Lattice Thermal Expansion and Ionicity for III<Subscript>2</Subscript>–VI<Subscript>3</Subscript> Binary Defect Tetrahedral Compound Semiconductors and Their Alloys

A model for calculating the lattice thermal expansion is modified to be applicable to binary defect tetrahedral compounds that belong to the III₂–VI₃ group. The number of valence electrons for the expected missing atom as a vacancy is used to correlate the deviations caused by the ionicity of this group of compounds. The ionicity effects which are due to the different numbers between vacancy atom types, which in this case is the group III element, and the element itself, were also added to the correlation equation. In general, the lattice thermal expansion for a compound semiconductor can be calculated from a relation containing the melting point, the mean atomic distance, and the number of valence electrons for the atoms forming the compound. For compounds that undergo a structural change during heating, the phase transition temperature has the same role as the melting point for calculating the lattice thermal expansion that belongs to the related structure phase. The value of the mean ionicity for this group of compounds is also calculated and found to be equal to 0.416.     

Lattice thermal expansion for normal tetrahedral compound semiconductors

The cubic root of the deviation of the lattice thermal expansion from that of the expected value of diamond for group IV semiconductors, binary compounds of III-V and II-VI, as well as several ternary compounds from groups I-III-VI₂, II-IV-V₂ and I-IV₂V₃ semiconductors versus their bonding length are given straight lines. Their slopes were found to be 0.0256, 0.0210, 0.0170, 0.0259, 0.0196, and 0.02840 for the groups above, respectively. Depending on the valence electrons of the elements forming these groups, a formula was found to correlate all the values of the slopes mentioned above to that of group IV. This new formula which depends on the melting point and the bonding length as well as the number of valence electrons for the elements forming the compounds, will gives best calculated values for lattice thermal expansion for all compounds forming the groups mentioned above. An empirical relation is also found between the mean ionicity of the compounds forming the groups and their slopes mentioned above and that gave the mean ionicity for the compound CuGe₂P₃ in the range of 0.442.     

New compounds Cu2MnTi3S8 and Cu2NiTi3S8 with thiospinel structure

Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈ compounds were prepared by high-temperature synthesis. The crystal structure of these quaternary phases was investigated by X-ray powder diffraction. The compounds are described in the thiospinel structure (space group ) with the lattice constants a = 1.00353(1) nm (Cu₂MnTi₃S₈) and a = 0.99716(1) nm (Cu₂NiTi₃S₈). The atomic parameters were calculated in anisotropic approximation (R_I = 0.0456 and R_I = 0.0520 for Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈, respectively).     

Lattice thermal expansion studies of V2GeO4F2: A topaz type oxide-fluoride

A new compound V₂GeO₄F₂ was earlier found to exist in the V₂O₃-VF₃-GeO₂ system and the structure elucidation revealed it to be iso-structural to the mineral topaz. Herein, we report the lattice thermal expansion data of this compound. The lattice thermal expansion of V₂GeO₄F₂ was studied in the temperature range of 298-873 K under a flowing helium atmosphere by the high temperature XRD (HTXRD). The coefficients of axial thermal expansions of V₂GeO₄F₂ were found to be as: α_a = 3.5 × 10⁻⁶, α_b = 6.1 × 10⁻⁶ and α_c = 7.6 × 10⁻⁶ K⁻¹. The coefficient of volume (α_V) thermal expansion was 17.3 × 10⁻⁶ K⁻¹, which is relatively low compared to many analogues silicates.     

K2(Rb2,Cs2,Tl2)TeBr6(I6) and Rb3(Cs3)Sb2(Bi2)Br9(I9) perovskite compounds

We systematize available experimental data on the crystal structure of the ternary halides K₂(Rb₂,Cs₂,Tl₂)TeBr₆(I₆) and Rb₃(Cs₃)Sb₂(Bi₂)Br₉(I₉), analyze the general trends in the properties of their single crystals, and examine the key features of the physicochemical interaction in related systems.     

The crystal structure of eulytite Pb3BiV3O12

The crystal structure of Pb₃BiV₃O₁₂ was solved using single-crystal X-ray diffraction technique. The compound crystallizes in the cubic system (No. 220) with eulytite structure with a = 10.7490(7) Å, V = 1241.95(14) Å³ and Z = 4. The final R₁ value of 0.0198 (wR₂=0.0384) was achieved for 359 independent reflections during the structure refinement. The Pb²⁺ and Bi³⁺ cations occupy the special position (16c) while the oxygen anions occupy the general position (48e) in the crystal structure. Unlike many other eulytite compounds, all the crystallographic positions are fully occupied. The structure consists of edge-shared Pb/Bi octahedra linked at the corners to independent [VO₄]³⁻ tetrahedra units, generating a eulytite-type network in the crystal lattice.     

Synthesis and crystal structure of Sr10Al6O19: a derivative of the perovskite structure type in the system SrO-Al2O3

Sr₁₀Al₆O₁₉ is monoclinic, space group C12/c1, a=34.5823(21) Å, b=7.8460(6) Å, c=15.7485(9) Å, β=103.68(1)°, V=4151.9(7) Å³, Z=8. The structure has been solved from a single crystal diffraction dataset by direct methods and subsequently refined by a full-matrix least-squares process to a residual index of R(|F|)=0.038 for 2537 observed reflections with I>2σ(I). The compound is an oligoaluminate containing highly puckered [Al₆O₁₉]-groups of corner-sharing tetrahedra; it is the first purely aluminate cluster of this type, but it resembles the [□₆O₁₉]-group recently found in α-Sr₁₀□₆O₁₉. Linkage between the hexamers is provided by 11 crystallographically different strontium atoms located in planes parallel (1 0 0). They are coordinated by six-eight next oxygen neighbours. The structure can be derived from perovskite, ABO₃, by introducing ordered vacancies into the substructure of the oxygen atoms. The A-sites in Sr₁₀Al₆O₁₉ are exclusively occupied by Sr atoms, whereas strontium and aluminum atoms reside on the B-positions in the ratio 1:3. The relationship with perovskite can be expressed in the crystal chemical formula Sr(Al_3/4Sr_1/4)(O_19/8□_5/8).     

The system Ag2Se-Ho2Se3 in the 0-50 mol.% Ho2Se3 range and the crystal structure of two polymorphic forms of AgHoSe2

The phase diagram of the Ag₂Se-Ho₂Se₃ system in the range of 0-50 mol.% Ho₂Se₃ was constructed with the results of XRD and differential thermal analysis. A dimorphous compound exists in the system at the equimolar ratio of the components. The investigated part of the Ag₂Se-AgHoSe₂ diagram is of the eutectic type with the eutectic coordinates 7 mol.% Ho₂Se₃ and 1125 K. The crystal structure of the high-temperature modification of AgHoSe₂ was studied by X-ray powder diffraction method. α-AgHoSe₂ is described as a NaCl structure (space group ) with the lattice parameter а = 5.7623(3) Å. Atomic parameters were calculated in the isotropic approximation (R_I = 0.0434 and R_Р = 0.0636). The crystal structure of β-AgHoSe₂ was determined by X-ray structure analysis and was refined to R = 0.0487.     

Crystal growth and characterization of Yb-doped Gd3Ga5O12

Single crystals of (Yb_xGd_1−x)₃Ga₅O₁₂ (0.0 ≤ x ≤ 1.0) have been grown by the micro-pulling-down method. Formation of continuous solid solutions with a garnet structure was confirmed. Composition dependence of the lattice constant, thermal diffusivity, specific heat capacity and thermal conductivity was investigated. Assignment of the Yb³⁺-energy levels in Gd₃Ga₅O₁₂-host lattice has been performed by using absorption, emission and Raman spectroscopy measurements at both, room temperature and at 12 K.     

Synthesis and crystal structure of two new oxychalcogenides: Eu5V3S6O7 and La10Se14O

The crystal structure determination of two new oxychalcogenides, namely Eu₅V₃S₆O₇ and La₁₀Se₁₄O, is reported. Eu₅V₃S₆O₇ crystallizes in the orthorhombic symmetry (space group Pmmn) with unit cell parameters (in Å): a=17.463(2), b=3.6732(4), and c=10.007(1). This compound is isotypic with the Ln₅V₃S₆O₇ compounds (Ln=La-Nd), and its structure has been refined to R1=0.0248. Eu atoms, which are nine-coordinated by O and S atoms, are associated to form ribbons that are interconnected by [VS₄O₂] octahedrons. La₁₀Se₁₄O crystallizes in the tetragonal symmetry (space group I4₁/acd) with unit cell parameters (in Å): a=15.926(2), and c=21.061(5). The structure was refined to R1=0.0347. La₁₀Se₁₄O is isostructural with the Pr₁₀X₁₄O compounds (X=S and Se). The only structure difference is observed for one La site that is found split, in connection with a mixed O/Se site filling.     

Synthesis and crystal structure of InP3

Higher indium phosphide InP₃ is obtained under high pressure of 3 GPa at 1200°C. The crystal structure was analyzed to be isomorphous with SnP₃, and GeP₃ having lattice parameters of $\text{a}\text{= 7.449}\text{A}\text{?}$ and $\text{c}\text{= 9.885}\text{A}\text{?}$. InP₃ is a metallic conductor although it is less in the amount of valence electrons than its isomorphous MP₃ of Ge and of Sn.     

High-pressure synthesis, electrical and magnetic properties of new filled skutterudites LnOs4P12 (Ln = Eu, Gd, Tb, Dy, Ho, Y)

New filled skutteudites LnOs₄P₁₂ (Ln: Eu, Gd, Tb, Dy, Ho and Y) have been prepared at high temperatures and at high pressures. X-ray diffraction of these compounds is studied at room temperature. The relationship between lattice constants and atomic numbers of lanthanide (including Y) is obtained for LnOs₄P₁₂ (Ln: lanthanide). Electrical and magnetic properties of the new filled skutterudites with heavier lanthanide have been investigated at low temperatures. EuOs₄P₁₂ and GdOs₄P₁₂ show ferromagnetic transitions at around 15 and 22 K, respectively. The valence states of both compounds are +2 for the Eu compound and +3 for the Gd compound. DyOs₄P₁₂ does not show the magnetic transition down to 2 K. However, a small electrical anomaly is found at around 10 K. YOs₄P₁₂ exhibits a superconducting transition at around 3 K. This compound is a new superconductor. Electrical and magnetic anomalies of new filled skutterudites with heavier lanthanide LnOs₄P₁₂ (Ln: Eu, Gd, Dy and Y) are discussed. We have also found the electrical anomaly based on the magnetic transition at around 22 K for GdFe₄P₁₂.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Influence of Sm2O3 on the crystallization and luminescence properties of boroaluminosilicate glasses

Sm₂O₃-doped SiO₂-B₂O₃-Al₂O₃-BaO glasses were prepared by melting method in order to study the influence of Sm₂O₃ on the crystallization behavior and luminescence properties. Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy were used to characterize the rare earth glasses and the crystalline phases after heat-treatment. The course of phase separation and devitrification of the glasses were also investigated. The results show that the thermal stability of the glasses decreases with the increase of content of Sm₂O₃. The crystalline phase changed from SmAl_2.07(B₄O₁₀)O_0.6 to SmBO₃. Divalent Sm²⁺ ions were detected in the crystallization product after heat-treatment. The valence transformation from Sm³⁺ to Sm²⁺ in the crystal suggests the samarium atoms entering the barium sites. The charge carried in vacancy defect induced by the substitution led to the partial reduction process. The reduction of Sm³⁺ ions was promoted by the increasing of Sm₂O₃ content or the extending of heat-treated holding time in boroaluminosilicate glass.     

Preparation and crystal structure of a new cesium iron niobium oxide: Cs3Fe0.44Nb5.56O16

Single crystals of a new niobium oxide, Cs₃Fe_0.44Nb_5.56O₁₆ were prepared at 1200°C under an Ar atmosphere. This compound has the orthorhombic space group Pbcm and Z=4. The lattice parameters were a=10.470(3), b=7.514(4) and c=21.312(3) Å, and the final R-factors were R=0.027 and R_w=0.033 for 1085 unique reflections. The crystal structure is a three-dimensional tunnel structure built up by edge- and corner-sharing NbO₆ octahedra and (Fe,Nb)O₄ tetrahedra and cesium atoms are located in two types of tunnels. The Cs⁺ ion in the tunnels was ion-exchanged partially with Rb⁺ ion.     

Crystallographic and dielectric properties of barium-substituted Pb(Mg1/3Ta2/3)O3 ceramics

Ceramic powders of (Ba,Pb)Pb(Mg_1/3Ta_2/3)O₃ were prepared via a B-site precursor route. Crystal symmetries and lattice parameters were determined. Monophasic perovskite was developed after the two-step reaction process, in which the lattice parameters showed linear changes in the entire composition range. Dielectric responses of the ceramics with compositional and frequency changes were investigated. The results were also compared with the (Ba,Pb)(Zn_1/3Ta_2/3)O₃ data.     

Self-propagating high-temperature synthesis of Y2O3 powders from Y(NO3)3x(CH3COO)3(1 ? x) · nH2O

We have studied the self-propagating high-temperature synthesis (SHS) of yttrium oxide from Y(NO₃)_3x (CH₃COO)_{3(1 − x)} · nH₂O (0.3 ≤ x ≤ 0.7) acetate nitrates, calculated their standard enthalpies of formation using the method of valence states of atoms in a chemical compound, and compared calculated and experimentally determined yttrium oxide SHS temperatures. Using thermogravimetry and differential scanning calorimetry data and thermodynamic analysis, we have determined the optimal range of yttrium acetate nitrate compositions for the SHS of Y₂O₃ powder.     

Crystal structures of KBa2Nb5O15 and LaK2Nb5O15 with the TTB-type structure

Single crystals of two niobates, KBa₂Nb₅O₁₅ and LaK₂Nb₅O₁₅, were synthesized by high-temperature reaction and the crystal structures were determined by single crystal X-ray diffraction data. Although the space groups for these compounds were different (the non-centrosymmetrical space group P4bm (#100) for KBa₂Nb₅O₁₅ and the centrosymmetrical one P4/mbm (#127) for LaK₂Nb₅O₁₅), both compounds had the same tetragonal tungsten bronze-type (hereafter TTB-type) structure. The lattice parameters and R-factors of KBa₂Nb₅O₁₅ (LaK₂Nb₅O₁₅) were a = 12.533(2) (12.563(2)) and c = 4.0074(9) (3.9179(9)) Å, and R₁ = 0.040 (0.047) and wR₂=0.131 (0.120), respectively. From the crystal structural analysis, it was clarified that distribution of two large cations was different from each other in the way that K and Ba atoms in KBa₂Nb₅O₁₅ were distributed statistically at two crystallographic sites and K and La atoms in LaK₂Nb₅O₁₅ were ordered.