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.     

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.     

EPR and dielectric properties of Pb5Ge3O11 crystals with off-center Cu2+ ions

The electron paramagnetic resonance (EPR) and dielectric properties of Pb₅Ge₃O₁₁ crystals activated by copper ion are investigated. It is shown that Cu²⁺ ions replace Pb²⁺ in trigonal symmetry positions and occupy three off-center positions displaced from a crystal lattice site in a plane perpendicular to the polar axis C. The temperature variation of EPR spectra and dielectric properties indicates the presence of thermally activated jumps of Cu²⁺ ions between off-center positions. The EPR and dielectric data are used to determine the activation energy W=0.24 eV and the eigenfrequency τ ₀ ^?1 ～ 10¹² Hz of local dynamics of Cu²⁺ ions.     

Determination of thermal conductivity coefficient of crystals with the garnet structure at high temperatures

At high temperatures, the simple expression for thermal conductivity of crystals with the garnet structure is obtained, which allows one to determine this quantity if the lattice constant or density of these crystals is known. The thermal conductivity coefficients for the garnet crystals of different compositions calculated from the obtained formula are in a good agreement with the experimentally measured values.     

Electrical conductivity in magnesium-doped Al2O3 crystals at moderate temperatures

Abstract

AC and DC electrical measurements between 273 and 800 K were used to characterize the electrical conductivity of Al₂O₃: Mg single crystals containing [Mg]⁰ centers. At low fields contacts are blocking. At high fields, electrical current flows steadily through the sample and the I–V characteristic corresponds to a directly biased barrier with a series resistance (bulk resistance). AC measurements yield values for the junction capacitance as well as for the sample resistance, and provide reproducible conductivity values. The conductivity varies linearly with the [Mg]⁰ concentration and a thermal activation energy of 0.67 eV was obtained, which agrees very well with the activation energy previously reported for the motion of free holes.     

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.     

Dc electrical conductivity of Ge2S3Agx glasses at high hydrostatic pressure

The paper deals with the influence of hydrostatic pressure on d.c. electrical conductivity in Ge₂S₃Ag _x glasses forx10%. The initial material exhibits high resistivity and the presence of Ag impurity yields strong increase in electrical conductivity. The experimental results suggest that there is a non-linear decrease of electrical resistivity at pressure ranging from 0·1 to 10³ MPa. The pressure coefficient of resistivity is a function ofx. All measurements were performed on bulk samples using graphite contacts. The experimental results are interpreted by means of ionic conductivity.     

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.     

Influence of composition nonstoichiometry on the electrical conductivity of LiNaGe4O9 crystals

The electrical conductivity σ of Li_{2 ? x} Na _x Ge₄O₉ (x = 1, 0.5, 0.2) crystals in an alternating-current electric field has been investigated at a frequency of 1 kHz in the temperature range of 300–800 K. A considerable anisotropy of the electrical conductivity has been revealed for crystals with a sodium concentration x = 1 at T > 500 K. It has been shown that the electrical conductivity σ along certain crystallographic directions increases by more than three orders of magnitude with a change in the sodium concentration from x = 1 to x = 0.2. The results have been discussed taking into account the specific features of the structure of the crystals under investigation. Presumably, the major charge carriers are interstitial Li ions migrating along channels of the framework structure of the Li_{2 ? x} Na _x Ge₄O₉ crystals.     

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)     

Observation of the ferroelectric phase transition in Pb5Ge3O11 by the chemical potential changes

We observed the transition from the ferroelectric (FE) to paraelectric (PE) phase in the semiconducting, ferroelectric Pb₅Ge₃O₁₁ single crystal with the use of the contact electrode method. To this purpose a thin, metallic layer was placed onto the Pb₅Ge₃O₁₁ crystal surface, forming the contact electrode. At opposite ends of the contact electrode, silver wires were glued and a voltage was applied to the contact electrode in such a way that the electric current could flow only through the attached electrode. The electric resistance R(T) of the electrode was measured as a function of temperature. Two series of measurements were performed. In one of them the ferroelectric c-axis of the investigated crystal was perpendicular to the contact electrode. In the second one the c-axis was parallel to the attached electrode. We used gold as the contact electrode material. The anomaly in the R(T) in a form of a kink at T _kink?=?452?K was found for both c-axis orientations. The measured value of T _kink, appearing in the temperature dependence of contact electrode resistance, corresponds exactly to the phase transition temperature T _C from the FE to PE phase of the investigated Pb₅Ge₃O₁₁ material. This result demonstrates that the contact electrode method, primarily proposed exclusively to find critical temperatures of metallic samples, also works well in the case of ferroelectric and semiconducting materials like Pb₅Ge₃O₁₁. We ascribe the effect of the resistance kink in the temperature dependence of the contact electrode R(T) to thermal excitations of the electrons with different rates below and above T _C due to different electronic activation energies in the FE and PE phases of the investigated Pb₅Ge₃O₁₁ crystal. It, however, means that the phase transition in the electronic subsystem of the Pb₅Ge₃O₁₁ transfers into the electron gas of the contact electrode via the chemical potential relation µ _sample?=?µ _electrode due to the contact between the sample and the electrode. The magnitude of the kink, observed in the R(T) dependence, was higher on heating than on cooling. The additional measurement of the thermally stimulated current (TSC) was carried out on the non-polarised Pb₅Ge₃O₁₁ sample. In this series of measurements, the sample was covered with gold layers sputtered on the two opposite surfaces of the crystal. The TSC anomaly occurred, related to the residual pyroelectric effect, several degrees below the Curie temperature, T _C, and does not disturb the detection of the critical point with the use of the contact electrode method.     

Thermal hardening of Ni3Ge alloy single crystals with an L12 superstructure at low temperatures

The mechanical properties and the dislocation structure of Ni₃Ge alloy single crystals have been experimentally studied at low temperatures. It is found that the flow stresses increase beginning with 4.2 K, and the observed rise in the stresses depends on the orientation of the strain axes of the crystals. The dislocation structure is investigated thoroughly. It is revealed that the mean density of dislocations and the interdislocation interaction parameter α anomalously increase as the temperature increases in the range 4.2–293 K. The mechanisms providing an explanation for the temperature anomaly of flow stresses and the α parameter are considered. The activation energy of thermal hardening is evaluated. It is assumed that the low activation energies of thermal hardening are due to the motion of dislocations at velocities close to the velocity of sound at these temperatures.     

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.     

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)     

Structural investigations of the ionic conductivity in zirconia single crystals by neutron diffraction at high temperatures and simultaneously applied electric field

In situ neutron diffraction studies of CaO and Y₂O₃ stabilized zirconia single crystals were performed at elevated temperatures and simultaneously applied DC electric field, i.e. lasting ionic current. Bragg data from Zr_0.85Ca_0.15O_1.85 (CSZ15) were collected at room temperature without electric field, at 1170 K and 1370 K without and with 3.5 V and 1.8 V, respectively, (field vector Ell[111]), which generated a current of 60 mA in each case. In case of Zr_0.70Y_0.30O_1.85 (YSZ15) the electric field vector was directed along [001]. At 1170 K three data sets were collected: without field, with 1.5 V (I=60 mA), and with 2.5 V (I=120 mA). Atomic displacement parameters (a.d.p.'s) were derived in the frame of a non-Gaussian Debye-Waller factor formalism for the oxygens. Corresponding probability density function (p.d.f.) maps and pseudo potential maps were calculated. Most probable curved diffusion pathways run close to 〈 100 〉, independent of the external field direction, applied voltage and the kind of dopant. With lasting ionic current the potential corresponding to p.d.f. >1% is lowered by about 0.06–0.07 eV.     

Emissivity measurements of 3D photonic crystals at high temperatures

An accurate methodology is presented to measure photonic crystal emissivity using a direct method. This method addresses the issue of how to separate the emissions from the photonic crystal and the substrate. The method requires measuring two quantities: the total emissivity of the photonic crystal–substrate system, and the emissivity of the substrate alone. Our measurements have an uncertainty of 4% and represent the most accurate measure of a photonic crystal's emissivity. The measured results are compared to, and agree very well with, the independent emitter model.