2D degenerate electron gas at Ba/<Emphasis Type="Italic">n</Emphasis>-AlGaN and Ba/<Emphasis Type="Italic">n</Emphasis>-GaN interfaces

Ba/n-GaN(0001) and Ba/n-AlGaN(0001) interfaces were investigated for the first time by means of ultraviolet photoelectron spectroscopy. The spectra of the photoemission from a valence band along with the spectra of the core levels of Ga 3d, Al 2p, and Ba 4d were studied. The formation of a 2D degenerate electron gas (an accumulated layer on the n-GaN and n-AlGaN surfaces during adsorption of Ba atoms) was revealed.     

Photoemission studies of ultrathin Cs,Ba/InN interfaces

Cs/InN and Ba/InN interfaces were studied by UV photoelectron spectroscopy in the submonolayer coverage range for the first time. Normal photoemission spectra from the valence band and spectra from In 4d, Ba 5p, Ba 4d, and Cs 5p core levels were investigated in the excitation energy range of 60–800 eV. It was found that metallization of the interface and narrowing of the valence band is observed upon increasing coverage.     

Modification of the electronic structure and formation of an accumulation layer in ultrathin Ba/n-GaN and Ba/n-AlGaN interfaces

The electronic structure of the n-GaN(0001) and Al _x Ga_{1 ? x} N(0001) (x = 0.16, 0.42) surfaces and the Ba/n-GaN and Ba/AlGaN interfaces is subjected to in situ photoemission investigations in the submonolayer Ba coverage range. The photoemission spectra of the valence band and the spectra of the surface states and the core 3d level of Ga, the 2p level of Al, and the 4d and 5p levels of Ba are studied during synchrotron excitation in the photon energy range 50–400 eV. A spectrum of the surface states in Al _x Ga_{1 ? x} N (x = 0.16, 0.42) is found. The electronic structure of the surface and the near-surface region is found to undergo substantial changes during the formation of the Ba/n-GaN and Ba/AlGaN interfaces. The effect of narrowing the photoemission spectrum in the valence band region from 10 to 2 eV is detected, and surface eigenstates are suppressed. The Ba adsorption is found to induce the appearance of a new photoemission peak in the bandgap at the Fermi level in the Ba/n-GaN and Ba/n-Al_0.16Ga_0.84N interfaces. The nature of this peak is found to be related to the creation of an accumulation layer due to a change in the near-surface potential and enriching band bending. The energy parameters of the potential well of the accumulation layer are shown to be controlled by the Ba coverage.     

Surface states and accumulation nanolayer induced by Ba and Cs adsorption on the n-GaN(0 0 0 1) surface

The Ba and Cs adsorption on the n-GaN(0 0 0 1) surface has been studied in situ by the threshold photoemission spectroscopy using s- and p-polarized light excitation. Two surface bands induced by Ba (Cs) adsorption are revealed in surface photoemission spectra below the Fermi level. The surface-Fermi level position is found to be changed from significantly below the conduction band minimum (CBM) at clean n-GaN surface to high above the CBM at Ba, Cs/n-GaN interfaces, with the transition from depletion to electron accumulation occurring at low coverages. Photoemission from the accumulation nanolayer is found to excite by visible light in the transparency region of GaN. Appearance of an oscillation structure in threshold photoemission spectra of the Ba, Cs/n-GaN interfaces with existing the accumulation layer is found to originate from Fabry–Perot interference in the transparency region of GaN.     

UV-photoemission study of barium,europium and ytterbium

Measurements are reported of the photoemission spectra and absolute yield of thin films of Eu, Ba and Yb for the photon energy range 2 to 21 eV. Transitions from the occupied 4f-states in Eu and Yb have been observed and the binding energies deduced. The excitation probability of the 4f electrons is found to be very low and an explanation based on their atomic-like nature is given. Transitions involving valence band states are compared with predictions based on published energy band schemes and the density of states for the unoccupied 5d band in Yb is deduced. The effect of chemisorbed oxygen on Ba and Eu surfaces is reported.     

Charge accumulation layer on the <Emphasis Type="Italic">n</Emphasis>-GaN (0001) surface with ultrathin Ba coatings

The adsorption of Ba on the n-type GaN(0001) surface is studied. It is found that submonolayer Ba coatings induce cardinal changes in the electronic properties of the surface with the formation of a charge accumulation layer in the region of the near-surface band bending. The excitation of the Ba/n-GaN system by light from the region of GaN transparency results in photoemission. The lowest value of the work function corresponds to ～1.90 eV at a Ba coverage of ～0.4 ML. Two surface bands induced by Ba adsorption are found in the surface photoemission spectra.     

Surface electronic structure of the organic superconductor κ-(ET)2Cu(NCS)2 studied via photoemission microscopy

The surface electronic structure of cleaved single crystals of the organic superconductor κ-(ET)₂Cu(NCS)₂ has been studied using photoemission microscopy. Two types of cleaved surfaces were observed, displaying different valence band photoemission spectra and different spectral behavior near the Fermi level, E_F. In particular, spectra from one surface type display relatively broad spectral features in the valence band and finite spectral intensity at E_F, while spectra from the other surface type show well-defined valence band emission features and zero photoemission intensity at E_F. We propose that the spectral differences are due to a very short electron mean free path in this material, and our results are used to explain the differences between previously published photoemission spectra from this superconductor. We also report the results of an investigation of the electronic structure of defects in this material.     

Synchrotron-radiation photoemission study of the ultrathin Ba/3C–SiC(111) interface

Electronic structure of the Ba/3C–SiC(111) interface has been detailed studied in situ in an ultrahigh vacuum using synchrotron radiation photoemission spectroscopy with photon energies in the range of 100–450 eV. The 3C–SiC(111) samples were grown by a new method of epitaxy of low-defect unstressed nanoscaled silicon carbide films on silicon substrates. Valence band photoemission and both the Si 2p, C 1s core level spectra have been investigated as a function of Ba submonolayer coverage. Under Ba adsorption two induced surface bands are found at binding energies of 2 eV and 6 eV. It is obtained that Ba/3C–SiC(111) interface can be characterized as metallic-like. Modification of both the Si 2p and C 1s surface-related components were ascertained and shown to be provided by redistribution effect of electron density between Ba adatoms and both the Si surface and C interface atoms.     

Electronic structure of copper halides CuI and CuCl: A comparative X-Ray photoelectron and absorption spectroscopy study

The energy distributions of the occupied and unoccupied electronic states for copper halides CuCl and CuI have been investigated using X-ray photoemission and absorption spectroscopy with a highenergy resolution on the equipment of the Russian-German beamline for outlet and monochromatization of synchrotron radiation from the electron storage ring BESSY II. A quasi-molecular analysis of the obtained experimental spectra has revealed that there is a fundamental similarity of the energy structures of the valence band and the conduction band of copper halides CuX (X = Cl, I) due to the identical atomic structure of the studied compounds. The differences in the positions of individual energy subbands in the valence band and the conduction band of CuX and in their intensities in the spectra are associated with different degrees of hybridization of the Cu 3d, 4s and X(n + 1)s, np valence states, as well as with different sizes of structural units (CuCl₄ and CuI₄ quasi-molecules) of the studied crystals.     

Charge accumulation layer in Cs,Ba/<Emphasis Type="Italic">n</Emphasis>-GaN(0001) ultrathin interfaces: Electronic and photoemission properties

Experimental studies and theoretical calculations of the photoemission from Cs/n-GaN(0001) and Ba/n-GaN(0001) ultrathin interfaces were carried out. The electronic properties of the interfaces were studied in situ using threshold photoemission spectroscopy under vacuum at a residual pressure of P ～ 5 × 10^?11 Torr. A new effect was revealed, namely, photoemission with a high quantum yield under excitation with light in the transparency region of GaN. It was shown that adsorption of Cs or Ba on n-GaN brings about the formation of a quasi-two-dimensional electron channel, i.e., a charge accumulation layer directly near the surface. The dependences of the photoemission spectra and work function on the thickness of Cs and Ba coatings were investigated. It was established that adsorption of Cs and Ba leads to a sharp decrease in the work function by ～1.45 and ～1.95 eV, respectively. The photoemission spectra were calculated, and parameters of the accumulation layer, such as the energy position of the layer below the Fermi level for different Cs and Ba coverages, were determined. It was demonstrated that the energy parameters of the accumulation layer on the n-GaN(0001) surface can be controlled by properly varying the Cs or Ba coverage. The layer thickness was found to reach a maximum for a cesium coverage of ～0.5 monolayer.     

On the valence band photoemission of highT c superconductors

The valence band photoemission spectrum of highT _c -superconductors is discussed based on the half-filled single band Hubbard Hamiltonian with the strong Coulomb interaction. We discuss how to analyze these valence band and deep core level excitation spectra, concerning particularly with which orbital, Cud or Op state, a hole will occupy in the CuO₂ plane.     

Photoemission from Co on Pt(111) using synchrotron radiation in the range 40 eV ω 150 eV

Photoelectron spectra for CO adsorbed on the (111)-face of Pt have been measured using synchrotron radiation of energy 40 eV ω 150 eV. A dramatic increase of the molecular orbital (MO) intensity relative to the intensity of the Pt 5d valence band (VB) is observed for ω > 100 eV, to a ratio at that is a factor of three higher than at . The energy variation of the Pt 5d VB photoemission peak intensity has been derived independently in the 40–200 eV range from measurements on clean Pt. The 5d peak intensity is found to decrease steeply (by more than an order of magnitude) between 100 and 150 eV. The observed increase of the MO peak intensity relative to that of the 5d VB is attributed to this cross-section effect. The Pt VB peak nearest the Fermi energy which is mainly t_2g in character, is found to decrease in intensity on adsorption of CO. In the present case synchrotron radiation in the ω > 100 eV range appears to be especially valuable for studies of adsorbates.     

Thickness dependence of X-ray absorption and photoemission in Fe thin films on Si(0 0 1)

To investigate the initial growth of Fe films on Si(0 0 1) and the Fe/Si interface, Fe films at various thicknesses have been systematically studied by soft X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The Fe L edge XAS spectrum shows a strong thickness dependence with broader line-width for thinner films. Detailed analysis of the Fe absorption signal as a function of the thickness shows that the broad linewidth of Fe L edge XAS spectra is mostly contributed by the first Fe layer at the Fe/Si interface. In contrast to XAS, Fe 2p photoemission spectra for these films are identical. However, valence band photoemission also shows a strong thickness dependence. Comparing the valence band photoemission spectra of the thin Fe/Si(0 0 1) films with that of pure Si and the thickest Fe film, the difference spectra at all thicknesses show almost identical shape indicating the same origin: the Fe/Si interface. Thus, it is mainly the first Fe layer at Fe/Si layer that is reactive with the Si substrate changing its electronic structure.     

Valence band photoemission spectroscopy of a ternary layered semiconductor: ZnIn2S4

UV photoemission spectroscopy (UPS) experiments have been carried out on the layer compound ZnIn₂S₄ employing several different photon energies in the range $\text{h}\text{?}{}_{\mathrm{\omega }}\text{= 9.5?21.2}\text{eV}$. The energy distribution curves (EDC's) exhibit four valence band density of states structures besides the Zn 3d peak. These five peaks appear 0.90 eV, 1.6 eV, 4.3 eV, 5.8 eV and 8.7 eV respectively below the top of the valence band, E_v. The atomic orbital character of the shallowest peak A appears different from that of the three deeper valence band peaks B, C and D and this is discussed in terms of the more or less pronounced ionic character of the intralayer chemical bonds. These results demonstrate that an overall understanding of the electronic states in complex structures can be achieved by an approach based on photoemission experiments and chemical bonding considerations which has been widely used in the past to study simple binary layer compounds.     

Valence of “divalent” rare earth metals

It is generally recognized that light rare earths change their valence from 2 to 3 when forming a bulk metal while remaining divalent at the surface. However, performed DFT calculations ultimately indicate that the higher-binding-energy peaks in photoemission spectra (like the −5.3 eV peak for Sm), characteristic of the trivalent 4fⁿ⁻¹5d¹ configuration, correspond not to the ground state, but to excited states induced by radiation. This means that the trivalent state is not inherent for the bulk of divalent rare earths, and therefore they do not become trivalent.     

Resonant photoemission and absorption spectroscopy of the Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiSe<Subscript>2</Subscript> compound

Single crystals of the Cu _x TiSe₂ compound with x = 0.05, 0.09, and 0.33 have been grown. Resonance photoelectron Cu 3p-3d and 2d-3d spectra of the valence bands, the spectra of the core levels, and the L absorption spectra for titanium and copper have been obtained. It is shown that the degree of oxidation of titanium atoms is +4 and the state of copper atoms is close to the state of free copper ions. It is found that the spectra of the valence bands obtained under the Cu 3p and 2p resonance conditions radically differ. For the spectra in the Cu 2p excitation regime, several bands corresponding to different decay channels of the excited state are observed. According to calculations of the density of states, the 3d states of copper are filled incompletely; the occupancy of the 3d band of copper is 9.5 electrons per atom.     

Angle-dependent ultraviolet photoelectron spectroscopy of sputter cleaned polycrystalline noble metals

Polycrystalline noble metal films are commonly used in practical applications across a variety of different fields. However, the surface electronic structure of the noble metals has primarily only been studied on single crystal substrates. In addition, sputter cleaned polycrystalline noble metal films are commonly used substrates in ultraviolet photoelectron spectroscopy (UPS) studies, but have yet to be systematically studied in terms of their photoemission anisotropy. The angle-dependence of the valence band spectra of sputter cleaned polycrystalline Au, Ag and Cu were studied using angle-resolved UPS. It is found that the photoemission is anisotropic with respect to photoelectron take-off angle. The results for Ag and Cu are in good agreement with previous reports of surface d-band narrowing in polycrystalline noble metal films. However, significant anisotropies in the d-band, s-band and Fermi edge of sputter cleaned Au are observed, which cannot be attributed to surface d-band narrowing alone. The unusual results for Au are attributed to drastic changes in the film morphology near the surface as a result of sputter cleaning.     

The specific oxidation mechanism in the initial stages of O2 adsorption on submonolayer Ba covered W(1 1 0) surface

The initial oxidation of a polarized 0.35-ML Ba-covered W(1 1 0) surface has been investigated in detail by high-resolution photoemission spectroscopy using synchrotron radiation. Upon small exposures (?0.15 L) to O₂, both interfacial W 4f (Ba-coordinated W) and Ba 4d core levels shift simultaneously toward smaller binding energies and then fix during 0.15-0.25 L, finally disappear at 0.6 L. The concurrent negative shifts of both interfacial W 4f and Ba 4d peaks can be attributed to be a consequence of the increased occupancy of 5d states. This explanation is supported by the variations of 5d stats in valence band spectra upon the initial oxidation. Our results clearly demonstrate that charge rearrangement is the dominant effect in the surface reactivity of our oxidized surface. We also found that this charge redistribution is associated with a structural change during oxidation, which is in contrary to previous studies of alkali-metal promotion. That is, oxygen is first chemisorbed atop the polarized Ba adlayer, then incorporates beneath Ba adatoms to form a covalent Ba-O-W complex upon further dosage, and reacts strongly with the Ba overlayer to become an ionic Ba⁺²O⁻² surface dipole layer at 0.6 L.     

Electronic structures of MRhO2, MRh2O4, RhMO4 and Rh2MO6 on the basis of X-ray spectroscopy and ESCA data

X-ray O Kα, Rh Mγ and a series of M Lα emission spectra, ESCA spectra of the valence and inner levels, and O K and Rh M_III quantum-yield spectra for X-ray photoemission of the rhodium double oxides MRhO₂ (M = Li, Na, K), MRh₂ O₄ (M = Be, Mg, Ca, Sr, Ba, Co, Ni, Cu, Zn, Cd, Pb), RhMO₄ (M = V, Nb, Ta) and Rh₂MO₆ (M = Mo, W) have been measured and the dependence of electronic structure on the metal M analysed. For all compounds the inner part of the valence band corresponds to O 2p_σ + O 2p_π + Rh 4d states, while the outer part corresponds to Rh 4d. The valence band is separated from the conduction band by a narrow gap of width less than 1 eV. The first empty band, near the bottom of the conduction band, is formed by Rh 4d states, followed by a band due to vacant O 2p states.