Phase transitions in SrTiO3-based solid solutions

Phase transitions in solid solutions of strontium titanate with titanates of the divalent metals Pb, Ba, and Ca are considered. It is shown that the critical concentration x _c in the well-known expression relating the transition temperature to the polar state in SrTiO₃ with the concentration x of divalent metals, T _c=A(x−x _c)^1/2, is practically the same for all impurities. For large values of x, the ferroelectric transition temperature T _c depends linearly on x. The volume and impurity contributions to the T _c(x) relation are determined for this concentration range. Fiz. Tverd. Tela (St. Petersburg) 39, 1645–1651 (September 1997)     

Spontaneous photorefractive effect in Sr1−x CaxTiO3 (x=0.014)

The temperature dependence of the principal values of the refractive index in Sr_1−x Ca_xTiO₃ (x=0.014) has been measured in the 17–275 K range under various conditions of sample illumination with 1.96 eV photons. The spontaneous photorefractive contribution δn ^ph to the temperature-induced variation of the refractive index of Sr_1−x Ca_xTiO₃, which appears after illumination of the sample in the ferrophase (transition temperature T _c=32 K) and persists in the paraphase under heating up to 150 K, has been separated. The photoinduced polarization has been estimated. Fiz. Tverd. Tela (St. Petersburg) 39, 711–713 (April 1997)     

Dielectric nonlinearity of crystalline Li2−x NaxGe4O9 (x≈0.23)

The dielectric nonlinearity of ferroelectric Li_2−x Na_xGe₄O₉ (x≈0.23) crystals is measured in the neighborhood of the phase transition temperatures. The magnitude of the nonlinear coefficient β is estimated from the shift in T _c and the reduction in ɛ _max under the influence of E ₌, from the dielectric nonlinearity in the paraphase, and from the temperature dependence of P _s in crystalline Li_2−x Na_xGe₄O₉ (x≈0.23). The resulting values of β are 1.87, 1.26, 2.17, and 1.17×10⁻⁹ (CGSE cm²)⁻², respectively. The mechanism for the phase transition in crystalline Li_2−x Na_xGe₄O₉ (x≈0.23) is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1070–1072 (June 1999)     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

Critical concentrations in Ba-doped incipient ferroelectric SrTiO3

Temperature-induced variations of light refraction and dielectric permittivity in single-crystal Sr_1−x Ba_xTiO₃ (x=0.02, 0.05, 0.07, and 0.14), Sr_1−x Ca_xTiO₃ (x=0.014), and in nominally pure strontium titanate have been studied within the 17–300 K temperature range. The spontaneous polar contribution to the refractive index has been isolated. It was used to calculate the temperature and concentration dependences of the polarization autocorrelation function 〈P _s ^2〉 in the Sr_1−x Ba_xTiO₃ system. For x⩽0.07, the polarization P _s=〈P _s ² 〉^1/2 varies proportional to (x−x _g)^1/2, where x _g=0.0027 is the new critical concentration in Sr_1−x Ba_xTiO₃, below which short-range polar order vanishes. Fiz. Tverd. Tela (St. Petersburg) 39, 704–710 (April 1997)     

Metal-insulator transition in electron-doped Ba1−x La x MnO3 compounds

Electron-doped (Ba_1−x La _x )MnO₃ compounds were prepared for x=0−0.5. Measurements of X-ray diffraction (XRD) at room temperature and temperature variation of dc electrical resistivity down to 20 K were carried out. Samples with x=0.2–0.5 exhibit metal-insulator (M-I) transition. The maximum M-I transition temperature (T _c) of 289 K was observed for 30% of La doping (x=0.3). XRD patterns of these samples (x=0.2−0.5) were analyzed using Rietveld refinement. These samples are found to be mostly in single-phase form with orthorhombic symmetry (space group Pbnm). We have found strong correlation between Mn-O-Mn bond angles and T _c of M-I transition. The resistivity data below T _c could be fitted to the expression ρ=ρ ₁+ρ ₂ T ² and this shows that double exchange interaction plays a major role even in Mn⁴⁺-rich compound. Above T _c the resistivity data were fitted to variable range hopping and small polaron models.     

Dielectric properties of (1−x)[0.7PbZrO3·0.3K0.5Bi0.5TiO3]·xSrTiO3 solid solutions in the vicinity of phase transitions

The dielectric properties of polycrystalline (1−x)[0.7PbZrO₃·0.3K_0.5Bi_0.5TiO₃]·xSrTiO₃ solid solutions, where x=0–0.7, are studied in the temperature range 150–600 K. Systematic spreading of the ferroelectric phase transition with increasing strontium titanate content is discovered. The dispersion of the dielectric constant at frequencies from 10⁻¹ to 10⁶ Hz is investigated for a composition with x⋍0.7. The existence of two relaxation processes characterized by diffuse relaxation time spectra, which broaden with decreasing temperature, is established. It is postulated that a transition to a glasslike state takes place in the material with x⋍0.7. Zh. Tekh. Fiz. 69, 35–38 (March 1999)     

EPR of trivalent iron ions in a LiCaAlF6 crystal

The orientational dependences of the EPR spectra of Fe³⁺-doped LiCaAlF₆ single crystals (space group P31c, Z=2), grown at the Laboratory of Magnetic Radio Spectroscopy at Kazan’ State University, have been investigated in detail. The spectrum is described by a trigonal spin Hamiltonian with the following parameters: B ₂₀=40.072×10⁻⁴ cm⁻¹, B ₄₀=−5.799×10⁻⁴ cm⁻¹, B ₄₃=−4.281×10⁻⁴ cm⁻¹, A _s=24.33±1, A _p=6.13±1, g _∥=g _⊥=2.00217±0.0003. A theoretical calculation of the hyperfine structure parameters shows that they are described quite well when allowance is made for the overlapping of the wave functions of the paramagnetic center and the ligands (F⁻). Fiz. Tverd. Tela (St. Petersburg) 39, 488–490 (March 1997)     

Spin susceptibility of neutron-irradiation-disordered YBa2Cu3O6.9 in the normal and superconducting states

The spin-spin relaxation rate ⁶³ T ₂ ⁻¹ of ⁶³Cu nuclei in CuO₂ layers is measured in the normal and superconducting states of the compound YBa₂Cu₃O_6.9 (T _c ^onset =94 K) subjected to radiation-induced disordering by a fast-neutron flux Φ to T _c ^onset =68 K (Φ=7×10¹⁸ cm⁻²) and T _c ^onset <4 K (Φ=12×10¹⁸ cm⁻²). It is found that as the structural disorder increases, the contribution of the indirect spin-spin interaction ⁶³ T _2G ⁻¹ , which is related to the value of the spin susceptibility at the boundary of the Brillouin zone of the copper planes χ_s(q={π/a; π/a}), decreases slightly at the transition to the superconducting state for the initial sample and remains unchanged for the weakly disordered sample. This behavior of the short-wavelength contribution to the spin susceptibility attests to the stability of the x ²−y ² symmetry of the energy gap against structural disorder, in accordance with proposed theoretical models of Cooper pairing for high-T _c cuprates. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 3, 172–177 (10 February 1998)     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

Magnetic properties of multiferroics Bi1 ? xAxFeO3 ? x/2 (A = Ca, Sr, Pb, Ba)

The magnetic properties of Bi_{1 − x} A _x FeO_{3 − x/2} (A is an alkaline-earth ion) solid solutions have been studied in magnetic fields of up to 140 kOe. The ferroelectric phase (space group R3c) transforms into the nonpolar pseudocubic phase at x ≈ 0.2. It is demonstrated that the substitution of alkaline-earth ions for bismuth ions (x ≥ 0.1) leads to a complete destruction of the modulated antiferromagnetic structure and the appearance of a weakly ferromagnetic state within the R3c state. In the pseudocubic phase, the spontaneous magnetization is absent; however, the field dependence of the magnetization is nonlinear and depends on the magnetic prehistory.     

Galvanomagnetic properties of the Al1−x Six nonequilibrium substitutional solid solutions

Galvanomagnetic characteristics of the A_1−x Si_x solid solutions (x<12 at. %) have been studied within a broad range of temperatures (1.8–290 K) and magnetic fields (up to 15 T). An anomaly in the concentration dependence of the Hall coefficient R _H (x,T=290 K) has been revealed near the boundary of absolute instability (x<8.5 at. %) of compounds in the Al_1−x Si_x series. The variation of the Hall coefficient and of the magnetoresistance in the A_1−x Si_x series at low (T<77 K) temperatures is analyzed within models taking into account the anisotropy in conduction-band electron scattering. Fiz. Tverd. Tela (St. Petersburg) 41, 3–10 (January 1999)     

Correlation between the electric-field effect and weak-link type in YBa2Cu3−x Oy and YBa2Cu3−x Oy /Agx high-T c superconducting ceramics

An experimental study is reported of the effect of an electric field E⩽120 MV/m and of temperature T on the critical current I _c and I-V characteristics of yttrium-based high-T _c superconducting ceramics. The materials studied were copper-deficient ceramics, YBa₂Cu_3−x O_y (D samples), and YBa₂Cu_3−x O_y/Ag_x ceramics [S samples with silver present in amounts equal to the copper deficiency (0⩽x⩽0.4)]. It has been established that in D samples at 77 K, the electric field increases I _c and reduces substantially R for I>I _c, whereas in S samples no field effect is observed. Measurements of the I _c(T) dependence near the critical temperature showed that they can be described for all samples by a relation of the type I _c =const(1−T/T _c )^α, where α≈1 for the D samples, and α≈2 for the S samples. The results obtained suggest that the electric-field effect correlates with the existence in the ceramic of SIS-type weak links at grain boundaries. Fiz. Tverd. Tela (St. Petersburg) 40, 1195–1198 (July 1998)     

Mott-insulator-superfluid-liquid transition in a one-dimensional bosonic Hubbard model: Quantum Monte Carlo method

The values of the insulator gap Δ in one-dimensional systems of interacting bosons described by the Hubbard Hamiltonian are calculated at low temperatures by the quantum world-line Monte Carlo algorithm. The dependence of Δ on the size of the system, the temperature, and the parameters of the model is investigated. It is shown that a chain with N _a=50 sites is already sufficient to estimate the thermodynamic value of the critical quantity (t/U)_c for which a transition from the insulator into the superfluid state occurs in a commensurate system. To within the computational error, this value, (t/U)_c=0.300±0.005, agrees with the value (t/U)_c=0.304±0.002 obtained previously by the combined “exact diagonalization + renormalization-group analysis” method. The characteristic Kosterlitz-Thouless behavior of the insulator gap is demonstrated near the critical region: Δ∼exp[−b(1−t/t _c)^−1/2]. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 92–96 (25 July 1996)     

Effect of Fe substitution on the thermal expansion of the highT c superconductor Y1Ba2Cu3O y

Thermal expansion measurements have been carried out on Fe substituted superconducting compounds Y₁Ba₂(Cu_1−x Fe _x )₃O _y (0<x<4%) using a high resolution dilatometer employing the three terminal capacitance technique. The experimental set up is sensitive enough to detect changes in α of less than 10⁻⁸K⁻¹. Results show that the jump Δα in the coefficient of linear thermal expansion at the superconducting transition temperature,T _c, increases almost linearly with Fe concentration. The normal state thermal expansion coefficient α first decreases, attains a minimum value aroundx=1% and then increases for higher Fe concentrations. The oxygen content per unit formula is almost constant up tox=1% and then increases rapidly withx. It has also been observed that the anomalous behaviour of α around 260 K observed by Meingastet al [22] for Fe concentrationx=5% is due to inadequate annealing of the sample.     

Modeling a dimer state in CuGeO3 in the two-dimensional anisotropic Heisenberg model with alternated exchange interaction

The two-dimensional Heisenberg spin-1/2 model with alternated exchange interaction along the c axis and an anisotropic distribution of the exchange interaction in the lattice, J _b/J _c=0.1, is examined. A quantum Monte Carlo method is used to calculate the phase diagrams of the antiferromagnet, the dimer state in a plane, the value of the alternation δ of the exchange interaction, and the anisotropy Δ=1−J ^xy/J ^z of the exchange interaction, Δ∼δ ^0.58(6). The following characteristics are calculated for Δ=0.25: the dependence of the temperature of the dimer-state-paramagnet transition on the alternation of the exchange interaction, T _c(δ)=0.55(4)(δ−0.082(6))^0.50(3), the singlet-triplet energy gap, and the dependence of the magnetization on the external field for some values of δ. The value of the exchange interaction, J _c=127 K, the alternation of the exchange interaction, δ=0.11J _c, and the correlation radius along the c axis, ξ _c≈28c, are determined. Finally, it is found that the temperature dependence of the susceptibility and the specific heat are in good agreement with the experimental data. Zh. éksp. Teor. Fiz. 112, 2184–2197 (December 1997)     

Ferroelectric phase stabilization, phase transformations and?thermal properties in (1? x )PbZrO3– x Pb(Co1/3Nb2/3)O3 solid solution

The solid solution between the antiferroelectric PbZrO₃ (PZ) and relaxor ferroelectric Pb(Co_1/3Nb_2/3)O₃ (PCoN) was synthesized by the columbite method. The phase structure and thermal properties of (1−x)PZ–xPCoN, where x=0.0–0.3, were investigated. With these data, the ferroelectric phase diagram between PZ and PCoN has been established. The crystal structure data obtained from XRD indicates that the solid solution PZ–PCoN, where x=0.0–0.3, successively transforms from orthorhombic to rhombohedral symmetry with an increase in PCoN concentration. The AFE→FE phase transition was found in the compositions of 0.0≤x≤0.10. The AFE→FE phase transition shift to lower temperatures with higher compositions of x. The width of the temperature range of FE phase was increased with increasing amount of PCoN. It is apparent that the replacement of the Zr⁴⁺ ion by (Co_1/3Nb_2/3)⁴⁺ ions would decrease the driving force for antiparallel shift of Pb²⁺ ions, because they interrupt the translational symmetry. This interruption caused the appearance of a rhombohedral ferroelectric phase when the amount of PCoN was more than 10 mol%.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

Magnetic and structural transitions in La1−x Sr x MnO3: T-x phase diagram

The electrical conductivity, magnetic susceptibility, magnetization, and submillimeter (v=5∓20 cm⁻¹) permittivity and dynamic conductivity of La_1−x Sr _x MnO₃ (0≤x≤ 0.45) single crystals are investigated. The anomalies in the temperature dependences of these quantities are identified with diverse magnetic and structural phase transformations, including antiferromagnetic and ferromagnetic ordering, structural transitions between strongly distorted (Jahn-Teller) and weakly distorted (pseudocubic) orthorhombic phases, structural transitions to a rhombohedral phase and unusual transitions to a polaron-ordering state. As a result, the complete T-x phase diagram of the system La_1−2x Sr _x MnO₃ is constructed in a wide interval of temperatures T=4.2∓1050 K and concentrations x=0−0.45. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 4, 331–336 (25 August 1998)