Structural and dielectric properties of Pb5(Ge,Si)O11

The ferroelectric lead germanate (Pb₅Ge₃O₁₁) and its isomorphous compounds are important because of their uses as pyroelectric and electro-optic devices. Comparison of inter-planar d-spacings of Pb₅Ge_3−x Si _x O₁₁ (x=0, 0.3, 0.7 and 1.00) suggests that there is no change in basic structure of Pb₅Ge_3−x Si _x O₁₁ when Si is substituted for Ge in small quantity (x<1). The dielectric properties of the Si-substituted compounds have been studied as a function of temperature (30 to 200°C). The ferroelectric-paraelectric phase transition has been observed at 185°C. The Si doping causes (a) Curie point to shift towards low temperature, (b) peak value of the dielectric constant to decrease and (c) phase transition diffuse. The fast increase in dielectric constant of pure Pb₅Ge₃O₁₁ with temperature (beyond transition temperature) may be attributed to the development of space charge polarization in the system.     

Second-order ferroic properties of a Pb5Ge3O11 uniaxial ferroelectric

The ferrobielastic properties (ferroic properties of the second order) earlier theoretically predicted for lead germanate uniaxial ferroelectric crystals are justified experimentally. It is demonstrated that single-domain samples are formed upon cooling to temperatures below the Curie point under uniaxial mechanical stresses corresponding to a combination of mechanical stresses σ₁₁σ₁₃ or σ₂₂σ₂₃. The macroscopic mechanism of this phenomenon is considered.     

Mechanisms of EPR line broadening in Pb5Ge3O11 near a structural transition

The polar angular dependence of the anomalous linewidth of three EPR transitions in the Gd³⁺ trigonal center has been used to determine the broadening mechanism. It is shown that the dominant mechanism of Gd³⁺ EPR signal broadening in the vicinity of the ferroelectric transition is the critically growing spread of the b ₂₁ and c ₂₁ parameters accounting for the odd-order fields of remote charge-compensating defects. Fiz. Tverd. Tela (St. Petersburg) 40, 321–326 (February 1998)     

EPR study of Dy 3 + ions in DyBa 2 Cu 3 O 6 + x

Concentrated polycrystalline DyBa₂Cu₃O_6+x compounds are studied by X-band EPR spectroscopy. A broad resonance line due to the highly anisotropic EPR spectrum of Dy³⁺ ions is identified on several specimens at low temperatures. Powder simulation of the EPR spectra complies with the ground Kramers doublet predicted by crystal field analysis of Dy³⁺ ions. Calculations of the second and fourth moments of the resonance lines due to the dipole-dipole interactions of Dy³⁺ indicate the presence of substantial exchange narrowing of the dipolar-broadened EPR linewidth. Received 3 June 2001     

Trigonal and triclinic Fe3+ paramagnetic centers in ferroelectric Pb5Ge3O11

In the EPR spectra of iron-doped lead germanate single crystals, triclinic Fe³⁺ paramagnetic centers have been found in addition to trigonal centers. Their contribution increases upon annealing in a chlorine-containing atmosphere. The parameters of the spin Hamiltonian of three triclinic centers assigned to Fe³⁺-Cl^? dimeric complexes have been determined. The localization of iron and chlorine ions in Pb₅Ge₃O₁₁ has been discussed.     

Optical and EPR spectroscopy of manganese ions in Sr3Ga2Ge4O14 crystals

Results of investigations of the spectroscopic properties of manganese-activated single crystals of Sr₃Ga₂Ge₄O₁₄ by the methods of optical and EPR spectroscopy are reported. It is shown that magnagese activator ions form substitutional centers Mn³⁺ and Mn²⁺ in 1a-octahedral positions of the Sr₃Ga₂Ge₄O₁₄ lattice. Changes in the opticla properties of Sr₃Ga₂Ge₄O₁₄: Mn after vacuum thermal annealing are attributed to charge transfer of some of the manganese ions (Mn³⁺→Mn²⁺). The relationship between the spectroscopical properties of Mn²⁺ ions and the crystallochemical structure of the system are discussed. I. Franko L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 779–783, November–December, 1997.     

Nonlinear properties of Pb5Ge3O11:Gd3+ in an electric field: Paramagnetic resonance

This paper discusses the field and temperature dependences of the shift in position of EPR signals in an external electric field, which is linearly related to the polarization in the paraelectric phase of Pb₅Ge₃O₁₁:Gd³⁺. Fiz. Tverd. Tela (St. Petersburg) 39, 1643–1644 (September 1997)     

High pressure raman scattering in Pb5Ge3O11

The pressure dependence of various phonon modes has been investigated through the ferro-paraelectric phase transition. Most mode frequencies harden before levelling off above the phase transition. Mode Grüneisen parameters are estimated from the pressure dependence of phonon frequencies.     

The effect of off-center Cu2+ ions on the phase transition in lead germanate crystals

The properties of Pb₅Ge₃O₁₁: Cu²⁺ crystals near the temperature of the ferroelectric phase transition are discussed in terms of a phenomenological approach. Assuming a quadratic interaction with the order parameter, the effect of Cu²⁺ is considered a result of static distortions, which result from the off-center position of the copper impurity ions in the lead germanate structure. In this approximation, Cu²⁺ jumps between off-center positions do not affect the dynamic properties of the crystal matrix near T _C.     

EPR of Pb3+ ion in LiBaF3 crystals

Complex EPR spectra of paramagnetic centers Pb³⁺ formed in LiBaF₃:Pb²⁺ crystals under X-ray irradiation are studied in the temperature range of 10–150 K. It is shown that lead ions substitute Ba²⁺ ions in the LiBaF₃ crystal and are in the cubic-octahedral 12-fold environment of the fluorine ions. The hyperfine structure constants describing the observed spectrum are determined and parameters of superhyperfine interaction with the nearest fluorine ions are estimated.     

Temperature behavior of the order parameter in Pb5Ge3O11

The temperature dependence of the spontaneous polarization in the Pb₅Ge₃O₁₁ lead germanate (PGO) is experimentally investigated using optical, magnetic resonance, and conventional electrical measurements. The deviations from the temperature dependence typical of second-order phase transitions at temperatures below 420 K are explained in terms of incomplete polarization switching and polarization induced by a residual depolarization field. The low-temperature anomalies are interpreted without consideration of additional structural transformations. The internal bias field is determined from the experimental temperature dependence of the perfect polarization of PGO single crystals in an electric field.     

Two-magnon Raman scattering in dielectric and superconducting YBa2Cu3O6+x crystals

Two-magnon Raman scattering in dielectric, as well as superconducting, YBa₂Cu₃O_{6 + x} single crystals with mobile oxygen content x = 0.2–0.7 and superconducting transition temperature T _c = 0–74 K is studied in detail. Doping with oxygen in the range of x = 0.2–0.5 leads to two-magnon scattering peak broadening and a shift in the spectral position of the peak towards lower energies. The most significant qualitative changes in two-magnon scattering in YBa₂Cu₃O_{6 + x} crystals are observed in a narrow oxygen concentration range near x = 0.7. This is explained by a considerable decrease in the correlation length ξ_AF of antiferromagnetic (AF) correlations upon an increase in the concentration of free carriers. For instance, doping is accompanied with a reduction of ξ_AF to values of several lattice constants a for x ≈ 0.7, a transition to the regime of short-range AF order, and local scattering of light from a small AF cluster with a size of 3 × 4 lattice constants. An increase in the free charge carrier concentration destroys the short-range AF order in a narrow range of the stoichiometry index near x = 0.7. Experimental data also indicate heterogeneity of cuprate planes at microscopic level, which leads to coexistence of superconducting and AF regions in YBa₂Cu₃O_{6 + x} super-conducting crystals.     

EPR of the ferroelectric phase transition in Li2Ge7O15:Cr3+ crystals

A Cr³⁺ EPR study of lithium heptagermanate crystals, Li₂Ge₇O₁₅ (LHG), close to the phase transition is reported. Orientation dependences of the spectra in the paraelectric phase of LHG have been measured. An anomalous broadening of the resonant lines accompanied by a crossover in their shape was found in the vicinity of the transition point. Doublet splitting of the EPR lines was observed to occur below T _C as a result of emergence of two structurally nonequivalent positions for Cr³⁺ ions. Fiz. Tverd. Tela (St. Petersburg) 40, 1102–1105 (June 1998)     

Influence of the defect structure on the electrical conductivity of Pb5Ge3O11 single crystals at high temperatures

The impedance spectra of Pb₅Ge₃O₁₁ single crystals are measured in the frequency range from 5 Hz to 13 MHz at temperatures of 600 to 800 K in dry air and in a dry or wet nitrogen gas. It is found that the temperature and the gas composition significantly affect the electrical properties of the compound. The data obtained are used to discuss the origin of crystal lattice defects and their influence on charge transfer. It is concluded that the conduction is mixed in character (p-type electronic and ionic due to oxygen ions). The proton conduction is shown experimentally to be feasible. The possible mechanisms of proton transport in Pb₅Ge₃O₁₁ are discussed.     

Anomalous properties of crystals with ferroelectric phase transition induced by off-center ions

It is given the theoretical study of some properties of strongly polarizable dielectric crystals in which off-center impurity ions induce ferroelectric phase transition. The spontaneous polarization, transition temperature, soft mode frequency, dielectric susceptibility, ultrasonic attenuation, nuclear spin-lattice relaxation are analyzed. The theory explains observed in K_1?xLi_xTaO₃ saturation of remanent polarization with off-center Li⁺ concentration increasing, close to $\text{x}$ dependence of phase transition temperature, the anisotropy of ultrasonic attenuation, the absence of anomalies of Li nuclear spin-lattice relaxation rate near T_c.     

EPR study of the Jahn-Teller effect of Cu2+ ions in ZnGa2O4

The Jahn-Teller effect in the ZnGa₂O₄ spinel single crystal has been investigated using electron paramagnetic resonance of Cu²⁺ ions in the temperature range 110–560 K. It has been shown that copper ions occupy octahedral sites 16d in the ZnGa₂O₄ crystal with cubic symmetry O _h ⁷ (Fd-3m). At T < 560 K, the octahedra undergo tetragonal distortions (predominantly tension) and rotation around the fourfold axes by the angle θ ≈ 2.6°. The parameters of the spin Hamiltonian, which characterize the prolate (g _‖ = 2.355, g _⊥ = 2.077, A _‖ = 116 Oe, A _tp = 12 Oe) and oblate (g _‖ = 2.018, g _⊥ = 2.246, A _‖ = 75 Oe, A _⊥ = 44 Oe) octahedra, have been determined. At temperatures above 560 K, the static Jahn-Teller effect transforms into the dynamic effect and the spectrum of the magnetic resonance becomes isotropic with g = 2.116 (the experimental frequency corresponds to the X band).     

Absorption and EPR spectra of Cr3+ ions in a LaBeAl11O19 crystal

Electron spectra of optical absorption and EPR of Cr³⁺ ions in a LaBeAl₁₁O₁₉ crystal are investigated. It is shown that the Cr³⁺ ions occupy, three different octahedral positions of Al³⁺ in the LaBeAl₁₁O₁₉ structure, namely, 12k, 2a, and 4f₂; the ratio of their intensitites is 1∶2∶30, respectively. Parameters of the Cr³⁺ centers are determined and its is shown that the optical absorption spectra in the visible region are practically determined by the Cr³⁺ (III) occupying the 4f₂-positions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 275–277, March–April, 1999.     

EPR of Yb3+ ions in Ba1−xLaxF2+x mixed crystals

Electron paramagnetic resonance (EPR) spectra of impurity Yb³⁺ ions (about 0.1 at.%) in mixed crystals BaF₂(1-x) plus LaF₃(x) have been investigated for different values of the concentrationx at a frequency of about 9.5 GHz by both continuous-wave (CW) EPR and electron spin echo methods. A spectrum of trigonal symmetry with a complex hyperfine structure is observed in “pure” BaF₂:Yb³⁺ (x=0). Upon admixture of small amounts of LaF₃ (x=0.001), additional EPR lines arise with intensities increasing with the increase ofx up to 0.005. These lines are attributed to trigonal centers including two rare-earth ions and two compensating fluorine ions. A further increase ofx results in a decrease of the total EPR spectrum intensity, and atx≥0.05 the CW resonance becomes practically unobservable. This may be due to the formation of rare-earth ion clusters with paramagnetic Yb³⁺ ions occurring in domains with a disordered structure of surroundings resulting in very broad EPR lines, which cannot be registered by CW EPR. Indeed, very broad (not less than 1 KG) EPR lines were observed by the electron spin echo method for concentrationsx<-0.02.