Valence Band Photoemission Spectroscopy Research Articles

Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures.

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100ps) and electron (∼1ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Atomic and Electronic Structure of Metal–Salen Complexes [M(Salen)], Their Polymers and Composites Based on Them with Carbon Nanostructures: Review of X-ray Spectroscopy Studies

Currently, electrically conductive polymers based on transition metal complexes [M(Salen)], as well as their composites, are among the systems showing promise as catalysts, electrochromic and electroluminescent materials, and electrodes for energy storage (for batteries and supercapacitors). The current review focuses on elucidating the atomic and electronic structure of metal–salen complexes, their polymers, and composites with nanostructured carbon (carbon nanotubes and graphene) using modern X-ray spectroscopy methods (X-ray photoelectron (XPS) and valence-band photoemission (VB PES) spectroscopy, as well as near-edge (NEXAFS) and extended (EXAFS) X-ray absorption fine structure spectroscopy). We trust that this review will be of valuable assistance to researchers working in the field of synthesizing and characterizing metal–salen complexes and composites based on them.

Role of electron correlation and disorder on the electronic structure of layered nickelate (La0.5Sr0.5)2NiO4

We investigate the role of electron correlation and disorder on the electronic structure of layered nickelate ${({\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5})}_{2}{\mathrm{NiO}}_{4}$ using core level and valence band photoemission spectroscopy in conjunction with density functional theory (DFT) and dynamical mean-field theory (DMFT) calculations. Sr $3d$ and La $4d$ core level spectra exhibit multiple features associated with photoemission final-state effects. An increase of unscreened features in the Sr $3d$ and La $4d$ core level spectra with lowering temperature suggests the reduction in density of states (DOS) at the Fermi level, ${E}_{F}$. Valence band spectra collected using different photon energies reveal finite intensity at ${E}_{F}$ and overall spectra are well captured by $\mathrm{DFT}+\mathrm{DMFT}$. Strong renormalization of partially filled ${e}_{g}$ bands in $\mathrm{DFT}+\mathrm{DMFT}$ result indicates strong correlation in this system. Mass enhancement factor, ${m}^{*}/{m}_{\text{DFT}}\ensuremath{\sim}$ 3, agrees well with values obtained from specific heat measurements. High-resolution spectra in the vicinity of ${E}_{F}$ show monotonically decreasing spectral intensity with lowering temperature, which evolves to exhibit a Fermi cutoff at low temperatures indicating metallic character in contrast to insulating transport, suggesting Anderson insulating state. $|E\ensuremath{-}{E}_{F}{|}^{1/2}$ dependence of the spectral DOS and square-root temperature dependence of spectral DOS at ${E}_{F}$ evidences the role of disorder in the electronic structure of ${({\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5})}_{2}{\mathrm{NiO}}_{4}$.

Evidence of electron correlation and weak bulk plasmon in SrMoO3

We investigate the electronic structure of highly conducting perovskite SrMoO3 using valence band photoemission spectroscopy and electronic structure calculations. Large intensity corresponding to coherent feature close to Fermi level is captured by density functional theory (DFT) calculation. An additional satellite at ∼3 eV binding energy remains absent in DFT, hybrid functional (DFT-hybrid) and dynamical mean field theory (DFT + DMFT) calculations. Mo 4d spectra obtained with different surface sensitive photoemission spectroscopy suggest different surface and bulk electronic structures. DFT + DMFT spectral function is in excellent agreement with the coherent feature in the bulk Mo 4d spectra, revealing moderate electron correlation strength. A large plasmon satellite and signature of strong electron correlation are observed in the surface spectra, while the bulk spectra exhibits a weak plasmon satellite.

Strength of correlations in a silver-based cuprate analog

${\mathrm{AgF}}_{2}$ has been proposed as a cuprate analog, which requires strong correlation and marked covalence. On the other hand, fluorides are usually quite ionic, and $4d$ transition metals tend to be less correlated than their $3d$ counterparts, which calls for further scrutiny. We combine valence band photoemission and Auger-Meitner spectroscopy of AgF and ${\mathrm{AgF}}_{2}$ together with computations in small clusters to estimate values of the Ag $4d$ Coulomb interaction ${U}_{4d}$ and charge-transfer energy ${\mathrm{\ensuremath{\Delta}}}_{pd}$. Based on these values, ${\mathrm{AgF}}_{2}$ can be classified as a charge-transfer correlated insulator according to the Zaanen-Sawatzky-Allen classification scheme. Thus, we confirm that the material is a cuprate analog from the point of view of correlations, suggesting that it should become a high-temperature superconductor if metallization is achieved by doping. We present also a computation of the Hubbard $U$ in density functional ``$+U$'' methods and discuss its relation to the Hubbard $U$ in spectroscopies.

Determination of band alignment in liquid exfoliated few-layer WSe2/SiO2 interface

In this work, we study the band alignment of few-layer thick WSe2/SiO2 heterointerface. The few monolayer thick WSe2 nanosheets are synthesized on 300 nm SiO2/Si substrate by employing liquid exfoliation method. Structural and optical investigations of fabricated WSe2 nanosheets were investigated using X-ray diffraction (XRD), Raman, valence band photoemission spectroscopy, and atomic force microscopy (AFM). By resorting to X-ray photoelectron spectroscopy (XPS) and valence band photoemission spectroscopy (VBPES) measurements, we found that WSe2/SiO2heterointerface Type-I band alignment. Moreover, our calculations reveal that values of valence band offset and conduction band offset at the WSe2/SiO2 interface were found to be 3.79 ± 0.05 and 3.21 ± 0.05 eV, respectively.

Investigation of single-domain Au silicide nanowires on Si(110) formed for Au coverages in the monolayer regime

The self-organized formation of single domain Au silicide nanowires is observed on Si(110). These nanowires are analysed using scanning tunnelling microscopy (STM) and spectroscopy (STS) as well as photoemission spectroscopy (PES). Core-level PES is utilised to confirm the formation of Au silicide and establish its presence as the top most surface structure, i.e., the nanowires. The growth of the Au silicide nanowires and their dimensions are studied by STM. They form for Au coverages of about 1 monolayer and are characterized by widths of about 2 to 3 nm and heights below 1 nm while reaching lengths exceeding 500 nm when choosing appropriate annealing temperatures. Valence band PES and STS indicate a small but finite density of states at the Fermi level typical for compound metals.

Electronic structure of ternary palladates and effect of hole doping: a valence band photoemission spectroscopic study

We investigate the electronic structure of ternary palladates APd3O4 (A = Sr, Ca) using valence band photoemission spectroscopy and band structure calculations. Energy positions of various features and overall width of the experimental valence band spectra are well captured by band structure calculations using hybrid functional. Band structure calculations within local density approximations lead to metallic ground state while the calculations using hybrid functional provide band gap of 0.25 eV and 0.22 eV for CaPd3O4 and SrPd3O4 respectively, suggesting moderate to strong electron correlation strength in these narrow band gap semiconducting palladates. High resolution spectra reveal negligibly small intensity at Fermi level, E F, for parent compounds, while hole doped SrPd3O4 (by 15% Li substitution at Sr site) exhibits a Fermi cut-off suggesting metallic character in contrast to semiconducting transport. These observations reveal the importance of localization of electrons in case where the Fermi edge falls in the mobility edge.

Influence of finite size and image charge screening on the antiferromagnetic ordering of CoO ultrathin films

The surface antiferromagnetic (AFM) ordering of ultrathin CoO(001) films grown on Ag(001) has been investigated using low energy electron diffraction (LEED) and valence band photoemission spectroscopy. We have observed coherent exchange scattered half-order spots in LEED with a periodicity of the magnetic unit cell of the CoO(001) surface. These spots show very low intensities (2–3% of the integer-order spots) and are visible only below a critical temperature for low electron beam energies (<70 eV), revealing its AFM origin. Significant enhancement of surface Nèel temperature (TN) of CoO(001) for different film coverages has been observed and it is exceeding the bulk TN even in the ultrathin limit. The enhancement of surface TN has been explained by the combined effects of finite size, surface strain, and polarizability of the underlying substrate. The critical behaviour near TN shows a coverage dependent evolution as the magnetic critical exponent (β) varies from 0.16 to 0.48 upon increasing film coverage from 0.5 ML to 10 ML, suggesting crossovers in the critical behaviour. Furthermore, upon transition from paramagnetic (PM) to AFM phase, minor modifications of the valence band electronic structure have been observed such as enhancement of spectral weight in the Co 3d band as well as widening of an energy gap relative to EF by ~150 meV, in agreement with the theoretical predictions.

Interplay among work function, electronic structure and stoichiometry in nanostructured VOx films.

The work function is the parameter of greatest interest in many technological applications involving charge exchange mechanisms at the surface. The possibility to produce samples with a controlled work function is then particularly interesting, albeit challenging. We synthetized nanostructured vanadium oxide films by a room temperature supersonic cluster beam deposition method, obtaining samples with tunable stoichiometry and work function (3.7-7 eV). We present an investigation of the electronic structure of several vanadium oxide films as a function of the oxygen content via in situ Auger, valence-band photoemission spectroscopy and work function measurements. The experiments probed the partial 3d density of states, highlighting the presence of strong V 3d-O 2p and V 3d-V 4s hybridizations which influence 3d occupation. We show how controlling the stoichiometry of the sample implies control over work function, and that the access to nanoscale quantum confinement can be exploited to increase the work function of the sample relative to the bulk analogue. In general, the knowledge of the interplay among work function, electronic structure, and stoichiometry is strategic to match nanostructured oxides to their target applications.

Optimized Ni1-x Al x O hole transport layer for silicon solar cells.

NiO alloyed with aluminum, Ni1−xAlxO, is analyzed in terms of its stoichiometry, electronic and transport properties, as well as interfacial band alignment with Si to evaluate its potential use as a hole transport layer (HTL) in p–i–n type solar cells. The analysis is based on component material and slab structural simulations, as well as simulated and measured angle-resolved valence-band photoemission spectroscopy (PES) data, in order to reveal the best suitable stoichiometry. It is concluded that the ionization energy from the highest occupied states tends to increase with Al content as the simulated work function grows from 4.1 eV for pure NiO to 4.7 eV for heavily alloyed Al0.50Ni0.50O. The electronic structure as a function of the interface design between crystalline silicon and the transport layer is used to assess the band lineup and its correlation with the discontinuity of the affinities. The affinity rule is tested by evaluating the workfunctions of the component layers and justified best for a particular Ni-enriched interface design. Technology Computer-Aided Design (TCAD) device simulations show, that the band offset between oxide and crystalline silicon remains within the range of values to sustain a staggering alignment – a condition suitable for effective charge separation, similar to a situation in a tunneling diode. The self-energy of the hole carriers is estimated by contrasting simulated and measured photoemission data, which in the case of non-annealed Al-rich samples is shown to be an order of magnitude higher due to the disorder effects. The work functions derived from the measured PES data for the epitaxially grown oxide films with nearly identical alloy stoichiometry correlate well with the simulated values. The findings suggest that the optimal HTL is formed by starting with a pure Ni layer, followed by a graded doping AlxNi1−xO, with x high at contact/oxide interface and low at the oxide/semiconductor.

Broadening of van Hove Singularities Measured by Photoemission Spectroscopy of Single- and Mixed-Chirality Single-Walled Carbon Nanotubes

The occupied valence electronic states of single-walled carbon nanotubes (SWCNTs) are responsible for their optoelectronic properties and are unique for each SWCNT chirality. Photoemission spectroscopy (PES) is one of the few methods capable of directly measuring the electron density in the valence states of materials, but there are only a few reports which have observed the valence states of SWCNTs and no examples for single-chirality SWCNTs. Here, we prepare single- and mixed-chirality SWCNT films and characterize their valence states using PES. Chirality-pure SWCNTs were isolated using both gel permeation chromatography and single-stranded DNA-facilitated aqueous two-phase extraction from starting materials consisting of mixed-chirality species. Chirality separation and purity was confirmed with UV-vis-NIR absorption spectroscopy. SWCNT films were prepared for the single-chirality species (10,3), (7,6), (7,3), (6,5), (8,3), (9,1) along with SWCNT chirality mixture of metallic and semiconducting SWCNTs, and as-synthesized mixtures possessing a range of SWCNT diameter. PES using synchrotron radiation was completed for all samples with survey and C 1s core-level spectra obtained to confirm SWCNT coverage, defect level, and purity. Valence band PES was obtained to characterize the valence electronic states and showed significant broadening of the signal, in comparison to calculated density of states, which could not be accounted for by instrument resolution. An inverse diameter dependence of the broadening was observed with greater broadening for smaller-diameter SWCNTs. The broadening is hypothesized to be related to the photohole lifetime, which was found to be significantly longer for wide-diameter SWCNTs. The diameter dependence of the broadening and photohole lifetimes is discussed in terms of both Tomonaga-Luttinger and Landau theories of Fermi liquids.

Probing single-unit-cell resolved electronic structure modulations in oxide superlattices with standing-wave photoemission

Control of structural couplings at the complex-oxide interfaces is a powerful platform for creating new ultrathin layers with electronic and magnetic properties unattainable in the bulk. However, with the capability to design and control the electronic structure of such buried layers and interfaces at a unit-cell level, a new challenge emerges to be able to probe these engineered emergent phenomena with depth-dependent atomic resolution as well as element- and orbital selectivity. Here, we utilize a combination of core-level and valence-band soft x-ray standing-wave photoemission spectroscopy, in conjunction with scanning transmission electron microscopy, to probe the depth-dependent and single-unit-cell resolved electronic structure of an isovalent manganite superlattice [Eu0.7Sr0.3MnO3/La0.7Sr0.3MnO3]x15 wherein the electronic-structural properties are intentionally modulated with depth via engineered oxygen octahedra rotations/tilts and A-site displacements. Our unit-cell resolved measurements reveal significant transformations in the local chemical and electronic valence-band states, which are consistent with the layer-resolved first-principles theoretical calculations, thus opening the door for future depth-resolved studies of a wide variety of hetero-engineered material systems.

ZnO nanorods decorated with nanocrystalline (nc) Au Particles:Electronic structure and magnetic behaviours

Electronic structures and magnetic behaviours of zinc oxide nanorods (ZnO-NRs) decorated with nanocrystalline “Au”-particles (nc-Au) have been studied using different spectroscopies, superconducting quantum interference device-type magnetometer and plane wave pseudopotential density functional theory calculations. The presence of intrinsic defects viz. zinc interstitials (Zni) and/or oxygen vacancies (VO) are established using different spectroscopies measurements. Ultraviolet photoelectron spectroscopy and valence band photoemission spectroscopy suggests that the valence band density of states of O 2p - Zn 4sp hybridized states of nc-Au/ZnO-NRs is higher than pure ZnO-NRs that could be correlated with its higher ferromagnetic behaviour. An enhanced room temperature ferromagnetism has been observed when nanocrystalline (nc) gold (Au) particles are decorated on the surface of ZnO-nanorods (ZnO-NRs). This enhanced magnetic moment in nc-Au/ZnO-NRs comes from the metallic electrons of nc-Au that induces large orbital magnetic moment at the nc-Au/ZnO-NR interface. Theoretical calculations shows the enhancement of the density of states at the valence band region of ZnO with a decoration of optimum content nc-Au particles along with the increase of oxygen vacancies in nc-Au/ZnO-NRs; that further confirms the enhancement of magnetization.

Photoemission and soft X-ray absorption spectroscopy study of Gd-substituted thermoelectric and topological Bi2Te3

The electronic structures of Gd-substituted Bi2−xGdxTe3 single crystals have been investigated by employing synchrotron-radiation spectroscopies, such as soft X-ray absorption spectroscopy (XAS), soft X-ray magnetic circular dichroism (XMCD), photoemission spectroscopy (PES), and scanning photoelectron microscopy (SPEM). SPEM measurements confirm that Gd ions are substituted homogeneously in Bi2−xGdxTe3 crystals. The measured Gd 3d XAS and XMCD spectra provide evidence that the substituted Gd ions are trivalent and magnetic. The hν-dependence of the valence-band (VB) PES spectra are described well by the hν-dependent contributions of the Te 5p and Bi 6p states. A good agreement is found between the measured VB PES spectra of Bi2−xGdxTe3 and the calculated partial densities of states, revealing that the Te 5p states will play an important role in determining the thermoelectric and topological properties of Bi2−xGdxTe3.

X-ray absorption, photoemission and electron spin resonance studies of Ar+ ion implanted ZnO

Defect induced room temperature ferromagnetism (RT-FM) in Ar+ implanted ZnO single crystal (ZnO-SC) is observe from the electron Spin Resonance (ESR) spectra and is correlated with their electronic structure studies using synchrotron radiation based X-ray absorption near edge structure (XANES) spectroscopy and valence band photoemission spectroscopy (VB-PES). Enhancement of absorption intensity at the edge of XANES spectra of Ar+ implanted ZnO indicates the increase of local density of states (DOS); which arises from the surface defects and/or dangling bonds in ZnO. VB-PES spectra change upon Ar+ implantation, becoming broader, implying the induced surface defects in ZnO-SC. X-ray photoelectron spectroscopy studies confirm that the Zn 2p3/2 core level peak shifts in lower energy side in Ar+ implanted ZnO-SC that is associated with the formation of oxygen vacancies/defects in ZnO-SC which is responsible for the RT-FM.

Tuning of the electronic structure and magnetic properties of xenon ion implanted zinc oxide

A correlation between the electronic structure and magnetic properties of ZnO single crystals (ZnO SCs) and 300 keV xenon ion (Xe3+) implanted ZnO SCs has been studied using x-ray absorption near edge structure (XANES) spectroscopy, valence band photoemission spectroscopy (VB-PES), x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and a superconducting quantum interference device-type magnetometer. The XANES studies revealed that the number of unoccupied p-states in the implanted ZnO SCs is higher than in the pristine ZnO SCs. In the implanted ZnO SCs, the binding energy of the Zn 2p3/2 core level peak shifted to higher energy which further confirmed the increase in the valence band maximum (VBM) energy level. The VBM of the xenon ion (Xe3+) implanted ZnO SCs increased from 3.17–3.49 eV, obtained from UPS (He-I) measurements. A VB-PES study revealed that the number of electrons in the valence band of the O 2p–Zn 4sp hybridized states of the implanted ZnO SCs is higher than in the pristine ZnO SCs. The magnetic M–H loops demonstrated enhanced room temperature ferromagnetism in the Xe implanted ZnO SCs, attributable to the increasing number of surface defects and native defect sites in oxygen vacancies and zinc interstitials.

Surface, final state, and spin effects in the valence-band photoemission spectra ofLaCoO3(001)

The electronic structure of a ${\mathrm{LaCoO}}_{3}$(001) perovskite is analyzed using simulated and measured angle-resolved valence-band photoemission spectroscopy data with emphasis on the effects of the surface truncation, the final state effects, and the spin degeneracy removal. Supercell simulations reveal instability towards the formation of nonuniform spin polarization in the Co-containing layers under tensile stress. Lattice expansion reduces antiferrodistortive octahedron tilting and tips the ratio between the crystal field parameter and the exchange energy in favor of local magnetization. While the magnitude of the local moment scales with lateral strain, the Curie temperature saturates for straight Co-O-Co chains below 75 K. The comparison of simulated photoemission spectra with experiments suggests Co-${\mathrm{O}}_{2}$ to be the most stable surface stoichiometry, as proposed from transport and catalytic studies.

Defect induced room temperature ferromagnetism in single crystal, poly-crystal, and nanorod ZnO: A comparative study

A comparative study has been made for the defect induced room temperature ferromagnetism of single crystal, poly-crystal, and nanorod zinc oxide (ZnO), based on the magnetic properties and electronic properties by means of X-ray absorption near edge structure spectroscopy (XANES), X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), valence band photoemission spectroscopy (VB-PES), and SQUID-type magnetometry. Magnetic measurement demonstrates the defect-induced ferromagnetic nature at room temperature in different ZnO films and a strong correlation between their electronic properties and magnetic responses. The higher ferromagnetic behaviour in polycrystalline ZnO is attributed to the increasing number of surface defects and native defect sites (oxygen vacancies and zinc interstitials) present in ZnO. XANES studies reveal that the number of unoccupied p states in polycrystalline ZnO is higher than single crystal ZnO as well as nanorod ZnO. The more amount of oxygen vacancy causes the highest intensity the O 1 s peak to appear in the XANES spectra of polycrystalline ZnO. In polycrystalline ZnO, the binding energy of the Zn 2p3/2 core level peak shifted to lower energy that further confirms the increase of the valence band maximum (VBM) position. The VBM of single crystal, poly-crystal, and nanorod-ZnO is 3.64 eV, 3.99 eV, and 3.71 eV, respectively, obtained from UPS (He-I) measurements. VB-PES studies confirm that the number of electrons in the valence band of O 2p - Zn 4sp hybridized states of poly-crystal ZnO is higher than single crystal and nanorod-ZnO.

Anisotropy in the thermal hysteresis of resistivity and charge density wave nature of single crystal SrFeO3-\u03b4: X-ray absorption and photoemission studies

The local electronic and atomic structures of the high-quality single crystal of SrFeO3-δ (δ~0.19) were studied using temperature-dependent x-ray absorption and valence-band photoemission spectroscopy (VB-PES) to investigate the origin of anisotropic resistivity in the ab-plane and along the c-axis close to the region of thermal hysteresis (near temperature for susceptibility maximum, Tm~78 K). All experiments herein were conducted during warming and cooling processes. The Fe L3,2-edge X-ray linear dichroism results show that during cooling from room temperature to below the transition temperature, the unoccupied Fe 3d eg states remain in persistently out-of-plane 3d3z2-r2 orbitals. In contrast, in the warming process below the transition temperature, they change from 3d3z2-r2 to in-plane 3dx2-y2 orbitals. The nearest-neighbor (NN) Fe-O bond lengths also exhibit anisotropic behavior in the ab-plane and along the c-axis below Tm. The anisotropic NN Fe-O bond lengths and Debye-Waller factors stabilize the in-plane Fe 3dx2-y2 and out-of-plane 3d3z2-r2 orbitals during warming and cooling, respectively. Additionally, a VB-PES study further confirms that a relative band gap opens at low temperature in both the ab-plane and along the c-axis, providing the clear evidence of the charge-density-wave nature of SrFeO3-δ (δ~0.19) single crystal.