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.     

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.     

A threshold electric field for acoustic emission from ferroelectric Pb5Ge3O11

Acoustic emission has been observed in ferroelectric Pb₅Ge₃O₁₁ and TGS near saturation polarisation. An abrupt electric field threshold for AE has been discovered in Pb₅Ge₃O₁₁ (but not in TGS) which is related to the onset of domain wall movement.     

The temperature dependence of the ALO-modes in Pb5Ge3O11

The temperature dependence of the LO-TO splitting of the A-modes of Pb₅Ge₃O₁₁ between room temperature and T_c=450K was determined from the Raman spectrum. The finite splitting of two A-modes above T_c leads to the conclusion that the space group of Pb₅Ge₃O₁₁ in the paraelastic phase deviates from P6 which was determined by X-ray and other physical methods.     

High-temperature heat capacity of oxides in the GeO<Subscript>2</Subscript>-PbO system

Data on the heat capacity of Pb₃GeO₅, Pb₅Ge₃O₁₁, PbGeO₃, and PbGe₃O₇ oxides over a wide range of temperatures have been obtained.     

Acoustic emission from domain wall motion in ferroelectric lead germanate

Simultaneous visual observation and monitoring of the ultrasonic signals show that acoustic emission (AE) produced as Pb₅Ge₃O₁₁c-plate crystals undergo the ferroelectric hysteresis cycle results from domain wall nucleation and collapse. AE activity takes place predominantly at applied electric fields large enough to bring a crystal substantially towards its saturation polarisation. A notable feature observed in Pb₅Ge₃O₁₁ and Pb_5?xBa_xGe₃O₁₁ alloys is the existence of an abrupt threshold electric field, denoted by E_∞ in the high gain limit, for production of AE: as the electric field is increased beyond the threshold value, the amount of AE observed increases by several orders of magnitude. E_∞ depends linearly on the inverse of the c-plate sample thickness (1/d) and also upon sample temperature—falling to a minimum at about 70°C for Pb₅Ge₃O₁₁ and then rising steeply as the Curie temperature (178°C) is approached. E_∞ is also dependent on the rate of change of the applied electric field and as this is increased extrapolates to the high frequency limit of the coercive field. Measurements of crystal polarisation indicate a one-to-one correspondence between AE and the electrical Barkhausen pulses which occur during polarisation reversal—further evidence for domain nucleation and collapse as the source of AE. Optical and AE studies made simultaneously on gadolinium molybdate add confirmation that these particular processes are responsible for the AE produced by ferroelectric crystals.     

Effective charge of divalent lead: Application to the assignment of infrared modes in ferroelectric Pb5Ge3O11

A correlation between Szigeti effective charge and the electronic polarizability is found for the eight compounds containing divalent lead where experimental data are available. Results in Pb₅Ge₃O₁₁ contribute to remove some ambiguity about the assignment of polar vibrational modes as external or internal to GeO₄ and Ge₂O₇ entities in ferroelectric lead germanate. Complete TO-LO splittings are also deduced from infrared reflection spectra obtained at room temperature. Results are compared with previous controversial Raman measurements of the polar character of the modes including the soft mode.     

Oriented surface autosegregation in the lead germanate single crystals

High-resolution raster electron microscopy, X-ray phase analysis, and atomic force microscopy were used to study the phase composition and morphological features of Pb₅Ge₃O₁₁ surface nanostructure formed as a result of thermostimulated surface segregation. It was experimentally established that, at some temperature, oriented Pb₃GeO₅ nanoparticles of 10–50 nm in size appeared. A probable mechanism of this phenomenon (which can be attributed to a new type of epitaxy implemented by selective intrinsic mass transfer to the surface) was discussed.     

Isofrequency Opalescence in Ferroelectrics

Isofrequency dependences of the spectral intensities of inelastic scattering in LiTaO₃, Pb₅Ge₃O₁₁, BaTiO₃, and KNbO₃ crystals are registered at a fixed frequency of the spectrometer close to that of the exciting radiation. Results from soft mode analysis are presented.     

Polarization-optical study of the Barkhausen effect and domain structure of lead germanate

A method of localized polarization-optical measurement of dielectric hysteresis loop parameters on microscopical areas of ferroelectric samples combined with simultaneous observation of their domain structure is proposed. A sensitive two-beam differential polarization-optical hysteresisgraph is built for performing the experiments. Examples are given of the study of slow domain structure relaxation processes and dielectric hysteresis curves of lead germanate Pb₅Ge₃O₁₁.     

Impurities and the static central peak in lead germanate

The static central peak in the Raman spectrum of lead germanate (Pb₅Ge₃O₁₁) has been studied as a function of barium-doping and oxygen concentration. It is found that the substitution of barium for lead dramatically increases the intensity and temperature spread of the central peak while also shifting it and the Curie point to much lower temperatures. On the other hand, variations in the observed central peak intensity in nominally pure samples cannot be correlated with variation in oxygen content and must be attributed to some as yet unidentified impurities or defects.     

Specific features of the electron paramagnetic resonance spectrum in the vicinity of the convergence of the transitions of gadolinium centers in Pb5(Ge1 − x Si x )3O11

An anomalous electron paramagnetic resonance spectrum of the transitions ?1/2 ? +1/2 of four Gd³⁺-Si dimer clusters in the Pb₅(Ge_{1 ? x} Si _x )₃O₁₁ crystals doped with gadolinium has been found in the vicinity of the orientation of the magnetic field along the optic axis of the crystal. It has been assumed that this spectrum is caused by rapid transitions between the spin packets of the initial resonances due to the crossrelaxation. A computer simulation of the spectrum has been carried out. The results obtained adequately describe the experiment.     

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)     

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.     

Paramagnetic copper centers in ferroelectric lead germanate with halogens

The electron paramagnetic resonance spectrum of triclinic bivalent copper centers in copper-doped Pb₅Ge₃O₁₁ single crystals has been investigated. The spectrum intensity increases after thermal treatment in a chlorine- or fluorine-containing atmosphere. The parameters of the electron Zeeman, hyperfine, and nuclear quadrupole interactions have been determined. The model of the observed centers has been proposed.     

Effects of the interaction of electron paramagnetic resonance transitions of copper and gadolinium centers in lead germanate single crystals

This paper reports on the results of investigations into the temperature and orientation dependences of the electron paramagnetic resonance spectrum in the vicinity of accidental coincidence of the spectral lines attributed to the signals (homogeneously broadened or with an antisymmetric arrangement of the spin packets) from Cu²⁺ and Gd³⁺ impurity centers in the ferroelectric lead germanate Pb₅Ge₃O₁₁. The parameters of the broadening and coupling of the spectral components are determined using computer simulation of the electron paramagnetic resonance spectra involving coupling (exchanging) components.     

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.     

Analysis of the exchange magnetic structure in Pb<Subscript>3</Subscript>Mn<Subscript>7</Subscript>O<Subscript>15</Subscript>

The indirect-coupling model is used to analyze the exchange magnetic structure of Pb₃Mn₇O₁₅ in the hexagonal setting. The ratios of manganese ions Mn⁴⁺/Mn³⁺ in each nonequivalent position are determined. Pb₃(Mn_0.95Ge_0.05)₇O₁₅ and Pb₃(Mn_0.95Ga_0.05)₇O₁₅ single crystals are grown by the solution–melt method in order to test the validity of the proposed model. The structural and magnetic properties of the single crystals are studied. The magnetic properties of the grown single crystals are compared with those of nominally pure Pb₃Mn₇O₁₅.     

Gd<Superscript>3+</Superscript> EPR in solid solutions based on ferroelectric lead germanate

The splitting of the ERP spectrum of a single Gd³⁺ ion into four intense components has been observed in crystals of Pb₅(Ge_{1 − x} Si _x )₃O₁₁ solid solutions, which is caused by the appearance of silicon ions in three nearest germanium spheres. The atomic structure of the observed centers has been determined. The conclusion has been made that silicon mainly substitutes for germanium in oxygen tetrahedra and for one of germanuim atoms in oxygen bitetrahedra, which is based on comparison of the measured ratio of component intensities with the results of the calculation of the concentrations of Gd³⁺ associations with silicon ions.     

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.