Electronic structure of PbI2 from photoelectron spectra and the exciton problem

The valence band density of states for PbI₂ is determined from X-ray and u.v. induced photoelectron spectra. It is shown that the band derived from Pb 6s states is at 8 eV binding energy and not at the top of the valence bands as suggested by band structure and charge density calculations. A rigid shift in the predominantly iodine 5p derived bands to lower binding energy brings the band structure calculations into essential agreement with experiment. Pb 5d core level binding energies determined here are used to derive core level exciton energies of 0.7 eV from published reflectivity spectra.     

Photoemission studies of single crystals of titanium carbide

The electron distribution in the valence band from single crystals of titanium carbide has been studied by photoelectron spectroscopy with photon energies h?ω = 16.8, 21.2, 40.8 and 1486.6 eV. The most conspicious feature of the electron distribution curves for TiC is a hybridization between the titanium 3d and carbon 2p states at ca. 3–4-eV binding energy, and a single carbon 2s band at ca. 10 eV. By taking into account the strong symmetry and energy dependence of the photoionization crosssections, as well as the surface sensitivity, we have identified strong emission from a carbon 2p band at ? 2.9-eV energy. Our results are compared with several recent energy band structure calculations and other experimental data. Results from pure titanium, which have been used for reference purposes, are also presented.The valence band from single crystals of titanium carbide have been studied by means of photoelectron spectroscopy, with photon energies ranging from 16.8 to 1486.6 eV.By taking into account effects such as the symmetry and energy dependence of the photoionization cross-sections and surface sensitivity, we have found the valence band of titanium carbide to consist of two peaks. The upper part of the valence band at 3–4 eV below the Fermi level consists of a hybridization between Ti 3d and C 2p states. The C 2p states observed in our spectra were mainly excited from a band about 2.9 eV below the Fermi level. The APW^5–9, MAPW¹⁰ and EPM¹¹ band structure calculations predict a flat band of p-character between the symmetry points X′₄ and K₃, most likely responsible for the majority of C 2p excitations observed. The C 2s states, on the other hand, form a single band centered around ?10.4 eV.The results obtained are consistent with several recent energy band structure calculations^{5–11, 13} that predict a combined bonding of covalent, ionic and metallic nature.     

Electronic structure and thermal stability of rare earth metalloporphyrins based on ytterbium

The features of the electronic structure of Yb4d, N1s, C1s, O1s, Br3d core levels and the valence band of ytterbium metalloporphyrins Yb(acac)TPPBr8, Yb(acac)TPP, TPPBr8, and TPP are studied by photoelectron spectroscopy. The position and structure of the Yb4f level for Yb(acac)TPPBr8 are determined by resonant photoemission at the BESSY-II synchrotron center. Simulations of the electronic structure of the valence band show good agreement between the calculated and experimental data. The change in the electronic structure of porphyrins during implantation of the central atom of ytterbium, namely, a more uniform redistribution of the electron density between nitrogen atoms of pyrrole and aza groups, is revealed. The photoelectron spectra of Yb4d states demonstrate the trivalent metal state (Yb³⁺) in rare-earth metalloporphyrins. The partial destruction of bromine ytterbium tetraphenylporphyrin compound as a result of thermal action is demonstrated.     

Separation of the partial s- and p-densities of valence states of ZnO from UPS-measurements

UPS-spectra of the cleaved (0001) Zn and (000$\text{1}$) O surfaces of ZnO are taken at hv = 16.8, 21.2, 26.9, and 40.8 eV. Two maxima in the spectra at constant final energy are ascribed to high densities of conduction band states. Using the hv-dependence of the valence band emission, the partial s- and p-densities of states are separated. They yield similar excitation probabilities for Zn-4s-, 3d-, and O-2p-electrons.     

Ultraviolet photoemission study of LiF

Photoemission from evaporated films of LiF were measured at photon energies of 10-27 eV. The photoelectron spectra exhibit features that can be identified as density-of-states structures in the valence and conduction bands of LiF. Regions of high density of states can be seen at ca. 3.3 and 7.8 eV above the vacuum level. The valence-band spectrum shows a doublet structure similar to the calculated density of states for the F^?2p band of LiF. The base width of this structure is found to be 4.6 ± 0.3 eV. The photoelectron spectra for photon energies > 15 eV indicate that the highest occupied states of the F^?2p band are located at 11.8 ± 0.3 eV below the vacuum level. The photoelectron spectra in the exciton region, however, show photo-emission from higher occupied states.     

X-ray photoelectron spectroscopy of tin oxide nanolayers

X-ray photoelectron spectra of 30- and 100-nm nanolayers, recorded in the energy range 0–35 eV, show a strong dependence of both the distribution of the density of Sn 5s, p+ O₂ p valence states and the change in the intensity ratio for the Sn 4d and O 2s subvalence states on the annealing temperature and nanolayer thickness. In the nanolayers fabricated at an annealing temperature of 450°C, an unusually strong band of O 2s states of unbound oxygen is observed, which is retained for nanolayers doped with palladium and disappears for nanolayers doped with gold and silver.     

Laser photoelectron spectrometry of Sc− and Y−: A determination of the order of electron filling in transition-metal anions

The photoelectron spectra of Sc^? and Y^? have been obtained in a crossed ion- and laser-beam experiment. Analysis of the Sc^? spectrum yields two bound terms of 3d4s² 4p configuration (¹D⁰ and ³D⁰), with EA(Sc) = 0.189 ± 0.020 eV and an excited-state binding energy of 0.042 ± 0.020 eV. Similarly, the (4d5s² 5p) ¹D⁰ ground state of Y^?is bound by 0.308±0.012eV and a (4d5s²5P)³D⁰ excited term is bound by 0.165± 0.025 eV. With the determination of the bound electronic configuration of Sc^? as 3d4s²4p, the order of filling of electron shells of the first transition series negative ions is found to be 4s²4p, 3d4s²4p, followed by 3d^k4s² (k = 3,4,…, 10).     

Structure relations in the x-ray photoelectron spectra of three chromium compounds

The chemical shift in electron binding energy, magnetic splitting of electron shells, and structures in the valence band are examined for chromium in the 3 + and 6 + oxidation states.The splitting of the Cr 3s energy level is associated with the appearance of a sharp Cr 3d line in the valence band. The relative chemical shift in the Cr 2p_{$\text{3}\text{2}$} line between Cr₂O₃ and K₂Cr₂O₇ is verified in the mixed compound KCr₃O₈ which contains both types of Cr ions, and the structure of this compound is verified by the X-ray photoelectron spectra. The spin-orbit intensity ratio of the 2p doublet of Cr⁶⁺ is 3, instead of the theoretical value of 2, and the spin-orbit splitting is less than for Cr³⁺. In the 3p level of Cr the relative chemical shift is 3.5 eV whereas for the 2p_{$\text{3}\text{2}$} level the shift is only 2.4 eV. The differences in chemical shift and intensity ratio can not be explained.     

X-ray emission from multi-inner-shell excited states produced by high-intensity short-pulse X-rays

We study the double inner-shell ionization produced by high-intensity short-pulse X-rays and the X-ray emission from doubly inner-shell excited states of Mg (1s ²2s ²2p ⁴3s ²) and Xe (1s ²2s ²2p ⁶3s ²3p ⁶4s ²4p ⁶4d ⁸5s ²5p ⁶). The intensity and pulse width dependence on the X-ray emission is studied.     

Electroreflectance observation of localized and itinerant electron states in NiO

We have observed electroreflectance spectra in NiO at 6 eV which we believe represent transitions from the oxygen 2_p derived valence band to the nickel 4s derived conduction band. We also observe the spectrum seen earlier by McNatt near 4 eV but interpret it differently in terms of transitions from the localized 3d⁸ state to the 4s band. These interpretations are consistent with the recent model of Adler and Feinleib.     

Electronic structure of CdTe probed by Cd and Te M4,5 X-ray emission spectra

We have investigated the bulk electronic structure of CdTe focusing on the Cd 5p and Te 5p valence states by X-ray emission spectroscopy (XES). Despite the very low fluorescence yields the Cd and Te M_4,5 (5p → 3d_3/2,5/2) spectra have been recorded successfully. A good correspondence has been found between the valence band XES and X-ray photoelectron spectra (XPS) by comparison on a common binding energy scale. We also performed a density functional theory calculation of the CdTe valence band, obtaining the Cd 4d, 5s, 5p and Te 5s, 5p local partial densities of states. The experimental Cd 5p and Te 5p derived from the X-ray emission spectra are in good agreement with the calculation. The intensity ratio of the Cd M_4,5 to the Te M_4,5 spectrum is obtained to be 0.25, in agreement with the ratio of the calculated Cd 5p to the Te 5p density of states in the CdTe upper valence band (0.22).     

Chemical bonds and electronic states in antimony triiodide

The use of synchrotron radiation has been crucial in revealing all the features of the SbI₃ UV photoemission spectra. In particular we have found structure closer than 1 eV to the top of the valence band, i.e. above all the iodine p-like peaks. This structure is related to a partial rehybridization of the iodines s-p hybrids with lone-pair-like Sb s-electrons. From our results the presence of s-like atomic orbital character at the edge of the valence band appears a general property of layered iodides.     

Resonant photoemission at the 3s threshold of Ni

A resonant enhancement of valence band photoemission features in Ni near the 3s threshold is presented. The emission behavior with photon energy of the Ni-3d band is characteristic of a Fano-type resonance. In addition to the main 3d-band emission and 6eV binding energy satellite, a weak satellite is observed at 7.2eV below the Fermi level with photon energies in the vicinity of the 3s threshold.     

Electronic band structure of In2S3 and CdIn2S4 semiconductor spinels from the data of x-ray spectroscopy and theoretical calculations

The electronic band structure of the chalcogenide spinels In₂S₃ and CdIn₂S₄ has been studied using the FEFF8 program. It is shown that the valence band top is formed by the S p states mixed with the In s and In p states for In₂S₃ or with the Cd s, Cd p, In s, and In p states for CdIn₂S₄. Compared to In₂S₃, the presence of Cd atoms in the nearest environment of S atoms in CdIn₂S₄ does not considerably affect the electronic band structure. In CdIn₂S₄ the Cd 4d states, as well as the In 4d states, form a narrow localized band shifted deep into the valence band. The theoretical results are in good agreement with the experimental x-ray photoelectron and x-ray spectra.     

Zur Interpretation der Röntgenemissionsbanden von AIII BV-Verbindungen

The experimental data on the x-ray emission bands of AIII BV compounds corresponding to transitions with valence band states as initial states are compiled. The comparison of the observed emission band widths and line shapes with band structure data and also with the simple semiconductor model due to PENN shows that most of the observed structure can be explained if one assumes that the K-emission bands reflect the p-like part and the L-emission bands the s-(and d-) like parts of the total valence band state density.     

Observation of p- and d-like surface states on CuCl(100) by angle-resolved photoemission

In the course of a systematic ultraviolet photoemission study of the electronic band structure of CuCl, we have identified two occupied surface states on CuCl(100), situated at 0.25 and 3.0 eV below valence band maximum in normal emission spectra. They essentially show pure p- and d-like orbital symmetry, respectively. We interpret them as a chlorine p_x,y-like occupied antibonding resonance and a copper Γ₁₂-derived state split off from the bulk orbitals by the surface potential. We also present critical point energies along Γ-X and Γ-L.     

Valence band density of states of amorphous and trigonal selenium determined by X-ray and U.V. photoemission

The densities of states of the entire valence bands of amoprhous and trigonal selenium have been measured by X-ray (hv = 1486.6 eV) and u.v. (hv = 21.2 eV) photoemission. It is found that the primary differences in the density of states of the two forms occurs in the p-like valence bands, in particular the lower bonding set. The density of states calculated by Kramer et al. for the amorphous form is shown to be in better agreement with the experimental density of states of the trigonal form than with that of the amorphous form.     

Structure electronique des oxydes de cobalt CoO et Co3O4

The total density of occupied states in the valence band of CoO and Co₃O₄ is determined by XPS and UPS. From variations of excitation probability of the bands, the 4 e V wide O2_p band is shown to be located around 5 eV for both oxides, while structures obtained from photoionisation of the localized 3d band spread over 10 eV range below the Fermi level overlapping with O2_p band. The 3d peaks located at binding energy <3 eV correspond to the calculated energy of the d_n ?1 manifold final state in the octahedral and tetrahedral crystal field of CoO and Co₃O₄. The 3d levels at higher binding energy are shown to occur from configuration interaction in both final and initial states. These last peaks are higher in intensity for CoO relative to Co₃O₄. A superior limit for the width of the 3d initial band in a one electron energy diagram is given to be <3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV from shake-up and Auger energy confirms the Mott insulator nature of CoO.     

Calculation of band offset in chalcopyrite system

A recently reformulated tight binding method is used to calculate valence band offset (VBO) at the CuInSe₂/CuGaSe₂ heterojunction. The hybrid energy is calculated in the s²p² configuration and a new model for the average hybrid energy is used. The theoretical VBO value of 0.05 eV is in good agreement with recent experimental value of 0.04 eV. The value of conduction band offset is 0.60 eV giving a type I alignment. The VBO varies linearly with bond length difference (l), as VBO=(0.24)l.     

Electronic structure of the CuBS2 crystal

The band structure and spectra of the total and projected densities of states of a new crystal of the chalcopyrite family, namely, CuBS₂, have been calculated in terms of the density functional theory. It has been found that the crystal is a pseudo-direct-band-gap semiconductor, and the best theoretical estimate of the optical band gap is 3.44 eV. The upper valence band of the CuBS₂ crystal basically consists of the contributions from the p states of S atoms and the d states of Cu atoms. The crystal splitting is 0.2 eV. The bottom of the conduction band is basically formed by the sp states of boron and sulfur atoms with an admixture of the s states of copper atoms.