The use of surface charging in the SEM for lithium niobate domain structure investigation

The different lithium niobate crystals with opposite domain structure (ODLN) were studied in the SEM using e-beam negative surface charging. In the ODLN the polarization vector Ps alternates periodically "tail-to-tail" and "head-to-head" and arranges perpendicular to the domain boundaries. In the investigation we have used congruent LiNbO(3) crystals (CLN) and Cr(2)O(3)- and In(2)O(3)-doped LN with the ODLN structure. Initial surface potential images in secondary electron (SE) mode and charge accumulation on the Y-cut surfaces of different LiNbO(3) crystals were compared. The initial surface potential relief in ODLN was found to depend on the position of "tail-to-tail" and "head-to-head" domain walls in the structure. In the doped LN with the periodical domain structure formed during the growth process, the surface potential changes near the domain walls are much weaker than in the structures of CLN obtained by the aftergrowth thermoelectrical treatment technique. A well-defined SE image of "tail-to-tail" domain walls was observed upon special surface negative charging in all types of investigated LN crystals. The negative surface charging in the "tail-to-tail" domain wall areas proceeded slower and the SE exit from these areas decreased as compared to other crystal areas. The charging conditions for the domain wall observation in all samples were comparatively analyzed. The width and uniformity along the boundary images were different and correlated with doping in the crystals. The formation of different charge images could be explained by a variety of positive point defect distributions near the "tail-to-tail" domain walls in different LN crystals. The defects and doping ions screen polarization charges in the "tail-to-tail" wall area and can influence recombination rates of charges induced by an electron beam. Therefore, these domain wall areas are charged much weaker at negative surface charging than other domain areas. This SEM approach could afford a possibility to compare the distribution of the defects that screen the polarization charges and accumulate near the ferroelectric domain wall areas in LN crystals.     

Dielectric loss as an indication of the kinetics of the ferroelectric phase transition

The dependences tanδ(f, T) for triglycine sulfate and diglycine nitrate single crystals are investigated in the frequency range f = 1?2 × 10⁷ Hz at temperatures from ?150 to 50°C for triglycine sulfate and from ?150 to ?60°C for diglycine nitrate. The results are discussed in the framework of the model according to which two or more types of media with different dielectric properties are formed in the ferroelectric phase. The polar volumes of domains themselves and the volumes of domain walls with different symmetries are treated as individual media. The dependences tanδ(f, T) make it possible to separate the contribution of a particular medium and to trace its evolution with temperature. The results of the analysis of the relaxation properties confirm that the phase transitions lead to the formation of two media (the polar medium and domain walls) in triglycine sulfate and three media (the polar medium and two types of domain walls) in diglycine nitrate. It is demonstrated that the relaxation properties are not steady-state characteristics of the samples but depend on their prehistory.     

The effects of external influences on the distribution of polarization in calcium barium niobate crystals of differing composition

The pyroelectric properties and state of polarization of calcium barium niobate single crystals Ca_xBa_1–xNb₂O₆ (CBN) with x = 0.28, 0.30, and 0.32 are studied. It is shown that in contrast to CBN30 and CBN32 crystals, the effect of the alternating electric fields higher than the coercive field changes the state of polarization in the surface layer of the CBN28 crystal. At the same time, thermal cycling to temperatures higher than the Curie point leads to the formation of a system of antiparallel domains in CBN30 and CBN32 crystals, and to complete depolarization of CBN28 crystals.     

Recording of domains by an electron beam on the surface of +Z cuts of lithium niobate

Using an electron beam, spontaneous polarization on the surface of +Z cuts of lithium niobate crystals of various compositions is switched. Domains 100–200 nm in size are formed in a thin surface layer, with the thickness dependent on the primary-electron energy. The sizes of segments, on which submicron domains are formed, exceed the sizes of the irradiation region. The distributions of domains on the surface in crystals of various compositions are different and depend on the method of moving the electron beam and irradiation conditions. The results are discussed in the context of notions on the charging of dielectric materials by the electron beam. It is assumed that the spontaneous polarization in the surface layer of +Z cuts of lithium niobates is switched by the field of a double layer of charges formed as a result of the charging process near the surface.     

Intermediate phases in [111]- and [001]-oriented PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>–29PbTiO<Subscript>3</Subscript> single crystals

Phase transformations in [111]- and [001]-oriented PbMg_1/3Nb_2/3O₃–29PbTiO₃ single crystals have been studied using dielectric and optical measurements before and after applying an electric field. It is shown that the subsequence of phase transitions rhombohedral (R)—tetragonal (T)—cubic (C) phases is observed in nonpolarized samples of both orientations as temperature increases. In the [111]-oriented crystal, an additional intermediate monoclinic phase (it is possible, M _a ) is induced after preliminary polarization at room temperature and the R–M _a –T–C phase transitions are observed on heating. In the [001]-oriented crystal, after its polarization, the monoclinic phase forms instead of the rhombohedral phase even at room temperature and the M _a –T–C transitions occur on heating. The results are discussed from the point of view of the existence polar nanoregions with different local symmetries in a glasslike matrix.     

Dielectric properties of glycine phosphite crystals in the model of a phase transition with inclusion of high-order invariants

Dielectric anomalies in the vicinity of the ferroelectric phase transition in nominally pure glycine phosphite (GPI) crystals and glycine phosphite crystals containing 2 mol % glycine phosphate (GP) are studied. It is revealed that the impurity-induced internal macroscopic polarization observed for GPI-GP crystals brings about smearing of the dielectric anomalies in directions both parallel and perpendicular to the axis of spontaneous polarization. The ferroelectric phase of the GPI and GPI-GP crystals is characterized by an unusual variation in the inverse permittivity in the Z direction perpendicular to the Y axis of spontaneous polarization. The temperature dependence of the inverse permittivity is described by a power expression (T _c ? T) ⁿ with an exponent n larger than unity. The experimental data are analyzed in terms of the proposed thermodynamic model with two order parameters, namely, the displacement parameter η and the order-disorder parameter P, which have different physical natures but the same symmetry and allow for coupling invariants of the ηP and η³ P types, as well as for the built-in polarization in the case of GPI-GP crystals. The experimental and theoretical dependences are in good agreement. The coefficients of bilinear and nonlinear coupling between the order parameters are determined. It is shown that the phase transition in the crystals occurs in the vicinity of the tricritical point and that the unusual behavior of the permittivity with a variation in the temperature is explained by the contribution from high-order invariants of coupling.     

Influence of the defect state of samples on the luminescence spectra of CdS single crystals irradiated by electrons

The photoluminescence spectra of CdS single crystals irradiated by electrons (E = 1.2 MeV, Φ = 2×10¹⁷ cm^?2) are investigated in the visible and near-infrared regions of electromagnetic radiation. Some samples of the CdS single crystals are preliminarily irradiated by neutrons (E = 2 MeV, Φ = 2 × 10¹⁸ cm^?2) with the aim of increasing the concentration of initial structural defects. From analyzing the peak intensities of photoluminescence in the irradiated single crystals at the wavelengths λ_m = 0.720, 1.030, and 0.605 μm, it is concluded that the CdS samples with a low concentration of structural defects in the initial state possess the highest resistance to electron radiation. It is assumed that the observed transformation of the photoluminescence spectra of the imperfect CdS single crystals subjected to electron irradiation is determined by either the mechanisms of subthreshold defect formation or the transformation of the defect complexes in elastic and electric fields near the large structural damages of the crystal lattice.     

Dependence of the X-Ray Dosimetric Parameters of AgGaS<Subscript>2<Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>2–2<Emphasis Type="Italic">x</Emphasis></Subscript> Single Crystals on Their Composition

It is demonstrated that AgGaS_2xSe_2–2x single crystals grown by the chemical transport method are characterized by high X-ray conductivity and X-ray sensitivity coefficients at room temperature. The X-ray dosimetric parameters of crystals are compared. For example, the X-ray conductivity coefficient of AgGaS₂ samples varies within the range of 0.22–3.20 min/R at effective radiation hardness V _a = 25–50 keV and dose rate E = 0.75–78.05 R/min. Single-crystalline AgGaSe₂ samples have higher X-ray dosimetric coefficients than AgGaS₂-based samples. The X-ray conductivity coefficient of AgGaSe₂ varies within the range of 1.2–8.5 min/R at effective radiation hardness V _a = 25–50 keV and dose rate E = 0.75–31.3 R/min. The dose dependences of steady-state X-ray current in AgGaS_2xSe_2–2x are determined.     

Specific Features of the Domain Structure of BaTiO<Subscript>3</Subscript> Crystals during Thermal Heating and Cooling

This paper presents the results of the study of the domain structure of barium titanate crystals in a wide temperature range including the Curie point (T_C) using the polarization-optical method in the reflected light and the force microscopy of the piezoelectric response. It is shown that a new a–c domain structure forms during cyclic heating of the crystal above T_C and subsequent cooling to the ferroelectric phase. The role of uncompensated charges appeared on the crystal surface during the phase transition and their influence on the formation of the domain structure during cooling are discussed.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.     

Observation of electric polarization in Gd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> (<Emphasis Type="Italic">x</Emphasis> = 0.5, 0.6, 0.7) single crystals

In Gd_1?xSr_xMnO₃ (x = 0.5, 0.6, 0.7) single crystals, a change in electric polarization (ΔP ～ 100 μK/m²) is found to accompany the suppression of the charge-ordered spin-glass state and the transition to the ferromagnetic conducting phase (H_cr ～ 100 kOe at 4.5 K). The transition is also characterized by jumps in magnetization and magnetostriction. The sign of the induced polarization depends on the polarity of the electric field in which the sample was preliminarily cooled. This dependence testifies to the presence of spontaneous electric polarization in the system. The effect is maximal at x = 0.5 and decreases by more than an order of magnitude as x increases to 0.7. The phenomenon observed in the experiment may be associated with the new noncentrosymmetric structures with an electric dipole moment that were recently predicted for manganites (x ～ 0.5) [Nature Materials 3, 853 (2004)]. These structures exhibit charge-orbital ordering such that e _g electrons are not localized by one of the manganese ions but distributed between neighboring ions, thus forming an ordered dimer structure.     

Dual structures and transition regions in <Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript>-(1−<Emphasis Type="Italic">x</Emphasis>)Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> crystals

Model concepts of dual structures are developed as applied to crystals of xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ solid solutions in the range 0 ≤ x ≤ 0.08. The conditions of the formation of dual structures upon partial and complete relaxation of internal mechanical stresses are considered. A new model of transition regions is proposed for analyzing several variants of changing the unit cell parameters that satisfy the condition of complete stress relaxation inside the transition regions in crystals at concentrations x = 0.045 and 0.08. The influence of the intermediate phase P4mm and stability of its 90° domain structure on the formation of dual structures at x ≥ 0.045 is discussed.     

Optical properties of lithium niobate and lithium tantalate crystals with impurities and defects

The photoinduced and Raman scattering in lithium niobate and lithium tantalate crystals with impurities and defects have been studied. An exciting laser beam propagated either along the ferroelectric Z axis or perpendicular to it. The conditions for exciting transverse and longitudinal polar optical modes in Raman spectra are established. The regularities of the excitation of Raman spectra in several polarization geometries (X(ZZ)Y, Z(XX, Y Y)Z, Z(XX, Y Y)Z, X(ZX)Y, X(ZX)X and X(ZX)X) have been investigated. Additional (extra) spectral lines are interpreted as a manifestation of a biphonon enhanced by the Fermi resonance and the result of violation of selection rules for pseudoscalar modes of the A ₂ type due to the reduction of the point symmetry group caused by the presence of impurities and defects in real crystals. The conditions for exciting coherent longitudinal and transverse modes in lithium niobate and lithium tantalate single crystals upon stimulated Raman scattering are analyzed. The temperature evolution of the spectra recorded in the X(ZZ)Y geometry near the ferroelectric phase transition point is explained based on the concept of effective soft mode and analysis of the isofrequency opalescence effect. Strong photoluminescence is found in copper-doped lithium niobate crystals.     

Thermooptical and Dielectric Studies of a Calcium-Induced Ferroelectric Phase in a SrTiO<Subscript>3</Subscript> Incipient Ferroelectric

We have examined temperature changes of the light refraction, birefringence, dielectric permittivity, and dielectric hysteresis loops in Sr_{1 – x}Ca_xTiO₃ single crystals with x = 0.014 (SCT-1.4). The dielectric properties of Sr_{1 – x}Ca_xTiO₃ with x = 0.007 (SCT-0.7) have been studied. We have performed ab initio calculations of equilibrium structures and total energies for three low-temperature phases of SrTiO₃ and CaTiO₃, based on which we have determined an expected symmetry of the ground state of their solid solution and spontaneous polarization directions in a calcium-induced ferroelectric phase in Sr_{1 – x}Ca_xTiO₃. In SCT-1.4, we have separated a spontaneous contribution to the light refraction, which arises due to the spontaneous electrooptical effect caused by the spontaneous polarization and its fluctuations. From the spontaneous contribution to the light refraction, based on a previously developed our phenological approach, we have quantitatively determined for the first time the values and temperature dependences of root-mean-square fluctuations of the order parameter—the polarization P_sh = 〈P _fl ² 〉^1/2(short-range, local polar order) in the ferroelectric phase. From optical and dielectric measurements in SCT-1.4, the average value of spontaneous polarization P_s (the contribution from the long-range order) has been determined. We have estimated the values of P_sh and P_s, which characterize the short- and long-range orders in the ferroelectric phase of SCT-0.7. Separate determination of the values and temperature dependences of P_s and P_sh (which considerably exceeds the value of P_s in the ordered phase) has allowed us to reveal on a quantitative level new particular features of the formation of the induced polar phase in Sr_{1 – x}Ca_xTiO₃.     

Polar phonons and specific features of the ferroelectric states in cadmium titanate

Polarized spectra of reflectance R(ν) and transmittance Tr(ν) of single-crystal CdTiO₃ samples have been obtained in the frequency range 7 < ν < 1000 cm^?1 and for temperatures from 5 to 300 K using IR Fourier spectroscopy and submillimeter-range techniques. Dispersion analysis was carried out in terms of the additive-oscillator model, and dielectric responses ε(ν) and ε″(ν) were calculated. The polar modes were assigned to particular symmetry types, and their oscillator parameters (dielectric contributions, normal frequencies, damping constants) were determined. The numerical values of the components of the static permittivity tensor, ε₁₁ and ε₃₃, are shown to be almost fully determined by the total dielectric contributions due to the B_3u and B_1u phonons, respectively. In the low-frequency domain, lines showing anomalous behavior of the oscillator parameters, which is characteristic of soft ferroelectric modes, were observed. It is shown that, in CdTiO₃ at cryogenic temperatures, there exist several different polar states with switching in the direction of the spontaneous polarization vector.     

Dielectric and magnetic properties of the multiferroic Tb<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Bi<Subscript>x</Subscript>MnO<Subscript>3</Subscript>: Electric dipole glass and self-organization of charge carriers

Single crystals of the new multiferroic Tb_(1?x)Bi_xMnO₃ have been grown and studied. A semiconductor compound with x = 0.05 is investigated in most detail. At temperatures T ≥ 165 K, the electric dipole glass state is realized in the crystal. Localized charge carriers form conducting drops of electrons and holes, which are located predominantly in thin layers at the boundaries of polar domains. When drops escape as the temperature increases, jumps in conductance and capacitance are observed. The state of drops is controlled by low bias voltage. The long-range magnetic order arises at temperatures T ≤ 90 K. Negative magnetoresistance is observed at temperatures of the existence of localized charge carriers.     

Unipolar conductivity of SrTiO<Subscript>3</Subscript> crystals with light-induced drop in electrical resistance

This paper reports on the results of the experimental investigation of unipolar (diode) current–voltage characteristics of local regions in high-resistance SrTiO₃ crystals that experienced a light-induced drop in electrical resistance. This behavior has been explained by the influence exerted on the electrical conductivity by the irradiated region in the Schottky barrier of one of the contacts. The ideality factor of the Schottky barrier has been determined and the barrier height for a number of regions has been estimated from measurements of the forward branch of the current–voltage characteristics. An analysis of the specific features in the behavior of the reverse branch of the current–voltage characteristics has revealed that, in the SrTiO₃ crystals with p-type conductivity, the resistance switching occurs through a pure electronic mechanism, in contrast to models based on electrochemical processes, in particular, the migration of oxygen vacancies.     

Effect of gamma radiation on the surface and bulk properties of poly(tetrafluoroethylene)

The effect of gamma radiation on the contact angle θ, the work of adhesion γ _SL for polar and nonpolar liquids, disperse and polar components of the surface energy γ _S , the magnitude of bulk dielectric polarization P ₀, and the dielectric increment Δε for sintered and non-sintered poly(tetrafluoroethylene) (PTFE) of suspension polymerization are studied. Sintered PTFE exhibits anomalously high growth of the studied parameters with an absorbed dose up to 500 kGy: Δε by more than four orders of magnitude, the work of adhesion of the polar liquid \(\gamma _{SL}^{{H_2}O}\) by a factor of 1.5, the polar component of the surface energy γ^pol _S by 20 times. The observed changes are found to be considerably larger than those expected from the viewpoint of the amplification of dipole–dipole and donor–acceptor molecular interactions with the participation of polar groups formed in poly(tetrafluoroethylene) upon irradiation. The similar behavior of Δε, \(\gamma _{SL}^{{H_2}O}\), and γ^pol _S parameters depending on the exposed dose and subsequent annealing of the samples at 150°C is revealed. A unified mechanism for changes in the bulk polarization and surface properties caused by the formation in poly(tetrafluoroethylene) of long-lived electron–hole pairs is suggested.     

Schwingungszustände und optische Eigenschaften von Molekelkristallen

A discussion of the Born-Huang theory of dispersion in polar crystals with regard to the internal vibrations of molecular crystals (organic crystals, ionic crystals with complex ions) connects the imaginary part (?″) of the optical dielectric tensor (?)=(?′)?i(?″) with the eigenfrequencies of the vibrations active in absorption and with the direction and magnitude of the transition moments in crystals. The limits are shown, within which this theory gives a Lorentzian line shape, often found in experiment. The propagation of an electromagnetic wave in a strongly absorbing, anisotropic medium and its reflection at crystal boundaries are investigated with special emphasis on the experimental determination of (?). This treatment leads to expressions for (?), which are not limited to the case of weak absorption and which are valid for all crystal symmetries.