubbard U (GGA+U) and using a hybrid functional (Becke, three-parameter, Lee-Yang-Parr [B3LYP])]. For these different approaches total density of states and partial valence-band density of states have been investigated. The best qualitative agreement with experimental results has been obtained by using a GGA+U functional with U=2.9eV .

Effect of relativity on the ionization spectra of the xenon fluorides XeFn (n=2, 4, 6).

PubMed

Pernpointner, Markus; Cederbaum, Lorenz S

2005-06-01

Noble gas compounds exhibit special chemical bonding situations and have been investigated by various spectroscopic and theoretical techniques. In this work we calculate the ionization spectra of the xenon fluorides (XeF2,XeF4, and XeF6) in the valence and subvalence (down to Xe 4d) areas by application of the recently developed Dirac-Hartree-Fock one-particle propagator technique. In this technique, the relativistic (four-component) and electron correlation effects are computed simultaneously. The xenon compounds show considerable spin-orbit splitting strongly influencing the photoelectron spectrum not reproducible in prior calculations. Comparison to one-component methods is made and the occurring satellite structures are interpreted. The satellite structures can be attributed either to the breakdown of the one-particle picture or to a reflection of intra-atomic and interatomic Auger decay processes within the molecule.

Efficient evaluation of epitaxial MoS2 on sapphire by direct band structure imaging

NASA Astrophysics Data System (ADS)

Kim, Hokwon; Dumcenco, Dumitru; Fregnaux, Mathieu; Benayad, Anass; Kung, Yen-Cheng; Kis, Andras; Renault, Olivier; Lanes Group, Epfl Team; Leti, Cea Team

The electronic band structure evaluation of two-dimensional metal dichalcogenides is critical as the band structure can be greatly influenced by the film thickness, strain, and substrate. Here, we performed a direct measurement of the band structure of as-grown monolayer MoS2 on single crystalline sapphire by reciprocal-space photoelectron emission microscopy with a conventional laboratory ultra-violet He I light source. Arrays of gold electrodes were deposited onto the sample in order to avoid charging effects due to the insulating substrate. This allowed the high resolution mapping (ΔE = 0.2 eV Δk = 0.05 Å-1) of the valence states in momentum space down to 7 eV below the Fermi level. The high degree of the epitaxial alignment of the single crystalline MoS2 nuclei was verified by the direct momentum space imaging over a large area containing multiple nuclei. The derived values of the hole effective mass were 2.41 +/-0.05 m0 and 0.81 +/-0.05 m0, respectively at Γ and K points, consistent with the theoretical values of the freestanding monolayer MoS2 reported in the literature. HK acknowledges the french CEA Basic Technological Research program (RTB) for funding.

Impact of Coulomb potential on peak structures arising in momentum and low-energy photoelectron spectra produced in strong-field ionization of laser-irradiated atoms

NASA Astrophysics Data System (ADS)

Pyak, P. E.; Usachenko, V. I.

2018-03-01

The phenomenon of pronounced peak structure(s) of longitudinal momentum distributions as well as a spike-like structure of low-energy spectra of photoelectrons emitted from laser-irradiated Ar and Ne atoms in a single ionization process is theoretically studied in the tunneling and multiphoton regimes of ionization. The problem is addressed assuming only the direct above-threshold ionization (ATI) as a physical mechanism underlying the phenomenon under consideration (viz. solely contributing to observed photoelectron momentum distributions (PMD)) and using the Coulomb-Volkov (CV) ansatz within the frame of conventional strong-field approximation (SFA) applied in the length-gauge formulation. The developed CV-SFA approach also incorporates the density functional theory essentially exploited for numerical composition of initial (laser-free) atomic state(s) constructed from atomic orbitals of Gaussian type. Our presented CV-SFA based (and laser focal-volume averaged) calculation results proved to be well reproducing both the pronounced double-peak and/or ATI-like multi-peak structure(s) experimentally observed in longitudinal PMD under conditions of tunneling and/or multiphoton regime, respectively. In addition, our CV-SFA results presented for tunneling regime also suggest and remarkably reproduce a pronounced structure observed in relevant experiments as a ‘spike-like’ enhanced maximum arising in low-energy region (around the value of about 1 eV) of photoelectron spectra. The latter consistency allows to identify and interpret these results as the so-called low-energy structure (LES) since the phenomenon proved to appear as the most prominent if the influence of Coulomb potential on photoelectron continuum states is maximally taken into account under calculations (viz. if the parameter Z in CV’s functions is put equal to 1). Moreover, the calculated LES proved to correspond (viz., established as closely related) to the mentioned double-peak structure arising

Photoluminescence and Band Alignment of Strained GaAsSb/GaAs QW Structures Grown by MBE on GaAs

PubMed Central

Sadofyev, Yuri G.; Samal, Nigamananda

2010-01-01

An in-depth optimization of growth conditions and investigation of optical properties including discussions on band alignment of GaAsSb/GaAs quantum well (QW) on GaAs by molecular beam epitaxy (MBE) are reported. Optimal MBE growth temperature of GaAsSb QW is found to be 470 ± 10 °C. GaAsSb/GaAs QW with Sb content ~0.36 has a weak type-II band alignment with valence band offset ratio QV ~1.06. A full width at half maximum (FWHM) of ~60 meV in room temperature (RT) photoluminescence (PL) indicates fluctuation in electrostatic potential to be less than 20 meV. Samples grown under optimal conditions do not exhibit any blue shift of peak in RT PL spectra under varying excitation.

Band Anticrossing in Highly Mismatched Compound Semiconductor Alloys

NASA Technical Reports Server (NTRS)

Yu, Kin Man; Wu, J.; Walukiewicz, W.; Ager, J. W.; Haller, E. E.; Miotkowski, I.; Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

2001-01-01

Compound semiconductor alloys in which metallic anions are partially replaced with more electronegative isoelectronic atoms have recently attracted significant attention. Group IIIN(sub x)V(sub 1-x) alloys with a small amount of the electronegative N substituting more metallic column V elements has been the most extensively studied class of such Highly Mismatched Alloys (HMAs). We have shown that many of the unusual properties of the IIIN(sub x)V(sub 1-x) alloys can be well explained by the Band Anticrossing (BAC) model that describes the electronic structure in terms of an interaction between highly localized levels of substitutional N and the extended states of the host semiconductor matrix. Most recently the BAC model has been also used to explain similar modifications of the electronic band structure observed in Te-rich ZnS(sub x)Te(sub 1-x) and ZnSe(sub y)Te(sub 1-y) alloys. To date studies of HMAs have been limited to materials with relatively small concentrations of highly electronegative atoms. Here we report investigations of the electronic structure of ZnSe(sub y)Te(sub 1-y) alloys in the entire composition range, y between 0 and 1. The samples used in this study are bulk ZnSe(sub y)Te(sub 1-y) crystals grown by either a modified Bridgman method or by physical vapor transport. Photomodulated reflection (PR) spectroscopy was used to measure the composition dependence of optical transitions from the valence band edge and from the spin-orbit split off band to the conduction band. The pressure dependence of the band gap was measured using optical absorption in a diamond anvil cell. We find that the energy of the spin-orbit split off valence band edge does not depend on composition and is located at about 3 eV below the conduction band edge of ZnSe. On the Te-rich side the pressure and the composition dependence of the optical transitions are well explained by the BAC model which describes the downward shift of the conduction band edge in terms of the

Ligand-Sensitive But Not Ligand-Diagnostic: Evaluating Cr Valence-to-Core X-ray Emission Spectroscopy as a Probe of Inner-Sphere Coordination

PubMed Central

2015-01-01

This paper explores the strengths and limitations of valence-to-core X-ray emission spectroscopy (V2C XES) as a probe of coordination environments. A library was assembled from spectra obtained for 12 diverse Cr complexes and used to calibrate density functional theory (DFT) calculations of V2C XES band energies. A functional dependence study was undertaken to benchmark predictive accuracy. All 7 functionals tested reproduce experimental V2C XES energies with an accuracy of 0.5 eV. Experimentally calibrated, DFT calculated V2C XES spectra of 90 Cr compounds were used to produce a quantitative spectrochemical series showing the V2C XES band energy ranges for ligands comprising 18 distinct classes. Substantial overlaps are detected in these ranges, which complicates the use of V2C XES to identify ligands in the coordination spheres of unknown Cr compounds. The ligand-dependent origins of V2C intensity are explored for a homologous series of [CrIII(NH3)5X]2+ (X = F, Cl, Br, and I) to rationalize the variable intensity contributions of these ligand classes. PMID:25496512

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection.

PubMed

Lehmann, C Stefan; Ram, N Bhargava; Powis, Ivan; Janssen, Maurice H M

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flight mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

Imaging photoelectron circular dichroism of chiral molecules by femtosecond multiphoton coincidence detection

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

Lehmann, C. Stefan; Ram, N. Bhargava; Janssen, Maurice H. M., E-mail: m.h.m.janssen@vu.nl

2013-12-21

Here, we provide a detailed account of novel experiments employing electron-ion coincidence imaging to discriminate chiral molecules. The full three-dimensional angular scattering distribution of electrons is measured after photoexcitation with either left or right circular polarized light. The experiment is performed using a simplified photoelectron-photoion coincidence imaging setup employing only a single particle imaging detector. Results are reported applying this technique to enantiomers of the chiral molecule camphor after three-photon ionization by circularly polarized femtosecond laser pulses at 400 nm and 380 nm. The electron-ion coincidence imaging provides the photoelectron spectrum of mass-selected ions that are observed in the time-of-flightmore » mass spectra. The coincident photoelectron spectra of the parent camphor ion and the various fragment ions are the same, so it can be concluded that fragmentation of camphor happens after ionization. We discuss the forward-backward asymmetry in the photoelectron angular distribution which is expressed in Legendre polynomials with moments up to order six. Furthermore, we present a method, similar to one-photon electron circular dichroism, to quantify the strength of the chiral electron asymmetry in a single parameter. The circular dichroism in the photoelectron angular distribution of camphor is measured to be 8% at 400 nm. The electron circular dichroism using femtosecond multiphoton excitation is of opposite sign and about 60% larger than the electron dichroism observed before in near-threshold one-photon ionization with synchrotron excitation. We interpret our multiphoton ionization as being resonant at the two-photon level with the 3s and 3p Rydberg states of camphor. Theoretical calculations are presented that model the photoelectron angular distribution from a prealigned camphor molecule using density functional theory and continuum multiple scattering X alpha photoelectron scattering calculations

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

NASA Astrophysics Data System (ADS)

Powell, C. J.; Smekal, W.; Werner, W. S. M.

2005-09-01

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. We report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

NASA Astrophysics Data System (ADS)

Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra; Boll, Rebecca; Bari, Sadia; Bomme, Cédric; Brouard, Mark; Burt, Michael; de Miranda, Barbara Cunha; Düsterer, Stefan; Erk, Benjamin; Géléoc, Marie; Geneaux, Romain; Gentleman, Alexander S.; Guillemin, Renaud; Ismail, Iyas; Johnsson, Per; Journel, Loïc; Kierspel, Thomas; Köckert, Hansjochen; Küpper, Jochen; Lablanquie, Pascal; Lahl, Jan; Lee, Jason W. L.; Mackenzie, Stuart R.; Maclot, Sylvain; Manschwetus, Bastian; Mereshchenko, Andrey S.; Mullins, Terence; Olshin, Pavel K.; Palaudoux, Jérôme; Patchkovskii, Serguei; Penent, Francis; Piancastelli, Maria Novella; Rompotis, Dimitrios; Ruchon, Thierry; Rudenko, Artem; Savelyev, Evgeny; Schirmel, Nora; Techert, Simone; Travnikova, Oksana; Trippel, Sebastian; Underwood, Jonathan G.; Vallance, Claire; Wiese, Joss; Simon, Marc; Holland, David M. P.; Marchenko, Tatiana; Rouzée, Arnaud; Rolles, Daniel

2018-04-01

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I ) is investigated by ionization above the iodine 4 d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Photo-electronic current transport in back-gated graphene transistor

NASA Astrophysics Data System (ADS)

Srivastava, Ashok; Chen, Xinlu; Pradhan, Aswini K.

2017-04-01

In this work, we have studied photo-electronic current transport in a back-gated graphene field-effect transistor. Under the light illumination, band bending at the metal/graphene interface develops a built-in potential which generates photonic current at varying back-gate biases. A typical MOSFET type back-gated transistor structure uses a monolayer graphene as the channel layer formed over the silicon dioxide/silicon substrate. It is shown that the photo-electronic current consists of current contributions from photovoltaic, photo-thermoelectric and photo-bolometric effects. A maximum external responsivity close to 0.0009A/W is achieved at 30μW laser power source and 633nm wavelength.

Acoustical phonon anomaly in the Raman spectra of intermediate valent TmSe 1-xTe x and Tm xSe

NASA Astrophysics Data System (ADS)

Treindl, A.; Wachter, P.

1980-12-01

In the Raman spectra of intermediate valent TmSe 1- xTe x the same anomaly within the acoustical phonon band at 60 cm -1 is found as in Tm xSe. The connection of this anomaly with the valence mixing is confirmed. In a one-dimensional model calculation it is shown that a renormalized LA dispersion curve can produce the observed anomalous peak in the phonon DOS. As an alternative interpretation the possibility of a low energy electronic excitation at 60 cm -1 is discussed.

X-ray photoelectron spectroscopic study of water adsorption on iron sulphide minerals

NASA Astrophysics Data System (ADS)

Knipe, S. W.; Mycroft, J. R.; Pratt, A. R.; Nesbitt, H. W.; Bancroff, G. M.

1995-03-01

Samples of natural pyrrhotite and pyrite were fractured within the analytical chamber of an X-ray photoelectron spectrometer. The pristine mineral surfaces were then exposed, in the absence of oxygen, to total doses of 100, 200, 400, 800, 1400, 28,000, and 300,000 Langmuirs (L) of D2O. X-ray photoelectron spectroscopic (XPS) analyses were performed between each water dose, to investigate the interaction of these iron sulphide surfaces with water vapour. Recorded Fe and S photoelectron spectra showed no evidence of oxidation products on either mineral, even at highest D2O doses, nor could an oxide oxygen signal be fitted in the spectra for either mineral. On pyrrhotite, the O 1s spectra are composed of contributions from dominantly hydroxyl (at 532.0 ± 0.2 eV ) and subordinate chemisorbed water (at 533.5 ± 0.2 eV) signals. The main O is peak on pyrite is also formed from hydroxyl (531.0 ± 0.3 eV) and adsorbed water/hydroxyl (at 532.3 eV) signals. However, some O is spectra recorded on pyrite have peaks at anomalously high binding energies (>535 eV ). The anomalous high binding energy species are attributed to electrically-isolated OH/H2O, as reported elsewhere, and to liquid-like water, which has not previously been described in the literature. Pyrrhotite and pyrite interact with water via fundamentally different processes. Pyrrhotite reaction involves the donation of electron charge through Fe vacancies, whereas the water species detected on pyrite interact with the Fe 3d (eg) molecular orbital, and it is suggested that hydrogen bonding with the disulphide moiety may be important.

Zero kinetic energy photoelectron spectroscopy of triphenylene.

PubMed

Harthcock, Colin; Zhang, Jie; Kong, Wei

2014-06-28

We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S1 of the neutral molecule is of A1' symmetry and is therefore electric dipole forbidden in the D3h group. Consequently, there are no observable Franck-Condon allowed totally symmetric a1' vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E' third electronically excited state S3. The assignment of all vibrational bands as e' symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C2v and resulting in two nearly degenerate electronic states of A2 and B1 symmetry. Here we follow a crude treatment by assuming that all e' vibrational modes resolve into b2 and a1 modes in the C2v molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm(-1). The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

X-ray photoelectron spectrometry and binding energies of Be 1s and O 1s core levels in clinobarylite, BaBe{sub 2}Si{sub 2}O{sub 7}, from Khibiny massif, Kola peninsula

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

Atuchin, V.V.; Kesler, V.G.; Sapozhnikov, V.K.

2008-09-15

The electronic structure of BaBe{sub 2}Si{sub 2}O{sub 7}, clinobarylite, has been investigated by means of X-ray photoelectron spectroscopy (XPS). The valence band of the crystal is mainly formed by Ba 5p, Ba 3s and O 2s states. At higher binding energies the emission lines related to the Si 2p, Be 1s, Si 2s, O 1s and numerous Ba-related states were analyzed in the photoemission spectrum. The Si KLL Auger line has been measured under excitation by the bremsstrahlung X-rays from the Al anode. Chemical bonding effects for Be 1s core level have been considered by comparison with electronic parameters measuredmore » for other beryllium containing oxides.« less

Quantitative x-ray photoelectron spectroscopy: Quadrupole effects, shake-up, Shirley background, and relative sensitivity factors from a database of true x-ray photoelectron spectra

NASA Astrophysics Data System (ADS)

Seah, M. P.; Gilmore, I. S.

2006-05-01

An analysis is provided of the x-ray photoelectron spectroscopy (XPS) intensities measured in the National Physical Laboratory (NPL) XPS database for 46 solid elements. This present analysis does not change our previous conclusions concerning the excellent correlation between experimental intensities, following deconvolving the spectra with angle-averaged reflection electron energy loss data, and the theoretical intensities involving the dipole approximation using Scofield’s cross sections. Here, more recent calculations for cross sections by Trzhaskovskaya involving quadrupole terms are evaluated and it is shown that their cross sections diverge from the experimental database results by up to a factor of 5. The quadrupole angular terms lead to small corrections that are close to our measurement limit but do appear to be supported in the present analysis. Measurements of the extent of shake-up for the 46 elements broadly agree with the calculations of Yarzhemsky but not in detail. The predicted constancy in the shake-up contribution by Yarzhemsky implies that the use of the Shirley background will lead to a peak area that is a constant fraction of the true peak area including the shake-up intensities. However, the measured variability of the shake-up contribution makes the Shirley background invalid for quantification except for situations where the sensitivity factors are from reference samples similar to those being analyzed.

Crossover from impurity to valence band in diluted magnetic semiconductors: Role of Coulomb attraction by acceptors

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

Popescu, Florentin; Sen, Cengiz; Dagotto, Elbio R

2007-01-01

The crossover between an impurity band (IB) and a valence band (VB) regime as a function of the magnetic impurity concentration in a model for diluted magnetic semiconductors (DMSs) is studied systematically by taking into consideration the Coulomb attraction between the carriers and the magnetic impurities. The density of states and the ferromagnetic transition temperature of a spin-fermion model applied to DMSs are evaluated using dynamical mean-field theory and Monte Carlo (MC) calculations. It is shown that the addition of a square-well-like attractive potential can generate an IB at small enough Mn doping x for values of the p-d exchangemore » J that are not strong enough to generate one by themselves. We observe that the IB merges with the VB when x>=xc where xc is a function of J and the Coulomb strength V. Using MC simulations, we demonstrate that the range of the Coulomb attraction plays an important role. While the on-site attraction, which has been used in previous numerical simulations, effectively renormalizes J for all values of x, an unphysical result, a nearest-neighbor range attraction renormalizes J only at very low dopings, i.e., until the bound holes wave functions start to overlap. Thus, our results indicate that the Coulomb attraction can be neglected to study Mn-doped GaSb, GaAs, and GaP in the relevant doping regimes, but it should be included in the case of Mn-doped GaN, which is expected to be in the IB regime.« less

Direct time-domain observation of attosecond final-state lifetimes in photoemission from solids

DOE PAGES

Tao, Z.; Chen, C.; Szilvasi, T.; ...

2016-06-01

Attosecond spectroscopic techniques have made it possible to measure differences in transport times for photoelectrons from localized core levels and delocalized valence bands in solids. Here, we report the application of attosecond pulse trains to directly and unambiguously measure the difference in lifetimes between photoelectrons born into free electron–like states and those excited into unoccupied excited states in the band structure of nickel (111). An enormous increase in lifetime of 212 ± 30 attoseconds occurs when the final state coincides with a short-lived excited state. Moreover, a strong dependence of this lifetime on emission angle is directly related to themore » final-state band dispersion as a function of electron transverse momentum. Our finding underscores the importance of the material band structure in determining photoelectron lifetimes and corresponding electron escape depths.« less

Charge transfer transitions in optical spectra of NicMg1-cO oxides

NASA Astrophysics Data System (ADS)

Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Druzhinin, A. V.; Korolyov, A. V.; Kim, G. A.; Zatsepin, A. F.; Kuznetsova, J. A.

2017-04-01

Radiative recombination with charge transfer was observed in NicMg1-cO (c = 0.008) oxides over the 8-300 K temperature range. This recombination occurs as a result of strong hybridization of the Ni2+ ion 3d-states and the band states. The charge transfer radiation excitation spectrum shows vibrational LO repeats of two exciton lines having charge transfer energy intervals of about 35 meV. The NiO nanocrystal absorption spectrum shows two weak peaks with energies of 3.510 and 3.543 eV, which are highly dependent on temperature. They are interpreted as charge transfer excitons at the edge of NiO fundamental absorption. The distance between the charge transfer exciton lines in the NicMg1-cO oxide spectra are caused by spin-orbit splitting of the valence band peak that was formed by the p-states of the oxygen ion.

Stabilization of Wide Band-Gap p-Type Wurtzite MnTe Thin Films on Amorphous Substrates

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

Zakutayev, Andriy A; Siol, Sebastian; Han, Yanbing

An important challenge in the development of optoelectronic devices for energy conversion applications is the search for suitable p-type contact materials. For example, p-type MnTe would be a promising alternative back contact to due to their chemical compatibility, but at normal conditions it has too narrow band gap due to octahedrally coordinated nickeline (NC) structure. The tetrahedrally coordinated wurtzite (WZ) polymorph of MnTe has not been reported, but it is especially interesting due to its predicted wider band gap, and because of better structural compatibility with CdTe and related II-VI semiconductor materials. Here, we report on the stabilization of WZ-MnTemore » thin films on amorphous indium zinc oxide (a-IZO) substrates relevant to photovoltaic applications. Optical spectroscopy of the WZ-MnTe films shows a wide direct band gap of Eg = 2.7 eV, while PES measurements reveal weak p-type doping with the Fermi level 0.6 eV above the valence band maximum. The results of electron microscopy and photoelectron spectroscopy (PES) measurements indicate that the WZ-MnTe is stabilized due to interdiffusion at the interface with IZO. The results of this work introduce a substrate stabilized WZ-MnTe polymorph as a potential p-type contact material candidate for future applications in CdTe devices for solar energy conversion and other optoelectronic technologies.« less

Measurement of magnetic field aligned potential differences using high resolution conjugate photoelectron energy spectra

NASA Technical Reports Server (NTRS)

Peterson, W. K.; Doering, J. P.; Potemra, T. A.; Bostrom, C. O.; Brace, L. H.; Heelis, R. A.; Hanson, W. B.

1977-01-01

Simultaneous high-resolution observations of a distinctive feature in the energy spectrum of conjugate photoelectrons and spacecraft potential relative to the local ionosphere have allowed the net potential difference between magnetic conjugate points at latitudes below the region of low-energy (i.e., lower than 100 eV) auroral electron precipitation to be determined. Measurements made at 300 km from Atmosphere Explorer C show that there is normally no net potential difference between hemispheres in this region, which extended up to invariant latitudes as high as 74 deg. Two types of apparently related anomalous behavior were infrequently observed at high latitudes. During these periods the incident flux of conjugate photoelectrons was either decelerated by about 3 eV or was not detected.

Cs(2)K(UO)(2)Si(4)O(12): a mixed-valence uranium(IV,V) silicate.

PubMed

Lee, Cheng-Shiuan; Wang, Sue-Lein; Lii, Kwang-Hwa

2009-10-28

The first mixed-valence uranium(IV,V) silicate is synthesized under high-temperature, high-pressure hydrothermal conditions. The structure contains chains of corner-sharing U(IV,V)O(6) octahedra which are interconnected by Si(4)O(12) four-membered rings to form a 3-D framework. XPS and XANES spectra were measured to identify the valence state of uranium.

Recent trends in spin-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Okuda, Taichi

2017-12-01

Since the discovery of the Rashba effect on crystal surfaces and also the discovery of topological insulators, spin- and angle-resolved photoelectron spectroscopy (SARPES) has become more and more important, as the technique can measure directly the electronic band structure of materials with spin resolution. In the same way that the discovery of high-Tc superconductors promoted the development of high-resolution angle-resolved photoelectron spectroscopy, the discovery of this new class of materials has stimulated the development of new SARPES apparatus with new functions and higher resolution, such as spin vector analysis, ten times higher energy and angular resolution than conventional SARPES, multichannel spin detection, and so on. In addition, the utilization of vacuum ultra violet lasers also opens a pathway to the realization of novel SARPES measurements. In this review, such recent trends in SARPES techniques and measurements will be overviewed.

The Valence- and Conduction-Band Structure of the Sapphire (1102) Surface.

DTIC Science & Technology

1984-12-01

surface. The pbotomission spectrum of the valece-baud region has boon adjusted to rmove croas-section effect s and comparod to the recent theoretical ...transitions in Al203. Several theoretical deteminations of the electron structure of various A1203 analoaues have bes performed. These calculations were...picture of the valence sad core density of states in sapphire. The rew, 31 velesee-bend data of Fit. I& and the theoretical 003 shows is Fig. 1.. which

Band alignment measurements at heterojunction interfaces in layered thin film solar cells & thermoelectrics

NASA Astrophysics Data System (ADS)

Fang, Fang

2011-12-01

Public awareness of the increasing energy crisis and the related serious environmental concerns has led to a significantly growing demand for alternative clean and renewable energy resources. Thin film are widely applied in multiple renewable energy devices owing to the reduced amount of raw materials and increase flexibility of choosing from low-cost candidates, which translates directly into reduced capital cost. This is a key driving force to make renewable technology competitive in the energy market. This thesis is focused on the measurement of energy level alignments at interfaces of thin film structures for renewable energy applications. There are two primary foci: II -VI semiconductor ZnSe/ZnTe thin film solar cells and Bi2Te3/Sb2Te3 thin film structures for thermoelectric applications. In both cases, the electronic structure and energy band alignment at interfaces usually controls the carrier transport behavior and determines the quality of the device. High-resolution photoemission spectroscopy (lab-based XPS & synchrotron-based UPS) was used to investigate the chemical and electronic properties of epitaxial Bi2Te3 and Sb2Te3 thin films, in order to validate the anticipated band alignment at interfaces in Bi 2Te3/Sb2Te3 superlattices as one favoring electron-transmission. A simple, thorough two-step treatment of a chemical etching in dilute hydrochloric acid solution and a subsequent annealing at ˜150°C under ultra-high vacuum environment is established to remove the surface oxides completely. It is an essential step to ensure the measurements on electronic states are acquired on stoichimetric, oxide-free clean surface of Bi 2Te3 and Sb2Te3 films. The direct measurement of valence band offsets (VBO) at a real Sb 2Te3/Bi2Te3 interface is designed based on the Kraut model; a special stacking film structure is prepared intentionally: sufficiently thin Sb2Te3 film on top of Bi2Te 3 that photoelectrons from both of them are collected simultaneously. From a

A New NIST Database for the Simulation of Electron Spectra for Surface Analysis (SESSA): Application to Angle-Resolved X-ray Photoelectron Spectroscopy of HfO2, ZrO2, HfSiO4, and ZrSiO4 Films on Silicon

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

Powell, C.J.; Smekal, W.; Werner, W.S.M.

2005-09-09

We describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA). This database provides data for the many parameters needed in quantitative Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). In addition, AES and XPS spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra. In this way, AES and XPS can provide more detailed characterization of multilayer thin-film materials. Wemore » report on the use of SESSA for determining the thicknesses of HfO2, ZrO2, HfSiO4, and ZrSiO4 films on Si by angle-resolved XPS. Practical effective attenuation lengths (EALs) have been computed from SESSA as a function of film thickness and photoelectron emission angle (i.e., to simulate the effects of tilting the sample). These EALs have been compared with similar values obtained from the NIST Electron Effective-Attenuation-Length Database (SRD 82). Generally good agreement was found between corresponding EAL values, but there were differences for film thicknesses less than the inelastic mean free path of the photoelectrons in the overlayer film. These differences are due to a simplifying approximation in the algorithm used to compute EALs in SRD 82. SESSA, with realistic cross sections for elastic and inelastic scattering in the film and substrate materials, is believed to provide more accurate EALs than SRD 82 for thin-film thickness measurements, particularly in applications where the film and substrate have different electron-scattering properties.« less

Electronic structure investigation of MoS2 and MoSe2 using angle-resolved photoemission spectroscopy and ab initio band structure studies.

PubMed

Mahatha, S K; Patel, K D; Menon, Krishnakumar S R

2012-11-28

Angle-resolved photoemission spectroscopy (ARPES) and ab initio band structure calculations have been used to study the detailed valence band structure of molybdenite, MoS(2) and MoSe(2). The experimental band structure obtained from ARPES has been found to be in good agreement with the theoretical calculations performed using the linear augmented plane wave (LAPW) method. In going from MoS(2) to MoSe(2), the dispersion of the valence bands decreases along both k(parallel) and k(perpendicular), revealing the increased two-dimensional character which is attributed to the increasing interlayer distance or c/a ratio in these compounds. The width of the valence band and the band gap are also found to decrease, whereas the valence band maxima shift towards the higher binding energy from MoS(2) to MoSe(2).

The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Zander, R.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Grunson, M. R.; Farmer, C. B.

1991-01-01

The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

In-situ growth of HfO2 on clean 2H-MoS2 surface: Growth mode, interface reactions and energy band alignment

NASA Astrophysics Data System (ADS)

Chen, Chang Pang; Ong, Bin Leong; Ong, Sheau Wei; Ong, Weijie; Tan, Hui Ru; Chai, Jian Wei; Zhang, Zheng; Wang, Shi Jie; Pan, Ji Sheng; Harrison, Leslie John; Kang, Hway Chuan; Tok, Eng Soon

2017-10-01

Room temperature growth of HfO2 thin film on clean 2H-MoS2 via plasma-sputtering of Hf-metal target in an argon/oxygen environment was studied in-situ using x-ray photoelectron spectroscopy (XPS). The deposited film was observed to grow akin to a layer-by-layer growth mode. At the onset of growth, a mixture of sulfate- and sulfite-like species (SOx2- where x = 3, 4), and molybdenum trioxide (MoO3), are formed at the HfO2/MoS2 interface. An initial decrease in binding energies for both Mo 3d and S 2p core-levels of the MoS2 substrate by 0.4 eV was also observed. Their binding energies, however, did not change further with increasing HfO2 thickness. There was no observable change in the Hf4f core-level binding energy throughout the deposition process. With increasing HfO2 deposition, MoO3 becomes buried at the interface while SOx2- was observed to be present in the film. The shift of 0.4 eV for both Mo 3d and S 2p core-levels of the MoS2 substrate can be attributed to a charge transfer from the substrate to the MoO3/SOx2--like interface layer. Consequently, the Type I heterojunction valence band offset (conduction band offset) becomes 1.7 eV (2.9 eV) instead of 1.3 eV (3.3 eV) expected from considering the bulk HfO2 and MoS2 valence band offset (conduction band offset). The formation of these states and its influence on band offsets will need to be considered in their device applications.

The Ma_Miss instrument performance, II: Band parameters of rocks powders spectra by Martian VNIR spectrometer

NASA Astrophysics Data System (ADS)

De Angelis, Simone; De Sanctis, Maria Cristina; Ammannito, Eleonora; Carli, Cristian; Di Iorio, Tatiana; Altieri, Francesca

2015-11-01

The Ma_Miss instrument (Mars Multispectral Imager for Subsurface Studies, Coradini et al. (2001)) is a Visible and Near Infrared miniaturized spectrometer that will observe the Martian subsurface in the 0.4-2.2 μm spectral range. The instrument will be entirely hosted within the Drill of the ExoMars-2018 Pasteur Rover: it will allow analyzing the borehole wall excavated by the Drill, at different depths, down to 2 m. The aim will be to investigate and characterize the mineralogy and stratigraphy of the shallow Martian subsurface. A series of spectroscopic measurements have been performed in order to characterize the spectral performances of the laboratory model of the instrument (breadboard). A set of six samples have been analyzed. Each sample (four volcanic rocks, a micritic limestone and a calcite) has been reduced in particulate form, ground, sieved and divided into nine different grain sizes in the range d<0.02÷0.8 mm. Spectroscopic measurements have been performed on all samples using two distinct experimental setup: (a) the Ma_Miss breadboard, and (b) the Spectro-Goniometer setup, both in use in the laboratory at INAF - IAPS. In a previous paper spectral parameters such as the continuum slope and the reflectance level of the spectra have been discussed (De Angelis et al., 2014). In this work we focus our discussion on absorption band parameters (position, depth, area, band slope and asymmetry). We analyzed/investigated the absorption features at 1 μm for the volcanic samples and at 1.4, 1.9 and 2.2 μm for the two carbonate samples. Band parameters have been retrieved from spectra measured with both experimental setup and then compared. The comparison shows that band parameters are mutually consistent: band centers (for carbonate samples) are similar within few percent, and band depth and area values (for carbonates) show consistent trends vs. grain size (decreasing towards coarser grains) for most of samples.

Unambiguous observation of F-atom core-hole localization in CF 4 through body-frame photoelectron angular distributions

DOE PAGES

McCurdy, C. W.; Rescigno, T. N.; Trevisan, C. S.; ...

2017-01-17

A dramatic symmetry breaking in K-shell photoionization of the CF 4 molecule in which a core-hole vacancy is created in one of four equivalent fluorine atoms is displayed in the molecular frame angular distribution of the photoelectrons. In observing the photoejected electron in coincidence with an F + atomic ion after Auger decay we see how selecting the dissociation path where the core hole was localized was almost exclusively on that atom. A combination of measurements and ab initio calculations of the photoelectron angular distribution in the frame of the recoiling CF 3 + and F + atoms elucidates themore » underlying physics that derives from the Ne-like valence structure of the F(1s -1) core-excited atom.« less

Temperature-dependent internal photoemission probe for band parameters

NASA Astrophysics Data System (ADS)

Lao, Yan-Feng; Perera, A. G. Unil

2012-11-01

The temperature-dependent characteristic of band offsets at the heterojunction interface was studied by an internal photoemission (IPE) method. In contrast to the traditional Fowler method independent of the temperature (T), this method takes into account carrier thermalization and carrier/dopant-induced band-renormalization and band-tailing effects, and thus measures the band-offset parameter at different temperatures. Despite intensive studies in the past few decades, the T dependence of this key band parameter is still not well understood. Re-examining a p-type doped GaAs emitter/undoped AlxGa1-xAs barrier heterojunction system disclosed its previously ignored T dependency in the valence-band offset, with a variation up to ˜-10-4 eV/K in order to accommodate the difference in the T-dependent band gaps between GaAs and AlGaAs. Through determining the Fermi energy level (Ef), IPE is able to distinguish the impurity (IB) and valence bands (VB) of extrinsic semiconductors. One important example is to determine Ef of dilute magnetic semiconductors such as GaMnAs, and to understand whether it is in the IB or VB.

Micro-Valences: Perceiving Affective Valence in Everyday Objects

PubMed Central

Lebrecht, Sophie; Bar, Moshe; Barrett, Lisa Feldman; Tarr, Michael J.

2012-01-01

Perceiving the affective valence of objects influences how we think about and react to the world around us. Conversely, the speed and quality with which we visually recognize objects in a visual scene can vary dramatically depending on that scene’s affective content. Although typical visual scenes contain mostly “everyday” objects, the affect perception in visual objects has been studied using somewhat atypical stimuli with strong affective valences (e.g., guns or roses). Here we explore whether affective valence must be strong or overt to exert an effect on our visual perception. We conclude that everyday objects carry subtle affective valences – “micro-valences” – which are intrinsic to their perceptual representation. PMID:22529828

Angle-resolved photoelectron spectroscopy of cyclopropane

NASA Astrophysics Data System (ADS)

Keller, P. R.; Taylor, J. W.; Carlson, Thomas A.; Whitley, T. A.; Grimm, F. A.

1985-10-01

The angular distribution parameter, β, determined for the valence orbitals (IP < 18 eV) of cyclopropane in the 10-30 eV photon energy range using dispersed polarized synchrotron radiation. The energy dependence of β for photoelectron energies between, 2 and 10 eV above threshold was found to be similar to those found previously for other σ orbitals. The effects of Jahn-Teller splitting on β for the 3e' orbital were found to be small but definitely present. The overall shape and magnitude of the β( hv) curve are, however, sufficiently for the different Jahn-Teller components that, for purposes of orbital assignments using β( hv) curves the shape and magnitude of the curves can be considered associated only with the initial state. Resonance photoionization features at a photon ener of ≈ 18 eV were observed in the 3e' and 3a' 1 orbitals and tentatively assigned to autoionization.

Modeling a Large Heterogeneous Set of CIRS Spectra of Titan: The ν4 band of 12C2HD

NASA Astrophysics Data System (ADS)

Boyle, Robert J.; Jennings, Donald, Dr.; Bjoraker, Gordon, Dr.

2018-01-01

A technique has been developed which allows global average abundances of trace species to be derived from large heterogeneous data sets using the Spectral Synthsis Program [SSP] originally developed by Kunde & McGuire (1974). The method was applied to a large average of 24,000 individual spectra of Titan from the Composite Infrared Spectrometer (CIRS) on Cassini. The spectra were centered on the 581.6 cm‑1 ν4 band of 12C2HD and were taken in order to obtain a global average abundance for this species. The spectra covered a wide range of planetary latitudes and emission angles. The results obtained are generally in agreement with those derived by Coustenis et al. (2008) derived from their analysis of the ν5 band of this species at 678 cm‑1.ReferencesCoustenis, A., Jennings, D. E., Jolly, A., Bnilan, Y., Nixon, C. A., Vinatier, S., Gautier, D., Bjoraker, G. L., Romani, P. N., Carlson, R. C., & Flasar, F. 2008, Icarus, 197, 539-548.Kunde, V. G. & Maguire, W. C. 1974, JQSRT, 14, 803-817

HeI photoelectron spectroscopic studies on the electronic structure of alkyl nitrosamines

NASA Astrophysics Data System (ADS)

Jiang, Peng; Qian, Ximei; Li, Chunhui; Qiao, Chunhua; Wang, Dianxun

1997-10-01

HeI photoelectron spectroscopic (PES) studies on the electronic structure of alkyl nitrosamines R 2N 2O (R = CH 3-, CH 3CH 2-, and CH 3CH 2CH 2-) are reported. The assignment of the PES bands for this series of compounds has been made with the aid of the band shapes, the band intensity and ab initio SCF MO calculations based on the 631 ∗ G basis sets. Both PES experiment and the ab initio SCF MO calculations show that the detoxification ability of nitrosamine with longer alkyl chain is stronger.

Integrated J- and H-band spectra of globular clusters in the LMC: implications for stellar population models and galaxy age dating

NASA Astrophysics Data System (ADS)

Lyubenova, M.; Kuntschner, H.; Rejkuba, M.; Silva, D. R.; Kissler-Patig, M.; Tacconi-Garman, L. E.

2012-07-01

Context. The rest-frame near-IR spectra of intermediate age (1-2 Gyr) stellar populations are dominated by carbon based absorption features offering a wealth of information. Yet, spectral libraries that include the near-IR wavelength range do not sample a sufficiently broad range of ages and metallicities to allow for accurate calibration of stellar population models and thus the interpretation of the observations. Aims: In this paper we investigate the integrated J- and H-band spectra of six intermediate age and old globular clusters in the Large Magellanic Cloud (LMC). Methods: The observations for six clusters were obtained with the SINFONI integral field spectrograph at the ESO VLT Yepun telescope, covering the J (1.09-1.41 μm) and H-band (1.43-1.86 μm) spectral range. The spectral resolution is 6.7 Å in J and 6.6 Å in H-band (FWHM). The observations were made in natural seeing, covering the central 24″ × 24″ of each cluster and in addition sampling the brightest eight red giant branch and asymptotic giant branch (AGB) star candidates within the clusters' tidal radii. Targeted clusters cover the ages of ~1.3 Gyr (NGC 1806, NGC 2162), 2 Gyr (NGC 2173) and ~13 Gyr (NGC 1754, NGC 2005, NGC 2019). Results.H-band C2 and K-band 12CO (2-0) feature strengths for the LMC globular clusters are compared to the models of Maraston (2005). C2 is reasonably well reproduced by the models at all ages, while 12CO (2-0) shows good agreement for older (age ≥ 2 Gyr) populations, but the younger (1.3 Gyr) globular clusters do not follow the models. We argue that this is due to the fact that the empirical calibration of the models relies on only a few Milky Way carbon star spectra, which show different 12CO (2-0) index strengths than the LMC stars. The C2 absorption feature strength correlates strongly with age. It is present essentially only in populations that have 1-2 Gyr old stars, while its value is consistent with zero for older populations. The distinct spectral

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.

Permanent magnet focused X-band photoinjector

DOEpatents

Yu, David U. L.; Rosenzweig, James

2002-09-10

A compact high energy photoelectron injector integrates the photocathode directly into a multicell linear accelerator with no drift space between the injection and the linac. High electron beam brightness is achieved by accelerating a tightly focused electron beam in an integrated, multi-cell, X-band rf linear accelerator (linac). The photoelectron linac employs a Plane-Wave-Transformer (PWT) design which provides strong cell-to-cell coupling, easing manufacturing tolerances and costs.

Electronic absorption and MCD spectra of M sub 2 (TMB) sub 4 sup 2+ , M = Rh and Ir. A valence-bond description of the upper electronic excited states

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

Smith, D.C.; Miskowski, V.M.; Gray, H.B.

1990-05-09

Electronic absorption and magnetic circular dichroism (MCD) spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are reported along with polarized single-crystal absorption spectra of (Ir{sub 2}(TMB){sub 4})(B(C{sub 6}H{sub 5}){sub 4}){sub 2} {times} CH{sub 3}C{sub 6}H{sub 5} (TMB = 2,5-diisocyano-2,5-dimethylhexane). Interpretation of the spectra is based on a valence-bond model that accommodates highly perturbed dimer transitions as well as monomer-like dimer excitations. In this model, half of the dimer electronic excited states possess ionic character; these states involve metal-to-metal charge transfer (MMCT). The most prominent of the weak features ({approximately} 430 nm) is assigned to the transition tomore » {sup 1}A{sub 1g} (a single-center d{sub z{sup 2}} {yields} p{sub z} excitation). High-energy features ({lambda} < 300 nm) in the spectra of Rh{sub 2}(TMB){sub 4}{sup 2+} and Ir{sub 2}(TMB){sub 4}{sup 2+} are assigned to MMCT arising from d{sub xzyz} {yields} p{sub z} excitations.« less

Type-II InP quantum dots in wide-bandgap InGaP host for intermediate-band solar cells

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

Tayagaki, Takeshi, E-mail: tayagaki-t@aist.go.jp; Sugaya, Takeyoshi

2016-04-11

We demonstrate type-II quantum dots (QDs) with long carrier lifetimes in a wide-bandgap host as a promising candidate for intermediate-band solar cells. Type-II InP QDs are fabricated in a wide-bandgap InGaP host using molecular beam epitaxy. Time-resolved photoluminescence measurements reveal an extremely long carrier lifetime (i.e., greater than 30 ns). In addition, from temperature-dependent PL spectra, we find that the type-II InP QDs form a negligible valence band offset and conduction band offset of ΔE{sub c} ≈ 0.35 eV in the InGaP host. Such a type-II confinement potential for InP/InGaP QDs has a significant advantage for realizing efficient two-step photon absorption and suppressed carriermore » capture in QDs via Auger relaxation.« less

Electronic and chemical structure of an organic light emitter embedded in an inorganic wide-bandgap semiconductor: Photoelectron spectroscopy of layered and composite structures of Ir(BPA) and ZnSe

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

Dimamay, Mariel; Laboratoire de Chimie des Polymères Organiques, CNRS, Université de Bordeaux, UMR 5629-16 Avenue Pey-Berland, 33607 Pessac; Mayer, Thomas

Luminescent organic phases embedded in conductive inorganic matrices are proposed for hybrid organic-inorganic light-emitting diodes. In this configuration, the organic dye acts as the radiative recombination site for charge carriers injected into the inorganic matrix. Our investigation is aimed at finding a material combination where the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the organic dye are situated in between the valence and conduction bands of the inorganic matrix in order to promote electron and hole transfer from the matrix to the dye. Bilayer and composite thin films of zinc selenide (ZnSe) and a redmore » iridium complex (Ir(BPA)) organic light emitter were prepared in situ via UHV thermal evaporation technique. The electronic and atomic structures were studied applying X-ray and ultraviolet photoelectron spectroscopies. The measured energy band alignments for the ZnSe/Ir(BPA) bilayer and ZnSe+Ir(BPA) composite reveal that the HOMO and LUMO of the organic dye are positioned in the ZnSe bandgap. For the initial steps of ZnSe deposition on a dye film to form Ir(BPA)/ZnSe bilayers, zinc atoms intercalate into the dye film leaving behind an excess of selenium at the interface that partly reacts with dye molecules. Photoelectron spectroscopy of the composites shows the same species suggesting a similar mechanism. This mechanism leads to composite films with increased content of amorphous phases in the inorganic matrix, thereby affecting its conductivity, as well as to the presence of nonradiative recombination sites provided by the intercalated Zn atoms.« less

Electronic Structure and Band Alignment at the NiO and SrTiO3 p-n Heterojunctions.

PubMed

Zhang, Kelvin H L; Wu, Rui; Tang, Fengzai; Li, Weiwei; Oropeza, Freddy E; Qiao, Liang; Lazarov, Vlado K; Du, Yingge; Payne, David J; MacManus-Driscoll, Judith L; Blamire, Mark G

2017-08-09

Understanding the energetics at the interface, including the alignment of valence and conduction bands, built-in potentials, and ionic and electronic reconstructions, is an important challenge in designing oxide interfaces that have controllable multifunctionalities for novel (opto-)electronic devices. In this work, we report detailed investigations on the heterointerface of wide-band-gap p-type NiO and n-type SrTiO 3 (STO). We show that despite a large lattice mismatch (∼7%) and dissimilar crystal structure, high-quality NiO and Li-doped NiO (LNO) thin films can be epitaxially grown on STO(001) substrates through a domain-matching epitaxy mechanism. X-ray photoelectron spectroscopy studies indicate that NiO/STO heterojunctions form a type II "staggered" band alignment. In addition, a large built-in potential of up to 0.97 eV was observed at the interface of LNO and Nb-doped STO (NbSTO). The LNO/NbSTO p-n heterojunctions exhibit not only a large rectification ratio of 2 × 10 3 but also a large ideality factor of 4.3. The NiO/STO p-n heterojunctions have important implications for applications in photocatalysis and photodetectors as the interface provides favorable energetics for facile separation and transport of photogenerated electrons and holes.

Surface Defects Enhanced Visible Light Photocatalytic H2 Production for Zn-Cd-S Solid Solution.

PubMed

Zhang, Xiaoyan; Zhao, Zhao; Zhang, Wanwan; Zhang, Guoqiang; Qu, Dan; Miao, Xiang; Sun, Shaorui; Sun, Zaicheng

2016-02-10

In order to investigate the defect effect on photocatalytic performance of the visible light photocatalyst, Zn-Cd-S solid solution with surface defects is prepared in the hydrazine hydrate. X-ray photoelectron spectra and photoluminescence results confirm the existence of defects, such as sulfur vacancies, interstitial metal, and Zn and Cd in the low valence state on the top surface of solid solutions. The surface defects can be effectively removed by treating with sulfur vapor. The solid solution with surface defect exhibits a narrower band gap, wider light absorption range, and better photocatalytic perfomance. The optimized solid solution with defects exhibits 571 μmol h(-1) for 50 mg photocatalyst without loading Pt as cocatalyst under visible light irradiation, which is fourfold better than that of sulfur vapor treated samples. The wavelength dependence of photocatalytic activity discloses that the enhancement happens at each wavelength within the whole absorption range. The theoretical calculation shows that the surface defects induce the conduction band minimum and valence band maximum shift downward and upward, respectively. This constructs a type I junction between bulk and surface of solid solution, which promotes the migration of photogenerated charges toward the surface of nanostructure and leads to enhanced photocatalytic activity. Thus a new method to construct highly efficient visible light photocatalysts is opened. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the fast phase-change mechanism of tetrahedrally bonded Cu2GeTe3 : Comprehensive analyses of electronic structure and transport phenomena

NASA Astrophysics Data System (ADS)

Kobayashi, Keisuke; Skelton, Jonathan M.; Saito, Yuta; Shindo, Satoshi; Kobata, Masaaki; Fons, Paul; Kolobov, Alexander V.; Elliott, Stephen; Ando, Daisuke; Sutou, Yuji

2018-05-01

Cu2GeTe3 (CGT) phase-change material, a promising candidate for advanced fast nonvolatile random-access-memory devices, has a chalcopyritelike structure with s p3 bonding in the crystalline phase; thus, the phase-change (PC) mechanism is considered to be essentially different from that of the standard PC materials (e.g., Ge-Sb-Te) with threefold to sixfold p -like bonding. In order to reveal the PC mechanism of CGT, the electronic structure change due to PC has been investigated by laboratory hard x-ray photoelectron spectroscopy and combined first-principles density-functional theory molecular-dynamics simulations. The valence-band spectra, in both crystalline and amorphous phases, are well simulated by the calculations. An inherent tendency of Te 5 s lone-pair formation and an enhanced participation of Cu 3 d orbitals in the bonding are found to play dominant roles in the PC mechanism. The electrical conductivity of as-deposited films and its change during the PC process is investigated in connection with valence-band spectral changes near the Fermi level. The results are successfully analyzed, based on a model proposed by Davis and Mott for chalcogenide amorphous semiconductors. The results suggest that robustness of the defect-band states against thermal stress is a key to the practical application of this material for memory devices.

8-band and 14-band kp modeling of electronic band structure and material gain in Ga(In)AsBi quantum wells grown on GaAs and InP substrates

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

Gladysiewicz, M.; Wartak, M. S.; Department of Physics and Computer Science, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5

The electronic band structure and material gain have been calculated for GaAsBi/GaAs quantum wells (QWs) with various bismuth concentrations (Bi ≤ 15%) within the 8-band and 14-band kp models. The 14-band kp model was obtained by extending the standard 8-band kp Hamiltonian by the valence band anticrossing (VBAC) Hamiltonian, which is widely used to describe Bi-related changes in the electronic band structure of dilute bismides. It has been shown that in the range of low carrier concentrations n < 5 × 10{sup 18 }cm{sup −3}, material gain spectra calculated within 8- and 14-band kp Hamiltonians are similar. It means that the 8-band kp model can be usedmore » to calculate material gain in dilute bismides QWs. Therefore, it can be applied to analyze QWs containing new dilute bismides for which the VBAC parameters are unknown. Thus, the energy gap and electron effective mass for Bi-containing materials are used instead of VBAC parameters. The electronic band structure and material gain have been calculated for 8 nm wide GaInAsBi QWs on GaAs and InP substrates with various compositions. In these QWs, Bi concentration was varied from 0% to 5% and indium concentration was tuned in order to keep the same compressive strain (ε = 2%) in QW region. For GaInAsBi/GaAs QW with 5% Bi, gain peak was determined to be at about 1.5 μm. It means that it can be possible to achieve emission at telecommunication windows (i.e., 1.3 μm and 1.55 μm) for GaAs-based lasers containing GaInAsBi/GaAs QWs. For GaInAsBi/Ga{sub 0.47}In{sub 0.53}As/InP QWs with 5% Bi, gain peak is predicted to be at about 4.0 μm, i.e., at the wavelengths that are not available in current InP-based lasers.« less

Statistical observations of martian 20-30 eV photoelectrons by MAVEN/SWEA

NASA Astrophysics Data System (ADS)

Garnier, P.; Steckiewicz, M.; Andre, N.; Mazelle, C. X.; Sauvaud, J. A.; Sakai, S.; Cravens, T.; Mitchell, D. L.; Lillis, R. J.; Espley, J. R.; Brain, D.; Andersson, L.; Jakosky, B. M.

2016-12-01

Photoelectron peaks in the 20-30 eV energy range are commonly observed in planetary atmospheres, produced by intense photoionization from solar 30.4 nm photons. At Mars, these photoelectrons are known to escape the planet down its tail (Frahm et al., 2006). Assuming overall charge neutrality, the number of corresponding electrons must be identical to the number of ion charges escaping the planet. Studying the photoelectrons is thus important to understand and quantify the erosion of the martian atmosphere. Moreover, the photoelectrons also play a significant role for the heating and ionization of the atmosphere. The MAVEN (Mars Atmosphere and Volatile EvolutioN) spacecraft has provided detailed observations of the Martian environment for the last two years thanks to its unique orbital coverage and comprehensive plasma instrument suite. The low periapsis altitudes (down to 125 km altitude) and combined presence of an electron spectrometer (Solar Wind Electron Analyzer, SWEA) and of a magnetometer (MAG) provide a unique opportunity to investigate the source region of the photoelectrons and their transport and escape down the tail. We will present statistical results of an automatic detection of 20-30 eV photoelectrons at Mars, based on a simple algorithm using three levels of confidence. More than 150,000 spectra (each averaged over 30s) revealed clear photoelectron peaks from October 2014 to May 2016. The analysis reveals several interesting features such as: the evolution of the peak shape from their source region to higher altitudes, the influence of the magnetic field topology on photoelectron transport, a clear dusk-dawn asymmetry in agreement with the recently-discovered neutral density asymmetry, the statistical influence of the EUV and solar wind parameters and the location of the photoelectron boundary. These results will also be compared with an electron transport code (Sakai et al., 2015, 2016) to better constrain the photoelectron production and transport.

Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state

NASA Astrophysics Data System (ADS)

Rogers, Joshua P.; Anstöter, Cate S.; Verlet, Jan R. R.

2018-03-01

The primary electron-attachment process in electron-driven chemistry represents one of the most fundamental chemical transformations with wide-ranging importance in science and technology. However, the mechanistic detail of the seemingly simple reaction of an electron and a neutral molecule to form an anion remains poorly understood, particularly at very low electron energies. Here, time-resolved photoelectron imaging was used to probe the electron-attachment process to a non-polar molecule using time-resolved methods. An initially populated diffuse non-valence state of the anion that is bound by correlation forces evolves coherently in ∼30 fs into a valence state of the anion. The extreme efficiency with which the correlation-bound state serves as a doorway state for low-energy electron attachment explains a number of electron-driven processes, such as anion formation in the interstellar medium and electron attachment to fullerenes.

On the origin of an unusual dependence of (bio)chemical reactivity of ferric hydroxides on nanoparticle size.

PubMed

Chernyshova, I V; Ponnurangam, S; Somasundaran, P

2010-11-14

Application of in situ UV-Vis absorption spectroscopy and ex situ X-ray photoelectron spectroscopy (XPS) makes it possible to resolve the controversies about the electronic properties of hematite (α-Fe(2)O(3)) nanoparticles (NPs) and, on this basis, to rationalize the unusual dependence of aquatic (bio)chemistry of these NPs on NP size. 2-Line ferrihydrite (FH) is also included in the study as the end polymorph of the size-driven phase transformation of hematite NPs in aqueous media. It is shown that the absorption edge of all NPs studied is due to the direct O 2p-Fe 3d charge transfer (CT) process, while a manifold of weak bands superimposed onto two main p-d CT bands is attributed to the d-d ligand field transitions. The band gap decreases from 2.95 to 2.18 eV with increasing NP size from 7 nm to 120 nm. This effect is attributed to restoration of hematite lattice structure, which ultimately results in an increase in the O 2p-Fe 3d hybridization, stabilization of the valence band, and delocalization of valence electrons, as confirmed by XPS. Finally, we show that the optical effects such as the Mie resonance significantly distort absorption spectra of hematite NPs larger than ∼120 nm. Possible impacts of these findings on (photo)catalytic and biochemical properties of ferric (hydr)oxide NPs are discussed.

Origins of extreme broadening mechanisms in near-edge x-ray spectra of nitrogen compounds

NASA Astrophysics Data System (ADS)

Vinson, John; Jach, Terrence; Elam, W. T.; Denlinger, J. D.

2014-11-01

We demonstrate the observation of many-body lifetime effects in valence-band x-ray emission. A comparison of the N K α emission of crystalline ammonium nitrate to molecular-orbital calculations revealed an unexpected, extreme broadening of the NO σ recombination—so extensively as to virtually disappear. GW calculations establish that this disappearance is due to a large imaginary component of the self-energy associated with the NO σ orbitals. Building upon density-functional theory, we have calculated radiative transitions from the nitrogen 1 s level of ammonium nitrate and ammonium chloride using a Bethe-Salpeter method to include electron-hole interactions. The absorption and emission spectra of both crystals evince large, orbital-dependent sensitivity to molecular dynamics. We demonstrate that many-body effects as well as thermal and zero-point motion are vital for understanding observed spectra. A computational approach using average atomic positions and uniform broadening to account for lifetime and phonon effects is unsatisfactory.

Performance of a first generation X-band photoelectron rf gun

DOE PAGES

Limborg-Deprey, C.; Adolphsen, C.; McCormick, D.; ...

2016-05-04

Building more compact accelerators to deliver high brightness electron beams for the generation of high flux, highly coherent radiation is a priority for the photon science community. A relatively straightforward reduction in footprint can be achieved by using high-gradient X-band (11.4 GHz) rf technology. To this end, an X-band injector consisting of a 5.5 cell rf gun and a 1-m long linac has been commissioned at SLAC. It delivers an 85 MeV electron beam with peak brightness somewhat better than that achieved in S-band photoinjectors, such as the one developed for the Linac Coherent Light Source (LCLS). The X-band rfmore » gun operates with up to a 200 MV/m peak field on the cathode, and has been used to produce bunches of a few pC to 1.2 nC in charge. Notably, bunch lengths as short as 120 fs rms have been measured for charges of 5 pC (~3×10 7 electrons), and normalized transverse emittances as small as 0.22 mm-mrad have been measured for this same charge level. Bunch lengths as short as 400 (250) fs rms have been achieved for electron bunches of 100 (20) pC with transverse normalized emittances of 0.7 (0.35) mm-mrad. As a result, we report on the performance and the lessons learned from the operation and optimization of this first generation X-band gun.« less

Performance of a first generation X-band photoelectron rf gun

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

Limborg-Deprey, C.; Adolphsen, C.; McCormick, D.

Building more compact accelerators to deliver high brightness electron beams for the generation of high flux, highly coherent radiation is a priority for the photon science community. A relatively straightforward reduction in footprint can be achieved by using high-gradient X-band (11.4 GHz) rf technology. To this end, an X-band injector consisting of a 5.5 cell rf gun and a 1-m long linac has been commissioned at SLAC. It delivers an 85 MeV electron beam with peak brightness somewhat better than that achieved in S-band photoinjectors, such as the one developed for the Linac Coherent Light Source (LCLS). The X-band rfmore » gun operates with up to a 200 MV/m peak field on the cathode, and has been used to produce bunches of a few pC to 1.2 nC in charge. Notably, bunch lengths as short as 120 fs rms have been measured for charges of 5 pC (~3×10 7 electrons), and normalized transverse emittances as small as 0.22 mm-mrad have been measured for this same charge level. Bunch lengths as short as 400 (250) fs rms have been achieved for electron bunches of 100 (20) pC with transverse normalized emittances of 0.7 (0.35) mm-mrad. As a result, we report on the performance and the lessons learned from the operation and optimization of this first generation X-band gun.« less

X-ray magnetic circular dichroism and hard X-ray photoelectron spectroscopy of tetragonal Mn72Ge28 epitaxial thin film

NASA Astrophysics Data System (ADS)

Kim, Jinhyeok; Mizuguchi, Masaki; Inami, Nobuhito; Ueno, Tetsuro; Ueda, Shigenori; Takanashi, Koki

2018-04-01

An epitaxially grown Mn72Ge28 film with a tetragonal crystal structure was fabricated. It was clarified that the film had a perpendicular magnetization and a high perpendicular magnetic anisotropy energy of 14.3 Merg/cm3. The electronic structure was investigated by X-ray magnetic circular dichroism and hard X-ray photoelectron spectroscopy. The obtained X-ray magnetic circular dichroism spectrum revealed that the Mn orbital magnetic moment governed the magnetocrystalline anisotropy of the Mn72Ge28 film. A doublet structure was observed for the Mn 2p3/2 peak of hard X-ray photoelectron spectrum, indicating the spin exchange interaction between the 2p core-hole and 3d valence electrons.

Ultraviolet photoelectron spectroscopy reveals energy-band dispersion for π-stacked 7,8,15,16-tetraazaterrylene thin films in a donor-acceptor bulk heterojunction.

PubMed