DC conductivity studies in K3Na(SeO4)2 single crystals

DC electrical conductivity studies were carried out along the three crystallographic axes for Tripotassium sodium diselenate (K₃Na(SeO₄)₂ or KNSe). Earlier studies of phase transition in this crystal show successive phase transitions at 334 K, 346 K, 730 K, and 758 K. In this paper we report the dc electrical conductivity measurements in the temperature region 303 K – 430 K along a, b and c – axes. An anomaly in conductivity was obtained around 341 K and another one around 333 K. These can be attributed as due to phase transitions in this crystal. A strong anomaly also has been observed along the c‐axis and comparatively week one along a and b axes around 395 K for the first time. This can be due to newly observed phase transition in the crystal. DSC taken for the sample also shows endothermic peak supporting the occurrence of newly observed phase transition. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Superconducting Transition of (TMTSF)2CLO4 in Magnetic Fields

Abstract

Superconducting transition of (TMTSF)₂ClO₄ was studied by conductivity measurements along the most conductive a-axis in magnetic fields applied along three different principal crystallographic axes. The GL coherence lengths at OK along the a-, b-, and c*-axes, ?_a(0)≈ 600A, ?(0) ≈ 540A, and ?_c*(0) ≈ 60A were obtained from the measurements of the temperature dependence of the upper critical field H_C2 near the transition temperature. The anisotropy is discussed in terms of the dimensionality arising from the crystal structure and of the conductivity anisotropy in the normal state.     

Principal Electrical Conductivities in the Organic Conductors TEA.(TCNQ)2 and TTF.TCNQ: The Microwave Approach

Abstract

We describe a microwave technique to measure the directions and magnitude of the principal electrical conductivities and permittivities of organic conductors. The method is applied to single crystals of triethylammonium-bis 7,7,8,8-tetracyano-p-quinodimethane (TEA.(TCNQ)₂) and of tetrathiafulvalenium-7,7,8,8-tetracyano-p-quinodimethane (TTF.TCNQ). For the former, the apriori set of principal axes (a*, (a*∧c), c) is confirmed with principal conductivities of 430, 5.3 and 0.41–0.77 Ω^?1m^?1 respectively. The room temperature permittivities have been measured for the first time (ε*_α ～ 5.4–5.5, ε*_α∧c ～ 7.5). For the latter it is clearly shown that the principal electrical axes are (a, b, c*) and, in contrary to earlier d.c data, we observe σ_c· < σ<a which is more consistent with the anisotropy of interchain interactions in this compound. The observed transverse and longitudinal anisotropies (～3.3 10² and 2.8 10⁴ respectively) are larger than believed up to now.     

Thermal Expansion of HMX

Abstract  

Thermal expansion of the β-phase of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (β-HMX, C₄H₈N₈O₈) was studied in the temperature range of −150 to 30 °C. β-HMX is monoclinic (a = 6.5255(10) ?, b = 11.0369(18) ?, c = 7.3640(12) ?, and β = 102.67(1)°), space group P2₁/n. On cooling from room temperature to −150 °C the crystal under goes an anisotropic contraction with the a-axis virtually unchanged while the b and c axes contract by approximately 1.8 and 0.6% respectively. The disproportionate change in the a and c axes results in approximately a 0.4% change in the β angle. Despite the large differences in expansion along the different axes no phase change was observed.     

Cd‐Doping Effects on The Properties of Polycrystalline α‐In2Se3 Thin Films

The X‐ray diffraction has revealed that the polycrystalline hexagonal structured α‐In₂Se₃ thin films grown at substrate temperature of 200 °C with the unit cell parameters a = 4.03 Å and c = 19.23 Å becomes polycrystalline hexagonal structured InSe with a unit cell parameters of a = 4.00 Å and c = 16.63 Å by Cd‐doping. The analysis of the conductivity temperature dependence in the range 300‐40 K revealed that the thermionic emission of charged carriers and the variable range hopping are the predominant conduction mechanism above and below 100 K, respectively. Hall measurements revealed that the mobility is limited by the scattering of charged carriers through the grain boundaries above 200 K and 120 K for the undoped and Cd‐doped samples, respectively. The photocurrent (I_ph) increases with increasing illumination intensity (F) and decreasing temperature up to a maximum temperature of ∼100 K, below which I_ph is temperature invariant. It is found to have the monomolecular and bimolecular recombination characters at low and high illumination intensities, respectively. The Cd‐doping increases the density of trapping states that changes the position of the dark Fermi level leading to the deviation from linearity in the dependence of I_ph on F at low illumination intensities.     

High temperature x‐ray diffraction studies of zirconia thin films prepared by reactive pulsed laser deposition

Zirconium oxide thin films have been deposited on Si (100) substrates at room temperature at an optimized oxygen partial pressure of 3x10^‐2 mbar by reactive pulsed laser deposition. High temperature x‐ray diffraction (HTXRD) studies of the film in the temperature range room temperature‐1473 K revealed that the film contained only monoclinic phase at temperatures ≤ 673 K and both monoclinic and tetragonal phases were present at temperatures ≥ 773 K. The tetragonal phase content was significantly dominating over monoclinic phase with the increase of temperature. The phase evolution was accompanied with the increase in the crystallite size from 20 to 40 nm for the tetragonal phase. The mean thermal expansion coefficients for the tetragonal phase have been found to be 10.58x10^‐6 K^‐1 and 20.92x10^‐6K^‐1 along a and c‐axes, respectively. The mean volume thermal expansion coefficient is 42.34x10^‐6 K^‐1 in the temperature range 773‐1473 K. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New Ln[B6O9(OH)3] borates (Ln = Sm-Lu): Structure, properties, and structural relation to cationic Li4[B7O12]Cl conductors (Li-Boracites)

Crystals of new rare earth borates of the composition Ln[B₆O₉ (OH)₃] (Ln = Sm-Lu), sp. gr. R3c are synthesized under hydrothermal conditions. Their crystal structures are determined on single crystals with Ln = Ho, Gd without preliminary determination of their chemical formulas. The polar anionic framework of the crystals consists of BO₃ triangles and BO₄ tetrahedra and has wide channels along the threefold axis of the structure, which are similar to the channels along the a, b, and c axes in cubic Li₄[B₇O₁₂]Cl boracite with Li conductivity. Rare earth atoms are arranged in the structure over the cubic F pseudolattice, whereas the analogous positions in Li boracites are filled with Cl anions. The squared optical nonlinearity of the new crystals is comparable with the nonlinearity of quartz, whereas the electrical conductivity in borates at 300°C exceeds 10⁻⁶ S/cm. __________ Translated from Kristallografiya, Vol. 49, No. 4, 2004, pp. 681–691. Original Russian Text Copyright ? 2004 by Belokoneva, Ivanova, Stefanovich, Dimitrova, Kurazhkovskaya.     

Crystal structure and phase transition of single crystalline CsNH2SO3

Differential scanning calorimetry (DSC) and X‐ray diffraction measurements have been performed on cesium sulfamate CsNH₂SO₃ single crystal. Two distinct endothermic peaks in the DSC curves are observed at 330 and 436 K. It is pointed out that the peak at 330 K is attributed to the structural phase transition, and the other peak at 436 K is associated with the thermal decomposition of the crystal. The structures in room‐ and high‐temperasture phases are determined, and the space group of the sample crystal is found to change from monoclinic P 2₁/c to orthorhombic Pnma. The structure of the room‐temperature phase consists of two different types of N‐H···O hydrogen bond, but in the high‐temperature phase there is no specific hydrogen bond between the NSO₃ pseudo‐tetrahera. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal Growth and Properties of the Compounds CuGa3Se5 and CuIn3Se5

CuIn₃Se₅ and CuGa₃Se₅ uniform single crystals 12 mm in diameter and 40 mm in length with the chalcopyrite‐related structure were prepared by directed crystallization of the melt. The melting points of these compounds were defined by means of the differential thermal analysis (DTA). The lattice parameters a and c as well as the axial thermal expansion coefficients α_a and α_c were determined as a function of temperature in the range from 90 to 650 K by the X‐ray diffraction method (XRD). It is found that for both the compounds the coefficients of expansion along the a ‐axis are larger than those along the c ‐axis over the entire temperature range studied.     

Low-temperature X-ray studies of a [(CH3)2NH2]2 · CuCl4 crystal

The a, b, c lattice parameters of a [(CH₃)₂NH₂]₂ · CuCl₄ crystal have been measured by the X-ray diffraction method within the temperature range of 100–300 K. The temperature dependences of thermal expansion coefficients α_a = f(T), α_b = f(T), and α_c = f(T) along the principal crystallographic axes and thermal expansion coefficient of the unit-cell volume αV = f(T) are determined. It is found that all the three parameters, a, b, and c, vary with temperature in a complicated way and show jumplike anomalies in the a = f(T), b = f(T), and c = f(T) curves at phase-transition temperatures T _c1 = 255 K and T _c2 = 279 K. An incommensurate phase with the modulation wave vector q _i = (1/2 + δ)(a* + c*) is revealed in the temperature range 279–296 K. It is shown that the incommensurability parameter δ increases with an increase in temperature.     

Electrical conductivity of sulfamic acid single crystals

Single crystals of sulfamic acid have been grown by the method of slow evaporation at constant temperature. DC electrical conductivity was measured in the temperature range 300 ‐ 440 K along a, b and c‐axes. Conductivity measurements show slope change near 330 K and 410 K. The slope change observed around 330 K may be attributed as due to a phase transition which has been well supported by the DSC and DTA measurements. Slope change observed around 410 K is attributed as the onset of the thermal decomcoposition as evidenced by TGA curve. TGA studies show the crystal is very stable up to 440 K. Activation energies for the conduction process are calculated for all measured crystallographic directions. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoelectronic and electrical properties of CuIn5S8 single crystals

To identify the impurity levels in CuIn₅S₈ single crystals, the dark electrical conductivity and photoconductivity measurements were carried out in the temperature range of 50–460 K. The data reflect the intrinsic and extrinsic nature of the crystals above and below 300 K, respectively. Energy band gaps of 1.35 and 1.31 eV at 0 K and 300 K, were defined from the dark conductivity measurements and the photocurrent spectra, respectively. The dark and photoconductivity data in the extrinsic temperature region reflect the existence of two independent donor energy levels located at 130 and 16 meV. The photocurrent‐illumination intensity dependence (F) follows the law I_phαF^γ, with γ being 1.0, 0.5 and 1.0 at low, moderate and high intensities indicating the domination of monomolecular, bimolecular and strong recombination at the surface, respectively. In the intrinsic region and in the temperature region where the shallow donor energy level 16 meV is dominant, the free electron life time, τ_n, is found to be constant with increasing F. In the temperature region 140 K < T < 210 K, the free electron life time increases with increasing illumination intensity showing the supralinear character. Below 140 K, τ_n decrease with decreasing illumination intensity. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Domain structure in strontium tetraborate single crystal

Partially ordered domain structure is discovered for the first time in strontium tetraborate single crystal that is not known to be a ferroelectric. Domains are visualized by etching and are shown to have the form of sheets with domain walls perpendicular to a-axis. The structure is rather well-ordered along b and c crystallographic axes of the crystal but highly randomized along a-axis.     

Electron‐phonon short‐range interactions mobility and p‐ to n‐type conversion in TlGaS2 crystals

The conductivity type conversion from p ‐ to n ‐type at a critical temperature of 315 K in TlGaS₂ crystals is observed through the Hall effect measurements in the temperature range of 200–350 K. The analysis of the temperature‐dependent electrical resistivity, Hall coefficient and carrier concentration data reveals the extrinsic type of conduction with donor impurity levels that behave as acceptor levels when are empty. The data analysis allowed the calculation of hole and electron effective masses of 0.36m ₀ and 0.23m ₀, respectively. In addition, the temperature‐dependent Hall mobility is found to decrease with temperature following a logarithmic slope of ∼1.6. The Hall mobility in the n ‐region is limited by the electron‐phonon short‐range interactions scattering with an electron‐phonon coupling constant of 0.21. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of single crystals of the layered copper hydroxide acetate Cu2(OH)3(CH3COO)·H2O

Single‐crystals of the layered copper hydroxide acetate Cu₂(OH)₃(CH₃COO)·H₂O were synthesized by heating copper acetate solution at 60 °C. The standard synthesis of the title compound based on slow titration of copper acetate solution with NaOH yielded materials with worse morphology and an additional phase present. The obtained products were characterized with powder X‐ray diffraction, high temperature powder X‐ray diffraction, scanning electron microscopy and infrared spectroscopy. The crystal structure was determined from single‐crystal X‐ray diffraction data, collected both at 120 K and at 293 K. The title compound crystallizes in the monoclinic botallackite‐type layered structure, space group P 2₁, with the lattice parameters a = 5.5776(3) Å, b = 6.0733(2) Å, c = 18.5134(8) Å, β = 91.802(4)° and a = 5.5875(4)Å, b = 6.0987(4) Å, c = 18.6801(10)Å, β = 91.934(5)° for 120 K and for 293 K, respectively. Acetate groups and water molecules are interlayered between corrugated sheets of edge‐sharing CuO6 octahedra exhibiting strong distortion resulted from the Jahn‐Teller effect. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Properties,Conductivity and Structure of the DTT-TCNQ CT Complex

Abstract

The crystal structure, the optical spectra and electrical conductivity of dithieno(3,2-b; 2′,3′-d)thiophene-tetracyanoquinodimethane (DTT-TCNQ) charge-transfer complex have been measured. DTT-TCNQ crystallizes in the monoclinic space group P2₁/c with a = 7.206(2), b = 7.574(2), c = 32.324(9), β - 92.18(4)°, Z - 4, and the donor and acceptor molecules are arranged in alternated stacks.

The low conductivity (a = 10^?2 S cm^?1 for the single crystal, along the stacking axis a) is characteristic of a semiconductor with activation energy of .61-.76 eV, and is related to the alternate stack structure.

Despite the poor condctivity of the DTT-TCNQ CT complex we estimated, from structure and IR data, a low degree of ionicity (p = .2–.3) which characterizes the DTT molecule as an interestign donor.

The polarized IR spectra shows the effect of vibronic activation of some of the a_g modes of TCNQ.     

Anisotropy of the ionic conductivity of CsCu2Cl3 single crystals

The conductivity of CsCu₂Cl₃ single crystals (orthorhombic system, sp. gr. Cmcm) has been investigated for different electric-field directions, perpendicular to the crystallographic c axis and along it, in the temperature range 390–530 K. The increase in conductivity with temperature is due to the ion-carrier transport with activation energies E _a = 0.65 and 0.80 eV for the directions perpendicular to and along the crystallographic axis, respectively. The anisotropy of the crystal ionic conductivity is found to be σ_⊥c /σ_∥c ≈ 40 at 435 K. The thermally activated contribution to the conductivity in the CsCu₂Cl₃ structure is determined by the transport of Cu⁺ ions.     

X-ray Diffraction and DFT Studies of 2-Methoxy-5-phenylaniline

Abstract 2-Methoxy-5-phenylaniline, a promissor monomer for PANI studies, has been characterized by single-crystal X-ray diffraction at two temperatures: orthorhombic, space group P2₁2₁2₁, Z = 12 with a = 5.9900(2) ?, b = 20.4873(6) ?, c = 26.3727(8) ? and R = 0.0868 for 293(2) K and a = 5.8337(9) ?, b = 20.4428(31) ?, c = 26.0773(40) ? and R = 0.0669 for 120(2) K. There are three independent molecules in the unit cell. One of them is approximately planar, the other two have the phenyl rings rotated. At room temperature the two latter molecules are joined in dimers through H-bonds and at low temperature the same molecules are joined in columns that run along the a-axis. Index Abstract X-ray Diffraction and DFT Studies of 2-Methoxy-5-phenylaniline Ana T. Marques, Joana A. Silva, Manuela Ramos Silva, Ana Matos Beja, Licinia L. G. Justino, Abilio J. F. N. Sobral 2-Methoxy-5-phenylaniline, a promissor monomer for PANI studies, has been characterized by single-crystal X-ray diffraction at 293(2) K and 120(2) K. The three independent molecules in the unit cell show different conformations and establish distinct intermolecular H-bonds.      

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.     

Annealing effect on electrical and photoconductive properties of Si implanted GaSe single crystal

GaSe single crystals grown by Bridgman method have been doped by ion implantation technique. The samples were bombarded in the direction parallel to c‐axis by Si ion beam of about 100 keV to doses of 1 × 10¹⁶ ions/cm² at room temperature. The effects of Si implantation with annealing at 500 and 600 °C on the electrical properties have been studied by measuring the temperature dependent conductivity and photoconductivity under different illumination intensities in the temperature range of 100–320 K. It is observed that Si implantation increases the room temperature conductivity 10⁻⁷ to 10⁻³ (Ω‐cm)⁻¹ depending on the post annealing temperature. The analysis of temperature dependent conductivity shows that at high temperature region above 200 K, the transport mechanism is dominated by thermal excitation in the doped and undoped GaSe samples. At lower temperatures, the conduction of carriers is dominated by variable range hopping mechanism in the implanted samples. Annealing of the samples at and above 600 °C weakens the temperature dependence of the conductivity and photoconductivity. This indicates that annealing of the implanted samples activates Si‐atoms and increases structural deformations and stacking faults. The same behavior was observed from photoconductivity measurements. Hence, photocurrent‐illumination intensity dependence in the implanted samples obeys the power low I_pc ∝ Φⁿ with n between 1 and 2 which is an indication of continuous distribution of localized states in the band gap. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)