Interpretation of the x-ray photoemission spectra of cobalt oxides and cobalt oxide surfaces

CoO and Co₃O₄ have been studied by high-resolution X-ray photoemission. The characteristic binding energies in the Co 2p_{$\text{3}\text{2}$}, 2p_{$\text{1}\text{2}$}, and 3s regions, their band shapes and widths, the associated shake-up structure, the O(1s) and O(2s) BE's, and the valence band spectra have been examined. The two oxides are readily distinguished from their spectra though it is shown that the O(1s) BE's are identical at 529.50 ± 0.14 eV. Argon and oxygen ion sputtered surfaces were examined to establish the integrity of the oxides. A higher BE O(1s) component (530.7–531.6 eV), the intensity and BE of which vary with the treatments mentioned above, corresponds to non-stoichiometric surface oxygen. The results are discussed with respect to the electronic structures of the oxides and the often conflicting earlier studies of these oxides.     

X- ray photoemission study of the interaction of oxygen and air with clean cobalt surfaces

The interaction of oxygen with polycrystalline cobalt surfaces has been studied at 300 K (1 × 10^?6 to 1 × 10^?5 Torr) using high-resolution (monochromatized) X-ray photoemission. At high exposures (> 100 L nominal) CoO is identified as the product from the nature of the $\text{Co}\text{2}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{, 2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{, 3}\text{s}$, and valence band spectra. There is no evidence for measurable amounts of Co₃O₄ or Co₂O₃. Two O 1s features are observed at both high and low (10L) exposures. The dominant O 1s feature at 529.5 ± 0.2 eV corresponds to the oxide and a minor feature at 531.3 ± 0.2 eV is attributed to non-stoichiometric surface oxygen. Exposure to air produces quite different results, with a dominant O 1s feature at 531.5 ± 0.2 eV and dominant $\text{Co}\text{2}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ features centered at 781.3 ± 0.2 eV and 797.1 ± 0.2 eV. These three values are very close to those reported here for bulk Co(OH)₂. Ion etching of the air-exposed surface removes this dominant surface product rapidly revealing some oxide and finally metal.     

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.     

Room temperature adsorption and growth of Ga and In on cleaved Si(111)

Low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and photoemission yield spectroscopy (PYS) measurements have been performed on a set of ultrahigh vacuum cleaved Si(111) surfaces with different bulk dopings as a function of Ga or In coverage θ. The metal layers are obtained by evaporation on the unheated substrate and θ varies from zero to several monolayers (ML). First, the 2×1 reconstruction of the clean substrate is replaced by a $\text{3}\text{×}\text{3}$ R30° structure at $\text{1}\text{3}$ ML, meanwhile the dangling bond peak at 0.6 eV below the valence band edge E_vs is replaced by a peak at 0.1 eV for Ga or 0.3 eV for In, below E_vs. At the same time, the ionization energy decreases by 0.4 eV (Ga) or 0.6 eV (In), while the Fermi level pinning position gets closer to the valence band edge by about 0.1eV. Upon increasing θ, new LEED structures develop and the electronic properties keep on changing slightly before metallic islands start to grow beyond θ ～1 ML.     

Electronic structure of PdO studied by photoemission (XPS,UPS)

In this paper we present the results of photoemission studies (XPS and UPS) performed on a polycrystalline surface of PdO. The electron density of states (EDOS) deduced both from XPS and UPS (He_I and He_II) are very similar. The valence band of PdO, which differs significantly from the Pd one, can be built up by four structures located at 0.5 eV, 2.2eV, 4.5 eV and 6.5 eV below E_F. The various electronic contributions (p or d) in the band are considered and, in order to explain our spectra, we discuss several hypothesis taking into account the possible existence of satellite lines or crystal field effects. Our XPS and UPS spectra show that the energy bands of PdO are narrow (～ 2–3 eV), moreover the energy shift of the core levels (|ΔE^F_B| = 2 eV) is important : these results suggest that the correlations between the d electrons may be important in PdO.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.     

Composition,structure, surface states,and O2 sticking coefficient for differently prepared GaAs(1&#x0304;1&#x0304;1&#x0304;)As surfaces

The polar GaAs(1&#x0304;1&#x0304;1&#x0304;)As surface can be prepared in three stable and ordered states: two by molecular beam epitaxy (MBE), namely the As-stabilized and the Ga-stabilized states and one simply by ion bombardment and annealing at 770 K. The respective LEED structures are $\text{(2 × 2), (}\text{19}\text{×}\text{19}\text{)}\text{R}\text{23.4°}$, and (1 × 1) with a diffuse faint (3 × 3) superstructure. Auger measurements and the comparison with the stoichiometric cleaved (110) surface show that there are different As concentrations in the first atomic layer associated with each of these three surfaces. Whereas about 10 to 15% of the first As layer appears to be missing on the (2 × 2) surface, about 50% is missing on the $\text{19}$ surface. On the (1 × 1) surface the first As layer is removed completely. The intensity of emission from the surface sensitive states between 1 and 4 eV below the valence band edge, as seen by angular resolved UPS, roughly corresponds to the amount of As at the surface thus confirming their interpretation as As-derived surface states. The inital sticking coefficent for oxygen depends strongly on the surface structure: ～10^?8 for the (2 × 2), ～10^?7 for the $\text{19}$, and ～10^?4 for the (1 × 1) surface. The sticking coefficient does not depend on the surface concentration of As but rather on the degree of saturation of dangling bonds on Ga atoms.     

Electron and hole conductivity in CuInS2

Single crystals of CuInS₂ have been grown from the melt and annealed in In or S to produce good n- or p-type conductivity, respectively. Two donor levels, one shallow and one deep (0.35 eV), and one acceptor level at 0.15 eV are identified. The hole-mobility data are best fitted with an effective mass $\text{m}{}_{\mathrm{<mtext>p</mtext>}}\text{1?1.3m}{}_{\mathrm{e}}$, which can be explained by simple, two band $\text{k}$. $\text{p}$ theory if the valence band has appreciable d character. Above 300°K, the hole mobility falls rapidly, evidently due to multiband conduction and/or interband scattering between the nondegenerate and degenerate valence bands. The conduction band mobility appears to be dominated, in many samples, by large concentrations ( >10¹⁸cm^?3) of native donors and acceptors, which are closely compensated.     

Electronic structure of gadolinium calcium oxoborate

Gadolinium calcium oxoborate (GdCOB) is a nonlinear optical material that belongs to the calcium-rare-earth (R) oxoborate family, with general composition Ca₄RO(BO₃)₃ (R³⁺ = La, Sm, Gd, Lu, Y). X-ray photoemission was applied to study the valence band electronic structure and surface chemistry of this material. High resolution photoemission measurements on the valence band electronic structure and Gd 3d and 4d, Ca 2p, B 1s and O 1s core lines were used to evaluate the surface and near surface chemistry. These results provide measurements of the valence band electronic structure and surface chemistry of this rare-earth oxoborate.     

Photoelectron emission from Mg(OH)2 single crystals in the valence band region

The x-ray stimulated photoelectron emission from a) the (10$\text{1}$0) and b) the (0001) surface of Mg(OH)₂ single crystals was studied. A marked anisotropy was observed in the valence band region. For a) three maxima were found at 4.6, 8.8 and 12.0 eV which can be assigned to the T_1u, E_g and A_1g states respectively, if regular O_h symmetry is assumed for the ligand field. For b) the A_1g band disappears which is attribu to the fact that in Mg(OH)₂ the octahedral symmetry is reduced to D_3d by the special orientation of the OH dipoles parallel to the c-axis.     

Stoichiometric and oxygen deficient MoO3(010) surfaces

The (010) surface of single crystal MoO₃ has been prepared and examined using LEED, XPS, UPS, and ELS. Three methods yield the stoichiometric surface: scraping in UHV and annealing, ion etching followed by reoxidation (770 K, 10² Pa O₂), or oxygen treatment to remove carbon contamination. LEED shows the surface periodicity is the same as that of the bulk (010). The MoO₃ valence band is 7 eV wide with density of states maxima at 1.5, 3.6, and 5.6 eV below the top of the valence band. Heating MoO₃ in vacuum reduces the surface region. XPS indicates the O/Mo atomic ratio decreases to 2.85 ± 0.12 on heating to 600 K. Ar ion bombardment disorders the surface and reduces the surface O/Mo atomic ratio to 1.6. Annealing of reduced surfaces at > 770 K incompletely reoxidizes them by diffusion of oxygen from the bulk. UPS of reduced and annealed MoO₃ exhibits two new emission features in the bandgap at 0.9 and 2.0 eV above the top of the valence band. These features originate from Mo derived states of a defect involving two or more Mo atoms, such as crystallographic shear planes. Because of the insulating nature of MoO₃, surface charging and electron beam induced damage were substantial hindrances to electron spectroscopic examination.     

A photoelectron spectroscopic investigation of the interaction between H2O and oxygen on Ag(110)

The adsorption and reaction of H₂O with adsorbed oxygen atoms on Ag(110) was examined by UPS. In agreement with previous EELS results, H₂O formed multilayers of ice upon adsorption at 140 K. The ice layers could be easily distinguished from monolayer coverages of chemisorbed H₂O (present above 160 K) by UPS. The ice layers produced (1) strong attenuation of the emission from the Ag d-bands, (2) a nearly 2 eV shift of H₂O valence levels to higher binding energy and (3) strong attenuation of emission from the H₂O 3a₁ orbital. H₂O was observed to react stoichiometrically with O(a) above 250 K to produce a pure layer of adsorbed hydroxyl species. The UPS spectra for these species exhibited features at ?5.8 and ?8.7 eV, as well as strong features above the d-bands. These spectra were compared with those for OH(a) on other surfaces, and the difficulties of identifying OH by UPS due to contamination by excess H₂O are discussed.     

Opto-electronic properties of CuAlO2

CuAlCO₂ is a p-type semiconductor with an average hole mobility of $\text{1.1 × 10}{}^{\mathrm{?7}}\text{m}{}^2\text{Vs}$. From photoelectrochemical measurements its bandgap is found to be indirect allowed at 1.65 eV; other interband transitions are at 2.3 and 3.5 eV. The valence band is made up mainly from Cu-3d wave functions and lies 5.2 eV below the vacuum level.     

Adsorbate enhanced Ti-3d photoemission from layered TiSe2 surfaces

Angle resolved photoelectron spectra of 1T-TiSe₂ single crystals $\text{(}\text{h}\text{?}\text{ω = 21.2}\text{eV}\text{)}$ have been investigated as a function of exposure to H₂O, CO, N₂ and O₂ at room temperature. A significant enhancement of the Ti-3d emission near the Fermi energy E_F is observed for H₂O and CO exposures of several kL. As compared to the clean surface this emission extends over the entire Brillouin zone. The results indicate that by H₂O and CO adsorption the lowest d-subband is pulled below E_F possibly by local band bending. Additional relaxation effects at the surface associated with changes in d-band matrix elements may occur. The intensity of the Se-4p derived valence band emission down to 7 eV below E_F remains essentially unchanged.     

Role of multielectron excitations in the L3 XANES of Pd

High resolution L₃ and L₂ XANES (X-ray absorption near edge structure) spectra of Pd metal have been measured at the Frascati synchrotron radiation facility. The L₃ XANES shows an intense 2p → 4d “white line” while at the L₂ a weaker structure appears. A good agreement between L₃ XANES and the one-electron theory of Muller et al. has been found. All the possible final state effects due to the relaxation of the many body system are discussed. No many body effects have been seen on the “white line” at threshold. The intensity ratio between L₃ and L₂ absorption is 2.1 in the high energy range of XANES and it is 2.7 at the white line maximum. A weak broad band extending up to 13 eV and centered at ～ 6 eV above the Fermi level, appearing in the L₃-L₂ difference spectrum, could be tentatively assigned either to the only possible very weak multielectron excitation present in XANES of Pd i.e. the “two hole-two electron” excited state or to the prevalence of the $\text{j}\text{=}\text{5}\text{2}$ total angular momentum for electrons in the 5sp band, hybridized with the 4d band, up to 3 eV above the Fermi level.     

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.     

Energy transfer in Li6Gd(BO3)3

The synthesis and structure of the new one-dimensional material Li₆Gd(BO₃)₃ are described. The Gd³⁺ fluorescence is studied from 300 to 1.5 K after selective pulsed excitation into the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ manifold. Above 40 K the fluorescence decays indicate fast diffusion of the energy among intrinsic and perturbed Gd³⁺ ions, and trapping by impurities. Below 40 K the energy transfer takes place dominantly towards perturbed Gd³⁺ ions and is diffusion limited. This behaviour is discussed in relation with the quasi one-dimensional crystal structure.     

Hole contribution to the elastic constants of SnTe

Ultrasonic wave velocities have been measured in SnTe single crystals with hole concentrations of 1.0 and 4.5 × 10²⁰/cm³. The shear elastic stiffness constant C₄₄ is sensitive to the hole concentration but $\text{1}\text{2}\text{(C}{}_{11}\text{? C}{}_{12}\text{)}$ is not, a result which is consistent with the valence band pockets being sited at the L points. The non-ellipsoidal, non-parabolic multivalley band model has been used to calculate the hole contribution to the elastic constants. The calculated difference between the shear constant C₄₄ (2.78 × 10¹⁰ dyne cm^-2) for the two crystals is in agreement with that measured experimentally (2.67 × 10¹⁰ dyne cm^-2). The shear deformation potential constant E_u for the SnTe valence band is 7.8 eV at 293°K.     

Delayed onset of 4d photoemission relative to the giant 4d photoabsorption of La

For the giant 4d photoabsorption of La, both the total photoabsorption spectrum and the N_4.5-derived Auger emission intensity spectrum increase significantly above hν ? 112 eV, with spectral peaks at hν = 118 and 119 eV, respectively. However, the predominant 4d photoemission partial cross section shows a delayed onset of ～ 4 eV, with a peak at hν = 121 eV, while the 5s, 5p, and 5d partial cross sections all show a strong resonant enhancement at lower energies, with spectral peaks at hν = 116.6 eV. These results are compared with a recent many-body calculation for Ce. The photon energy dependence of the La 4d_{$\text{5}\text{2}$}/4d_{$\text{3}\text{2}$} photo-emission branching ratio is consistent with a “final-state model.”     

Thermal decomposition and electrical conductivity of M(OH)3 and MOOH (M=Y, lanthanide)

The thermal decomposition of M(OH)₃ (M=Y, La, Nd, Sm, Gd) with the Y(OH)₃ structure was examined by the TG and DTA methods. Y(OH)₃, Nd(OH)₃, and Sm(OH)₃ decomposed to MOOH and then to M₂O₃. The decomposition of La(OH)₃ and Gd(OH)₃ occurred via the following schemes: La(OH)₃→LaOOH→La₂O₃·1/2H₂O→La₂O₃, and Gd(OH)₃→Gd₂O₃·3/2H₂O→GdOOH→Gd₂O₃. The highest conductivity of 5.9×1o^?9Scm^?1 at 250°C was found in Gd(OH)₃ and that of 8.9×10^?7 S cm^?1 400°C in GdOOH. The continuous-wave ¹H NMR absorption spectrum of LaOOH at room temperature exhibited no doublet line shape. This shows that protons are magnetically isolated from each other, and very little H₂O and H₃O⁺ can exist.