Site-specific valence-band X-ray photoelectron spectra of a SrTiO3 single-crystal by X-ray standing wave technique

Site-specific valence-band X-ray photoelectron spectra of SrTiO₃ (111) were successfully obtained by using X-ray standing wave technique. Contributions of the Ti and SrO₃ derived states to the valence-band spectra were clearly separated. The spectra provided not only site-specific but also bulk-sensitive information on the SrTiO₃ crystal because of the use of a high-energy synchrotron X-ray source (hν=4750 eV) for photoelectron excitation with the large escape depth. The electronic structures calculated by the DV-Xα method using a (Sr₈Ti₂₇O₁₀₈)⁹²⁻ cluster model well reproduced the observed structures in the valence-band spectra. The partial density of states of both Ti and Sr ions in SrTiO₃ were mainly distributed over the bottom of the valence-band to produce the covalent bonding with O ions.     

X-ray diffraction and photoelectron spectroscopy study of swift heavy ion irradiated Mn/p-Si structure

The electronic structure and interfacial chemistry of thin manganese films on p-Si (1 0 0) have been studied by photoelectron spectroscopy measurements using synchrotron radiation of 134 eV and from X-ray diffraction data. The Mn/p-Si structures have been irradiated from swift heavy ions (∼100 MeV) of Fe⁷⁺ with a fluence of 1 × 10¹⁴ ions/cm². Evolution of valence band spectrum with a sharp Fermi edge has been obtained. The observed Mn 3d peak has been related to the bonding of Mn 3d-Si 3sp states. Mn 3p (46.4 eV), Mn 3s (81.4 eV) and Si 2p (99.5 eV) core levels have also been observed which show a binding energy shift towards lower side as compared to their corresponding elemental values. From the photoelectron spectroscopic and X-ray diffraction results, Mn₅Si₃ metallic phase of manganese silicide has been found. The silicide phase has been found to grow on the irradiation.     

Electronic properties of free and supported metal clusters studied by photoelectron spectroscopy

The electronic properties of free and supported metal clusters are studied by photoelectron spectroscopy. Experimental as well as theoretical results clearly demonstrate a dramatic dependence of the level structure on the cluster size. By this an interesting way might be opened to modify the electronic, optical and chemical properties of surfaces.     

Electronic structure and band gap of the negative charge-transfer material Sr3Fe2O7

We studied the electronic structure of the Sr₃Fe₂O₇ compound using X-ray photoelectron spectroscopy (XPS). The charge-transfer satellites in the Fe 2p XPS spectra were analyzed using standard cluster model calculations. The analysis indicates that Sr₃Fe₂O₇ is in the negative charge-transfer regime, and that the ground state is dominated by the configuration (where denotes an O 2p hole in the oxygen band). These results are similar to those found in the related SrFeO₃ and Sr₂FeO₄ compounds. The band gap of the Sr₃Fe₂O₇ compound is split off by the relatively large value of the p-d transfer integral T_σ. The lowest lying excitations are and consequently the band gap is of the p-p type. The band gap in the Sr_n+1Fe_nO_3n+1 series can be understood taking into account the trend in the O 2p bandwidths.     

Application of X-ray photoelectron spectroscopy to characterization of Au nanoparticles formed by ion implantation into SiO2

In X-ray photoelectron spectroscopy (XPS) of Au nanoparticles, the width of 5d valence band changes with Au particle size. This enables us to estimate the size of Au nanoparticles by using XPS. In this work, the 5d-band width has been measured for Au nanoparticles formed by ion implantation into SiO₂. The 5d-band width is found to be correlated strongly with the Au concentration. As the Au concentration increases, the 5d-band width becomes larger, indicating that the Au nanoparticles with the larger size tend to be formed in the vicinity of the projected range of Au ions. This correlation agrees very well with the results from transmission electron microscopy.     

New method to calibrate binding energy using Au nanocolloids in X-ray photoelectron analysis of diamondlike carbon films with different electrical resistivities

A new method to calibrate the binding energy (E_B) using Au nanocolloids as a calibrant in XPS analysis of diamondlike carbon (DLC) is proposed by considering the DLC films with different electrical resistivities. A few microliters of a dilute aqueous solution containing Au nanocolloids were dropped onto a small local surface area of the DLC film, which became a stain before XPS measurements by gradually drying in vacuo. The observed peak E_B of the C 1s spectrum at another native surface (an area without Au nanocolloids) of the DLC film was calibrated by setting that of the Au 4f_7/2 spectrum of the Au nanocolloids to 84.0 (83.98 ± 0.02) eV. The adequacy of this method was investigated by considering the correlation among the full width at half maximums (FWHMs) of the Au 4f_7/2 spectra of the Au nanocolloids on the DLC surfaces and that of a Au plate as a reference. Consequently, the FWHM of the Au 4f_7/2 spectrum of the Au nanocolloids on the DLC surface is a candidate to investigate the differential charging effect of the DLC surface, and the calibration method is reliable if the FWHM agrees with that of the Au plate.     

Electronic structure of Cr1−δS (δ=0, 0.17) with NiAs-type crystal structure

Valence-band and conduction-band the electronic structure of the CrS (δ=0) and Cr₅S₆ (δ=0.17) has been investigated by means of photoemission and inverse-photoemission spectroscopies. The bandwidth of the valence bands of Cr₅S₆ (8.5 eV) is wider than that of CrS (8.1 eV), though the Cr 3d partial density of states evaluated from the Cr 3p-3d resonant photoemission spectroscopy is almost unchanged between the two compounds concerning shapes as well as binding energies. The Cr 3d (t_2g) exchange splitting energies of CrS and Cr₅S₆ are determined to be 3.9 and 3.3 eV, respectively.     

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

The general equation T_ove = L cos  θ ln(R_exp/R₀ + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO₂/SiO₂/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO₂ layer to the thickness of the HfO₂ overlayer was counterbalanced by multiplying the ratio between the intensity of Si⁴⁺ from a thick SiO₂ film and that of Si⁰ from a Si(1 0 0) substrate to the intensity of Si⁴⁺ from the HfO₂/SiO₂/Si(1 0 0) film. With this approximation, the thickness levels of the HfO₂ overlayers showed a small standard deviation of 0.03 nm in a series of HfO₂ (2 nm)/SiO₂ (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO₂ overlayers in a series of HfO₂ (1-4 nm)/SiO₂ (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO₂ overlayer could be determined.     

Preparation and characterization of carbonate terminated polycrystalline Al2O3/Al films

X-ray photoelectron spectroscopy (XPS) was applied to investigate the surface reactivity of polycrystalline Al films in contact with a gas mixture of carbon dioxide and oxygen at room temperature. Based on the characterization of interactions between these substrates and the individual gases at selected exposures, various surface functionalities were identified. Simultaneously dosing both carbon dioxide and oxygen is shown to create surface-terminating carbonate species, which contribute to inhibiting the formation of an Al₂O₃ layer. Finally, a reaction scheme is suggested to account for the observed dependence of surface group formation on the dosing conditions.     

Hard X-ray photoelectron spectroscopy from 5-14.5 keV

Photoemission spectroscopy at high energies can be used to probe bulk electronic states. We used a specially designed high-voltage retarding lens and a commercial Perkin-Elmer PHI 10-360 hemispherical electron analyzer to investigate the core and valence band region of Au, YBa₂Cu₃O_7−δ and highly oriented pyrolytic graphite samples with hard X-rays in the energy range 5-14.5 keV. The overall instrumental resolution obtained at 8 keV was 218 meV. The photo ionization cross-sections for Au 5d and 6s excitations were determined experimentally. In comparison with published calculations for atomic cross-sections neglecting corrections for angular anisotropy, the values we find are twice as large for the 5d and an order of magnitude larger for the 6s (conduction band) level. Our results demonstrate the feasibility of bulk sensitive valence band spectroscopy with high resolution at high brilliance X-ray sources such as the ESRF. The measured cross-sections provide important input for improving current theoretical models.     

Inverse photoemission spectroscopy of the unoccupied electronic structure of Na/Cu(110)

The unoccupied electronic states of Na thin films on a Cu(110) substrate have been measured by inverse photoemission spectroscopy (IPES). The IPES spectrum provides the intensity of the unoccupied states, which decreases with increasing Na coverage at off-normal incidence of the electron beam. The IPES spectra at 17 and 19 eV incident electron energies show a shift towards the Fermi level with increasing Na coverage for the peak at ∼7.8 eV.     

Charge-density-wave partial gap opening in quasi-2D KMo6O17 purple bronze studied by angle resolved photoemission spectroscopy

Low dimensional (LD) metallic oxides have been a subject of continuous interest in the last two decades, mainly due to the electronic instabilities that they present at low temperatures. In particular, charge density waves (CDW) instabilities associated with a strong electron-phonon interaction have been found in Molybdenum metallic oxides such as KMo₆O₁₇ purple bronze. We report an angle resolved photoemission (ARPES) study from room temperature (RT) to T ∼40 K well below the Peierls transition temperature for this material, with CDW transition temperature T_CDW ∼120 K. We have focused on photoemission spectra along ΓM high symmetry direction as well as photoemission measurements were taken as a function of temperature at one representative k_F point in the Brillouin zone in order to look for the characteristic gap opening after the phase transition. We found out a pseudogap opening and a decrease in the density of states near the Fermi energy, E_F, consistent with the partial removal of the nested portions of the Fermi surface (FS) at temperature below the CDW transition. In order to elucidate possible Fermi liquid (FL) or non-Fermi liquid (NFL) behaviour we have compared the ARPES data with that one reported on quasi-1D K_0.3MoO₃ blue bronze.     

Probing buried interfaces on Ge-based metal gate/high-k stacks by hard X-ray photoelectron spectroscopy

In this contribution, we present results of a non-destructive in-depth analysis of concentration of chemical components at buried interfaces on Ge-based CMOS by means of hard X-ray photoelectron spectroscopy (HAXPES) and low angle X-ray reflectivity (XRR). Two samples composed of a Ge/Si/SiO₂/HfO₂/TiN stack, with layer and interlayer thicknesses of 2500, 0.9, 0.5, 4.9, 3.4 nm and 2500, 0.7, 1, 5.8, 3 nm have been studied. The use of electrons with kinetic energies from few eV up to 15 keV enables to tune the information depth being able to analyze the desired interface in a non-destructive way. XRR enables the determination of the exact layer thickness and density. The results suggest that the Si interlayer prevents the Ge oxidation. Depth profiles of the electronic structure have been obtained for both samples by following the evolution of the photoemission signal from the Hf 2p_3/2 core level as a function of the photoelectron kinetic energy. The depth profile of the electronic structure reveals the presence of a chemical shift of the Hf 2p_3/2 core level, which is related to an interfacial bonding state. Our results demonstrate the excellent capability of HAXPES to study buried interfaces in a non-destructive way.     

Composition of Ta2O5 stacked films on N2O- and NH3-nitrided Si

The composition and microstructure of rf sputtered 20 nm Ta₂O₅ on N₂O or NH₃ Rapid Thermal Nitrided (RTN) Si substrates have been investigated by X-ray photoelectron spectroscopy. RTN at 800 and 850 °C is effective to suppress active oxidation of Si. There is no evidence for the presence of SiO₂ at Si interface. A lightly nitrided surface is established in both cases without a formation of detectable oxynitride layer at Si. A layered nature of the films is observed, with stoichiometric tantalum pentoxide at and close to the films’ surface. In the depth, the films are mixed ones whose composition depends on the nitridation ambient. N₂O treatment stimulates oxidation processes during the film deposition while NH₃ nitridation results to a less effective oxidation and produces Ta-silicate like film. The correlation between the composition of the interfacial regions and the nitridation gas is also discussed. The results suggest that hydrogen, as a component of nitridation ambient, plays significant role in the reactions controlling the exact composition of the deposited Ta₂O₅, activating reactions with nitrogen. Nitrogen related reactions likely occur with NH₃ processing but do not with N₂O one. The presence of nitrogen feature is not detected in N₂O-samples spectra at all. In the integration perspective, preliminary RTN of Si in N₂O or NH₃ could be a suitable way to produce layered Ta₂O₅-based films with more or less presence of tantalum silicate with a trace of nitrogen, either only at the interface with Si (N₂O-process) or in the whole film (NH₃-process).     

Analysis by using X-ray photoelectron spectroscopy for polymethyl methacrylate and polytetrafluoroethylene etched by KrF excimer laser

The C 1s, F 1s, and O 1s electron spectra for polymethyl methacrylate (PMMA) and polytetrafluoroethylene (PTFE) irradiated by KrF excimer laser with 248 nm wavelength were analyzed by the X-ray photoelectron spectroscopy (XPS) method. The results show that, after irradiation by the laser, the percentage of the carbon atoms of C-C bond decreases and the percentage of CO bond increases for PMMA, while for PTFE percentages of both C-C bond and CF₂ group decrease drastically, respectively. Moreover, it was found that C-O bond and other complex carbon-oxygen groups appeared for PTFE. The photon-chemical processes associated with the energy level transitions, energy diversion, and dissociation of bonds in the interaction were theoretically analyzed based on the chemical structures of PTFE and PMMA. Our analyses can successfully explain that PMMA can be effectively etched by KrF excimer laser with 248 nm wavelength can efficiently etch the PMMA, but the surface of PTFE can only be modified by it.     

Electronic structure and anomalous photoemission line-shape of quasi-2D oxide η-Mo4O11

The η-Mo₄O₁₁ compound is a layered two-dimensional (2D) metallic system whose reduced dimensionality originates non-linear properties as charge density wave (CDW) instabilities. We report on synchrotron radiation angle resolved photoemission spectroscopy (ARPES) measurements in order to obtain a detailed picture of the electronic structure of this material. The symmetry of the states near the Fermi level (E_F) has been discussed in relation to the photoemission symmetry selections rules. Our results are in excellent agreement with previous tight-binding calculations and support the hidden nesting concept proposed to explain the CDW instabilities exhibited by this family of compounds. In addition, a very peculiar photoemission line-shape has been found with the presence of localized non-dispersive states. Some possible explanations are discussed.     

Electronic structure and electron dynamics at the GaSb(0 0 1) surface studied by femtosecond pump-and-probe pulsed laser photoemission spectroscopy

Transiently excited electron states at the GaSb(0 0 1) surface have been studied by means of time- and angle-resolved photoemission spectroscopy based on a femtosecond laser system. A normally unpopulated surface electron state has been found at ∼250 meV above the valence band maximum with a strong confinement at the center of the surface Brillouin zone. The lifetime of transiently excited carriers at the intergap surface states has been found to be ∼11 ps, associated with rapid carrier diffusion.     

Is Auger-free luminescence present in CeF3?

It is well known that Auger-free luminescence (AFL) is observable when the condition E_g>E_VC is satisfied, where E_g is the band-gap energy between the lowest unoccupied band and the highest occupied band and E_VC the energy difference between the top of the highest occupied band and the top of the next lower occupied band. From measurements of reflection and X-ray photoelectron spectra, CeF₃ is demonstrated to really satisfy this condition. No evidence for AFL is found, nevertheless. The absence of AFL in CeF₃ is related to a characteristic nature of its highest and next lower occupied bands, which are quite different from those of previously studied AFL-materials.     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Electronic surface states on the MOVPE-prepared InGa-terminated InGaAs(1 0 0) (4 × 2)/c(8 × 2) surface

In this paper, the InGa-terminated InGaAs(1 0 0) (4 × 2)/c(8 × 2) surface was studied in detail, which turned out to be the most suitable to develop an InGaAs/GaAsSb interface that is as sharp as possible. In ultra high vacuum the InGaAs surface was investigated with low-energy electron diffraction, scanning tunneling microscopy and UV photoelectron spectroscopy employing synchrotron radiation as light source. Scanning the Γ−Δ−X direction by varying the photon energy between 8.5 eV and 50 eV, two surface states in the photoelectron spectra were observed in addition to the valence band peaks.