First-Principles Studies on Electronic Structures and Absorption Spectra of PbWO4 Crystals with Defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-c

Electronic structures and absorption spectra for perfect PbW04 （PWO） crystals and the crystal containing aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-have been calculated using density functional theory code CASTEP with the lattice structure optimized. The calculated absorption spectra of the PWO crystal containing the aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-exhibit two absorption bands peaking at 1.90eV （65Onto） and 3.02eV （41Onto）. It is predicted that the 420 and fiSOnm absorption bands are related to the existence of the aggregated defect [V^2- Pb-V^2＋ o-V^2- Pb]^2-in the PWO crystal.     

First Principles Study on Electronic Structures of Mn^2＋：CdMoO4 Crystals

Electronic structures of the Mn^2＋ ：CdMoO4 crystal axe studied within the framework of the fully relativistic self-consistent Dirac Slater theory, using a numerically discrete variation （DV-Xα） method. The calculated results indicate that the 3d states of Mn have donor energy level in the forbidden band of CdMoO4 crystal. The O^2- transition energy of O 2p→Mn 3d is 3.12eV under excitation corresponding electronic transition being O^2-＋Mn^2＋→↑hvex=3.12 eV O^-- ＋Mn^＋→↑hvem O^2-＋Mn^2＋. It is predicted that the wavelength of emission should be located in the range of the 500-600nm. Thus the 500-600mm emission bands peaking at 550nm （2.25eV） of CdMoO4 crystal under excitation may be related to the Mn-like dopant ion in CdMoO4 crystal.     

Studies on the origins of the absorption spectra in PbWO4 crystal

The electronic structures and absorption spectra for both the perfect PbWO₄ (PWO) crystal and the three types of PWO crystals, containing V_Pb²⁻, V_O²⁺ and a pair of V_Pb²⁻-V_O²⁺, respectively, have been calculated using CASTEP codes with the lattice structure optimized. The calculated absorption spectra indicate that the perfect PWO crystal does not occur absorption band in the visible and near-ultraviolet region. The absorption spectra of the PWO crystal containing V_Pb²⁻ exhibit seven peaks located at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), respectively. The absorption spectra of the PWO crystal containing V_O²⁺ occur two peaks located at 370 nm and 420 nm. The PWO crystal containing a pair of V_Pb²⁻-V_O²⁺ does not occur absorption band in the visible and near-ultraviolet region. This leads to the conclusions that the 370 and 420 nm absorption bands are related to the existence of both V_Pb²⁻ and V_O²⁺ in the PWO crystal and the other absorption bands are related to the existence of the V_Pb²⁻ in the PWO crystal. The existence of the pair of V_Pb²⁻-V_O²⁺ has no visible effects on the optical properties. The calculated polarized optical properties are well consistent with the experimental results.     

First-principles study on the electronic structures and absorption spectra for the PbWO4 crystal with lead vacancy

The electronic structures and absorption spectra for the perfect PbWO₄ (PWO) crystal and the crystal containing lead vacancy have been calculated using density functional theory code CASTEP with the lattice structure optimized. The calculated absorption spectra of the PWO crystal containing exhibit seven absorption bands peaking at 1.72 eV (720 nm), 2.16 eV (570 nm), 2.81 eV (440 nm), 3.01 eV (410 nm), 3.36 eV (365 nm), 3.70 eV (335 nm) and 4.0 eV (310 nm), which are very close to the experimental values. It predicts that the 330, 360, 420, 500-750 nm absorption bands are related to the existence of in the PWO crystal.     

Band-gap bowing and p-type doping of (Zn,Mg, Be)O wide-gap semiconductor alloys: a first-principles study

Using a first-principles band-structure method and a special quasirandom structure (SQS) approach, we systematically calculate the band gap bowing parameters and p-type doping properties of (Zn, Mg, Be)O related random ternary and quaternary alloys. We show that the bowing parameters for ZnBeO and MgBeO alloys are large and dependent on composition. This is due to the size difference and chemical mismatch between Be and Zn(Mg) atoms. We also demonstrate that adding a small amount of Be into MgO reduces the band gap indicating that the bowing parameter is larger than the band-gap difference. We select an ideal N atom with lower p atomic energy level as dopant to perform p-type doping of ZnBeO and ZnMgBeO alloys. For N doped in ZnBeO alloy, we show that the acceptor transition energies become shallower as the number of the nearest neighbor Be atoms increases. This is thought to be because of the reduction of p-d repulsion. The N_O acceptor transition energies are deep in the ZnMgBeO quaternary alloy lattice-matched to GaN substrate due to the lower valence band maximum. These decrease slightly as there are more nearest neighbor Mg atoms surrounding the N dopant. The important natural valence band alignment between ZnO, MgO, BeO, ZnBeO, and ZnMgBeO quaternary alloy is also investigated.     

Transferability of optical bowing parameters between binary and ternary group-IV alloys

We present a detailed analysis of the compositional dependence of the average of the E₁ and E₁+Δ₁ transition energies in Ge_1−x−ySi_xSn_y alloys. We show that this dependence can be explained in terms of three bowing parameters—b^SiGe, b^GeSn, and b^SiSn—which scale with the product ΔχΔR of the Phillips electronegativity and size mismatches between Si, Ge, and Sn.     

Principal energy band gaps of the quaternary alloy AlxGa1−xSbyAs1−y

The correlated function expansion (CFE) interpolation procedure was presented to efficiently estimate principal energy band gaps and lattice constants of the quaternary alloy Al_xGa_1−xSb_yAs_1−y over the entire composition variable space. The lattice matching conditions between x and y for the alloy Al_xGa_1−xSb_yAs_1−y substrated to InAs and GaSb were obtained by optimizing the alloy lattice constant to that of the substrates. The corresponding principal band gaps (E(Γ), E(L), and E(X)) were also calculated along the lattice matching condition on each substrate (InAs and GaSb).     

Electronic structure of Li3GaN2

First principles calculations, by means of the full-potential linearized augmented plane wave method within the local density approximation, were carried out for the electronic properties of Li₃GaN₂. The calculated lattice parameter is in good agreement with the measured one. The bandgap is direct at the Brillouin zone centre. The Li-N and Ga-N bonds are both ionic with a small covalent character of the latter one.     

First-principles study on electronic structures of BaWO4 crystals containing F-type color centers

The electronic structures of BaWO₄ crystals containing F-type color centers are studied within the framework of the fully relativistic self-consistent Dirac-Slater theory, using a numerically discrete variational (DV-Xα) method. It is concluded that F and F⁺ color centers have donor energy level in the forbidden band. The optical transition energies are 2.449 and 3.101 eV, which correspond to the 507 and 400 nm absorption bands, respectively. It is predicted that 400-550 nm absorption bands originate from the F and F⁺ color centers in BaWO₄ crystals.     

Microemulsion-directed synthesis of different CuS nanocrystals

Through a microemulsion-directed route, CuS nanoparticles, nanorods, nanowires and tube-like structures were prepared while different quantities of surfactant were used. The arrangement of the microemulsion vesicles directed the growth behavior of the nanocrystals. Transmission electron microscopy (TEM) was used to investigate the different morphology of the as-synthesized products. X-ray powder diffraction (XRD) and electron diffraction (ED) were applied to characterize the properties of the products obtained. The mechanism of the nanocrystals with different shapes is discussed.     

Atomic structure of pre‐Guinier–Preston zones in Al alloys

We propose X‐ray absorption (XAS) measurements as a novel approach to determine the atomic structure of pre‐Guinier–Preston zones. These nano‐clusters are formed during very early stages of aging AlCu alloys, immediately after solution heat treatment and quenching. X‐ray absorption near‐edge structure (XANES) spectra were taken from technical aluminum alloys at the copper K edge, revealing the local atomic environment of copper. The spectra of – after solution heat treatment – freshly quenched and of artificially aged alloys differ significantly from each other. We compare the measured XANES spectra with those calculated by the FEFF‐8 code. We show the importance of employing realistic, i.e. relaxed, atomic coordinates around the scattering atom type from ab‐initio calculations with SIESTA. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Synthesis of new pure ferromagnetic semiconductors: MnGeP2 and MnGeAs2

We have synthesized two new chalcopyrite compounds: MnGeP₂ and MnGeAs₂. Total energy calculations predicted that both compounds are indirect semiconductors with band gaps of 0.24 and 0.06 eV, respectively. Both compounds exhibit room-temperature ferromagnetism with T_C∼320 and 340 K for MnGeP₂ and MnGeAs₂, respectively, based on magnetization and resistance measurements. We have also observed the anomalous Hall effect, indicating polarization of the carriers.     

Effect of isotopic mass on the photoluminescence spectra of zinc oxide

ZnO is a wurtzite-type semiconductor at ambient conditions whose natural composition consists of almost pure ¹⁶O and a mixture of 48.6% ⁶⁴Zn, 27.9% ⁶⁶Zn, 4.1% ⁶⁷Zn, 18.8% ⁶⁸Zn, and 0.6% ⁷⁰Zn. In this work, we report a photoluminescence study of different samples of isotopically pure and natural zinc oxide between 15 and 300 K. The isotopic coefficients of the bound exciton energy have been obtained and compared with previous values for the shift of the free A exciton energy. The isotopic coefficients of the bound exciton energy have allowed us to estimate the contribution of the zinc and the oxygen vibrations to the bandgap renormalization by electron-phonon interaction. A two-oscillator model based on the zinc and oxygen renormalization energies has been used to account for the temperature dependence of the bandgap in ZnO.     

Systematic study on synthesis and structural, electrical transport and magnetic properties of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites

Single-phases of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites with various Pb concentrations have been synthesized and the Pb-substitution effects on the structural, electrical and magnetic properties have been systematically investigated. Powder X-ray diffraction analysis showed that the single-phases of Bi_1.8−x/2Pb_xCa₂Co₂O_z were obtained up to x=0.6-0.7 under the optimized synthesis conditions. The lattice parameters of Bi_1.8−x/2Pb_xCa₂Co₂O_z continuously changed with increasing Pb concentration. The electron diffraction analysis suggested that the structure consisted of two different sublattices with a rock salt structure (RS) and a hexagonal CdI₂ structure (H), respectively, without modulation. In combined with the chemical composition analysis, the chemical formulas of the x=0 and x=0.6 samples were determined approximately as [Bi_1.74Co_0.31Ca_2.01O₄]^RS[CoO₂]_1.69 and [Bi_1.47Pb_0.38Co_0.29Ca_1.98O₄]^RS[CoO₂]_1.71, respectively. The electrical resistivity became more metallic with increasing the Pb concentration up to x=0.6. Moreover, the Pb-substitution simultaneously increased the antiferromagnetic Weiss temperatures and decreased the effective magnetic moments of the Co ions.     

Dependence of electronic properties on nitrogen concentration in GaAs1−xNx dilute alloys

Based on the pseudopotential scheme, the effect of nitrogen concentration on electronic properties of zinc-blende GaAs_1−xN_x alloys has been investigated for small amounts of N. The agreement between our calculated electronic band parameters and the available experimental data is generally reasonable. In agreement with recent experiment, we find that the incorporation of a few percent of N in the material of interest reduces substantially the fundamental band-gap energy and narrows the full valence band width. The electron and heavy hole effective masses are found to decrease rapidly when adding a concentration of nitrogen less than 0.005 in GaAs. This may increase the mobility of electrons and heavy holes providing new opportunities regarding the transport properties. The information derived from the present study shows that GaAs_1−xN_x (0?x?0.05) properties may have an important optoelectronic applications in infrared and mid-infrared spectral regions.     

Origin of HfO2/GaAs interface states and interface passivation: A first principles study

First principles calculations of HfO₂/GaAs interfaces indicate that the interface states originate from the charge mismatch between HfO₂ and GaAs surfaces. We find that a model neutral interface (HfO₂ and GaAs surfaces terminated with two O and one Ga atoms per surface unit cell) removes gap states due to the balance of the interface charge. F and H can neutralize the HfO₂/GaAs interface resulting in useful band offsets, thus becoming possible candidates to passivate the interface states.     

Electronic Structure and Optical Properties of Semiconducting Orthorhombic BaSi2

Full potential linearized augmented plane wave （FPLAPW） method calculations are carried out for semiconducting orthorhombic BaSi2. The optical properties and the origin of the different optical transitions are investigated. Our calculated band gap of 1.0918eV is indirect, which is in good agreement with the experimental result. The bonds between Ba and Si are considered to be electrovalent bond. The anlsotropy in the imaginary part ε2（w） and real part εl（w） of the optical dielectric tensor are analysed. The contributions of various transition peaks are explained from the imagnary part of the dielectric function.     

Single-crystalline Zn2SnO4 hexangular microprisms: Fabrication, characterization and optical properties

Large-scale Zn₂SnO₄ hexangular microprisms were successfully synthesized through a simple thermal evaporation method by heating metal Zn and Sn powders under varying temperatures. The synthesized microprisms are single-crystalline, tens of micrometers in length. And their surfaces have many nano-scale skewed steps along the axial direction. Structurally, we supposed that the hexangular prism could be described as a row of inlaid octahedron of Zn₂SnO₄ crystals. A broad asymmetrical emission band was observed in the PL spectrum of these Zn₂SnO₄ microprisms, which was discussed in detail in the paper.     

Optical functions of chalcopyrite CuGaxIn1-xSe2 alloys

We report pseudodielectric functions <ε> of the quaternary semiconductor alloys CuGa_xIn_1-xSe₂. Measurements were done in polycrystalline samples from 0.7 to 5.2 eV at room temperature by spectral ellipsometry. Accurate values of refractive indices n and extinction coefficients k representative of the bulk materials are obtained from the data. The structures observed in <ε> are analyzed by fitting the numerically differentiated spectra of d²<ε>(ω)/dω² to analytic line shapes. The obtained energies are related to given inter-band transitions by taking into account the electronic band structures of the ternary end-point compounds. Received: 20 December 2000 / Accepted: 30 May 2001 / Published online: 25 July 2001