Electronic properties of orthorhombic LiGaS<Subscript>2</Subscript> and LiGaSe<Subscript>2</Subscript>

We report theoretical calculations of the band structure and density of states for orthorhombic LiGaS₂ (LGS) and LiGaSe₂ (LGSe). These calculations are based on the full potential linear augmented plane wave (FP-LAPW) method within a framework of density functional theory. Our calculations show that these crystals have similar band structures. The valence band maximum (VBM) and the conduction band minimum (CBM) are located at Γ, resulting in a direct energy band gap. The VBM is dominated by S/Se-p and Li-p states, while the CBM is dominated by Ga-s, S/Se-p and small contributions of Li-p and Ga-p. From the partial density of states we find that Li-p hybridizes with Li-s below the Fermi energy (E _F), while Li-s/p hybridizes with Ga-p below and above E _F. Also, we note that S/Se-p hybridizes with Ga-s below and above E _F.     

Structural and dehydriding properties of Ca(BH<Subscript>4</Subscript>)<Subscript>2</Subscript>

We have investigated the structural and dehydriding properties of Ca(BH₄)₂. It was found that Ca(BH₄)₂ undergoes a structural phase transformation from an orthorhombic low-temperature (LT) modification into a tetragonal high-temperature (HT) modification between 433 K and 523 K. The amount of hydrogen desorbed from Ca(BH₄)₂ during the pressure–composition (p–c) isotherm measurement was 5.9 mass%. This hydrogen desorption is caused by the partial dehydrogenation of Ca(BH₄)₂ accompanied by the formation of CaH₂ and orthorhombic intermediate phases.     

Electronic structure and magnetism of NpTAl (T=Co, Ni, Rh, Ir and Pt) and NpNiGa from first-principles calculations

First-principles calculations based on density-functional theory were performed for the first time on NpTAl (T=Co, Ni, Rh, Ir and Pt) and NpNiGa. The electronic density of states and equilibrium volume were studied using relativistic full-potential APW plus local-orbitals calculations. The magnetocrystalline anisotropy energy was estimated from total-energy calculations and the a-axis was predicted to be the easy axis of magnetization with the exception of T=Rh. Finally, we employed the LSDA+U method to mimic the orbital polarization and to obtain the correct total magnetic moments in experimental equilibrium.     

High pressure study of the organic compound (TMTTF)<Subscript>2</Subscript>BF<Subscript>4</Subscript>

High pressure resistivity measurements of the organic compound (TMTTF)₂BF₄ have been performed in a newly developped Bridgman cell providing good pressure conditions on a wide pressure range. For the first time in this compound a zero resistance superconducting state is observed between 3 and 4 GPa. At temperatures above the superconducting transition, the resistivities of the two high quality samples show a different behavior. One sample, provides indications for a magnetic quantum critical point at the maximum of T_c, whereas in the other antiferromagnetic spin-fluctuations are present above T_c.     

Thermo-optic coefficients of monoclinic KLu(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The three thermo-optic coefficients of the biaxial laser host KLu(WO₄)₂ are measured at 633 nm by a deflection method. Their values at 300 K amount to ∂ n _g /∂ T=−7.4×10⁻⁶ K⁻¹; ∂ n _m /∂ T=−1.6×10⁻⁶ K⁻¹ and ∂ n _p /∂ T=−10.8×10⁻⁶ K⁻¹. Nearly athermal propagation directions are found for polarizations along the N _m and N _p dielectric axes.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Magnetic properties, Mössbauer effect and first principle calculations study of laves phase HfFe2

The magnetic properties and hyperfine interaction parameters for Laves phase HfFe₂ with C14 type structure are studied using SQUID magnetometer and M?ssbauer measurement. The saturation magnetization, remanent magnetization, coercive field, magnetic moment per unit formula and the hyperfine magnetic field at Fe site are reported. In addition, a detailed theoretical study of the electronic structure and hyperfine magnetic fields of the two possible HfFe₂ structures, C15 and C14, is presented. Using the full-potential linearized augmented plane wave (FP-LAPW) method as implemented in the WIEN 97 package, the equilibrium volume, bulk moduli, magnetic moments and hyperfine magnetic fields for the two structures are calculated. The obtained results are compared with the measured data.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Sub-90 fs pulses from a passively mode-locked Yb:YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> laser

Passive mode locking of the self-frequency doubling Yb:YAB crystal with a saturable absorber mirror is studied at the fundamental wavelength. This laser has a very low threshold, and pulses as short as 85 and 87 fs are obtained for Ti:sapphire and diode laser pumping, respectively.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Observations of nanoscopic,face centered cubic Ti and TiH<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Transmission electron microscopy has been used to study ball milled and H cycled NaAlH₄ with 10 mol% TiCl₃. Isolated from the main phases in this hydrogen storage system, nanocrystalline aggregates of fcc TiH _x (0≤x<0.67) were found. The value of x was determined based on the assumption of a linear increase of the TiH _x lattice parameter by increasing H content. The size of the TiH _x crystallites was in the range 10 to 20 nm, and the lattice parameter decreased from 4.22 Å in TiH_0.67 to 4.10 Å in pure fcc Ti. Non-equilibrium ball milling and subsequent H cycling in combination with a small crystallite size are believed to make the TiH _x phase stable. The present results are the first observations of fcc TiH _x with low hydrogen content, and the measured fcc lattice parameter of Ti matches first-principles calculations.     

Ab initio study on elastic and thermodynamical properties of Ti<Subscript>1-x</Subscript>Zr<Subscript>x</Subscript>C

Elastic and Thermodynamical properties of Ti_1-xZr_xC have been investigated using LAPW + lo within the density-functional theory with the generalized gradient approximation. We have studied the stability of the alloy Ti_1-xZr_xC as a function of Zr composition in rocksalt (B1) structure by calculating the elastic constants C₁₁, C₁₂ and C₄₄ using the tetragonal and trigonal distortions. Mechanical properties such as Poisson ratio, bulk, shear and Young’s modulii of Ti_1-xZr_xC are calculated. The Debye temperature and hardness are also computed for the first time to our knowledge for Ti_1-xZr_xC in various compositions.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Electronic structure of thin film iron-tetracyanoethylene: Fe(TCNE)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Thin film iron-tetracyanoethylene Fe(TCNE) _x , x∼2, as determined by photoelectron spectroscopy, was grown in situ under ultra-high vacuum conditions using a recently developed physical vapor deposition-based technique for fabrication of oxygen- and precursor-free organic-based molecular magnets. Photoelectron spectroscopy results show no spurious trace elements in the films, and the iron is of Fe²⁺ valency. The highest occupied molecular orbital of Fe(TCNE) _x is located at ∼1.7 eV vs. Fermi level and is derived mainly from the TCNE⁻ singly occupied molecular orbital according to photoelectron spectroscopy and resonant photoelectron spectroscopy results. The Fe(3d)-derived states appear at higher binding energy, ∼4.5 eV, which is in contrast to V(TCNE)₂ where the highest occupied molecular orbital is mainly derived from V(3d) states. Fitting ligand field multiplet and charge transfer multiplet calculations to the Fe L-edge near edge X-ray absorption fine structure spectrum yields a high-spin Fe²⁺ (3d⁶) configuration with a crystal field parameter 10Dq∼0.6 eV for the Fe(TCNE) _x system. We propose that the significantly weaker Fe-TCNE ligand interaction as compared to the room temperature magnet V(TCNE)₂ (10Dq∼2.3 eV) is a strongly contributing factor to the substantially lower magnetic ordering temperature (T _C ) seen for Fe(TCNE) _x -type magnets.     

Microstructures and impedance studies of Bi<Subscript>3.15</Subscript>Nd<Subscript>0.85</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Microstructures and impedance characteristics of chemical-solution-derived Bi_3.15Nd_0.85Ti₃O₁₂ thin films were studied as functions of temperature. A dielectric anomaly was found at around 450°C, corresponding to the paraelectric to ferroelectric transition. Via complex impedance studies, grain and grain boundary contributions to the impedance were separated. The resistance of grain and grain boundaries is found governed by the same kind of space charge with an activation energy around 1.1 eV, close to that of oxygen vacancies in perovskite ferroelectrics. The low temperature ac conductance of BNdT thin films shows a frequency dispersion, which can also be ascribed to space charges mainly due to oxygen vacancies. The results were compared with SrBi₂Ta₂O₉ in terms of oxygen vacancy conductivity.     

Growth and magneto-optical properties of LiTb(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

Lithium terbium molybdate (LiTb(MoO₄)₂) single crystal was grown by the Czochralski method. The lattice parameters of the crystal were determined by X-ray diffraction analysis. The absorption coefficient and the Faraday rotation spectrum (B=1.07 T) were investigated at wavelengths of 400–1500 nm at room temperature. Verdet constants of LiTb(MoO₄)₂ crystal at 532-, 633- and 1064-nm wavelengths were measured by the extinction method. The results show that LiTb(MoO₄)₂ crystal has a larger magneto-optical figure of merit than that of terbium gallium garnet at wavelengths of 600–1500 nm.     

Deposition and stoichiometry control of Nd-doped gadolinium gallium garnet thin films by combinatorial pulsed laser deposition using two targets of Nd:Gd<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> and Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

We have demonstrated pulsed laser deposition of Nd-doped gadolinium gallium garnet on Y₃Al₅O₁₂ by the simultaneous ablation of two separate targets of Nd:Gd₃Ga₅O₁₂ (GGG) and Ga₂O₃. Such an approach is of interest as a method of achieving stoichiometry control over films whilst the growth parameters are kept constant and optimal for high quality crystal growth. We show here how the stoichiometry and resultant lattice parameter of a film can be controlled by changing the relative deposition rates from the two targets. Films have been grown with enough extra Ga to compensate for the deficiency that commonly occurs when depositing only from a GGG target. We have also grown crystalline GGG films with an enriched Ga concentration, and this unconventional approach to film stoichiometry control may have potential applications in the fabrication of films with advanced compositionally graded structures.     

Post-deposition processes for nanostructures formed by electron beam induced deposition with Pt(PF<Subscript>3</Subscript>)<Subscript>4</Subscript> precursor

Electron beam induced deposition was performed using a Pt(PF₃)₄ precursor gas. Self-standing nanowires were produced on the edge of a molybdenum film, followed by two post-deposition processes; electron beam irradiation at room temperature and heating at about 400 K in vacuum. The as-deposited nanowires were composed of an amorphous phase, of which the dominant composition was platinum but containing a small amount of phosphorus impurity. After irradiating with a 300 keV electron beam, the amorphous nanowires were transformed to crystalline ones. By heating, the as-deposited nanowires became single-crystal platinum with a large grain size and the phosphorus content disappeared.