Atomic structure of the (001) surface of CuGaSe2

Hybrid exchange density functional theory is used to study the wide band gap chalcopyrite CuGaSe₂. The formation energies of the experimentally observed (4 × 1) and (1 × 1) atomic scale reconstructions on the CuGaSe₂ (001) surface are calculated for different environmental conditions. The results suggest that a Se-rich (1 × 1) reconstruction, and a Cu-poor, Se-rich (4 × 1) reconstruction, are the only stable surfaces under all the studied environmental conditions. Two complementary mechanisms for the stabilisation of CuGaSe₂ surfaces are proposed, and it is suggested that the presence of Na stabilises the (4 × 1) reconstructions, making them the stable terminations under Na-rich conditions.     

Surface structure of γ-Fe2O3(111)

The surface structure of γ-Fe₂O₃(111) has been investigated with a range of surface techniques. Two different surface structures were discovered depending upon surface preparation techniques. Sputtering followed by annealing in vacuum produced a reduced surface characterised by a (2 × 2) LEED pattern, whereas sputtering followed by annealing in 1 × 10^? 6 mbar oxygen produced a surface characterised by a (√3 × √3)-R30° LEED pattern. The latter appears to be a very low conductivity surface, whereas the former has the band gap expected for maghemite (~ 2.0 eV). We propose that the reduced surface is a magnetite-like layer, whereas the oxidised surface is an Fe₂O₃-like layer.     

Electret properties of ethylene–propylene random co-polymer

Thermally stimulated current (TSC) spectra were examined for ethylene–propylene (EP) random co-polymer at different charging voltages V_p with positive and negative polarities. Observed TSC spectra showed two well-separated TSC bands, B_L and B_H, which respectively appeared in the temperature regions below and above 100 °C. Observed V_p dependence of B_L was quite different from that of typical polypropylene homo-polymer: As V_p increased, B_L band grew keeping its peak position same at 65 °C, and the band shape unchanged, as if the traps responsible for the B_L band are a single set of traps with the same trap depth and capture cross section. The trap depth of B_L was about 1.9 eV and 1.7 eV for positively charged EP and talc-containing EP samples, respectively. EP samples also showed unique TSC bands above 100 °C: one is a narrow TSC band peaked at 120 °C and the other is an unusual TSC band which was non-vanishing even at 165 °C just before destruction of samples by their melting. Consequently, the utmost stable charge density in EP co-polymer above 100 °C was found to be 3.5 × 10^?4 C/m² and 6.0 × 10 ^?4 C/m² for positively and negatively charged samples, respectively. These equivalent surface charge densities are much larger than those of usual polypropylene homo-polymer.     

Monochromatic soft X-ray-induced reactions of CCl2F2 adsorbed on Si(111)-7 × 7 near the Si(2p) edge

Continuous-time photoelectron spectroscopy (PES) and continuous-time core-level photon-stimulated desorption (PSD) spectroscopy were used to study the monochromatic soft X-ray-induced reactions of CCl₂F₂ molecules adsorbed on Si(111)-7 × 7 at 30 K (CCl₂F₂ dose = 2.0 × 10¹⁴ molecules/cm², ~ 0.75 monolayer) near the Si(2p) core level. Evolution of adsorbed CCl₂F₂ molecules was monitored by using continuous-time photoelectron spectroscopy at two photon energies of 98 and 120 eV to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are _~1.4 × 10^? 18 and ~ 8.0 × 10^? 18 cm², respectively. Sequential F⁺ PSD spectra obtained by using continuous-time core-level photon-stimulated desorption spectroscopy in the photon energy range of 98–110 eV show the variation of their shapes with photon exposure and depict the formation of surface SiF species. The dissociation of CCl₂F₂ molecules adsorbed on Si(111)-7 × 7, irradiated by monochromatic soft X-ray in the photon energy range of 98–110 eV, is mainly due to dissociative electron attachment and indirect dipolar dissociation induced by photoelectrons emitted from the silicon surface.     

Structural and electronic properties of group III Rich In0.53Ga0.47As(001)

The structural and electronic properties of group III rich In_0.53Ga_0.47As(001) have been studied using scanning tunneling microscopy/spectroscopy (STM/STS). At room temperature (300 K), STM images show that the In_0.53Ga_0.47As(001)–(4 × 2) reconstruction is comprised of undimerized In/Ga atoms in the top layer. Quantitative comparison of the In_0.53Ga_0.47As(001)–(4 × 2) and InAs(001)–(4 × 2) shows the reconstructions are almost identical, but In_0.53Ga_0.47As(001)–(4 × 2) has at least a 4× higher surface defect density even on the best samples. At low temperature (77 K), STM images show that the most probable In_0.53Ga_0.47As(001) reconstruction is comprised of one In/Ga dimer and two undimerized In/Ga atoms in the top layer in a double (4 × 2) unit cell. Density functional theory (DFT) simulations at elevated temperature are consistent with the experimentally observed 300 K structure being a thermal superposition of three structures. DFT molecular dynamics (MD) show the row dimer formation and breaking is facilitated by the very large motions of tricoodinated row edge As atoms and z motion of In/Ga row atoms induced changes in As–In/Ga–As bond angles at elevated temperature. STS results show there is a surface dipole or the pinning states near the valence band (VB) for 300 K In_0.53Ga_0.47As(001)–(4 × 2) surface consistent with DFT calculations. DFT calculations of the band-decomposed charge density indicate that the strained unbuckled trough dimers being responsible for the surface pinning.     

Chemical bath deposition of SnO2 and Cd2SnO4 thin films

A new approach of chemical bath deposition (CBD) of SnO₂ thin films is reported. Films with a 0.2 μm thickness are obtained using the multi-dip deposition approach with a deposition time as little as 8–10 min for each dip. The possibility of fabricating a transparent conducting oxide layer of Cd₂SnO₄ thin films using CBD is investigated through successive layer deposition of CBD-SnO₂ and CBD-CdO films, followed by annealing at different temperatures. High quality films with transmittance exceeding 80% in the visible region are obtained. Annealed CBD-SnO₂ films are orthorhombic, highly stoichiometric, strongly adhesive, and transparent with an optical band gap of ～4.42 eV. Cd₂SnO₄ films with a band gap as high as 3.08 eV; a carrier density as high as 1.7 × 10²⁰ cm^?3; and a resistivity as low as 1.01 × 10^?2 Ω cm are achieved.     

Photolysis of SF6 adsorbed on Si(111)-7 × 7 by monochromatic soft X-ray

Continuous-time photoelectron spectroscopy (PES) and photon-exposure-dependent photon-stimulated desorption (PSD) were employed to investigate the monochromatic soft X-ray-induced dissociation of SF₆ molecules adsorbed on Si(111)-7 × 7 at 30 K (SF₆ dose = 3.4 × 10¹³ molecules/cm², ～ 0.5 monolayer). The photon-induced evolution of adsorbed SF₆ was monitored at photon energies of 98 and 120 eV [near the Si(2p) edge], and sequential valence-level PES spectra made it possible to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are ～ 2.7 × 10^? 17 and ～ 3.7 × 10^?17 cm², respectively. The changes in the F^? and F⁺ PSD ion yields were also measured during irradiation of 120 eV photons. The photon-exposure dependencies of the F^? and F⁺ ion yields show the characteristics: (a) the dissociation of adsorbed SF₆ molecules is ascribable to the substrate-mediated dissociations [dissociative attachment (DA) and dipolar dissociation (DD) induced by the photoelectrons emitting from the silicon substrate]; (b) at early stages of photolysis, the F^? yield is mainly due to DA and DD of the adsorbed SF₆ molecules, while at high photon exposure the F^? formation by electron capture of the F⁺ ion is likely to be the dominant mechanism; (c) the F⁺ ion desorption is associated with the bond breaking of the surface SiF species; (d) the surface SiF is formed by reaction of the surface Si atom with the fluorine atom or F^? ion produced by scission of S–F bond of SF_n (n = 1–6) species.     

Water adsorption on SrTiO3(001): II. Water,water, everywhere

The role of water adsorption on Ti-rich SrTiO₃(001) surface reconstructions is studied. Density functional calculations with hybrid functionals of numerous adsorption configurations indicate that the relative stability of the different reconstructions is strongly altered by the addition of water, with all the reconstructions having comparable energy for half-monolayer coverage, most with a fair degree of hydrogen bonding. This strongly suggests that which reconstruction is observed depends upon a competition between the kinetics of ordering and dehydration. X-ray photoelectron spectra are consistent with the theoretical predictions for the dehydration of the 2 × 1 and c(4 × 2) reconstructions.     

Ab initio determination of atomic structure and energy of surface states of bare and hydrogen covered GaN (0001) surface — Existence of the Surface States Stark Effect (SSSE)

Density Functional Theory (DFT) calculations indicate that energetically stable structure of clean GaN(0001) surface posses (2 × 1) reconstruction, having every second row of Ga located near plane of N atoms, that gives rise to Ga-related dispersionless surface electronic state, already identified by angle resolved photoelectron spectroscopy (ARPES) measurements [S.S. Dhesi et al. Phys. Rev. B 56 (1997) 10271, L. Plucinski et al. Surf. Sci 507-10 (2002) 223, S. M. Widstrand et al. Surf. Sci. 584 (2005) 169]. The energy reduction in reconstruction proceeds via change of the hybridization of the occupied Ga surface states from sp³ to sp², transforming the empty states to p_z type. It is also shown that the electric subsurface field, modeled in new slab model which allows to simulate electric fields at the semiconductor surfaces [P. Kempisty et al., J. Appl. Phys. 106 (2009) 054901], strongly affects the energy of electronic states of GaN(0001) surfaces. The change of the field may shift the energy of surface states of bare and hydrogen covered GaN(0001) surface, by several eV with respect to the band states. The phenomenon, denoted as Surface States Stark Effect (SSSE), explains various band bending values, measured at differently doped n-type GaN(0001) surfaces. It is shown also that, for the adsorbate density up to one H atom for each Ga surface atom i.e. 1 monolayer coverage (1 ML), the hydrogen adatoms are located at the on-top positions, i.e. directly above Ga atoms. For these adsorbate densities, the H-related quantum surface state is located slightly below the valence band maximum (VBM) in the case of p-type GaN surface. For n-type GaN, the H-related surface state is located deeply in the valence band, about 2 eV below VBM. For higher, 1.25 ML hydrogen coverage, the two H adatoms create either surface attached H₂ ad-molecule (energetically stable) or triple bridge configuration is created (metastable). The H₂ ad-molecule is weekly attached to the surface, having the desorption energy barrier equal to 0.16 eV. For 1.25 ML coverage the DFT results were obtained for p-type GaN only. They show that in the ad-molecule case, a new surface electronic state arises which is located about 6.7 eV below VBM. In the case of the bridge configuration, the bridge related surface state is located closely to the conduction band minimum (CBM).     

Effect of oxygen partial pressure on the structure and properties of Cu–Al–O thin films

We have studied the electrical and optical properties of Cu–Al–O films deposited on silicon and quartz substrates by using radio frequency (RF) magnetron sputtering method under varied oxygen partial pressure P_O. The results indicate that P_O plays a critical role in the final phase constitution and microstructure of the films, and thus affects the electrical resistivity and optical transmittance significantly. The electrical resistivity increases with the increase of P_O from 2.4 × 10^?4 mbar to 7.5 × 10^?4 mbar and afterwards it decreases with further increasing P_O up to 1.7 × 10^?3 mbar. The optical transmittance in visible region increases with the increase of P_O and obtains the maximum of 65% when P_O is 1.7 × 10^?3 mbar. The corresponding direct band gap is 3.45 eV.     

Disordered reconstructions of the reduced SnO2-(110) surface

A detailed survey of reduced SnO₂-(110) surfaces is presented including novel and disordered reconstructions with cation surface interstitials as essential building block. Our results consistently explain the experimentally observed (1 × 1) and (1 × 2) reconstructions. A revised surface phase diagram containing all observed equilibrium reconstructions is proposed.     

Band offsets at ZnO/SiC heterojunction: Heterointerface in band alignment

Pulsed laser deposited ZnO layers on 6H-SiC substrates showed the six-fold symmetry, indicating a two-dimensional epitaxial growth mode. X-ray photoelectron spectroscopy was employed to study the valence band discontinuity and interface formation in the ZnO/6H-SiC heterojunction. The valence band offset was measured to be 1.38 ± 0.28 eV, leading to a conduction band offset value of 1.01 ± 0.28 eV. The resulting band lineup in epitaxial ZnO/6H-SiC heterojunction is determined to be of staggered-type alignment.     

ICLAS of water in the 770 nm transparency window (12 746–13 558 cm−1). Comparison with current experimental and calculated databases

The absorption spectrum of water vapor has been investigated by intracavity laser spectroscopy (ICLAS) in the 12 746–13 558 cm^?1 spectral region corresponding to an interesting transparency window of the atmosphere, partly obscured by the A band of molecular oxygen.The achieved sensitivity—in the order of α_min～10^?9 cm^?1—has allowed one to measure 1062 water lines with intensities ranging from 1.6×10^?28 to 2.35×10^?24 cm/molecule at 296 K. A total of 169 new and improved energy levels belonging to 21 vibrational states could be determined from 374 newly measured transitions. The retrieved experimental line list is compared with the spectra calculated by Schwenke and Partridge, and Barber and Tennyson. Comparison with the available experimental databases shows that the obtained results represent a significant improvement of the knowledge of the water absorption in the considered region, in particular in the region of the oxygen A band.     

LEED and STM studies of the stability of the MoO2(100) surface

Atomic scale images and low energy electron diffraction pattern of a MoO₂(100) single crystal surface are presented, which show different structural modifications depending on surface preparation. A short in-situ heat treatment of the as-grown single crystal results in an atomically ordered surface whose diffraction pattern and STM images are consistent with those expected from the bulk structure. The symmetry of the STM images suggests an oxygen termination of the surface. A significantly longer heat treatment causes a thermodynamically stable (4 × 1) reconstruction which is interpreted to be due to a loss of oxygen chains. The (4 × 1) reconstruction vanishes after Ar-ion-sputtering and subsequent annealing. Additional long sputtering cycles result in a (2 × 1) reconstruction. The observed surface reconstructions can be transformed into each other by heating or sputtering cycles.     

Understanding 4-bromostyrene Adsorption on the Si(001)-(1 × 2) surface: A density functional theory study

Adsorption properties of 4-bromostyrene (Br–Sty) on the Si(001)-(1 × 2) surface are investigated by ab initio calculation based on density functional theory (DFT). For the adsorption of Br–Sty molecule on the Si(001)-(1 × 2) surface, we have assumed two possible cases within: (i) binding on the partially H-terminated surface and (ii) binding on the clean surface. For the first case, we have estimated two different binding sides: (i) Bromine-terminated bindings and (ii) Carbon-terminated binding. The adsorption energies of Br-terminated and C-terminated binding were found as 0.36 eV and 3.76 eV, respectively. In the same manner, we have also assumed two possible binding sides for the clean surface: (i) Br-terminated binding and (ii) ring-shaped binding. We have found adsorption energies for Br-terminated and ring-shaped binding as 0.14 eV and 1.10 eV on the clean surface, respectively. Moreover, the nudged elastic band method (NEB) was used to reveal the adsorption pathway of these binding models. These results serve to understand the possibility of the adsorption of Br–Sty molecules onto different kind of silicon surfaces into different reaction conditions.     

Adsorption of O2 and CO2 on the Si(111)-7 × 7 surfaces

The interaction of O₂ and CO₂ with the Si(111)-7 × 7 surface has been studied with X-ray photoelectron spectroscopy (XPS). It was found that both O₂ and CO₂ molecules can readily oxidize the Si(111)-7 × 7 surface to form thin oxide films. Two oxygen species were identified in the oxide film: oxygen atoms binding to on-top sites of adatom/rest atoms with an O 1s binding energy of ~ 533 eV as well as to bridge sites of adatom/rest atom backbonds at ~ 532 eV. These two oxygen species can be interconverted thermally during the annealing process. Due to the low oxidation capability, the silicon oxide film formed by CO₂ has a lower O/Si ratio than that of O₂.     

First-principles investigations of low-coverage Ca-induced reconstructions on the Si(001) surface

Using the pseudopotential method and the local density approximation of density functional theory we have investigated the stability, atomic geometry, and electronic states for low-coverage Ca adsorbates on the Si(001) surface within the (2 × n) reconstructions with n = 2, 3, 4, 5. Our total energy calculations suggest that the (2 × 4) phase represents the most energetically stable structure with the Ca coverage of 0.375 ML. Within this structural model, each Ca atom is found to form a bridge with the inner two Si–Si dimers. The inner Si–Si dimers become elongated and symmetric (untilted). The band structure calculation indicates that the system is semiconducting with a small band gap. Significant amount of charge transfer from the Ca atoms to neighbouring Si atoms has been concluded by analysing the electronic charge density and simulation of scanning tunnelling microscopy images. The highest occupied and lowest unoccupied electronic states are found to arise from the inner and outer Si–Si dimer components, respectively.     

Tin-stabilized (1 × 2) and (1 × 4) reconstructions on GaAs(100) and InAs(100) studied by scanning tunneling microscopy,photoelectron spectroscopy,and ab initio calculations

Tin (Sn) induced (1 × 2) reconstructions on GaAs(100) and InAs(100) substrates have been studied by low energy electron diffraction (LEED), photoelectron spectroscopy, scanning tunneling microscopy/spectroscopy (STM/STS) and ab initio calculations. The comparison of measured and calculated STM images and surface core-level shifts shows that these surfaces can be well described with the energetically stable building blocks that consist of Sn–III dimers. Furthermore, a new Sn-induced (1 × 4) reconstruction was found. In this reconstruction the occupied dangling bonds are closer to each other than in the more symmetric (1 × 2) reconstruction, and it is shown that the (1 × 4) reconstruction is stabilized as the adatom size increases.     

Core hole and surface excitation correction parameter for XPS peak intensities

In XPS analysis, surface excitations and excitations originating from the static core hole created during the photoexcitation process are usually neglected. However, both effects significantly reduce the measured peak intensity. In this paper we have calculated these effects. Instead of considering the two effects separately, we introduce a new parameter, namely the Correction Parameter for XPS (or CP_XPS) defined as the change in probability for emission of a photoelectron caused by the presence of the surface and the core hole in comparison with the situation where the core hole is neglected and the electron travels the same distance in an infinite medium. The CP_XPS calculations are performed within the dielectric response theory by means of the QUEELS-XPS software determining the energy-differential inelastic electron scattering cross-sections for X-ray photoelectron spectroscopy (XPS) including surface and core hole effects. This study has been carried out for electron energies between 300 eV and 3400 eV, for angles to the surface normal between 0° and 60° and for various materials, especially metals, semiconductors and oxides. For geometries and energies normally used in XPS, i.e. for emission angle ≤ 60° and photoelectron energy ≤ 1500 eV, we find that CP_XPS values are significantly larger for oxides, (0.55 ? CP_XPS ? 0.75) than for metals and semiconductors (0.45 ? CP_XPS ? 0.6). We show that this behavior is due to the difference in the wave vector dispersion of the energy loss function. This dispersion has been determined from analysis of REELS and is found to be free electron like (α ? 1) for metals but is substantially smaller (α ≈ 0.02–0.05) for materials with a wide band gap. As a result, the group velocity of the valence electrons is very small for oxides with a large band gap. This leads to a reduction in the screening of the core-hole potential before the photoelectron has left the region of interaction and thereby to an increase in the intrinsic excitations caused by the core hole.     

An STM study of desorption-induced thallium structures on the Si(111) surface

The scanning tunneling microscopy is used to study morphology of a Tl adlayer in various stages of Tl desorption from the Si(111) surface. Transition from the Si(111)/(1 × 1)-Tl structure through the (√3 × √3)R30° mosaic phase to domains of metastable Si reconstructions is observed. Silicon substitutional atoms are found to be intrinsic to the (√3 × √3)R30° structure. The temperature dependence of the amount of residual Tl atoms on the surface is successfully fitted by a model using the first order desorption. The same desorption energy of (2.1 ± 0.3) eV and frequency prefactor 5 × 10^14 ± 2 s^? 1 during all stages of the desorption are sufficient for the fitting. It is concluded that bonding of Tl in both (1 × 1) and (√3 × √3) configurations is of the same nature.