Infrared modulated reflectance spectra of n and p type gallium antimonide and n type indium antimonide

We have observed the modulated reflectance spectra of n and p type GaSb at 300, 80, and 5 K from 0.56 to 2 eV. The modulated reflectance of intrinsic n type InSb was measured at 80 K from 0.2 to 2 eV. The “dry sandwich” vapor deposition technique was used to make the electroreflectance (ER) samples. The low-temperature spectrum of the undoped p type GaSb sample shows three peaks at the band edge that could be associated with transitions from the top of the valence band, the light (0.903 eV) and heavy (1.014eV) hole state Fermi levels to the conduction band. The energies of the observed peaks are in agreement with the Fermi level determination from Hall effect and Faraday rotation measurements. This modulation mechanism is based on band population effects. The ER signal of InSb under flatband condition at 80 K has five half oscillations at the direct band gap. The contribution of piezoelectric strain to ER is present since the dc bias required to achieve flatband condition is different at the band gap than at E₁. The ER signal corresponding to the direct gap energy E₀ and to the spin-orbit energy E₀ + Δ₀ was determined in the n and p type samples of GaSb at different temperatures. We have measured the intrinsic energy gap in GaSb at room temperature. E_g = 0.74 eV. The corresponding spin-orbit splitting was found to be Δ₀ = 0.733 ± 0.002 eV.     

Electronic structure and optical properties of LaNiO3: First-principles calculations

Using a first-principles method, we investigate the electronic structure and optical properties of rhombohedral LaNiO₃. The total density of states shows that there is no band gap and bulk LaNiO₃ is metallic. There is a strong hybridization between Ni and O orbits near the Fermi level, suggesting that the metallic nature of LaNiO₃ mainly originates from Ni 3d states and La atoms have no noticeable contribution to this. The absorption coefficient of LaNiO₃ is one order of magnitude less than that of nickel in the lower energy region (0–5 eV), and the interband optical transitions are mainly derived from O 2p and Ni 3d states. In reflectivity spectrum of LaNiO₃, there are three main reflectance peaks located at 0 eV, 15.6 eV and 22.9 eV, respectively. In the visible–ultraviolet energy range, the reflectivity of LaNiO₃ remarkably decreases with the increasing photon energy and the value is always smaller than that of nickel in the region.     

Imaging the phenol molecule adsorbed on TiO2(110) by scanning tunneling microscopy

The image of a phenol molecule adsorbed on a TiO₂(110) single crystal was obtained, for the first time, by using the STM. TiO₂(110) has a tunneling active free region from + 1.35 eV below the Fermi level to −0.25 eV above the Fermi level. This region was found after measuring the surface density of states by using tunneling spectroscopy. The phenol molecule was fixed on TiO₂ utilizing the amphoteric nature of the TiO₂ surface. The image of the phenol molecule was measured at a dp bias of + 443 mV, which almost matches the energy of the OH and C-H stretching bond of the phenol molecule, in the free of energy levels region of the TiO₂(110) substrate. The electron density of phenol ring is apparent in the STM picture.     

Photoemission study of oxygen chemisorption on tin

Photoemission measurements have been made at photon energies from 5–12 eV and at 21.2 eV on evaporated Sn films and the same films with varying room temperature exposure to oxygen. For hν ? 9 eV the quantum yield for Sn with exposures of as much as 4000 L oxygen (1 L = 1 Langmuir = 10^?6 Torr sec) differs only slightly from the clean metal. For hν ? 9 eV no change in yield is observed with oxygen exposure. The energy distribution of photoemitted electron (EDC's) from Sn with increasing exposure to oxygen above ? 20 L are characterized by the growth of two peaks which were not present in the EDC's for the clean metal, located 2.9 ± 0.1 eV and 4.8 ± 0.1 eV below the Fermi level. We associate this structure with the presence of SnO₂. No sharp resonance which could be associated with adsorbed oxygen was seen. Uniformly reduced emission from metallic Sn states and a Fermi level as sharp as for the clean metal is observed in the EDC's at all oxygen exposures. In addition, no change in work function with oxygen exposure was detected. The effects of oxygen saturate for exposures ? 4000 L. We suggest that under the conditions used in this experiment, the oxygen penetrates beneath the surface forming SnO₂ and leaving metallic Sn on the surface.     

Effective 4ƒ energy level in virtual excitation and in photoemission processes in Ce-pnictides

Effects of relaxation of occupied band electrons to the ?-hole state through the hybridization between ? and band states are studied based on a detailed model for Ce-monopnictides. The effective 4? level is shifted about 1–2 eV to shallow energy side from the unrenormalized bare level in processes in which the 4? electron is only virtually excited, such as in excitation to the vacant p band states through the p-? mixing. Photoemission spectra show two peaks, one near the Fermi energy and the other about 3 eV below it. The latter is shifted to deep energy side about 0.5–1 eV from the bare level when it lies near the bottom of the valence band. The discrepancy between the 4? level estimated from the low energy phenomena and that from photoemission is resolved.     

Electroreflectance study of CuIn1−xGaxSe2 thin film solar cells

We have investigated the optical properties of CuIn_1−xGa_xSe₂ (CIGS) thin film solar cells using their electroreflectance (ER) at room temperature. The ER spectra exhibited one broad and two narrow signal regions. Using the photoluminescence (PL) and photocurrent (PC) spectra, the peaks in the low-energy region (1.02–1.35 eV) can be assigned to the CIGS thin film. The PC results implied that the peaks in the high-energy region (2.10–2.52 eV) can be assigned to the CdS band-gap energy. Using the applied bias voltage, the broad signals in the 1.35–2.09 eV region can be assigned to the Franz–Keldysh oscillation (FKO) due to the internal electric field. The ER spectra exhibited a distorted CdS signal for the CIGS thin film solar cell with low shunt resistance and efficiency.     

Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations

Effects of alkyl side chains (R‐) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP < 290 eV (where IP is the ionization potential). The two glycyl parent spectral peaks of the amide 291.0 eV [C₍₂₎] and carboxylic 293.5 eV [C₍₁₎] C atoms are shifted in the aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12–16 eV, and hence this energy region of 12–16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO–LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.     

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.     

Cd:O共掺杂AlN的电子结构和p型特性研究

为研究Cd：O共掺杂纤锌矿AlN的p型特性,进而揭示导致纤锌矿AlN空穴浓度增加的机理,对Cd：O共掺杂AlN进行了基于密度泛函理论的第一性原理研究.通过计算Cd_n-O（n=1,2,3,4）复合体掺杂AlN的结合能,发现Cd：O在AlN中可以稳定存在,共掺杂提高了Cd在AlN中的固溶度.分析Cd和Cd₂-O掺杂AlN体系的激活能,发现Cd₂-O的激活能比Cd减小0.21 eV,表明Cd₂-O的空穴浓度比单掺Cd大约提高 关键词： Cd：O共掺杂 纤锌矿AlN 电子结构 p型掺杂特性     

Observation of charge transfer states of F4-TCNQ on the 2-methylpropene chemisorbed Si(1 0 0)(2 × 1) surface

We have investigated the valence electronic states of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄-TCNQ) on the 2-methylpropene chemisorbed Si(1 0 0)(2 × 1) surface using valence photoelectron spectroscopy. Since the electron affinity of condensed F₄-TCNQ is 5.24 eV and the energy from the valence band maximum of the 2-methylpropene saturated Si(1 0 0)(2 × 1) surface to the vacuum level is 4.1 eV, spontaneous charge transfer would be expected in the present system. At sub-monolayer coverage of F₄-TCNQ, characteristic peaks are observed at 1.1 and 2.5 eV below Fermi energy. The former peak is assigned to a singly occupied affinity level, and the latter is ascribed to a relaxed highest occupied molecular orbital of adsorbed F₄-TCNQ. The work function change is increased up to +1.3 eV as a function of F₄-TCNQ coverage. These results support the occurrence of charge transfer into F₄-TCNQ on the 2-methylpropene saturated Si(1 0 0)(2 × 1) surface.     

Valence band of molybdenum by photoelectron spectroscopy

Experimental photoelectron spectra of a clean polycrystalline Mo surface excited by monochromatized Al K _α X-rays are presented. The spectra are compared with valence bands obtained by UPS and by band structure calculations within the 5 eV region below the Mo Fermi level. All results mentioned above display peaks at 0.3, 1.7, 2.8 and 4 eV belowE _F. The energy distribution of the valence band does not vary with photon energy and electron emission angle for the four different polycrystalline Mo surfaces compared. It is concluded that the four peaks representing the Mo valence band are predominantly of bulk origin.     

Photoemission from Ni0.84Cu0.16(111): Observation of surface energy band dispersion

Angle-resolved photoemission spectra have been obtained for annealed Ni_0.84Cu_0.16(111) single crystals. Emission peaks 1.8–4.0 eV below the Fermi energy are attributed to electronic states of the Cu-rich surface layer. The measured dispersion of these peaks is in close correspondence with the calculated energy bands of a free Cu (111) monolayer. Ni-derived bulk transitions are also identified.     

Adsorption and decomposition of H2O on a K-covered Pt(111) surface

The adsorption of H₂O on clean and K-covered Pt(111) was investigated by utilizing Auger, X-ray and ultra-violet photoemission spectroscopies. The adsorption on Pt(111) at 100–150 K was purely molecular (ice formation) in agreement with previous work. No dissociation of this adsorbed H₂O was noted on heating to higher temperatures. On the other hand, adsorption of H₂O on Pt(111) + K leads to dissociation and to the formation of OH species which were characterized by a work function increase, an O 1s binding energy of 530.9 eV and UPS peaks at 4.7 and 8.7 eV below the Fermi level. The amount of OH formed was proportional to the K coverage for θ_K > 0.06 whereas no OH could be detected for θ? 0.06. Dissociation of H₂O occurred already at T = 100 K, with a sequential appearance of O 1s peaks at 531 and 533 eV representing OH and adsorbed H₂O, respectively. At room temperature and above only the OH species was observed. Annealing of the surface covered with coadsorbed K/OH indicated the high stability of this OH species which could be detected spectroscopically up to 570 K. The adsorption energy of H₂O coadsorbed with K and OH on Pt(111) is increased relative to that of H₂O on Pt. The work function due to this adsorbed H₂O increases whereas it decreases for H₂O on Pt(111). The energy shifts of valence and O1s core levels of H₂O on Pt + K as deduced from a comparison of gas phase and adsorbate spectra are 2.8–4.2 eV compared to ≈ 1.3–2.3 eV for H₂O on Pt (111). This increased relaxation energy shift suggests a charge transfer screening process for H₂O on Pt + K possibly involving the unoccupied 4a₁ orbital of H₂O. The occurrence of this mode of screening would be consistent with the higher adsorption energy of H₂O on Pt + K and with its high propensity to dissociate into OH and H.     

Giant nonlinear absorption in the NiO antiferromagnet

A study of the spectrum of nonlinear two-photon and two-step absorption in NiO single crystals, carried out in the energy region ?ω₁ + ?ω₂ = 2.45–4.575 eV, showed it to have a complex shape and consist of very strong peaks (from 0.05 to 2.7 cm/MW). Within the energy interval 2.45–3.3 eV, the spectrum is due to d-d transitions in the Ni²⁺ ion. The band gap width was determined to be E _g =3.466 eV. The spectral features seen above this energy originate from interband transitions from three valence subbands to the conduction band bottom.     

Low energy electron spectroscopy of Pt (100) and Pt (100)/CO

Fine structure in the n_vi, _VIIVV spectrum of clean Pt (100) has been observed, and interpreted as “band like” in origin rather than quasi-atomic. Differences in the dependence of the Auger yield on primary beam energy are observed between the N_VI, _VIIVV and O_IIIVV peaks, and are associated with anomalies in the dependence of the inner shell ionization crossection of the 4f level. Low energy electron loss spectra on the clean surface have been investigated at primary energies in the range 71–774 eV and at angles of incidence of the beam 0–60°. The results are related to high energy loss and optical data, and assignments are given for inter-band and plasmon losses. With approximately $\text{3}\text{4}$ of a monolayer of CO on the surface there is a prominent additional loss at around 13.5 eV, which is interpreted as a one electron transition from a σ state below the d band to available states several electron volts above the Fermi level.     

Comparative photoemission study of the electronic properties of L-CVD SnO2 thin films

In this work we present the results of comparative XPS and PYS studies of electronic properties of the space charge layer of the L-CVD SnO₂ thin films after air exposure and subsequent UHV annealing at 400 °C, with a special emphasis on the interface Fermi level position.From the centre of gravity of binding energy of the main XPS Sn 3d_5/2 line the interface Fermi level position E_F − E_v in the band gap has been determined. It was in a good correlation with the value estimated from the offset of valence band region of the XPS spectrum, as well as from the photoemission yield spectroscopy (PYS) measurements. Moreover, from the valence band region of the XPS spectrum and PYS spectrum two different types of filled electronic band gap states of the L-CVD SnO₂ thin films have been derived, located at 6 and 3 eV with respect to the Fermi level.     

Charge-transfer at silver/phthalocyanines interfaces

Valence band photoemission spectroscopy (VB-PES) and inverse photoemission spectroscopy (IPES) were employed to determine the occupied and unoccupied density of states upon silver deposition onto layers of two phthalocyanines (H₂Pc and CuPc). The two different Pc molecules give rise to very distinct behaviour already during the initial stage of silver deposition. While in the CuPc case no shift occurs in the energy levels, the H₂Pc highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are shifting simultaneously by 0.3 eV, i.e., the HOMO shifts away from the Fermi level while LUMO shifts towards the Fermi level. As the silver quantity increases the HOMO levels of both Pcs are shifting towards the Fermi level. When the Fermi level is resolved in the VB spectra, the characteristic features of H₂Pc and CuPc are smeared out to some extent. Shifts in HOMO and LUMO energy positions as well as changes in line shapes are discussed in terms of charge-transfer and chemical reactions at the interfaces.     

High-temperature superconductor Ba2YCu3O7-¢L: plasmon and ultraviolet optical transition studies

We present the first electron energy loss data on a high-temperature superconductor. A detailed comparison with photoemission energy distribution curves and partial-yield spectra identifies the nature of the corresponding features. This analysis shows that the bulk plasmon energy is 24.6 eV, and that there are two peaks in the density of empty states, 2.3–2.5 eV and 4.3–4.6 eV above the Fermi level.     

X-ray photoelectron (XPS) and Auger (XAES) spectroscopy study of rhodium dispersed on carbon substrate

Photoelectron 3d_5/2 binding and Auger M₅VV kinetic energies of dispersed rhodium have been measured. For the smallest deposition of Rh the shifts 0·6 eV and -2·5 eV of 3d_5/2 and M₅VV lines respectively have been found. Electron core level energy, Auger kinetic energy and Fermi edge shifts have been interpreted by a model based on electrostatic relaxation mechanism in metal particles and initial state contribution of surface atoms. Intensity and background height analysis indicate only surface distribution of Rh.I wish to express my gratitude to Dr. Zdenk Bastl for helpful discussions.     

Scanning tunnelling microscopy and spectroscopy of the reduced TiO2(1 0 0) surface

Scanning tunnelling microscopy and current imaging tunnelling spectroscopy were used to study the topographic and electronic structure of a reduced TiO₂(1 0 0) surface. The STM results showed that the TiO₂(1 0 0) surface is capable to form (1 × 7) reconstruction which can transform to (1 × 3) reconstruction due to reoxidation of the surface. The CITS results showed that the (1 × 7) reconstruction is much more metallic in compared to the (1 × 3) reconstruction showing pronounced surface states at energy 1.3 eV and 0.8 eV below the Fermi level and at energy 1.0-1.2 eV above the Fermi level.