Coexistence of the relaxor-like and ferroelectric behavior in K1-xLixTaO3

ABSTRACT

The results of low-temperature linear and nonlinear susceptibilities, polarization measurements and the dc electric field dependence of the dielectric properties of the lithium-doped potassium tantalate K_1-xLi_xTaO₃, x = 0.034 (KLT-3.4%Li) solid solution are presented. The coexistence of the relaxor-like and ferroelectric behavior and different mechanisms leading to either of them are discussed. The observed ferroelectric phase transition is of the first-order type with temperature hysteresis. This transition is due to the off-center motions of Ta ions in the octahedral environment of oxygen ions. Clusters of Li⁺ ions produce a relaxor-like behavior and random electric field. This field reduces the depolarization field and allows off-center motions of Ta ions and an appearance of spontaneous polarization.     

7Li NMR study on Li+ ionic diffusion and phase transition in LixCoO2

The temperature dependence of the spin-lattice relaxation time, T₁ and the line width of the ⁷Li nucleus were measured in delithiated Li_xCoO₂ (x = 0.6, 0.8, 1.0). Two different relaxation behaviors were observed in the temperature dependence of T₁^− 1 in a x = 0.8 sample. These would have arisen from inequivalent Li sites in two coexisting phases; an original hexagonal (HEX-I) and a modified hexagonal (HEX-II) phase in the x = 0.8 sample. We analyzed using a phenomenological non Debye-type relaxation model. Motional narrowing in the line width was observed in each sample, the result revealing that Li⁺ ions begin to move at low temperature in samples with less Li content. It was found that the activation energy associating with Li⁺ ion hopping in the HEX-II phase is smaller than that in the HEX-I phase. These results show that the HEX-II phase produced in the Li deintercalation process would be suitable for Li⁺ ionic diffusion in multi-phase Li_xCoO₂, and it is expected that this would enable fast ionic diffusion. Li⁺ ionic diffusion related to phase transition is discussed from ⁷Li NMR results.     

Electric field dependence of the dielectric susceptibility in K1−xLixTaO3

Results are presented for the dielectric function $\text{ε1 = ε}{}_1\text{+ iε}{}_2$ in K_1?xLi_xTaO₃ in the frequency range 10 < f < 10⁶ Hz and for several fields. The data are analysed in terms of dielectric relaxation, and it is shown that the electric bias field modifies the relaxation behaviour drastically.     

Phase transition and ferroelastic property studied by using the Cs nuclear magnetic resonance in a CsHSO4 single crystal

The ¹³³Cs spin-lattice relaxation time in a CsHSO₄ single crystal was measured in the temperature range from 300 to 450 K. The changes in the ¹³³Cs spin-lattice relaxation rate near T_c1 (=333 K) and T_c2 (=415 K) correspond to phase transitions in the crystal. The small change in the spin-lattice relaxation time across the phase transition from II to III is due to the fact that during the phase transition, the crystal lattice does not change very much; thus, this transition is a second-order phase transition. The abrupt change of T₁ around T_c2 (II-I phase transition) is due to a structural phase transition from the monoclinic to the tetragonal phase; this transition is a first-order transition. The temperature dependences of the relaxation rates in phases I, II, and III are indicative of a single-phonon process and can be represented by T₁⁻¹=A+BT. In addition, from the stress-strain hysteresis loop and the ¹³³Cs nuclear magnetic resonance, we know that the CsHSO₄ crystal has ferroelastic characteristics in phases II and III.     

Ionic lithium conductivity in sulphur base glasses. 7Li NMR study of xLi2S−(1−x)GeS2 system

The lithium mobility in glasses of composition xLi₂S?(1?x)GeS₂ has been followed by c.w. (for x = 0.3; 0.4 and 0.5) and pulsed NMR (for x = 0.3 and 0.5) between ? 150 and + 280°C.The second moment of the resonance line of ⁷Li(0.89–1.51 G²) is proportional to the molar fraction of Li₂S, which may be correlated to an homogeneous Li nuclei distribution.The resonance line profiles and their thermal evolution seem to show that some Li⁺ ions do not participate in the conduction.Thermal variation of the spin-lattice relaxation time T₁, shows a strongly asymmetrical shape, if one considers In $\text{T}{}^{\mathrm{?1}}{}_1\text{= ?(T}{}^{\mathrm{?1}}\text{)}$ on both sides of the observed maxima. This behaviour may be explained by a distribution of the Li correlation times τ corresponding to different jump distances between various possible sites. The Cole-Davidson model allows the best agreement between experimental and theoretical values of the correlation times.The activation energies deduced from this model are close to those obtained from conductivity measurements (0.43 eV by NMR, 0.56 eV by conductivity determinations for x = 0.50), they may be correlated to the longer Li⁺ jumps in the vitreous matrix.     

Dielectric anomaly in amorphous Si100-xAux system

In amorphous Si_100-xAu_x system the dielectric constant is decreasing with increasing frequency or with decreasing temperature at $\text{x ? 5.5\%}$. This is explained by considering the dispersion of the variable range hopping contribution to the dielectric constant. The dielectric constant at sufficiently high frequency or at sufficiently low temperature is increasing rapidly with increasing x in the region x ? 5.5%, which predicts the occurrence of the nonmetal-metal transition.     

Spin dynamics in the impurity-doped one-dimensional heisenberg paramagnet (CH3)4NMn(1-x)CuXCl3: Nuclear magnetic relaxation

Proton spin-lattice relaxation rate has been measured at room temperature in the impurity-doped (CH₃)₄NMn_(1-x)Cu_xCl₃ for X = 0.04, 0.1 and 0.17. The result for Hz. snfc;chain-axis as a function of resonance frequency clearly shows that the spectral density of the spin fluctuations in the impure system remains to have the characteristics 1-D diffusive term (ω^{-$\text{1}\text{2}$}), with a slower rate of the spin diffusion in accordance with the theory by Richards. The result for H⊥ chain-axis indicates, however, the existence of a singularity of the fluctuations near ω = 0.     

Lithium mobility in the layered oxide Li1−xCoO2

The Li⁺-ion chemical diffusion coefficient in the layered oxide Li_0.65CoO₂ has been measured to be $\text{D}\text{?}\text{= 5 × 10}{}^{\mathrm{?12}}$ m² s^?1 by three independent techniques: (1) from the Warburg prefactor, (2) from the transition frequency for semi-infinite to finite diffusion lengths in steady-state ac-impedence measurements and (3) from a modified Tubandt method that uses ac-impedance data to distinguish interfacial and surface-layer resistances from the bulk resistance of the sample. This value and a small increase in D? with (1 ? x) in Li_1?xCoO₂, 0.45 < (1 ? x) < 0.80, compare favorably with the $\text{D}\text{?}\text{= 5}\text{to}\text{7 × 10}{}^{-12}\text{m}{}^2\text{s}{}^{-1}$ obtained by Honders for this system with pulse techniques. A qualitative discussion is presented as to why this composition dependence and why D? for this system is a factor of five larger than that for Li⁺-ion diffusion in Li_xTiS₂.     

Diffusion and NMR spin lattice relaxation of 1H in α′ TaHx and NbHx

The concentration and temperature dependence of the self diffusion coefficient, D, of H in Group V transition metals Nb and Ta has been measured for the α^' phase. The nuclear magnetic resonance spin lattice relaxation time, T₁, was measured in Ta only. A pulsed field gradient, NMR spin echo technique was utilized to measure D. In both systems, the activation energy increases with hydrogen concentration while the pre-exponential factor is not strongly concentration dependent. The diffusion results are compared with published values of the macroscopic diffusion coefficient, $\text{D}{}^1$, obtained from Gorsky effect measurements. Values of the thermodynamic factor [$\text{(}\text{ρ}\text{kT}\text{)(}\text{?μ}\text{(?ρ)}$] are found for selected ρ and T, where μ is the chemical potential and ρ is the density of hydrogen atoms. These values agree with known determinations of the same factor obtained from the Gorsky effect relaxation strengths, but the agreement with results from solubility measurements is less satisfactory. NMR relaxation is partitioned into conduction electron (T^?1_1e) and dipolar (T^?1_1d) relaxation rates. The observed x dependence of ($\text{D}\text{T}{}_{\mathrm{1d}}$) is inconsistent with random occupancy of tetrahedral sites, and it is suggested that a repulsive interaction exists between H atoms on nearest neighbor sites.     

Temperature-induced local magnetic moments in CoSe2-59Co NMR

From the temperature dependences of the ⁵⁹Co Knight shift and the nuclear spin-lattice relaxation rate in the exchange-enhanced paramagnetic metal CoSe₂, it is shown that the amplitudes of the temperature-dependent spin density fluctuations are saturated at $\text{T}{}^1\text{= 130 K}$. This fact indicates that there exist local moment type fluctuations above T¹. The results obtained from the present NMR investigation are in general accord with the predictions based on the general theory of spin fluctuations in itinerant electron systems developed recently by Moriya and Takahashi.     

Electron spin relaxation of irradiated ferroelectric KDP: K2SeO4

Electron spin resonance relaxation times were measured for the radiation induced radical ion SeO₄^3? in selenium doped KDP single crystals. The spin-lattice relaxation time was found to obey the relation $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>R</mtext>}}{}^{\mathrm{?1}}\text{= AT + BT}{}^5\text{∫}{}_0{}^{\mathrm{<mtext>\theta </mtext><mtext>2T</mtext>}}\text{x}{}^4\text{csch}{}^2\text{x}\text{d}\text{x}$ from 7 K to 200 K except in the neighborhood of the transition temperature where the data fit the expression T₁^?1 = T_1R^?1b_±T ? T_c^m± where θ is the Debye temperature and the plus and minus signs refer to data at temperatures above and below T_c respectively.     

NMR investigation of the layered transition metal phosphorus trichalcogenides and the intercalation compounds LixNiPS3

The transition metal phosphorus trichalcogenides MPX₃ are layered semiconductors which can be intercalated either chemically or electrochemically by lithium atoms. We present a NMR study of the magnetic properties of the MPX₃ compounds (M = Ni, Mn, Fe; X = S, Se) and their modification as a function of intercalation in the compounds Li_xNiPS₃ (x = 0 ? 1.29). In the concentration range x = 0.02 ? 0.5, the relative shift of the P³¹ resonance line K_iso = -0.052 % and the Neel temperature T_N = 155 K are constant and barely different from that measured in pure NiPS₃ (K_iso = -0.057 %, T_N = 165 K). For x > 0.5 a new P³¹ resonance line is observed, which grows with x at the expense of the previous one. It corresponds to non magnetic layers $\text{S - Ni}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{(P}{}_2\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{- S}$, which progressively replace the paramagnetic ones up to the limit of intercalation x = 1.29. Investigation of the lithium ions mobility through Zeeman and dipolar spin lattice relaxation times T_1～ and T_1D measurements indicates a very low self-diffusion coefficient - D = 10^-13 ? 10^-14cms^-1 -, that is four orders of magnitude smaller than those measured in Li_xTiS₂ compounds. This strongly contrasts with the good electrochemical activity of the Li_xNiPS₃ system.     

Neutron diffraction investigation of the cationic distribution in the structure of the spinel-type solid solutions Li2−2xM1+xCl4 (M = Mg, V): Correlation with the ionic conductivity and NMR data

The structure of the spinel-type solid solutions Li_2?2xMin1+xCl₄ M = Mg, V has been studied by neutron diffraction. The cationic distribution in the stoichiometric phases Li₂MgC1₄ and Li₂ VCl₄ is inverse at room temperature, but some vacancies tend to appear in the tetrahedral 8(a) sites. With increasing temperature a gradual migration of the Li⁺ ions from the 8(a) positions into the octahedral 16(c) ones has been established for Li₂MgCl₄. The extra vacancies in the highly deficient spinels LiMgCl₃ and LiVCl₃ ($\text{x =}\text{1}\text{3}$) have been found to be located in the tetrahedral 8(a) sites only. The correlation between the thermal evolutiomn of the cationic dustribution and the corresponding conductivity and NMR data gives a satisfying interpretation of the jump mechanisms responsible for the high ionic mobility in these materials.     

Attenuation of longitudinal ultrasonic wave near the diffuse phase transition in CdF2

The attenuation of a longitudinal ultrasonic wave propagating in the [111] direction in CdF₂ is studied as function of temperature from 300K to 1030K. An ultrasonic attenuation peak has been observed for the first time near 983K. This peak is used to define the diffuse transition temperature (T_c = 983K) in CdF₂ which is well below its melting temperature of 1372K. The Arrhenius activation energy of anion motion above T_c was obtained from the temperature dependence of the attenuation and the theory of the dynamics of the coupled crystalline-cage-charged-liquid fluctuations. The elastic constant, $\text{C}{}_{11}\text{+2}\text{C}{}_{12}\text{+4}\text{C}{}_{44}\text{)}\text{3}$, measured simulataneously with the ultrasonic attenuation displays a large decrease near 983K in addition to the nearly linear decrease in the elastic constant with temperature.     

Raman study of charge-density-wave phase transition in quasi-one-dimensional conductor (TaSe4)2I

Polarized Raman spectra were obtained in the quasi-one-dimensional conductor (TaSe₄)₂I above and below the charge-density-wave (CDW) transition temperature (T_c=263 K). The Raman intensities of many peaks become intenser and two of the phonon peaks shift to higher frequency with decreasing temperature. Moreover a new broad peak at about 90 cm^?1 and a new peak around 166 cm^?1 appear in the low-temperature phase. The polarization characteristic shows that the former is assigned to totally symmetric mode. The damping constant of the phonon at 90 cm^?1 increases markedly with increasing temperature. The frequency shifts to higher frequency as the temperature increases and the coupling coefficient is approximately proportional to (T_c?T)^{$\text{1}\text{2}$}. This peak becomes Raman active owing to the CDW phase transition. The temperature dependence of the damping constant and the frequency shift may have a relation to the dynamical properties of the CDW phase transition.     

Ionic-electronic conductors based on lithium-containing oxide bronzes

Lithium-containing oxide bronzes Li_xV_2?yM_yO₅-β (M=Mo or W) have been studied in wide range of temperature (25–550°C) and composition (0.22?x?0.47, 0?y?0.25) as prospective ionic-electronic conductors. By coulometric titration tecknique, $\text{Δ}\text{G}{}_{\mathrm{<mtext>Li</mtext>}}$, $\text{Δ}\text{H}{}_{\mathrm{<mtext>Li</mtext>}}$ and $\text{Δ}\text{S}{}_{\mathrm{<mtext>Li</mtext>}}$ have been found and ordering of the lithium ions within the channel structure Li_xV₂O₅-β has been discussed depending on composition and temperature. The chemical diffusion coefficient for lithium D?_Li has been measured by potentiometric technique on hot-pressed ceramic samples. The lithium self-diffusion coefficient D_Li and partial lithium-ionic conductivity have been calculated.     

Neutron diffraction study on the hyperfine-induced nuclear spin order in the antiferromagnet PrSn3

At several $\text{(h+}\text{1}\text{2}\text{0 0)}$ reciprocal lattice positions of PrSn₃, we observed Bragg scattering of neutrons which is purely due to the nuclear spin polarization of ¹⁴¹Pr, and could measure the temperature dependence of the polarization between 10 mK and 4.2 K. From the perfectly polarized state of the nuclear spins, the difference between the spin-dependent nuclear scattering lengths b⁺ and b^- has been determined to be b⁺ - b^- = -0.110 ± 0.006 × 10^-12 cm, which is significantly larger in magnitude than the previously reported value. An additional electronic polarization which is linearly proportional to the nuclear spin polarization has also been observed.     

Electron diffraction and infrared study of the semimetallic layered compound Ti1−xVxSe2

The crystals of the system Ti_1?xV_xSe₂ (C ≤ x ≤ 0.05) undergo a second order structural phase transition. Electron diffraction studies show that the transition temperature decreases with progressive V-doping. The phase transition considerably affects the infrared reflectivity, measured at 300 and 77 K in the spectral range 40 cm^?1 to 4000 cm^?1.The presence of free carriers and the existence of optical infrared active E_u phonon modes $\text{(}\text{E}\text{⊥}\text{c}\text{)}$ confer their characteristic appearance to the spectra. At room temperature one phonon structure is measured at 143 cm^?1. At 77 K a new series of phonon peaks appears up to a V-concentration of 5 % as a direct consequence of superlattice formation.At room temperature the plasma-edge shifts towards higher frequencies as the vanadium concentration increases. This effect is caused by a large increase of $\text{N}\text{m}{}^1$, associated with the mixing of impurities. It is indicative of the small density of states at the Fermi level in semimetallic TiSe₂. Our results suggest a phase transition driven by lattice dynamical effects.     

Raman scattering from electronic excitations of samarium in semiconducting and metallic Sm1−xYxS

The Raman spectra of Sm_1?xY_xS for $\text{x?0.4}$ have been measured. Electronic scattering between the J = 0 ground state and the J = 1 and 2 excited states of Sm²⁺ is observed. The singlet-triplet transition is observed on both sides of the black to gold phase transition in Sm_1?xY_xS.     

Spectroscopic investigation of [(NH4)xK1−x]2SnCl6 mixed crystals

Polycrystalline samples of the solid solution [(NH₄)_xK_1?x]₂SnCl₆(0?x? 1) have been investigated by DSC, X-ray diffraction and Raman scattering experiments. Substitution of K⁺ by NH⁺₄ depresses the phase transition temperature T₁. For 0? x ?0.05 a linear temperature coefficient $\text{d}\text{T}{}_1\text{dx=?5.16}\text{K/mol}$ % is obtained. The cubic lattice constant roughly obeys Vegard's law, whereas the linewidth of the SnCl₆^2?F_2g internal vibration displays a nonlinear dependence on composition.