Core-level X-ray Photoemission Spectroscopy Research Articles

Valence and core-level X-ray photoemission spectroscopy of light-sensitive molecules: Lumazine and alloxazine

Valence and core-level photoemission spectra of two gaseous nitrogen containing heterocycles, lumazine and alloxazine, have been studied experimentally and theoretically. Comprehensive information about the electronic structure of these aromatic molecules has been acquired. The outer-valence Green’s function (OVGF) approach was used to calculate vertical ionization energies and relative intensities (pole strengths) of the valence band spectra. The C, N, and O 1s core level spectra of both compounds were measured and assigned on the basis of Δ-Kohn–Sham calculations. The relative stability of different tautomers of lumazine and alloxazine was investigated through DFT calculations. Only the single, most stable tautomer for lumazine and alloxazine was populated at the present experimental conditions and this finding is confirmed by the core-level photoemission signal, which is able to discriminate between different isomers of a molecule. Other tautomers of lumazine and alloxazine have not been clearly identified spectroscopically, however their relative free energies and Boltzmann populations were calculated and compared with previous studies.

Experimental evidence for fractional valence of La in LaAl2 : Electronic structure from x-ray photoelectron spectroscopy and band structure calculations

We confirmed the fractional filling of the $4f$ shell of La in ${\mathrm{LaAl}}_{2}$ by x-ray photoemission spectroscopy (XPS) and ab initio calculations. The La $3d$ core-level XPS spectra were analyzed by use of the Gunnarsson-Sch\"onhammer theoretical model, which allowed us to determine the valency of La smaller than 3 ($v=2.9$). A similar occupation of the La $4f$ shell results from the band structure calculations. In real unstable La atom charge is transferred in the mixing process from its outer $5d6s$ electron shells to the local $4f$ state, according to $4{f}^{\ensuremath{\nu}}(5{d}^{1\ensuremath{-}\ensuremath{\nu}}6{s}^{2})$, where $0<\ensuremath{\nu}\ensuremath{\ll}1$. The calculated density of states fit well the valence band XPS spectra. We have shown that the fractional valence of La plays a key role in electric transport properties of ${\mathrm{LaAl}}_{2}$ and the fractional filling of the $4f$ shell is really at the root of the resistivity anomalies either at the high or low temperatures.

Copper-Content Dependent Structural and Electrical Properties of CZTS Films Formed by “Green” Colloidal Nanocrystals

Thin films of colloidal CZTS nanocrystals (NCs) synthesized using a “green” approach in water with a variation of the copper-to-tin ratio are investigated by Raman scattering, mid-infrared (molecular vibrations) and near-infrared (free carrier) absorption, X-ray photoemission spectroscopy (XPS), electrical conductivity, and conductive atomic force microscopy (cAFM). We determined the effect of the actual Cu content on the phonon spectra, electrical conductivity, and spectral parameters of the plasmon band. An increase in the electrical conductivity of the NC films upon annealing at 220 °C is explained by three factors: formation of a CuxS nanophase at the CZTS NC surface, partial removal of ligands, and improved structural perfection. The presence of the CuxS phase is concluded to be the determinant factor for the CZTS NC film conductivity. CuxS can be reliably detected based on the analysis of the modified Auger parameter of copper, derived from XPS data and corroborated by Raman spectroscopy data. Partial removal of the ligand is concluded from the agreement of the core-level XPS and vibrational IR spectra. The degree of lattice perfection can be conveniently assessed from the Raman data as well. Further important information derived from a combination of photoelectron and optical data is the work function, ionization potential, and electron affinity of the NC films.

Core-Level X-Ray Spectroscopy of Infinite-Layer Nickelate: LDA+DMFT Study

Motivated by recent core-level x-ray photoemission spectroscopy, x-ray absorption spectroscopy (XAS), and resonant inelastic x-ray scattering (RIXS) experiments for the newly discovered superconducting infinite-layer nickelate, we investigate the core-level spectra of the parent compounds NdNiO2 and LaNiO2 using the combination of local density approximation and dynamical mean-field theory (LDA+DMFT). Adjusting a charge-transfer energy to match the experimental spectra, we determine the optimal model parameters and discuss the nature of the NdNiO2 ground state. We find that self-doping from the Nd 5d states in the vicinity of the Fermi energy prohibits opening of a Mott-Hubbard gap in NdNiO2. The present Ni L3 XAS and RIXS calculation for LaNiO2 cannot explain the difference from NdNiO2 spectra.1 MoreReceived 11 May 2021Revised 4 August 2021Accepted 7 September 2021Corrected 23 November 2021Corrected 11 November 2021DOI:https://doi.org/10.1103/PhysRevX.11.041009Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasElectronic structurePhysical SystemsCupratesMott insulatorsStrongly correlated systemsSuperconductorsTransition metal oxidesTechniquesDensity functional theoryDynamical mean field theoryResonant inelastic x-ray scatteringX-ray absorption spectroscopyX-ray photoelectron spectroscopyCondensed Matter, Materials & Applied Physics

Emerging oxidized and defective phases in low-dimensional CrCl3.

Two-dimensional (2D) magnets such as chromium trihalides CrX3 (X = I, Br, Cl) represent a frontier for spintronics applications and, in particular, CrCl3 has attracted research interest due its relative stability under ambient conditions without rapid degradation, as opposed to CrI3. Herein, mechanically exfoliated CrCl3 flakes are characterized at the atomic scale and the electronic structures of pristine, oxidized, and defective monolayer CrCl3 phases are investigated employing density functional theory (DFT) calculations, scanning tunneling spectroscopy (STS), core level X-ray photoemission spectroscopy (XPS), and valence band XPS and ultraviolet photoemission spectroscopy (UPS). As revealed by atomically resolved transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) analysis, the CrCl3 flakes show spontaneous surface oxidation upon air exposure with an extrinsic long-range ordered oxidized O–CrCl3 structure and amorphous chromium oxide formation on the edges of the flakes. XPS proves that CrCl3 is thermally stable up to 200 °C having intrinsically Cl vacancy-defects whose concentration is tunable via thermal annealing up to 400 °C. DFT calculations, supported by experimental valence band analysis, indicate that pure monolayer (ML) CrCl3 is an insulator with a band gap of 2.6 eV, while the electronic structures of oxidized and Cl defective phases of ML CrCl3, extrinsically emerging in exfoliated CrCl3 flakes, show in-gap spin-polarized states and relevant modifications of the electronic band structures.

Analysis of Metal-Insulator Crossover in Strained SrRuO3 Thin Films by X-ray Photoelectron Spectroscopy

The electronic properties of strontium ruthenate SrRuO3 perovskite oxide thin films are modified by epitaxial strain, as determined by growing on different substrates by pulsed laser deposition. Temperature dependence of the transport properties indicates that tensile strain deformation of the SrRuO3 unit cell reduces the metallicity of the material as well as its metal-insulator-transition (MIT) temperature. On the contrary, the shrinkage of the Ru–O–Ru buckling angle due to compressive strain is counterweighted by the increased overlap of the conduction Ru-4d orbitals with the O-2p ones due to the smaller interatomic distances resulting into an increased MIT temperature, i.e., a more conducting material. In particular, in the more metallic samples, the core level X-ray photoemission spectroscopy lineshapes show the occurrence of an extra-peak at the lower binding energies of the main Ru-3d peak that is attributed to screening, as observed in volume sensitive photoemission of the unstrained material.

Ambient aging effects on the effective energy gap of ZnO thin films

Using photoconductance spectroscopy, we have studied the influence of different types of thermal annealing on epitaxial ZnO thin films where band bending effects play a major role. Once the film is exposed to ambient air conditions after a simple thermal annealing in oxygen at 600°C, the effective energy gap is stable with a value of ≃3.15 eV, while after a corresponding annealing in vacuum and subsequent air exposure, it starts at ≃3.24 eV, and then it evolves along the days until it reaches the bulk energy gap value of ZnO. By means of valence band x-ray photoemission spectroscopy (XPS), we have confirmed that these phenomena are related via the Franz–Keldysh effect to a downward band bending in the former case and a time dependent upward band bending in the latter one that slowly tends to a flat band condition, tracking the behavior observed in the effective energy gap. Core level XPS measurements suggest that for each type of thermal annealing, a different adsorption kinetics of water and hydrogen take place.

The Itinerant 2D Electron Gas of the Indium Oxide (111) Surface: Implications for Carbon- and Energy-Conversion Applications.

Transparent conducting oxides (TCO) have integral and emerging roles in photovoltaic, thermoelectric energy conversion, and more recently, photocatalytic systems. The functional properties of TCOs, and thus their role in these applications, are often mediated by the bulk electronic band structure but are also strongly influenced by the electronic structure of the native surface 2D electron gas (2DEG), particularly under operating conditions. This study investigates the 2DEG, and its response to changes in chemistry, at the (111) surface of the model TCO In2 O3 , through angle resolved and core level X-ray photoemission spectroscopy. It is found that the itinerant charge carriers of the 2DEG reside in two quantum well subbands penetrating up to 65 Å below the surface. The charge carrier concentration of this 2DEG, and thus the high surface n-type conductivity, emerges from donor-type oxygen vacancies of surface character and proves to be remarkably robust against surface absorbents and contamination. The optical transparency, however, may rely on the presence of ubiquitous surface adsorbed oxygen groups and hydrogen defect states that passivate localized oxygen vacancy states in the bandgap of In2 O3 .

Linear polarization-dependent core-level photoemission spectroscopy in Yb-based valence fluctuating system

In this paper, we show the linearly polarized hard X-ray core-level photoemission spectroscopy of valence fluctuating system β-YbAlB4. Interestingly, we observed subtle but distinct linear dichroisms in Yb2+ 3d5/2 core-level spectra at several angles of β-YbAlB4. Basically linear dichroism in Yb2+ 3d5/2 core-level spectrum is not expected in the ionic picture because Yb2+ 4f orbital is fully occupied. These contradiction indicates the breakdown of ionic picture in β-YbAlB4.

Rumpling and Enhanced Covalency at the SrTiO3(001) Surface

The surface of SrTiO3 (001) is considered to be weakly polar, and in this work, we study the validity of this notion. It exhibits a surface structural distortion, quantified here using low energy electron diffraction at room temperature. Structural analysis shows the presence of strong surface rumpling in the TiO2 terminated surface with the oxygen atoms moving outward and Ti atoms moving inward. Density functional calculations confirm the measured rumpling, and experimental data show the distortion is localized at the surface. Angle-dependent core-level X-ray photoemission spectroscopy (XPS) shows that the surface rumpling strongly impacts the electronic structure of the surface. This observation is reinforced by density functional theory, which demonstrates that the valence state of Ti at the surface is reduced while O is enhanced, where we found the Ti–O bonds are more covalent near the surface. Our results show that surface rumpling is accompanied by a change in the bond hybridization of Ti–O at the s...

Combining Theory and Experiment for Multitechnique Characterization of Activated CO2 on Transition Metal Carbide (001) Surfaces

Early transition metal carbides (TMC; TM = Ti, Zr, Hf, V, Nb, Ta, Mo) with face-centered cubic crystallographic structure have emerged as promising materials for CO2 capture and activation. Density functional theory (DFT) calculations using the Perdew–Burke–Ernzerhof exchange–correlation functional evidence charge transfer from the TMC surface to CO2 on the two possible adsorption sites, namely, MMC and TopC, and the electronic structure and binding strength differences are discussed. Further, the suitability of multiple experimental techniques with respect to (1) adsorbed CO2 recognition and (2) MMC/TopC adsorption distinction is assessed from extensive DFT simulations. Results show that ultraviolet photoemission spectroscopies (UPS), work function changes, core level X-ray photoemission spectroscopy (XPS), and changes in linear optical properties could well allow for adsorbed CO2 detection. Only infrared (IR) spectra and scanning tunnelling microscopy (STM) seem to additionally allow for MMC/TopC adsorp...

Study of structural, dielectric, optical properties and electronic structure of Cr-doped LaInO3 perovskite nanoparticles

This work reports the change in the structural, dielectric and optical behaviour of Cr-doped LaInO3 nanoparticles synthesized via sol-gel method. X-ray diffraction patterns confirm that systems crystallize in orthorhombic Pnma space group. Raman spectroscopy measurements exhibit blue-shift in Raman modes with Cr-doping due to the compressive stress introduced by smaller Cr3+ cations. Trivalent oxidation state of Cr was confirmed from Cr(2p) core-level X-ray photoemission spectroscopy measurements, while valence band spectra suggest the absence of electronic states near Fermi level. High-resolution Ultraviolet photoemission spectra near Fermi level shows the electronic density of states arises sharply near Fermi level. Room temperature dielectric constant decreases with increasing Cr-concentration, which shows that conductivity has been increased after Cr-doping. Ultraviolet–visible spectroscopy measurements provide band gap of 4.8eV for LaInO3 and Cr-doped LaInO3nanoparticles.Moreover, Cr-doped LaInO3systems exhibit an intermediate band gap of 3eV, which might have been created from Cr(3d) states.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

The electronic and crystal structures of Cs2[Mo6X14] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al Kα, suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Tuning the Band Bending and Controlling the Surface Reactivity at Polar and Nonpolar Surfaces of ZnO through Phosphonic Acid Binding.

ZnO is a prime candidate for future use in transparent electronics; however, development of practical materials requires attention to factors including control of its unusual surface band bending and surface reactivity. In this work, we have modified the O-polar (0001̅), Zn-polar (0001), and m-plane (101̅0) surfaces of ZnO with phosphonic acid (PA) derivatives and measured the effect on the surface band bending and surface sensitivity to atmospheric oxygen. Core level and valence band synchrotron X-ray photoemission spectroscopy was used to measure the surface band bending introduced by PA modifiers with substituents of opposite polarity dipole moment: octadecylphosphonic acid (ODPA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylphosphonic acid (F13OPA). Both PAs act as surface electron donors, increasing the downward band bending and the strength of the two-dimensional surface electron accumulation layer on all of the ZnO surfaces investigated. On the O-polar (0001̅) and m-plane (101̅0) surfaces, the ODPA modifier produced the largest increase in downward band bending relative to the hydroxyl-terminated unmodified surface of 0.55 and 0.35 eV, respectively. On the Zn-polar (0001) face, the F13OPA modifier gave the largest increase (by 0.50 eV) producing a total downward band bending of 1.00 eV, representing ∼30% of the ZnO band gap. Ultraviolet (UV) photoinduced surface wettability and photoconductivity measurements demonstrated that the PA modifiers are effective at decreasing the sensitivity of the surface toward atmospheric oxygen. Modification with PA derivatives produced a large increase in the persistence of UV-induced photoconductivity and a large reduction in UV-induced changes in surface wettability.

Towards Photo-Switchable Transport in Quantum Dot Solids

Abstract We use the photochromic organic semiconductor 1,2-Bis(5′-carboxy-2′-methylthien-3′-yl)-cyclopentene (DTCP) to cross-link PbS quantum dots assembled into thin films. The ligand exchange is monitored by means of vibrational spectroscopy (FT-IR) and core-level X-ray photoemission spectroscopy (XPS). Transport measurements in a field-effect transistor (FET) set-up reveal ambipolar behavior with hole and electron mobilities on the order of 10−4 cm2/Vs and 10−5 cm2/Vs, respectively. Exposure to UV light from a 4 W UV lamp does not significantly change the transport properties, indicating that switching of DTCP is hindered in the hybrid film. We find a pronounced photo-conductance with rapid and reversible photo-response on the order of few seconds, which we attribute to (de-)filling of QD trap states. Our results indicate that hybrid, nanostructured networks of PbS QDs cross-linked with DTCP can be obtained by the presented procedure but that switching of the QD-bound DTCP appears to be hindered compared to the pure, unbound molecular species. We discuss future means to address this problem.

Time-resolved soft X-ray core-level photoemission spectroscopy at 880 °C using the pulsed laser and synchrotron radiation and the pulse heating current

We developed a time-resolved photoemission spectroscopy system for tracking the temporal variation in an electronic state of a heated sample. Our pump-probe method used laser and synchrotron radiation pulses on a silicon surface that was heated by a synchronized pulse current that did not interfere with the measurements. The transient surface photovoltage effect on the Si 2p core spectra was measured from room temperature to 880°C and was found to be consistent with the thermal carrier distributions in silicon crystals at the corresponding temperatures. This versatile technique may have applications studying molecular dynamics on high temperature surfaces such as in catalytic reactions.

염료감응 태양전지 전극용 반도체 나노 물질의 광전자분광 연구

The electronic structures of the potential candidate semiconductor nanoparticles for dye-sensitized solar cell (DSSC), such as and , have been investigated by employing X-ray photoemission spectroscopy (XPS). The measured X-ray diffraction patterns show that and samples have the single-phase ilmenite-type structure and the inverse spinel structure, respectively. The measured Zn 2p and Sn 3d core-level XPS spectra reveal that the valence states of Zn and Sn ions are divalent (Zn 2+) and tetravalent (Sn 4+), respectively, in both and . On the other hand, the shallow core-level measurements show that the binding energies of Sn 4d and Zn 3d core levels in are lower than those in . This work provides the information on the valence states of Zn and Sn ions and their chemical bonding in and .

Controlling the evolution of two-dimensional electron gas states at ametal/Bi2Se3interface

We have demonstrated that the evolution of the two-dimensional electron gas (2DEG) system at an interface of metal and the model topological insulator (TI) Bi$_2$Se$_3$ can be controlled by choosing an appropriate kind of metal elements and by applying a low temperature evaporation procedure. In particular, we have found that only topological surface states (TSSs) can exist at a Mn/Bi$_2$Se$_3$ interface, which would be useful for implementing an electric contact with surface current channels only. The existence of the TSSs alone at the interface was confirmed by angle-resolved photoemission spectroscopy (ARPES). Based on the ARPES and core-level x-ray photoemission spectroscopy measurements, we propose a cation intercalation model to explain our findings.

Strain dependence of the electronic properties of LaTiO3 thin films

We report on the transport and the core-level X-ray photoemission spectroscopy data of fully-strained LaTiO3 thin films grown on GdScO3 and SrTiO3 substrates. We observed that LaTiO3 thin film grown on GdScO3 showed insulating behavior but that grown on SrTiO3 exhibited a metallic character. We found that while the La 4d photoemission spectra of the two films were nearly the same, their Ti 2p and O 1s data revealed a difference. Our results suggest that strain-induced changes in the Ti-O bonding play an important role in the electronic properties of LaTiO3 thin films.

Soft X-ray Photoemission Study of New BiS2-Layered Superconductor LaO1−xFxBiS2

We use core level and valence band soft x-ray photoemission spectroscopy (SXPES) to investigate electronic structure of new BiS$_{2}$ layered superconductor LaO$_{1-x}$F$_{x}$BiS$_{2}$. Core level spectra of doped samples show a new spectral feature at the lower binding energy side of the Bi 4${f}$ main peak, which may be explained by core-hole screening with metallic states near the Fermi level ($E_{\rm F}$). Experimental electronic structure and its ${x}$ dependence (higher binding energy shift of the valence band as well as appearance of new states near $E_{\rm F}$ having dominant Bi 6${p}$ character) were found to be consistent with the predictions of band structure calculations in general. Noticeable deviation of the spectral shape of the states near $E_{\rm F}$ from that of calculations might give insight into the interesting physical properties. These results provide first experimental electronic structure of the new BiS$_{2}$ layered superconductors.