Incommensurate modulations in Ba2TiSi2O8, Sr2TiSi2O8, and Ba2TiGe2O8

Incommensurate modulations in Ba₂TiSi₂O₈, Sr₂TiSi₂O₈, and Ba₂TiGe₂O₈ are compared based on their corresponding electron diffraction patterns. The dependence of the modulations on chemical composition provides a suitable model system for the investigation of incommensurations in framework structures using high-resolution transmission electron microscopy (HRTEM). A widening of quantitative HRTEM utilising the concept of rigid units is proposed allowing for a determination of atomistic displacements responsible for the formation of incommensurately modulated structures.     

Optical properties of new photovoltaic materials: AgCuO2 and Ag2Cu2O3

AgCuO₂ and Ag₂Cu₂O₃ are new types of semiconductor materials. A theoretical study is presented for both the electronic and optical properties of these new photovoltaic materials in the framework of density functional theory (DFT). The calculated cohesive energy is −3.606 eV/atom and −3.723 eV/atom for Ag₂Cu₂O₃ and AgCuO₂, respectively. Electronic calculations indicate that AgCuO₂ is a small band gap semiconductor and Ag₂Cu₂O₃ is metallic in nature. The valency state of Cu is divalent in Ag₂Cu₂O₃ and trivalent in AgCuO₂. The largest absorption coefficient of CuO₂ is 332 244, which is significantly greater than that of CuInSe₂, CdTe, GaAs, etc.     

X-ray diffraction, Raman spectrum and magnetic susceptibility of the magnetic semiconductor Cu2FeSnS4

In an attempt to resolve the crystal structure and the corresponding space group of the magnetic semiconductor Cu₂FeSnS₄, samples of this compound were studied by X-ray diffraction, differential thermal analysis, Raman scattering and magnetic susceptibility. It was found that at room temperature this compound prepared by a careful crystal growth process, including annealing to equilibrium at a suitable temperature followed by slow cooling of the samples to 300 K, crystallizes in a tetragonal structure with space group .     

Synthesis of ZnFe2O4 nanocrystallites by mechanochemical reaction

Mechanochemical reaction of ZnO and α-Fe₂O₃ in a planetary mill formed an amorphous precursor, which was subsequently heated to successfully produce zinc ferrite (ZnFe₂O₄) nanocrystallites. The amorphous precursor and nanocrystallites were characterized by differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Calcination of the precursor powder at 600 °C led to the formation of ZnFe₂O₄ nanocrystallites of about 22 nm in crystal size, and most of particle was about 10-50 nm in diameter. Effect of calcination temperature on the crystal size of the nanoparticles was investigated. The mechanism of nanocrystallite growth was primarily investigated. The activation energy of ZnFe₂O₄ nanocrystallite formation during thermal treatment was calculated to be 18.5 kJ/mol.     

Electrical properties of TlGaTe2 single crystals under hydrostatic pressure

The effect of hydrostatic pressure (up to 0.82 GPa) on the electric properties of chain TlGaTe₂ single crystals has been investigated in the temperature range 77-296 K. It has been shown that pressure leads to a considerable increase of conductivity (σ_⊥) across the chains of TlGaTe₂ single crystals. Parameters of localized states in the band gap of TlGaTe₂ single crystal according to the low-temperature electrical measurements were obtained at various pressures.     

Study of molybdenum coordination state and crystallization behavior in MoO3-La2O3-B2O3 glasses by Raman spectroscopy

The ternary MoO₃-La₂O₃-B₂O₃ glasses containing a large amount of MoO₃ (10-50 mol%) are prepared, and their structure and crystallization behavior are examined from the Raman scattering spectrum measurements and X-ray diffraction analyses. It is found that the glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing MoO₃ content. It is suggested that the main coordination state of Mo⁶⁺ ions in the glasses is isolated (MoO₄)²⁻ tetrahedral units giving strong Raman bands at 830-860 and 930 cm⁻¹. It is found that the crystalline phases in the crystallized glasses are mainly LaMoBO₆ and LaB₃O₆, and the main crystallization mechanism in MoO₃-La₂O₃-B₂O₃ glasses is surface crystallization. LaMoBO₆ crystals are found to give strong Raman bands at 810-830 and ∼910 cm⁻¹.     

Preparation and properties of disordered NaBi(XO4)2, X=W or Mo, crystals doped with rare earths

NaBi_1−xRE_x(XO₄)₂, X=W or Mo and RE=Pr, Nd, Ho, Er and Yb single crystals have been grown by the Czochralski technique. Rare earth concentrations about 3.5×10²⁰ cm⁻³ have been achieved in crystals with good optical quality. Melt stability is obtained by synthesising NaBi(XO₄)₂ from the precursor Na₂X₄O₁₃ phase and minimising Mo volatility. The strength of W and Mo compounds to chemical attack and thermal annealing in several atmospheres is reported. Mo compound is etched by inorganic acids and becomes coloured after vacuum annealing. The optical absorption, photoluminescence and refractive indices of the hosts are characterised and show a dichroic character. The lattice disorder induces broadening of the 10 K optical absorption of the rare earth impurities.     

Growth and optical properties of Eu/Li-co-doped SrB4O7 single crystals

This paper reports the growth and optical properties of Eu²⁺/Li⁺-co-doped SrB₄O₇ single crystals. High-quality Eu,Li:SrB₄O₇ crystals without macro-defects or cracks were grown using the top-seeded solution growth (TSSG) method. The absorption and luminescent properties were measured and different spectra were observed in the as-grown crystals. As the doping amount of lithium increases, the absorption peak at 300 nm becomes stronger and the emission peak shifts to a longer wavelength. This phenomenon could be attributed to the doping lithium ions, which might affect the electric field distribution in the lattice structure.     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Structure instability of A2Al2B2O7 (A=K, Na) crystals

A theoretical study on the stabilities of the crystal structures of K₂Al₂B₂O₇ (KABO) and Na₂Al₂B₂O₇ (NABO) has been carried out using density functional theory with generalized-gradient corrections. All structures have been optimized by minimizing the total energies with respect to lattice constants and to the atomic coordinates within the unit cell. In the case of KABO, the structure with space group P321 always takes energy advantage over the whole volume range studied, whereas on both volume expansion and contraction, the original NABO structure becomes unstable, taking a structure transition from its space group to the P321 space group of KABO structure. The theoretical predictions were well realized in the experimental results on the structure changes of the (K_1−xNa_x)₂Al₂B₂O₇ solid solution system.     

Growth and characterization of new transparent conductive oxides single crystals β-Ga2O3: Sn

Tin oxide doped β-Ga₂O₃ single crystals are recognized as transparent conductive oxides (TCOs) materials. They have a larger band gap (4.8 eV) than any other TCOs, thus can be transparent in UV region. This property shows that they have the potential to make the optoelectronic device used in even shorter wavelength than usual TCOs. β-Ga₂O₃ single crystals doped with different Sn⁴⁺ concentrations were grown by the floating zone technique. Their optical properties and electrical conductivities were systematically studied. It has been found that their conductivities and optical properties were influenced by the Sn⁴⁺ concentrations and annealing.     

Characterization of multiferroic LiTMxCu2−xO2 (TM=Ni and Zn) single crystals

We investigate a series of single crystalline samples of LiT_MxCu_2−xO₂ (T_M=Ni and Zn) grown by floating-zone technique. As-grown crystals showed a clear X-ray diffraction pattern of pure(single) phase. These crystals exhibit varied magnetic and electrical properties owing to successful incorporation of Ni and Zn dopants.     

Reflection and vibrational spectra of SbSCl0.1I0.9 crystals in the ferroelectric phase-transition region

SbSCl_0.1I_0.9 crystals were grown from the vapor phase and reflection spectra were recorded using a Fourier-transform IR spectrometer. The optical parameters and optical functions along the c axis were calculated using an improved Kramers–Kronig technique with two confining spectral limits. The reflection spectra were analyzed using the oscillator parameter fitting technique for comparison of results. The vibrational frequencies ω_L and ω_T were evaluated. The ferroelectric phase-transition temperature was estimated as 330 K for SbSCl_0.1I_0.9 from experimental reflection measurements and theoretical investigation of the potential energy of Sb atoms for B_1u soft normal modes of SbSI and SbSCl_0.1I_0.9 crystals.     

Some crystallography,chemistry, physics,and thermodynamics of B12O2, B12P2, B12As2, and related alpha-boron type crystals

This paper shows that several alpha-boron type compounds may be useful as high-temperature semiconductors with decent carrier motilities, high electrical resistivity, good optical transparency, good stability under high radiation bombardment, and possess high neutron capture cross-sections. The most promising are B₁₂O₂, B₁₂P₂, and B₁₂As₂. Their relationship to alpha-boron, B₁₃C₂, and other derivative crystals is explained. A study of their chemical and thermodynamic properties indicates how single crystals useful for electronic devices can be grown.     

EPR and optical investigation of VO(II) in Zn(C3H3O4)2(H2O)2 single crystals: An interstitial site

EPR spectroscopic investigations on single crystals of diaquabis[malonato(1-)-κ²O,O′] zinc(II) doped with VO(II) ion have been carried out at X-band frequencies and at 300 K. The single crystal, rotated along the three mutually orthogonally axes, has yielded spin-Hamiltonian parameters g and A as: g_xx=1.980, g_yy=1.972, g_zz=1.937 and A_xx=8.4, A_yy=6.1, A_zz=18.1 mT, respectively. These spin-Hamiltonian parameters reflect a slight deviation from axial symmetry to rhombic, which is elucidated by the interstitial occupation of vanadyl ions. The isofrequency plots and powder EPR spectrum have been simulated. The percentage of metal-oxygen bond has been estimated. The optical absorption spectrum exhibits four bands at 257, 592, 720 and 764 nm suggesting a C_4v symmetry. The admixture coefficients and bonding parameters have also been calculated by collaborating EPR data with optical data.     

Structural studies of nanocrystalline SnO2 doped with antimony: XRD and Mössbauer spectroscopy

A series of Sb-doped SnO₂ samples, with doping levels 0, 3.1, 6.2, 11.9 and 14.0 at% Sb, has been hydrothermally prepared and characterized by X-ray powder diffraction. Diffraction lines were broadened, the line broadening being anisotropic. Both the line broadening and line anisotropy were dependent on the Sb doping level. The samples are tetragonal, space group P4₂/mnm and isostructural with TiO₂(rutile). Sb doping of SnO₂ causes the increase of unit-cell parameters. The structure of pure SnO₂ and of samples containing 6.2 and 11.9 at% Sb has been refined by the Rietveld method. Crystal structure indicated that both Sb³⁺ and Sb⁵⁺ are substituted for Sn⁴⁺ in the SnO₂ structure, Sb³⁺ being dominant for the investigated doped samples. The samples were also examined by ¹¹⁹Sn- and ¹²¹Sb-Mössbauer spectroscopy. Mössbauer spectroscopy confirmed the XRD results. Also, the values of the isomer shifts and quadrupole coupling constants indicated that the configuration around the Sb³⁺ site includes the presence of the stereochemically active lone pair electrons.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Preparation and characterization of the layered hybrids (CnH2n+1NH3)2FeCl4

The series of the hybrids (C_nH_2n+1NH₃)₂FeCl₄, where n=2, 4, 6, 8, 10 and 12, were synthesized in HCl solutions. The optimum conditions of synthesis were investigated including the sequence of adding reactants, the stoichiometric ratio of the reactants, the reaction time and the drying procedures. The results demonstrate that the order of adding reactants, the drying temperature and drying time have little effect on the structures of the products. But for the hybrids of n?10, longer reaction time is needed to form the layered structures. The X-ray diffraction (XRD) patterns and the images of scanning electron microscopy of the products demonstrate that the hybrids crystallize well with typical layered structures. Chemical analysis of C, H and N confirms that the hybrids consist of the elements in the ratio of the molecular formulas. The d values, the interlayer distance between the two adjacent inorganic sheets of each hybrid, are obtained from the XRD patterns and they suggest that the organic chains interdigitate between the inorganic sheets. The longer the organic chains are, the more interdigitations there are. This can be explained by the different interaction strengths between the organic species when the chain lengths change. These different interactions can also explain the phenomena observed in the synthesis and the decomposing temperatures of the hybrids.     

Transport properties of MgB2 single crystals doped with electrons and holes

The thermoelectric power of C, Mn, C:Li, and Al:Li substituted MgB₂ single crystals has been investigated in the temperature range 10-300 K. Both the in-plane (S_ab) and the out-of-plane (S_c) thermopowers are positive for the non-substituted crystal and both S_ab and S_c change a sign for crystals doped with electrons where C is substituted for B in the amount larger than 5 at%. When Li is substituted for Mg, the π band rather than the σ band is doped with holes and the doping effects are much more subtle. The anisotropy ratio of the non-substituted crystal S_ab/S_c≈3 and this ratio is strongly reduced by the substitution of C. Isovalent magnetic Mn ions, which substitute for Mg with a drastic reduction of T_c, do not influence the values and temperature dependences of both S_ab and S_c.