Ferroelectric phase transitions in NH4HSeO4 crystals

Results are presented of measurements of spontaneous polarization, electric permittivity and electrical conductance of NH₄HSeO₄ crystals in three principal crystallographic directions from liquid nitrogen temperature to 320 K. NH₄HSeO₄ crystals exhibit ferroelectric properties in the a-axis direction between 106–250 K, whereas in the b-direction they are pyroelectrie over the entire temperature range. The calculated activation energy (1.42 eV) is indicative of semiconducting behavior.     

Anisotropic thermopower of the organic metal, β-(BEDT-TTF)2I3

Thermopower of the ambient pressure organic superconductor β-(BEDT-TTF)₂I₃ has been studied. Measurements performed on, respectively, crystals of needle formed morphology and on flake-like crystals with hexagon shape showed equal thermopower results. S was measured along the a-axis as well as along the b′-axis. Marked anisotropy is observed in the entire temperature region studied. The temperature dependence, as represented by dS/dT, is, however, nearly isotropic. On the basis of an analysis of anisotropic thermopower we attribute the isotropic part of S to a term depending on the bond-properties and the anisotropic part of S to the scattering mechanism. The analysis yields transfer integrals of the order of 0.12 eV along both a- and b′-axes.     

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).     

Effects of uniaxial pressure and annealing on the resistivity of Ba(Fe1−xCox)2As2

Single crystals of underdoped Ba(Fe_1−xCo_x)₂As₂ were detwinned by applying uniaxial pressure. The anisotropic in-plane resistivity was measured using the Montgomery method without releasing pressure. The resistivity along the a-axis shows metallic behavior down to 5 K, while the resistivity along the b-axis shows an insulator-like behavior in some temperature range. Annealing the sample radically reduces the residual resistivity for x=0, and at the same time the anisotropy becomes much smaller at low temperatures.     

One-dimensional electronic order in underdoped surface of YBa2Cu3Oy studied by STM

We have performed low-temperature scanning tunneling microscopy (STM) experiments on the cold-cleaved surface of YBa₂Cu₃O_y single crystals to study the nanoscale electronic order in high-T_c superconductors. STM images measured at low-bias voltage below ∼50 meV show the one-dimensional (1D) electronic modulation along the Cu-O bonds (parallel to the b-axis). The 1D electronic modulation does not have long-range order and the periodicity along the a-axis varies within the range ∼2a-4a depending on the position on the surface, indicating the glassy electronic order in the underdoped CuO₂ plane.     

Systematics of EPR spectra of GD3+ in some isostructural rare-earth trisulphate octahydrate hosts

X-band data on Gd³⁺ ions doping some isostructural single crystals of rare-earth trisulphate octahydrate [R₂(SO₄)₃·8H₂O] single crystals (RSH) have been obtained at room temperature for the hosts characterized by R = Pr, Nd, Sm, Eu, Yb and Y, and at liquid nitrogen and liquid helium temperatures for the hosts characterized by R = Pr, Sm, Eu and Y. The data are analyzed using a rigorous least-squares fitting procedure in which all resonant line positions obtained for various orientations of the external magnetic field are fitted simultaneously to the same spin Hamiltonian parameters. The intensities of the lines obtained at liquid helium temperatures indicate the absolute sign of the parameter b₂⁰ to be negative for R = Pr, Eu and Y, whereas for the Sm host the sign of b₂⁰ is found to be positive. While the parameter b₂⁰ does not exhibit a clear cut linear dependence upon the host ion radius, the parameter b₂⁰ is found to behave approximately linearly as a function of the host-ion radius. On the other hand, the zero-field splitting is found to be a linear function of the host ion radius at all three temperatures—room, liquid nitrogen and liquid helium.A comparison is presented of the systematics of the EPR spectra for the RSH hosts with those for some other isostructural rare-earth hosts.     

Fine and hyperfine structure in 14N2+

The fine and hyperfine structure of ¹⁴N₂⁺ has been observed in 31 rotational lines of the (0, 1) band of the B²Σ_u⁺-X²Σ_g⁺ system using the method of Doppler-tuned laser-induced fluorescence on a molecular ion beam. The spin-rotation constants (γ′, γ″, γ′_J) are in good agreement with other experiments in which the hyperfine structure was not resolved. The Fermi-contact (b′_F, b″_F) and dipolar (t′, t″) hyperfine coupling constants are in reasonably good agreement with values calculated from ab initio wavefunctions. The least-squares experimental values in MHz are γ″ = 279.1(6), γ′ = 726.4(6), γ′_J = ?0.0460(2), b″_F = 105(4), b′_F = 708(3), t″ = 49(6), and t′ = 26(5).     

Investigations of the spin-Hamiltonian parameters and defect structures for Gd ions in YMO4 (M=V, P, As) crystals

A 56×56 energy matrix containing the ground multiplet ⁸S_7/2 and the excited multiplets ⁶L_7/2 (where L=P, D, F, G, H, I) for 4f⁷ ion Gd³⁺ at a tetragonal crystal field and under an external magnetic field is constructed. By diagonalizing the energy matrix, the spin-Hamiltonian parameters (g factors g_‖, g_⊥ and zero-field splittings b₂⁰, b₄⁰, b₄⁴, b₆⁰, b₆⁴) for Gd³⁺ ion at the tetragonal Y³⁺ site of YMO₄ (M=V, P, As) crystals are calculated. The calculated results are in reasonable agreement with the experimental values. The defect structures of Gd³⁺ centers in YMO₄ crystals are estimated from the calculation. The results are discussed.     

Ferroelectric properties of partly deuterated NH4HSeO4 crystals

Partly deuterated NH₄HSeO₄ crystals were grown from solutions containing 10, 20, 30, 40, 50 and 60% molar deuterium. The deuteration process leads to an increase in the phase transition temperatures. The extrapolated value of ΔT_c(∞) for completely deuterated crystals is 25 K. The I2 ? B2(C³₂) (if a axis is parallel to [110]) symmetry and the ferroelectric transition related to it is observed only in crystals growing from solution containing less than 50% deuterium. The crystals growing from solution containing more than 50% deuterium have a P2₁2₁2₁(D⁴₂) symmetry.     

Magnetization and magnetic susceptibility of single crystals of HoTiO3 and ErTiO3

Bulk magnetization measurements have been performed on single crystals of HoTiO₃ and ErTiO₃. The easy direction of magnetization is along the b-axis for HoTiO₃ and along the c-axis for ErTiO₃ with respect to the Pbnm chemical cell. These findings are in qualitative agreement with the results of two independent powder neutron diffraction studies. The saturation magnetic moments at 4.2 K along the easy axes are 7.3(2)μ_B per formula unit for HoTiO₃ and 6.9(2)μ_B for ErTiO₃. In addition, single crystal susceptibility data were analyzed using the theory of Boutron to yield values for the Heisenberg exchange coupling and the second-order crystal field terms B⁰₂ and B²₂.     

Studies of the electrical properties of nearly perfect K2ZnCl4 single crystals as measured during commensurate incommensurate-paraelectric phase transitions

Electrical conductivity and dielectric measurements were carried in the temperature range covering the commensurate ferroelectric-incommensurate-paraelectric normal phases (300-600 K) for the three main crystallographic axes of K₂ZnCl₄ single crystals. The values of activation energies in the three phases were calculated and discussed. A thermal hysteresis of about 12 K is observed which deduce the presence of first order transition for the lock-in ferroelectric transition at T_c=404 K. Conductivity anomalies were observed in both ferroelectric and paraelectric phases. The conduction mechanism was discussed. The suggested occurrence of discommensuration in K₂ZnCl₄ crystals upon the lock-in transition in contrast with conductivity and dielectric results explains the anomalous behavior for the b-axis measurements. The orientation of these discommensuration was discussed on a view of projection in the three standard crystallographic directions.     

Electronic structure and transport of Ca3Co2O6 and Ca3CoNiO6

We have calculated the band structure of Ca₃Co₂O₆ and Ca₃CoNiO₆ by using the self-consistent full-potential linearized augmented plane-wave method within density function theory and the generalized gradient approximation for the exchange and correlation potential. The spin-orbit interaction is incorporated in the calculations using a second variational procedure. The relation of these band structure calculations to thermoelectric transport is discussed. The results illustrate that transport is highly anisotropic with much larger mobility in the a-b plane than out of the a-b plane, and the introduction of Ni in Ca₃Co₂O₆ alters its electronic structure and its thermoelectric transport properties.     

Magnetic structures in the Ca2Fe2−xAlxO5 system-II

Recent structure analyses of crystals with different compositions in the Ca₂Fe_2?xAl_xO₅ system have led to a reinterpretation of the magnetic ‘phase diagram’ of this system. In the composition range 0 ? x ? 1, there are at least three and possibly four different magnetic structures. At room temperature, and between x = 0·00 and x less than but near 0·60 (the exact boundary is not known), the magnetic structure belongs to magnetic space group Pcm′n′; in a narrower range, approximately 0·57 ? x ? 0·65, the magnetic space group is I_pb′m′2; for x greater than about 0·80, the magnetic space group is I_pbm′2′. There is a substantial region of x and T (at room temperature 0·65 ? x ? 0·80), for which our experimental results cannot distinguish between two possibilities: either both the I_pb′m′2 and I_pbm′2′ structures coexist with spin-flipping as x or T changes or there is a continuous rotation of the spins with changing x or T. In the latter case, the most probable single magnetic space group in this region is C_pm′; with increasing x or T the transitions occur by way of I_pb′m′2 → C_pm′ → I_pbm′2′.     

The large anisotropy of the magnetic and transport properties in the Ba5Co5ClO13 single crystal

In this Letter, the single crystals of Ba₅Co₅ClO₁₃ were grown by the flux method successfully. Their structure, magnetic and transport properties were studied. A large anisotropy of the magnetic and transport properties has been detected in this compound. Below the TN∼108 K, the magnetic susceptibility exhibits an antiferromagnetic peak in χc and an upturn transition in χab. We suggest that this behavior is consistent with the competition of the ferromagnetic (FM) intra-blocks coupling and antiferromagnetic (AFM) inter-blocks coupling in this compound. The temperature dependence of the resistivity displays a hump in ρab and a kink in ρc around TN, suggesting the strong coupling between the transport and magnetic properties. Above and below the transition, the transport properties in ab plane follow the three-dimensional (3D) variable range hopping (VRH) mechanism.     

The temperature dependence of the angular variation of,and the critical point exponent for the EPR linewidth in the two-dimensional canted antiferromagnetic (C2H5NH3)2MnBr4: Evidence for a structural phase transition

The angular variation of the EPR linewidths in single crystals of (C₂H₅NH₃)₂MnBr₄ has been measured as a function of temperature. The angular dependence is well characterized by δH(θ) = a + b(3 cos²θ ? 1) + c(3 cos²θ ? 1)². The temperature dependence of the expansion coefficients is reported, and the effect of critical point fluctuations near the Néel temperature as well as a linear temperature dependence at high temperature are observed. A sharp decrease in linewidths at 160°K is attributed to a structural phase transition. The Néel temperature is determined to be 46°K (± 1°) from linewidth measurements of a powder sample. The linewidths diverge exponentially near the Néel temperature with a critical point exponent of 1.5.     

Electron paramagnetic resonance of Gd3 in YCl3·6H2O

The electron paramagnetic resonance spectrum of Gd³⁺ in YCl₃·6H₂0 with $\text{1}\text{100}$ dilution of Gd/Y ions, has been studied with an X-band spectrometer at 295, 77 and 1.77°K and with a K-band spectrometer at 295 and 77°K. The individual values of all the parameters are evaluated from the data at the three temperatures. In particular, the following values for the g-tensor and the zero-field splitting parameters b₂⁰ and b₂² are obtained from X-band data: at 295°K, g_zz = 1.994±0.005, g_xx = 1.992±0.005, g_yy = 1.997±0.005, b₂⁰ = 1.898 ±0.015 GHz, b₂² = ?2.247 ± 0.015GHz; at 77°K, g_zz = 1.999±0.008, g_xx = 2.000±0.008, b₂⁰= 1.978 ±0.022 GHz, b₂² = ?1.574±0.022GHz; at 1.77°K, g_zz = 2.002±0.010, g_xx = 1.990 ±0.010, b₂⁰ = 2.011 ± 0.025 GHz, b₂² = ?1.650 ±0.025 GHz. (The K-band values are found to be consistent with the X-band values). From the angular dependence of the data in the ZX plane (i) the angle X₀ which the Z axis makes with the a vector of the unit cell, is determined to be 58.00 ±0.25° and (ii) the existence of pseudo-symmetry axes at ±5° from the Z axis in the ZX plane as found by heat capacity and specific heat data has been confirmed. An estimate is also made of the extent of admixture of the excited ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ state with the ground state ${}^8\text{S}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$.     

Dependence of high electric-field-induced strain on the composition and orientation of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals

Electric-field-induced strain behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) crystals with different orientations and compositions was investigated for use as electromechanical actuators. Crystallographically, high strains with low hysteresis were achieved for 〈001〉 oriented rhombohedral crystals (29%≤x≤31%) near a morphotropic phase boundary, rather than 〈110〉 and 〈111〉. Domain instability could explain inferior strain levels and large hysteresis for 〈110〉 and 〈111〉 oriented crystals. Ultrahigh strain levels up to 1.8% could be achieved for 〈001〉 oriented PMNT crystals, being related to an E-field induced phase transition. −2 kV/cm negative E-field can be applied to PMNT ferroelectric material with low hysteresis. High strain with low hysteresis makes PMNT crystals promising candidates for high performance solid-state actuators.     

Superconducting properties of Sm0.33Eu0.33Gd0.33Ba2Cu3Oy films by metal-organic deposition using metal 2-ethylhexanates

We have prepared Sm_0.33Eu_0.33Gd_0.33Ba₂Cu₃O_y (SEGBCO) films on LaAlO₃ single-crystal substrates by metal-organic deposition using 2-ethylhexanate solutions which contain no fluorine. The SEGBCO film fired at 850 °C under a low oxygen partial pressure of 2 × 10⁻⁶ atm exhibited strong c-axis oriented X-ray diffraction peaks and weak a/b-axis oriented peaks of the SEGBCO phase, and had a granular surface. High resolution cross-sectional transmission electron microscope images indicated the epitaxial growth of the SEGBCO film on the substrate with overgrowth of a/b-axis oriented grains. The critical temperature and critical current density values of the SEGBCO film was 86.5 K and 1.29 MA/cm², respectively, at 77.3 K at the self-field.     

A nuclear magnetic resonance study of the structural properties and molecular motions of Li2KH(SO4)2 and LiKSO4 single crystals

The structural properties and relaxation mechanisms of Li₂KH(SO₄)₂ crystals were determined using the temperature dependences of NMR spectra and the spin-lattice relaxation times (T₁) of their ¹H, ⁷Li, and ³⁹K nuclei. The results obtained were compared with the previously reported physical properties of LiKSO₄ crystals. The substitution of the potassium ions with protons in the LiKSO₄ crystals were variations in the phase transition temperatures, and the non-appearance of ferroelastic properties. The ⁷Li T₁ for the Li₂KH(SO₄)₂ crystals was much shorter than the ⁷Li T₁ for the LiKSO₄ crystals, and these findings indicate that the presence of the protons in Li₂KH(SO₄)₂ causes the Li ions to move with greater freedom.     

Electron spin resonance studies on γ-irradiated KMnO4

Electron spin resonance (ESR) studies have been carried out on the radicals produced by the γ-irradiation of single crystals of KMnO₄.Analysis of the data yields at least two paramagnetic species. The first radical is produced by room temperature irradiation and gives a single line for each of two inequivalent magnetic sites. There is no resolvable hyperfine structure and the g tensor for the species is given by, g_b = g_μ′ = 2·0176, g_x′ = 2·0020, g_z′ = 2·0112. The spectrum is tentatively assigned to the O₃^? radical although MnO₂ and MnO₄ are also possibilities.The second radical is produced by irradiation at 77°K and the spectrum disappears irreversibly at slightly higher temperatures. Analysis of the very complicated spectra yields, g_b = 1·9617, g_x = 1·9452, g_u = 1·9940, A_b = 386 MHz, A₂ = 87 MHz, A₃ = 20 MHz. This spectrum is assigned to the MnO₄^?2 radical. The relationship of the radicals observed to the effect of high energy radiation on the decomposition of KMnO₄ in the light of current solid state theory is discussed.