Photoconductivity Spectra of n-type CuInSe2 Single Crystals

Photoconductivity spectra of n-type CuInSe₂ single crystals are measured in the photon energy range hv = 0.75 – 3.1 eV and as a function of temperature in the range T = 80 – 320 K. It is found that the photoconductivity of as-grown crystals is a nearly pure surface effect, while sensitization of the crystal volume is observed only after sufficiently long annealing in the presence of powdered material. To explain the temperature dependence of the photoconductivity carrier trapping processes must be taken into account.     

Anomalien der physikalischen Eigenschaften von Sb2Se3-Kristallen

This paper presents the results of investigations of the d.c. conductivity, complex dielectric constants ϵ* = ϵ' – iϵ″ at 9.3 GHz, birefringence as well as the width of band gap versus temperature in Sb₂Se₃ single crystals. The anomalies in these properties were observed in the temperature range from 400 to 450 which are expected to be related with diffuse phase transition in this semiconductive chain structure compound.     

Optical properties of non‐centrosymmetric mixed crystals K2(La1‐x Cex)(NO3)5 · 2 H2O (x = 0.0 – 1.0)

Large single crystals of optical quality of the non‐centrosymmetric orthorhombic potassium rare earth nitrate mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O were grown at 38 °C from diluted HNO₃. For crystals with x = 0.0, 0.19, 0.38 and 0.66 refractive indices and their dispersion were determined with an error less than 1 · 10^–4 in the wavelength range 0.404 – 1.083 μm by the prism method. Phase matching conditions for collinear SHG frequency conversion were analysed in detail, including calculation of the effective nonlinear optical susceptibility. By an appropriate choice of the fraction x of cerium the mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O allow an adjustment of non‐critical type I phase matching conditions to a desired wavelength of the fundamental wave within the range 1.055(4) – 1.107(6) μm. Non‐critical type II phase matching can be tuned in the wavelength range 0.949(2) – 0.931(2) μm. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature‐tuned band gap energy and oscillator parameters of Tl2InGaSe4 semiconducting layered single crystals

The optical properties of Tl₂InGaSe₄ layered single crystals have been studied through the transmission and reflection measurements in the wavelength range of 500‐1100 nm. The analysis of room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 1.86 and 2.05 eV, respectively. Transmission measurements carried out in the temperature range of 10‐300 K revealed that the rate of change of the indirect band gap with temperature is γ = – 4.4 × 10^‐4 eV/K. The absolute zero value of the band gap energy was obtained as E_gi(0) = 1.95 eV. The dispersion of the refractive index is discussed in terms of the single oscillator model. The refractive index dispersion parameters: oscillator wavelength and strength were found to be 2.53 × 10^–7 m and 9.64 × 10¹³ m^–2, respectively. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of KTiOAsO<Subscript>4</Subscript> single crystals at 293 and 30 K

The unit cell parameters of KTiOPO₄ and KTiOAsO₄ single crystals are measured in the temperature range from room temperature to 20 K. It is found that the unit cell volume of the single crystals changes smoothly. With a decrease in temperature, the c parameter remains almost unchanged. In a certain temperature range, the linear temperature dependence of the a and b parameters is violated. An X-ray diffraction study of KTiOAsO₄ single crystals is performed at T = 293 and 30 K. With a decrease in temperature, the electron density in the channels of the structure undergoes a redistribution, suggesting that at room temperature the state of the potassium ions is characterized by the dynamic and static disordering. The nonuniformity of the distribution of the electron density at the junctions of TiO₆ octahedra and AsO₄ tetrahedra is significantly enhanced in relation to that at the corresponding junctions in the KTiOPO₄ structure. It has been experimentally established that the geometry of the tetrahedral anions makes a decisive contribution to the nonlinearity of KTiOAsO₄ single crystals.     

Thermodynamic Analysis of Urea Physical Vapour Transport

The vaporisation-condensation scheme of urea has been investigated in the temperature region below the melting point, in order to establish the thermodynamic reactions on which the physical vapour transport (PVT) of urea is based. By making use of both reported data and experimental results of MS, DTA, DTG, and HPLC analysis, it was shown that PVT relevant reactions are basically molecular sublimation and partial decomposition in solid biuret and ammonia. MS analysis of urea crystals and source residues have also shown that no decomposition can be observed in the growing crystals, unless reheated during growth. The temperature dependence of the decomposition pressure has been found to be: log₁₀P_NH3 [torr] = 38 – 13840/T [K]. The use of this relation in diffusive mass transport calculations brought to linear growth rate values not in disagreement with the experimental values found in closed tube PVT grown crystals.     

Preparation and some properties of thallium orthothioarsenate single crystals

Growing of large (Ø 25–30 mm, L = 50–60 mm) optically homogenous single crystals of Tl₃AsS₄ using the Bridgman-Stockbarger method is described. Tl₃AsS₄ is orthorhombic (Pnma), a = 8.85 ± 0.03, b = 10.86 ± 0.03, c = 9.18 ± 0.03 Å; z = 4; ϱ_x = 6.15 g · cm⁻³; ϱ_p = 6.15 ± 0,03 g · cm⁻³, T_m = 424 ± 3°C, Moh's hardness = 3, microhardness and ultrasonics velocity along x, y, z are 65–85 kg · mm⁻² and 2.16 – 2.37 · 10⁵ cm · sec⁻¹, respectively. The crystals possess perfect cleavage plane (010). Their transparency range is 0.6–12 microns. – Unsuccessful attempts to obtain Tl₃AsS₄ and its alloys in the vitreous state were taken. The possibilities of glass formation and boundaries of the vitreous region in the system Tl–As–S based on the characteristic features of the melt forming structural units are analyzed.     

Temperature dependences of the optical characteristics of ZnMgSe single crystals

The temperature dependences of the refractive index of wide-gap Zn_{1 − x} Mg _x Se (x ∼ 0.5) single crystals are measured. It is established that, in the temperature range 300–530 K, the value of dn/dT for such crystals grown by the vertical Bridgman method is 9.31 × 10⁻⁵ at λ = 0.63 μm and 5.29 × 10⁻⁵ at λ = 10.6 μm. The obtained values of the coefficients dn/dT for hexagonal Zn_{1 − x} Mg _x Se single crystals are close to the corresponding values for cubic ZnSe single crystals and are much lower than those for hexagonal CdS. Examples of practical application of single crystals of the ZnMgSe substitutional solid solution as a thermostable material for polarization optical elements in the IR range are given.     

The crystallisation of chromite-magnesiochromite spinels from a calcium magnesium aluminosilicate glass: Nucleation,crystal growth and final crystal sizes

The crystallisation of chromite-magnesiochromite spinels was studied from a calcium magnesium aluminosilicate glass (a simulated slag) containing 3 to 12 percent total iron oxides and 0.3 to 1.5 percent chromium(III) oxide, at temperatures from 1400° to 700 °C. – Spinel crystallisation occurred in glasses with 3–7 percent FeO and 0.7–1.1 percent Cr₂O₃. At temperatures 1100 °C and above, the nucleation was rapid and crystal numbers very high, at FeO contents above 3 percent and Cr₂O₃ contents above 0.7 percent; at 1056° and 1000 °C however, the crystal numbers reached some optimum values but then decreased as clinopyroxene crystals grew onto and enveloped the spinel microcrystals. In these glasses, the crystal lengths varied with growth time according to the relation, l_t = 2 k_g t^α = R_g1 t^α, where α = 0.7–1.0: this time dependence was a compromise between a relation for dendritic growth and one for facetted growth. The growth rates generally increased about five to seven times for 160 °C temperature rise: the energy of activation for the spinel crystal growth was then estimated as 180 ± 60 kJ mole⁻¹. – No spinel crystals were observed in glasses with more than 7 percent FeO content, only clinopyroxene crystals. Probably, these latter had nucleated rapidly and grown onto spinel microcrystals, while the spinel microcrystals were still of < 0.1 μm size.     

Growth of big single crystals of Sr2YRu1‐xCuxO6 from high temperature solutions

Single crystals of Sr₂YRu_1‐xCu_xO₆ (x = 0 ‐ 0.4) have been grown from PbO‐PbF₂ based solutions in the temperature range 1150 – 1350°C. A silicon carbide heating element furnace (with a recrystallized alumina tube lining) in a vertical configuration was used to grow the crystals in platinum crucibles. Conditions for the stable growth of big crystals have been investigated. The morphology of the crystals containing Cu was found to change from octahedral to cube octahedral as the growth temperature is increased from 1150 to 1350°C. Crystals measuring up to 4.5 mm across and 2.5 mm thick have been grown from 1250°C. The incorporation of Cu into the crystals was ascertained by EDS and x‐ray diffraction analysis. A diamagnetic transition which increased in magnitude and temperature with x was observed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamics of twin layer widening in In-Pb crystals

The authors studied mobility of boundaries of plane-parallel twin layers in In-0.2 wt.% Pb and In-2 wt.% Pb crystals in the temperature range 290–373 K when stresses are applied τ/G = (1.35 – 7) × 10⁻⁶ (G is the shear modulus). They found that lead concentration increase as well as dislocation structure deterioration result in lower boundary velocity for a constant stress. In In-2 wt.% Pb crystals, the boundary velocity is well describable as V_n = V₀(τ) × × exp [ − ΔH (τ)/kT] where V₀(τ) = Ae^ατ/G (A = 10⁻³ cm/s, α = 1.1 × 10⁶) τ ΔH(τ) is the activation energy depending on the stress, ranging under these circumstances from 0.33 to 0.43 eV. At present it is difficult to interpret the results at hand. The analysis allows only to assume that the change in the boundary movement activation energy for impure crystals as against that for pure ones can be associated with the impurity effect on the structure of the intermediate zone between the twin and the matrix. The dependence of the pre-exponential factor on the stress is probably due to the effect of the internal long-range stress field on sources of twinning dislocations. Comparison with data for calcite and pure indium shows that twin boundary mobility parameters and their dependence on the stress are governed by the crystal type and defect structure.     

Crystallization and optical properties of CaWO4 and SrWO4

Single crystals of calcium tungstate and strontium tungstate have been grown by double decomposition flux reaction technique using lithium chloride as flux. Growth conditions are optimized to synthesize well faceted crystals. Effect of primary and secondary flux density in the growth charge has been studied. Thermogravimetric study reveals that the grown crystals are highly stable in the temperature range 25 – 1000°C. Analysis of optical absorption normal to the ab‐plane in the spectral range of 200 – 800 nm reveals the true absorption edge, the nature of transition being the allowed indirect one at 4.60 eV and 4.56 eV respectively for CaWO₄ and SrWO₄. The crystals have been characterized by determining useful pertinent optical and dielectric parameters. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Hydrothermal Effect on Crystal Development and Electrical Conductivity of Li2CO3

Lithiumcarbonat was treated hydrothermally in the range of temperature from 80 °C to 600 °C. The Li₂CO₃-crystals of the starting material were monoclinic with the unit cell a = 8.39 Å, b = 5.00 Å, c = 6.21 Å, β = 114.5° and the space group C2/c (Zemann). During the increase of temperature the habit of the Li₂CO₃-crystals changed in the ranges of higher temperatures that they could be described as pseudocubic. In parallel with this development the electrical conductivity of the crystals also changed.     

Effective electro‐optic coefficient of (1–x)Pb(Zn1/3Nb2/3)O3–xPbTiO3 single crystals

Refractive indices and effective electro‐optic coefficient γ_c of (1–x)Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PZN‐xPT, x = 0.05, 0.09 and 0.12) single crystals were measured at 532 nm wavelength. Orientation and temperature dependences of the electro‐optic coefficient were investigated. Large electro‐optic coefficient (γ_c = 470 pm/V) was observed in [001]‐poled PZN‐0.09PT crystal. More importantly, γ_c of tetragonal PZN‐0.12PT is almost unchanged in a temperature range −20 ∼ 80 °C. The γ_c of PZN‐xPT single crystals are much higher than that of widely used electro‐optic crystal LiNbO₃ (γ_c = 20 pm/V). These results show that PZN‐xPT single crystals are very promising materials for electro‐optic modulators in optical communications.     

Pyroelectric Properties of Potassium and Rubidium Titanyl—Arsenate Single Crystals in the Temperature Range of 4.2–300 K

The temperature dependences of the pyroelectric coefficients of KTiOAsO₄ and RbTiOAsO₄ single crystals grown by flux crystallization have been investigated in the temperature range of 4.2–300 K. With an increase in temperature, superionic conductivity first arises in KTiOAsO4 (at T > 200 K) and then (at T > 270 K) in RbTiOAsO₄. This conductivity is much higher in the samples polarized at T = 4.2 K. An exponential change in the crystal resistivity along the polar direction is simultaneously observed. The results of measurements in the range of 4.2–200 K indicate larger values of pyroelectric coefficients when compared with potassium and rubidium titanyl-phosphate crystals. A correlation between the pyroelectric coefficients and a change in the lattice constants at isomorphic substitutions of K atoms for Rb and P atoms for As has been revealed within the symmetry approach.     

Plastische Verformung von Siliziumeinkristallen unterschiedlicher Ausgangsversetzungsdichte im Streckgrenzenbereich

Floating-zoned Silicon crystals orientated for single slip both dislocation-free and with grown-in dislocations (EPD₀ = 6,5 · 10⁴ cm⁻²) were dynamically deformed in compression in the temperature range 1120 … 1300 K up to the lower yield point. The dislocation structure of plastically deformed crystals (T = 1138 K; a₀ = 1,45 · 10⁻⁴ s⁻¹) was examined by etching and high-voltage electron microscopy. The crystals exhibit essential differences in deformation behaviour and in the resulting dislocation structure. Typical for the dislocation-free basic material are (i) an inhomogeneous deformation in the range of the upper yield point (ii) a greater portion of sessile lomer dislocations at the lower yield point in relation to the crystal with grown-in dislocations. The measured stresses were related to those values calculated from structure data by employing plasticity theory of diamond-like semiconductors.     

Single crystal synthesis and properties of lithium-gallium-, lithium-aluminium-oxide and mixed compounds (I) growing of LiGaO2-, LiAlO2- and LiAlxGa1−x crystals from fluxes

LiGaO₂ forms a single eutectic with PbO/B₂O₃ (molar ratio 9:4). A nearly linear slope of the liquidus curve is followed by a steep rise of the temperature coefficient of solubility. The solvent power at 1300°C is 0.35 g LiGaO₂/g PbO, B₂O₃; from 1000 to 1300°C there exist only poor differences in solubility of LiGaO₂ and LiAlO₂ in PbO/B₂O₃. LiGaO₂ crystals up to 1 p in weight grew spontaneously by slow cooling from fluxes or by evaporation of the solvent, those of about 1–1.5 p from seeds by cooling stirred fluxes. LiAlO₂ crystals are essentially smaller (6 mm). – By partial substitution of Ga₂O₃ by Al₂O₃ mixed crystals LiAl_xGa_1−xO₂ result. In the case of x ≦ 0.5 the coefficient of segregation remains ≦1. The al concentrations along the polar axis decrease by more than 25 p.c., perpendicular to [001] they keep constant till to the crystal surface. – Crystals show hypermorphism from mm2 to mmm. With high initial exceedings only {110} and {011}, with lower ones also {120}, {130}, {210} and {310} as well as the reduced {100}, {010} combinations are observed. – LiGaO₂ crystals grow by nucleous, sceletal or faceted growth resp. during the cooling period. – Primarily at 1270°C formed nuclei up to 1150°C grow to critical dimensions (≈0.5 mm) and develop to the main branch along [001]. Primary branches deflect to [010]. The convex secondary branches intergrow along (110), often including flux. With decreasing temperature a new crystallisation front is formed at the periphery leading to a stable faceted growth at about 1000°C.     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A new equation for the temperature dependence of density of saturated aqueous solutions of electrolytes

A new empirical three-parameter equation d = d₀ exp[β′(T – T₀)²] (where β′, d₀, and T₀ are constants for a salt) has been proposed to describe the dependence of density d (g/ml³) of saturated aqueous solutions of electrolytes on temperature T (K) in the whole range of temperature in which solubility increases or decreases with an increase in temperature.     

X-ray diffraction study of (TlInSe<Subscript>2</Subscript>)<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>(TlGaTe<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> crystal system

The crystallographic and dynamic characteristics of TlInSe₂ and TlGaTe₂ crystals have been studied by X-ray diffraction in the temperature range of 85–320 K. The temperature dependences of the unit-cell parameters a of TlInSe₂ and TlGaTe₂ crystals, as well as their coefficients of thermal expansion along the [100] direction, are determined. The concentration dependences of the unit-cell parameters a and c for (TlInSe₂)_{1 − x} (TlGaTe₂) _x crystals are measured. Anomalies are found in the temperature dependences of the unit-cell parameters a and, correspondingly, the coefficient of thermal expansion, indicating the existence of phase transitions in TlInSe₂ and TlGaTe₂ crystals.