Photoelectron Valence-band Spectra Research Articles

Valence band XPS spectra of K silicate glasses: Effect of HOMO energies on K, Na and Li leach rates, activation energies and reaction mechanism

X-ray Photoelectron spectra of K-silicate glass valence bands (VBs) are composed of distinct upper and lower bands, separated by a minimum at ∼10 eV binding energy. A third, narrow band at ∼4.5 eV represents the highest energy occupied molecular orbitals (HOMOs). Na and Li glass VBs are similarly composed of upper, lower and HOMOs bands. The HOMOs reside only on NBO atoms (NBO = O atoms of the Si-O-M moiety; M = alkali), are non-bonding orbitals of O 2py character and are located at 4.5, 4.8 and 5.2 eV in K, Na and Li glasses. The order corresponds to alkali leach rates in water. We propose a SN reaction mechanism and Frontier Molecular Orbital concepts for leaching involving the HOMOs of the glasses and the LUMO of an adsorbed water molecule. The activated complex, Si-NBO*-M (NBO* = NBO•••HO-H), is formed through H-bonding of a solvent H2O molecule to NBO.

Intermediate tin oxide in stable core-shell structures by room temperature oxidation of cluster-assembled nanostructured Sn films

Room temperature oxidation of cluster-assembled nanostructured Sn films obtained by supersonic cluster beam deposition was investigated. Sn clusters smaller than about 10 nm are observed to be fully oxidized while in larger ones, as well as in Sn islands formed by clusters coalescence, completion of Cabrera-Mott process is prevented resulting in partial oxidation. Core-shell structures are therefore obtained, with shell thickness of about 4 nm. Core is composed by highly ordered, tetragonal β-tin, with micro-strain of 0.16 %, while shell is composed of tin oxides, where similar quantity of both Sn oxidation states Sn2+ and Sn4+ are observed, according to XPS. The presence in the samples of metallic tin, SnO, and SnO2 is confirmed by valence band photoelectron spectrum, whose components show edges at 0, 0.6, and 3.2 eV from Fermi level, respectively. Raman spectroscopy highlights the presence of Sn3O4 (short version of Sn2+2O2Sn4+O2), which confirms the spontaneous formation of this intermediate oxide. It is therefore proposed that an oxidation gradient Sn-SnO-Sn3O4-SnO2 characterizes core-shell system resulting from room temperature Cabrera-Mott oxidation of cluster-assembled nanostructured films.

Functionalization of the MoS2 basal plane for activation of molecular hydrogen by Pd deposition

We investigated the effects of gaseous hydrogen exposure on the bare MoS2 and Pd-deposited MoS2 basal surfaces using ambient-pressure X-ray photoelectron spectroscopy. In the Mo 3d core-level, S 2p core-level, and valence-band photoelectron spectra of a bare MoS2 surface, little change was observed in the energy shift before and after exposure to hydrogen gas. Upon hydrogen gas exposure on the Pd-deposited MoS2 surface, each peak in the photoelectron spectra (Mo 3d, S 2p, and valence-band) shifted to a lower binding energy with 0.1 eV. When hydrogen gas was evacuated, the peak energy remained lower compared with that before hydrogen gas exposure. The Pd 3d XPS spectra changed upon hydrogen gas exposure, which can be interpreted as the adsorption of dissociated hydrogen atoms on the Pd sites. These results indicate that the dissociation of molecular hydrogen and the adsorption of atomic hydrogen occur on the Pd-deposited sites on MoS2, and thereafter hydrogen atoms spillover onto the MoS2 surface. This study shows that the activation site for the dissociation of molecular hydrogen is created on an inert MoS2 basal surface by Pd deposition. In addition, the electronic states of the MoS2 substrate have been modulated by hydrogen atoms spilled over onto the MoS2 surface.

The atomic and electronic structure of Hf0.5Zr0.5O2 and Hf0.5Zr0.5O2:La films

HfxZr1-xO2 and lanthanum-doped HfxZr1-xO2:La thin films are candidates for applications in ferroelectric random-access memory. Here, we explore the atomic and electronic structure of Hf0.5Zr0.5O2 and Hf0.5Zr0.5O2:La thin films grown by atomic layer deposition. Using X-ray photoelectron spectroscopy, it was found that the oxides under study have an almost identical electronic structure and a bandgap of about 5.4 eV. The Hf0.5Zr0.5O2:La film was shown to consist of the mixture of Hf0.5Zr0.5O2 and La2O3 phases. The bombardment with argon ions of the studied films leads to oxygen vacancy generation in the near-surface layer. The oxygen vacancy concentrations in the bombarded films were evaluated from the comparison of experimental valence band photoelectron spectra with the theoretical ones calculated using the density functional theory.

Tunable Infrared Plasmonic Properties of Epitaxial Ti1-xMgxN(001) Layers.

Optical transmission and reflection spectra in combination with ellipsometry and transport measurements on epitaxial rocksalt structure Ti1-xMgxN(001) layers with 0.00 ≤ x ≤ 0.49 are employed to explore their potential as refractory infrared plasmonic materials. A red shift in the reflection edge ℏωe from 2.0 to 0.8 eV and the corresponding unscreened plasma energy ℏωpu from 7.6 to 4.7 eV indicate a linear reduction in the free carrier density N with increasing x. However, nitrogen vacancies in Mg-rich samples act as donors, resulting in a minimum N = 1.6 × 1022 cm-3 for x = 0.49. Photoelectron valence band spectra confirm the diminishing conduction band density of states and indicate a 0.9 eV decrease in the Fermi level as x increases from 0 to 0.49. The dielectric function ε = ε1 + iε2 can be divided into a low-energy spectral region where intraband transitions result in large negative and positive ε1 and ε2, respectively, and a higher energy interband transition region with both ε1 and ε2 > 0. The screened plasma energy Eps that separates these two regions red-shifts from 2.6 to 1.3 eV for x = 0-0.39, indicating a tunable plasmonic activity that extends from the visible to the infrared (470-930 nm). Electron transport measurements indicate a metallic temperature coefficient of resistivity (TCR) for TiN-rich alloys with x ≤ 0.26 but weak carrier localization and a negative TCR <60 K for x = 0.39 and <300 K for x = 0.49, attributed to Mg alloying-induced disorder. The plasmonic quality factor Q is approximately an order of magnitude larger than what was previously reported for polycrystalline Ti1-xMgxN, making Ti1-xMgxN(001) layers competitive with Ti1-xScxN(001).

Electronic Structure and Surface Properties of Copper Thiocyanate: A Promising Hole Transport Material for Organic Photovoltaic Cells.

Considering the significance of hexagonal copper thiocyanate (β-CuSCN) in several optoelectronic technologies and applications, it is essential to investigate its electronic structure and surface properties. Herein, we have employed density functional theory (DFT) calculations to characterise the band structure, density of states, and the energy-dependent X-ray photoelectron (XPS) valence band spectra at variable excitation energies of β-CuSCN. The surface properties in the absence and presence of dimethyl sulfoxide (DMSO), a solvent additive for improving perovskite solar cells’ power conversion efficiency, have also been systematically characterised. β-CuSCN is shown to be an indirect band gap material (Eg = 3.68 eV) with the valence band edge demonstrated to change from being dominated by Cu-3d at soft X-ray ionisation photon energies to Cu-3p at hard X-ray ionisation photon energies. The adsorption energy of dimethyl sulfoxide (DMSO) on the (100) and (110) β-CuSCN surfaces is calculated at −1.12 and −0.91 eV, respectively. The presence of DMSO on the surface is shown to have a stabilisation effect, lowering the surface energy and tuning the work function of the β-CuSCN surfaces, which is desirable for organic solar cells to achieve high power conversion efficiencies.

Single crystal growth and the electronic structure of Rb2Na(NO3)3: Experiment and theory

Rb2Na(NO3)3 crystals demonstrate nonlinear optical properties and can be used as a converter of laser radiation in the shortwave region. The crystals were grown in the present work by the Bridgman–Stockbarger method in a ratio of 75 ​wt%(RbNO3) and 25 ​wt%(NaNO3). After the growth, a transparent centimeter size single crystal (6 ​cm long) was obtained for the first time that is very important for its practical application. The unit cell volume of double Rb2Na(NO3)3 nitrate is intermediate between the cell volumes of simple rubidium and sodium nitrates, RbNO3 and NaNO3. Electronic structure of Rb2Na(NO3)3 was studied in the present work from both experimental and theoretical viewpoints. In particular, employing X-ray photoelectron spectroscopy, we have measured binding energies of core electrons and energy distribution of the electronic states within the valence band region of the Rb2Na(NO3)3 crystal and established rather big binding energies for N 1s and O 1s core-level electrons. The bombardment of middle-energy Ar+ ions induces transformation of some nitrogen atoms of the analyzing topmost layers of the Rb2Na(NO3)3 crystal surface from the NO3– group to the NO2– group. To explore in detail the filling of the valence band of Rb2Na(NO3)3 by electronic states associated with constituting atoms, we use first-principles calculations within a density functional theory (DFT) framework. The DFT calculations reveal that O 2p states are the principal contributors to the valence band bringing the main input in its upper portion. The theoretical finding is supported experimentally by fitting the X-ray photoelectron valence band spectrum and the X-ray emission O Kα band on the total energy scale. The conduction band bottom of Rb2Na(NO3)3 is composed by unoccupied O 2p and N 2p states in almost equal proportion.

Atomic and Electronic Structure of SiOx Films Obtained with Hydrogen Electron Cyclotron Resonance Plasma

The silicon oxide thin films obtained by thermal SiO2 treatment in hydrogen electron cyclotron resonance plasma at various exposure times are investigated. Using X-ray photoelectron spectroscopy, we have established that such treatment leads to a significant oxygen depletion of thermal SiO2, the more so the longer the treatment time. The atomic structure of the SiOx < 2 films obtained in this way is described by the random bonding model. The presence of oxygen vacancies in the plasma-treated films is confirmed by comparing the experimental valence band photoelectron spectra and those calculated from first principles, which allows the parameter x to be estimated. We show that thermal silicon oxide films treated in hydrogen plasma can be successfully used as a storage medium for a nonvolatile resistive memory cell.

J–V Characteristic of p–n Structure Formed on n-GaAs Surface by Ar+ Ion Beam

A highly defective ~10-nm-thick layer was fabricated in a high vacuum by 2.5 keV Ar+ ion bombardment of the n-GaAs surface. Valence band photoelectron spectra showed a p-type conductivity of the layer arising due to the high concentration of mechanically created point defects (p-centers). J–V characteristics measured ex situ for the structure consisting of the irradiated p-layer on the n-type substrate revealed a diode effect. Analysis of the data attributes the effect to the formation of a specific p–n junction. Thereby, we demonstrated that Ar+ ion bombardment of the n-GaAs surface results in that a nanostructure with the p–n junction properties is formed. The p–n junction under consideration seems to deserve further study and possible application since it can be formed in high-vacuum clean conditions directly by exposure to a low-energy Ar+ ion beam without wet lithography.

XPS evidence of degradation mechanism in CH3NH3PbI3 hybrid perovskite

In this study, we investigate the photo-/thermal degradation mechanism of hybrid perovskites by using x-ray photoelectron (XPS) valence band (VB) spectra coupling with density functional theory (DFT) calculations. Herein, CH3NH3PbI3 is respectively subjected to irradiation with visible light and annealing at an exposure of 0–1000 h. It is found from XPS survey spectra that, in both cases (irradiation and annealing), a decrease in the I:Pb ratio is observed with aging time, which unambiguously indicates the formation of PbI2 as the product of photo/thermal degradation. The comparison of the XPS VB spectra of irradiated and annealed perovskites with the DFT calculations of CH3NH3PbI3 and PbI2 compounds have showed a systematic decrease in the contribution of I-5p states, which allows us to determine the respective threshold for degradation, which is 500 h for light irradiation and 200 h for annealing. This discrepancy might be due to the fact that the relaxation of thermal excitations of the system is carried out only by the phonons (which are non-radiative physical processes) while the radiative processes occurred during the photoexcitation will elastically or inelastically divert part of the external energy from the system to reduce its impact on perovskite degradation.

Studies of electronic structure across a quantum phase transition in CeRhSb1\u2212xSnx

We study an electronic structure of CeRhSb1−xSnx system, which displays quantum critical transition from a Kondo insulator to a non-Fermi liquid at x = 0.13. We provide ultraviolet photoelectron spectra of valence band obtained at 12.5 K. A coherent peak at the Fermi level is not present in the data, but a signal related to 4f17∕2 final state is detected. Spectral intensity at the Fermi edge has a general tendency to grow with Sn content. Theoretical calculations of band structure are realized with full-potential local-orbital minimum-basis code using scalar relativistic and full relativistic approach. The calculations reveal a depletion of density of states at the Fermi level for CeRhSb. This gap is shifted above the Fermi energy with increasing Sn content and thus a rise of density of states at the Fermi level is reflected in the calculations. It agrees with metallic properties of compounds with larger x. The calculations also yield another important effect of Sn substitution. Band structure is displaced in a direction corresponding to hole doping, although with deviations from a rigid band shift scenario. Lifshitz transitions modify a topology of the Fermi surface a few times and a number of bands crossing the Fermi level increases.Graphical abstract

Experimental and theoretical study of electronic structure of disordered MWCNTs

Experimental study of electronic structure of the initial multi-walled carbon nanotubes (MWCNTs) as well as the exposed to annealing and irradiation N-MWCNTs, was carried out by XPS and NEXAFS methods. Based on the obtained photoelectron valence band spectra and C K-edge absorption spectra, a theoretical description of the density of electronic states (DOS) near the Fermi level was proposed to explain the dependence of the DOS and the band gap on temperature, concentration of doping atoms and various atomic configurations formed in a system during synthesis, subsequent ion-beam and heat treatment of MWCNTs.

To Be or Not To Be a Molecular Ion: The Role of the Solvent in Photoionization of Arginine.

Application of photoionization mass spectroscopy, a technique capable of assessing protonation states in complex molecules in the gas phase, is challenging for arginine due to its fragility. We report photoionization efficiencies in the valence region of aqueous aerosol particles produced from arginine solutions under various pH and vaporization conditions. By using ab initio calculations, we investigate the stability of different conformers. Our results show that neutral arginine fragments upon ionization in the gas phase but solvation stabilizes the molecular ion, resulting in different photoionization dynamics. We also report the valence-band photoelectron spectra of the aerosol solutions obtained at different pH values.

Valence and Core-Level X-ray Photoelectron Spectroscopy of a Liquid Ammonia Microjet.

Photoelectron spectroscopy of microjets expanded into vacuum allows access to orbital energies for solute or solvent molecules in the liquid phase. Microjets of water, acetonitrile and alcohols have previously been studied; however, it has been unclear whether jets of low temperature molecular solvents could be realized. Here we demonstrate a stable 20 μm jet of liquid ammonia (−60 °C) in a vacuum, which we use to record both valence and core-level band photoelectron spectra using soft X-ray synchrotron radiation. Significant shifts from isolated ammonia in the gas-phase are observed, as is the liquid-phase photoelectron angular anisotropy. Comparisons with spectra of ammonia in clusters and the solid phase, as well as spectra for water in various phases potentially reveal how hydrogen bonding is reflected in the condensed phase electronic structure.

STM/STS and photoemission study of Ag thin films on Ga/Si(111) ([formula omitted])R30°

Silver thin films have been formed by room temperature deposition of Ag on a Ga/Si(111) (3×3)R30° surface. Scanning tunneling microscopy and spectroscopy (STM/STS) have been used to study both the clean Ga/Si(111) (3×3)R30° surface and Ag films with different coverages. For the film formation, Ag first grows into 2D islands on Ga/Si(111) (3×3)R30°. The first layer of the islands forms atomic lines with three-fold symmetry in the 1 × 1 direction of the underlying Si(111) substrate. From a 2 ML coverage, the growth becomes layer-by-layer mode. STS measurements have been performed on Ag films with different coverages in order to investigate their electronic structures. Between 2–4 ML, the STS spectra reveal 2 and 3 peaks below the Fermi level. These peaks move towards the Fermi level with increased film thicknesses and thus share the same behavior as those of quantum well states (QWSs). The energy positions of the peaks have been compared with valence band photoelectron spectra in order to assign them to various parts of the QWSs. In addition, the photoemission results also confirm the existence of QWSs for a 2 ML Ag film on Ga/Si(111) (3×3)R30°.

Electronic structure and charge transport in nonstoichiometric tantalum oxide

The atomic and electronic structure of nonstoichiometric oxygen-deficient tantalum oxide TaOx<2.5 grown by ion beam sputtering deposition was studied. The TaOx film content was analyzed by x-ray photoelectron spectroscopy and by quantum-chemistry simulation. TaOx is composed of Ta2O5, metallic tantalum clusters and tantalum suboxides. A method for evaluating the stoichiometry parameter of TaOx from the comparison of experimental and theoretical photoelectron valence band spectra is proposed. The charge transport properties of TaOx 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.

Investigation of the spectral properties and magnetism of BiFeO3 by dynamical mean-field theory

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 ${\mathrm{BiFeO}}_{3}$, 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 $\mathrm{LDA}+U$ 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 $3d$ states, whereas the $\mathrm{LDA}+U$ 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 $3d$ orbitals to reproduce the experimental excitation spectra. Specifically, the LDA+DMFT derived density of states exhibits a significant amount of Fe $3d$ 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.

Electronic structure of Fe-Pd alloys studied by using photoemission spectroscopy

We investigated the electronic structure of Fe x Pd1−x (x = 0.25, 0.5, and 0.75) alloys by measuring valence-band and core-level photoelectron spectra. The Fe 3d and Pd 4d partial spectral weights were determined by using the Cooper minimum phenomenon of the Pd 4d photoionization cross section. We found that the experimentally determined Fe partial spectral weight of Fe50Pd50 alloy differ much from the band calculation results, and we could not observe a spectral structure due to the Pd 4d states mixed with the Fe 3d majority states at the binding energy of 0.9 eV. We suggest that a plausible explanation for these discrepancies should be the spin-dependent lifetime of the Fe 3d states.

Surface and bulk electronic structures of heavily Mg-doped InN epilayer by hard X-ray photoelectron spectroscopy

To evaluate the polarity, energy band diagram, and oxygen (O) distribution of a heavily Mg-doped InN (InN:Mg+) epilayer with a Mg concentration of 1.0 ± 0.5 × 1020 cm−3, the core-level and valence band (VB) photoelectron spectra are investigated by angle-resolved soft and hard X-ray photoelectron spectroscopies. The InN:Mg+ epilayers are grown by radio-frequency plasma-assisted molecular beam epitaxy. In this doping level, the polarity inversion from In-polar to N-polar occurs with the increase in the Mg flow rate under the same growth conditions, and the VB spectrum clearly indicates the direction of polarity of InN:Mg+, which is N-polar. The energy band diagram is considered to exhibit a two-step downward bending structure due to the coexistence of the n+ surface electron accumulation layer and heavily Mg-doped p+ layer formed in the bulk. The O concentration rapidly increases until ∼4 nm with respect to the surface, which is deduced to be one of the reasons of the formation of the anomalous two-step energy band profile.

Electronic structure of octahedrally coordinated Cr in CrxTiX2 (X = Se, Te) and TixCr1−xSe2

Influence of the covalence, octahedral distortion and the translation symmetry of the chromium ions in octahedral coordination on the electronic structure for compounds under investigation was clarified. Cr L2,3 and Ti L2.3 X-ray absorption spectra (XAS) along with atomic multiplet calculations and resonant Ti 2p-3d and Cr 2p-3d photoelectron spectra of valence band (RXPS) in the intercalated titanium dichalcogenides CrxTiX2 (X=Se, Te) and in the substitution compound TixCr1−xSe2 show the charge transfer between chromium and titanium sublattices.