The local electronic structure of PdO crystal and PdO catalyst supported on SiO2 and γ-Al2O3 from L3 and L1 x-ray absorption Pd edge in XANES spectra

We have studied the local electronic structure of PdO catalysts supported on characteristic inert and quasi-inert substrate from experiment on X-ray absorption near edge structure XANES using Synchrotron radiation. From the joint analysis of L₃ absorption edge and XPS core data in Pd and PdO we find that the white line in PdO XANES is an excitonic state with 0.8 eV binding energy. From the joint analysis of L₃ and L₁ edges the p-like and the d-like local unoccupied electronic states have been determined. The local structure of PdO catalysts is different from that of PdO crystal. Evidence for structural disorder in PdO catalysts and PdO-substrate interaction is reported.     

Adsorbate-induced surface resonances observed in photoemission from a (2 × 2)R45° sulphur layer on Pd(100)

Angular-resolved photoemission spectra from a $\text{(}\text{2}\text{×}\text{2}\text{)R45°}$ sulphur layer on Pd(100) reveal peaks independent of photon energy, which show strong dispersion in the electron energy range 3…9 eV relative to the vacuum level. The appearance of these levels can be correlated with absolute gaps in the projected bulk band structure of palladium. We interpret these features, which are also observed in secondary electron emission, as adsorbate-induced surface resonances above E_F. The sulphur 3p-derived levels below E_F show strong dispersion effects in the [110] but not in the [100] crystal azimuth. The projected band structure also shows that $\text{sd}$ hybridisation gives rise to an absolute gap at approximately this energy in the [110] $\text{(}\text{ΓX}\text{)}$ direction.     

Hyperfine structure in the EPR spectrum of O−2 on GaAs surfaces

It is shown that a previous interpretation of hyperfine structure in the O^?₂ — GaAs surface EPR spectrum is incorrect. The experimental spectrum is reproduced and re-interpreted in a consistent way. The surface Ga orbital is almost entirely p-like.     

Transport properties of CdIn2S4 single crystals

Several transport properties have been studied on CdIn₂S₄ singlê crystals with different degrees of deviation from stoichiometry. The energy gap at 0 K was determined from the electrical measurements to be 2.2 eV. The anisotropy of the magnetoresistance effect was found and it was suggested that the minima of the conduction band were located at points along the [100] directions in k space. From an analysis of the mobility data it was found that the high resistivity of the samples is due to compensation of donors by acceptors introduced by excess sulphur. Several band parameters, the carrier scattering mechanisms and the impurity levels were determined. The thermal conductivity was measured from 4 K to 300 K and analysed by Callaway's formalism.     

Crystal growth and the electronic structure of Tl3PbCl5

Total and partial densities of states of constituent atoms of two tetragonal phases of Tl₃PbCl₅ (space groups P4₁2₁2 and P4₁) have been calculated using the full potential linearized augmented plane wave (FP-LAPW) method and Korringa-Kohn-Rostoker method within coherent potential approximation (KKR-CPA). The results obtained reveal the similarity of occupations of the valence band and the conduction band in the both tetragonal phases of Tl₃PbCl₅. The FP-LAPW and KKR-CPA data indicate that the valence band of Tl₃PbCl₅ is dominated by contributions of the Cl 3p-like states, which contribute mainly to the top and the central portion of the valence band with also significant contributions throughout the whole valence-band region. Further, the bottom of the valence band of Tl₃PbCl₅ is composed mainly of the Tl 6s-like states, while the bottom of the conduction band is dominated by contributions of the empty Pb 6p-like states. The KKR-CPA results allow to assume that the width of the valence band increases somewhat while band gap, E_g, decreases when changing the crystal structure from P4₁2₁2 to P4₁. The X-ray photoelectron core-level and valence-band spectra for pristine and Ar⁺-ion-irradiated surfaces of a Tl₃PbCl₅ monocrystal grown by the Bridgman-Stockbarger method have been measured.     

Range of homogeneity and defect model for Bi2S3

Sulphur pressure measurements inside and at the boundaries of the homogeneity range of Bi₂S₃ were performed as a function of composition and temperature. From the results and literature data a defect model of this substance is deduced. Important defects are singly charged sulphur vacancies and neutral sulphur atoms on bismut sites (antistructure defects). The range of homogeneity is calculated from this model. Bi₂S₃ exists with both sulphur deficit and sulphur excess of up to about 0.002 atoms sulphur per mole of Bi₂S₃. The phase diagram Bi-S is confirmed.     

Electro- and thermoreflectance of Bi2Te3 and Bi2Se3

Electroreflectance measurements in Bi₂Te₃ and Bi₂Se₃ with the electric field vector of the incident light both inclined and perpendicular to the C-axis have been made at room temperature. The structures found by other workers in the reflection measurements are observed in the present experiment, together with new structures at 0.91 eV, 1.18 eV, 1.78 eV, and 2.61 eV in Bi₂Se₃ which are not related to formerly observed transitions. From these measurements, the selection rules for direct optical transitions in Bi₂Te₃ and Bi₂Se₃ are studied. Thermoreflectance measurements are also made at both room and liquid-nitrogen temperatures. The positions of the peaks obtained in the present work are compared with the electroreflectance and reflection data.     

半磁半导体Cd1-xMnxTe光吸收边的压力效应

本文研究了室温下1—40kbar流体静压力范围内三元化合物半磁半导体Cd_1-xMn_xTe光吸收边的压力效应。实验结果给出:x<0.5的样品,吸收边随压力增加向高能方向以α=6—8×10^-3eV/kbar的速率漂移,并具有10^-5/kbar²量级的二级非线性系数;x≥0.5的样品,表观吸收边随压力增加向低能方向漂移,压力系数为α-5×10^-3eV/kbar。高压下所研究的样品均有一从闪锌矿结构到NaCl结构的相变发生。这一相变可以是不可逆的,相变压力与样品组分有关,大致在25—40kbar范围内。根据半导体能带畸变势效应和晶体场理论模型估计了压力系数的理论值,讨论了不同压力系数的物理原因。 关键词：     

Electrical conductivity of Na2SO4(I)

The electrical conductivity of the solid phase Na₂SO₄(I) has been measured between the melting point at 884°C and the first order phase transition at about 240°C. The measurements have been performed using complex impedance measurements on pellet samples as well as on U-cells. The electrical conductivity is strongly dependent on sample at low temperatures and the activation energy ranges from 0.5 eV to 1.7 eV over the measured temperature range.     

Optical and electronic properties of NiFe2O4 and CoFe2O4 thin films

We report the optical and electronic properties of the inverse spinel ferrite NiFe₂O₄ and CoFe₂O₄ thin films deposited on single crystal sapphire by electron beam deposition. We carried out variable temperature (78–500 K) transmittance measurements on the thin films to investigate the optical properties and electronic structures of these ferrites. The absorption spectra of both NiFe₂O₄ and CoFe₂O₄ thin films show insulating characters with Ni (Co) d to d on-site transitions below 3 eV. The energy bands above 3 eV are mainly due to the O 2p to Fe 3d charge transfer transitions. The observed electronic transitions have been assigned based on the first principles calculations and comparisons with structurally similar Ni and Co-containing compounds. The Co²⁺ d to d transition in the CoFe₂O₄ thin film shows a strong temperature dependence, likely due to the spin-charge coupling effect.     

The 16O + p → 17F (T = 32) resonances at Ep = 11.26,12.71 and 14.57 MeV

Excitation functions for ¹⁶O+p reactions have been measured with high energy resolution in the region of the first, second and seventh $\text{T =}\text{3}\text{2}$ resonances in ¹⁷F at extreme backward angles. The observed resonance shapes have been analyzed with a single-level resonance formula taking the off-resonance spin-flip amplitude into account. The resonance parameters of the ¹⁷F first $\text{T =}\text{3}\text{2}$ state studied with special emphasis are E_x = 11193.3 ± 2.3 keV, Γ = 200 ± 40 eV and Γ_p0 = 19 ± 3 eV. This result and other results are compared with previous studies and theoretical predictions. The comparison with data of the mirror nucleus ¹⁷O is discussed with respect to the observed charge asymmetry of the isospin-forbidden particle decay widths.     

Electronic energy band calculation in β-PbO2 comparison with SnO2 and GeO2 energy band structures

The energy band structure of β-PbO₂ is determined semi-empirically by the Kohn-Korringa-Rostoker method. It is believed to be the first PbO₂ calculated band structure that appears in literature. The direct band gap value that is obtained directly from this method is 2.7eV. It is lowered to the value of 1.6 eV which seems to be the most likely value of β-PbO₂ energy gaps that were already obtained. This energy band structure is compared with those of other oxides whose lattices belong to the same space group (D¹⁴_4h).     

Electrical conduction and 1ƒ noise in Li-DOPED MnO

Electrical resistivity, thermoelectric power and current noise were measured on Li-doped MnO single crystals in the temperature range from 300 to 1000 K. Below 700 K the crystals are p-type and the activation energy of the resistivity is 0.75 eV. Around 700 K the activation energy changes from 0.75 to 1.25 eV owing to a change from p- to n-type conduction. The depth of the Li acceptor is found to be 0.65 eV. From resistivity and thermoelectric power data it is concluded that the bandgap in first approximation can be written as E_s(T) = E_o ? γT between 750 and 1000 K, with E_o = 1.9 eV and γ = 6 × 10^?4 eV/K. The current noise spectra show $\text{1}\text{?}$ noise. The magnitude of the $\text{1}\text{?}$ noise is strongly temperature dependent. From the noise data it is deduced that E_o = 2.2 eV and γ = 10^?3 eV/K in the temperature range 430–700 K.     

High inertness of W@Si12 cluster toward O2 molecule

The geometry, electronic structure, and reactivity with O₂ molecules of an isolated W@Si₁₂ cluster have been investigated by first principles simulations. The results confirm that O₂ can weakly adsorb on the HP-W@Si₁₂ cage with a binding energy of 0.004 to 0.027 eV. O₂ may dissociate on the cluster by overcoming energy barrier of at least 0.593 eV. However, this is a spin-forbidden reaction, rendering the high inertness of the HP-W@Si₁₂ cluster toward O₂. These results confirm the high inertness of the W@Si₁₂ cluster toward O₂ molecules in ambient conditions, in close agreement with experimental observations of magic cluster of W@Si₁₂.     

Structural,electronic and optical properties of Ca3Bi2: First-principles investigation

In this work by applying first principles calculations structural, electronic and optical properties of Ca₃Bi₂ compound in hexagonal and cubic phases are studied within the framework of the density functional theory using the full potential linearized augmented plane wave (FP-LAPW) approach. According to our study band gap for Ca₃Bi₂ in hexagonal phase are 0.47, 0.96 and 1?eV within the PBE-GGA, EV-GGA and mBJ-GGA, respectively. The corresponding values for cubic phase are 1.24, 2.08 and 2.14?eV, respectively. The effects of hydrostatic pressure on the behavior of the electronic properties such as band gap, valence bandwidths and anti-symmetry gap are investigated. It is found that the hydrostatic pressure increases the band widths of all bands below the Fermi energy while it decreases the band gap and the anti-symmetry gap. In our calculations, the dielectric tensor is derived within the random phase approximation (RPA). The first absorption peak in imaginary part of dielectric function for both phases is located in the energy range 2.0–2.5?eV which are beneficial to practical applications in optoelectronic devices in the visible spectral range. For instance, hexagonal phase of Ca₃Bi₂ with a band gap around 1?eV can be applied for photovoltaic application and cubic phase with a band gap of 2?eV can be used for water splitting application. Moreover, we found the optical spectra of hexagonal phase are anisotropic along E||x and E||z.     

Thermoelectric power of superionic conductor Ag7I4PO4

The thermoelectric power (θ) of Ag₇I₄PO₄ superionic conductor has been studied for the first time from 4 to 75°C; 80°C being its decomposition temperature. Relation between θ and temperature can be expressed by the equation

$\text{?θ = 0.20}\text{10}{}^3\text{T}\text{?0.255}$

for this solid. Analysis of the data yields 0.20 eV as heat of transport of Ag⁺ ion which is very close to its activation energy 0.21 eV. This supports the prediction of the theory of Rice and Roth based on “free-ion” model. This is also in consonance with earlier theories on heats of transport of ions in ionic solids. Indications have been found to justify the assumption that Ag₇I₄PO₄ has average structure.     

Synthesis of earth-abundant Cu2SnS3 powder using solid state reaction

Cu₂SnS₃ (CTS) powder has been synthesized at 200 °C by solid state reaction of pastes consisting of Cu and Sn salts and different sulphur compounds in air. The compositions of the products is elucidated from XRD and only thiourea is found to yield CTS without any unwanted CuS_x or SnS_y. Rietveld analysis of Cu₂SnS₃ is carried out to determine the structure parameters. XPS shows that Cu and Sn are in oxidation states +1 and +4, respectively. Morphology of powder as revealed by SEM shows the powder to be polycrystalline with porous structure. The band gap of CTS powder is found to be 1.1 eV from diffuse reflectance spectroscopy. Cu₂SnS₃ pellets are p-type with electrical conductivity of 10⁻² S/cm. The thermal degradation and metal–ligand coordination in CTS precursor are studied with TGA/DSC and FT-IR, respectively, and a probable mechanism of formation of CTS has been suggested.     

An MRD-CI study of the electronic spectrum of Si3C3

Large-scale multi-reference configuration interaction (MRD-CI) calculations are used to compute the electronic spectrum of the pyramidal Si₃C₃ cluster. The first dipole-allowed transition is predicted at 4.30 eV. The dominating transition (21A′′←X1A′) is calculated at 4.74 eV with a π→π∗-type oscillator strength of f=0.52. This excitation together with two somewhat less intense (f=0.01-0.07) transitions around 5.2 eV and higher excitations between 5.7 and 5.9 eV could serve as a guideline for experimental search.     

Structural and electronic properties of Fe-doped BaTiO3 and SrTiO3

We have performed first principles calculations of Fe-doped BaTiO3 and SrTiO3. Dopant formation energy, structure distortion, band structure and density of states have been computed. The dopant formation energy is found to be 6.8eV and 6.5eV for Fe-doped BaTiO3 and SrTiO3 respectively. The distances between Fe impurity and its nearest O atoms and between Fe atom and Ba or Sr atoms are smaller than those of the corresponding undoped bulk systems. The Fe defect energy band is obtained, which mainly originates from Fe 3d electrons. The band gap is still an indirect one after Fe doping for both BaTiO3 and SrWiO3, but the gap changes from Γ-R point to Γ-X point.     

Intrinsic polyatomic defects in Sc2(WO4)3

The intrinsic formation of polyatomic defects in Sc₂(WO₄)₃-type structures is studied by Mott Littleton calculations and Molecular Dynamics simulations. Defects involving the WO₄²⁻ tetrahedron are found to be energetically favorable when compared to isolated W and O defects. WO₄²⁻ Frenkel and (2Sc³⁺, 3WO₄²⁻) Schottky defects exhibit formation energies of 1.23 eV and 1.97 eV, respectively and therefore may occur as intrinsic defects in Sc₂(WO₄)₃ at elevated temperatures. WO₄²⁻ vacancy and interstitial migration processes have been simulated by classical Molecular Dynamics simulations. The interstitial defect exhibits a nearly 10 times higher mobility (with a migration energy of 0.68 eV), than the vacancy mechanism (with a slightly higher migration energy of 0.74 eV) and thus should dominate the overall ionic conduction. Still both models reproduce the experimental activation energy (0.67 eV) nearly within experimental uncertainty.