Investigations of the magnetic structure of the surface and volume of aluminum-substituted Sr-M type hexaferrites

The magnetic structure of the surface layer of single crystals of hexagonal ferrites of the type Sr-M (SrFe₁₂O₁₉) in which some iron ions are replaced by diamagnetic Al ions is investigated, in direct comparison with the magnetic structure in the bulk of the sample, by the method of simultaneous gamma, x-ray, and electron Mössbauer spectroscopy. It is found that under conditions of diamagnetic dilution of the magnetic lattice of hexagonal ferrites of the type Sr-M by Al ions, a layer ~200 nm thick in which the orientation of the magnetic moments is not collinear with the direction of the moments in the bulk of the sample is observed on the surface of SrFe_10.2Al_1.8O₁₉ crystals. Thus a “transitional” surface layer has been observed on macroscopic ferromagnetic crystals.     

Thermodynamic and elastic properties of AgInSe<Subscript>2</Subscript> and AgInTe<Subscript>2</Subscript>

The specific heat at constant volume as a function of temperature, the elastic constants, compressibility coefficients, and bulk moduli of AgInSe₂ and AgInTe₂ crystals with a chalcopyrite structure have been calculated in terms of the density functional theory using the pseudopotential method. A comparison of the calculated specific heat for the tellurium compound with the results of measurements has demonstrated good agreement between theory and experiment. The bulk moduli of the AgInSe₂ and AgInTe₂ crystals calculated from first principles (60.4 and 50.1 GPa, respectively) somewhat exceed the results available in the literature, which were obtained earlier from approximate semiempirical formulas.     

Excitation of bulk elastic waves at the surfaces of piezoelectric crystals with 422,622 symmetry

The problem of exciting bulk elastic waves at the surface of a piezoelectric with symmetries 422,622 has been solved by a successive approximation method. In the approximation of a fixed electric field, created at the surface of the piezoelectric crystal by a two-electrode transducer, the distributions are found for the shear wave stress and the energy flux density in the far zone. The equivalent circuit parameters for a two-electrode radiator are determined taking account of the dynamic piezoelectric correction obtained in the second approximation. The equivalent circuit parameters and the transducer loss are treated for TeO₂ crystals. A realistic possibility of using surface transducers in the development of acousto-optic modulators in the s.h.f. region is shown. Tomsk State Academy of Control Systems and Radio Electronics. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 8–15, January, 1997.     

Dispersion of the dielectric function real part for Mg:LiNbO3 crystals at terahertz frequencies

We study dispersion of the dielectric function real part ε′ in the terahertz-frequency range for bulk and periodically poled congruent LiNbO₃ and Mg:LiNbO₃ crystals. The concentration of Mg in Mg:LiNbO₃ samples was close to 5 mol%, which is the photorefractive threshold. Approximate expressions for extraordinary polariton dispersion dependence were obtained in the range 0.5–6.5 THz. The influence of Mg-dopant on the optical properties of crystals in the terahertz range is revealed. Changes of the defect structure of lithium niobate crystals are discussed.     

Application of glancing‐emergent‐angle fluorescence for polarized XAFS studies of single crystals

X‐ray absorption fine‐structure (XAFS) data were obtained for the V K‐edge for a series of anisotropic single crystals of (Cr_xV_1–x)₂O₃. The data and the results were compared for the as‐prepared bulk single crystals (measured in fluorescence in two different orientations) and those ground to powder (measured in transmission). For the bulk single crystals, the glancing‐emergent‐angle (GEA) method was used to minimize fluorescence distortion. The reliability of the GEA technique was tested by comparing the polarization‐weighted single‐crystal XAFS data with the experimental powder data. These data were found to be in excellent agreement throughout the entire energy range. Thus, it was possible to reliably measure individual V–V contributions parallel and perpendicular to the c axis of the single crystals, i.e. those unavailable by powder data XAFS analysis. These experiments demonstrate that GEA is a premiere method for non‐destructive high‐photon‐count in situ studies of local structure in bulk single crystals.     

A stable superconducting state at 8 K and ambient pressure in\alpha _t - (BEDT - TTF^ \star )_2 I_3 ^1

We report bulk superconductivity at 8 K and ambient pressure in crystals of α _t (BEDT-TTF)₂I₃. In contrast to the earlier observed metastable superconducting state at 8 K in crystals of β-(BEDT-TTF)₂I₃ here the superconducting state is stable and the crystals can be prepared by tempering α-(BEDT-TTF)₂I₃ above 70 °C for several days. ac-susceptibility measurements show that the observed superconducting state at 8 K is a bulk property of the crystals. Resistivity measurements indicate a sharp superconducting transition at 8 K with an onset temperature of about 9 K. The upper critical fields H_c2 at 1.3 K lie between 3 and 11 T depending on the direction of the magnetic field with respect to the crystal axes. ESR- as well as NMR-measurements indicate a total transformation of the α-phase crystals into the new superconducting α _t -crystals after tempering.     

Surface morphology of PrBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> single crystals after the long-lasting high-temperature reduction

The results of the detailed scanning electron microscopy study of PrBa₂Cu₃O_7-δ single crystals after the long-lasting high-temperature post-growth treatment are reported. The presence of the unstable decomposition products on the crystal surface indicates that the onset of superconductivity must be related to the structural transformations in the bulk (approximately 20% of the total volume of the examined crystals). The time-dependent character of the superconductivity in the Pr-123 crystals could be attributed to the migration of defects in the Pr−Ba sublattice from the bulk toward the surface.     

Self-neutralization via electroreduction in photoemission from?SrTiO3 single crystals

The effect of bulk mediated neutralization in photoemission from insulating monocrystalline SrTiO₃ was studied. Long-term measurements of the photoemission line shift and emission current allowed us to relate the observed systematic reduction of the surface charging to increasing conductivity of the samples. The bulk resistance of the SrTiO₃ samples was found to scale with their thickness. We present a model of the observed behaviour based on well-conducting filaments connecting the surface with the grounded sample holder, similar to the hypothesis explaining resistive switching in single crystals and thin films of SrTiO₃. In our model the changes of the local oxygen stoichiometry are driven by surface potential and consequently electric field and chemical gradients, which cause electroreduction and electromigration along extended defects in the crystals.     

Spin-reorientation phase transition on the surface and in the bulk of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> single crystals

Direct comparison of the properties of a thin surface layer and the bulk of macroscopic hematite (α-Fe₂O₃) crystals was used to study the magnetic structure of the surface layer and the bulk and the processes attendant on spin-reorientation phase transition (SRT). The investigation tool was simultaneous γ-ray, X-ray, and electronic Mössbauer spectroscopy, which enabled us to study the bulk and surface properties of macroscopic samples simultaneously and to compare them directly. Direct evidence of the existence of a surface “transition layer” on hematite crystals is obtained. The existence of this layer was suggested and described by Krinchik and Zubov [JETP 69, 707 (1975)]. The study in the SRT region showed that (1) the Morin SRT in the crystal bulk occurs in a jump (as a first-order phase transition), whereas in the surface layer of about 200 nm thick, some smoothness appears in the mechanism of magnetic-moment reorientation; (2) SRT in the surface layer, as in the bulk, involves an intermediate state in which low-and high-temperature phases coexist; and (3) SRT in the surface layer occurs at a temperature several degrees higher than in the bulk. Our experimental evidence on the SRT mechanism in the surface layer correlates with the inferences from phenomenological theory developed by Kaganov [JETP 79, 1544 (1980)].     

Emission characteristics, crystalline phase and composition of vapor-transport-equilibrated Er:LiNbO3 crystal codoped with 6 mol% MgO

Polarized downconversion, 980-nm-upconversion and near-infrared emission characteristics of vapor-transport-equilibrated (VTEed) bulk Er (0.4 mol%)/MgO (6 mol%)-codoped LiNbO₃ crystals were investigated. The downconversion and upconversion visible emissions display similar VTE effects including the drop of emission intensity and the weakening of polarization dependence. At 0.98 and 1.5 μm regions, the VTE has a weak effect on the emission intensity, but a strong effect on the spectral shape. The crystalline phases in these bulk Er/Mg-codoped VTE crystals are determined by comparing their infrared emission characteristics with those of pure ErNbO₄ powder and locally Er-doped MgO (4.5 mol%):LiNbO₃ crystal. The results show that the Er³⁺ ions present in these bulk Er/Mg-codoped VTE crystals as a mixture of Er:LiNbO₃ and ErNbO₄ phases. The percentages of the ErNbO₄ phase contained in these VTE crystals were evaluated from the 1531 and 1536 nm characteristic absorption areas. The contents of constituent elements were determined by chemical analysis.     

Mössbauer studies of the surface and bulk magnetic structure of scandium-substituted Ba-M-type hexaferrites

A direct comparison of the magnetic structures of a surface layer and of the bulk of Ba-M-type hexagonal ferrites with iron ions partially replaced by Sc diamagnetic ions (BaFe_12?x Sc_xO₁₉) has been made by simultaneous Mössbauer spectroscopy with detection of gamma rays, characteristic x-ray emission, and electrons. It has been found that, if the magnetic lattice of a Ba-M-type hexagonal ferrite is weakly diluted by Sc diamagnetic ions, a ～300-nm thick macroscopic layer forms on the surface of a BaFe_11.4Sc_0.6O₁₉ crystal, in which the iron-ion magnetic moments are noncollinear with the moments in the bulk. The noncollinear magnetic structure forms in the near-surface layer of BaFe_12?x Sc_xO₁₉ crystals because the exchange interaction energy is additionally reduced by the presence of such a “defect” as the surface. This is the first observation in ferromagnetic crystals of an anisotropic surface layer whose magnetic properties, as predicted by Néel, differ from those of the bulk.     

Transition to 1D conduction with decreasing thickness of the crystals of TaS3 and NbSe3 quasi-1D conductors

It is found that, with decreasing thickness of the crystals of TaS₃ and NbSe₃ quasi-1D conductors, the dependences of the conductivity of these crystals on temperature and electric field change from the form typical of bulk samples to a nearly power law behavior typical of 1D electron systems.     

Fine structure and magnetism of bulk Zn1 − x Cr x Se single-crystal cubic compounds (0 ≤ x ≤ 0.045)

The character of structural and magnetic features of the cubic lattice of bulk Zn_{1 ? x} Cr _x Se crystals (0 ≤ x ≤ 0.045) has been investigated using thermal neutron diffraction and magnetic measurements. It has been found that the diffraction scans of doped crystals contain effects of nuclear diffuse scattering caused by local static atomic displacements in the face-centered cubic (fcc) lattice. Results of magnetic measurements of doped crystals indicate the presence of weak antiferromagnetic correlations, which are a consequence of structural features of these compounds.     

Domain formation inside thick crystals of ferroelectric PbNb2O6

Stress dependence of domains in thick crystals of PbNb₂O₆ is reported. Successive etching shows numerous domains in the bulk not extending to the surface. These domains have correlation with the dislocation substructure in the bulk. The dislocations are in the form of small loops, and domain walls are found terminating along with these loops. The general problem of volume nucleation is discussed, and it is suggested that these dislocation loops play a significant role in domain formation.     

Electrical conductivity studies of cobalt-precipitation in RbCl crystals

The results of electrical conductivity measurements in heavily doped RbCl:CoCl₂ crystals with 2500 and 6000 ppm of cobalt are being reported in this paper. The different regions of the conductivity plots for the crystals with the two concentrations of cobalt have been explained and relevant energy parameters determined. The crystals with 6000 ppm of cobalt have been found to contain two types of precipitates one of these being of the same type as that existing in RbCl crystals with 2500 ppm of cobalt while the other being of a different composition. Further, it has been found that the crystals appear blackened after heating during measurements. The blackening has been attributed to the expulsion of cobalt from the bulk of the crystal which forms an oxide at the surface.     

Reduced space-charge fields in near-stoichiometric LiTaO3 for blue, violet, and near-ultraviolet light beams

The wavelength dependence of the space-charge field as induced in near-stoichiometric LiTaO₃ crystals is investigated by measuring the bulk photogalvanic effect and the photoconductivity. LiTaO₃ crystals of composition nearer to stoichiometry exhibit a pronounced reduction of the saturated space-charge field, which results from a larger increase in the photoconductivity relative to the photogalvanic effect. Especially, at near-UV wavelengths, the saturated space-charge field of the order of 0.1 kV/cm reaches a minimum that is two orders of magnitude lower than typical values observed in undoped near-stoichiometric LiNbO₃. Received: 11 July 2002 / Revised version: 2 September 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1056, E-mail: mojca@fiz.uni-lj.si     

Electrical conductivity in undoped and Mn2+-doped NaNO2 single crystals

Electrical conductivity studies in NaNO₂ single crystals with inherent impurities and also in crystals with added Mn²⁺ impurities have been reported. The heating conductivity runs of undoped and doped NaNO₂ crystals have been compared. The decrease in conductivity in cooling following a heating run has been attributed to the oxidation during heating leading to the bulk precipitation of impurities in the host. Above 170°C however the intrinsic defects are responsible for conduction. An anomaly is noticed in both the heating and cooling conductivity runs of the sample at about the Curie temperatures and has been found to show thermal hysteresis.     

Influence of surface on the effective magnetic fields in α-Fe2O3 and FeBO3

First measurements of the effective magnetic fields as a function of the depth at which the iron ions are in the surface layer of α-Fe₂O₃ and FeBO₃ single crystals are reported. The method used is the depth-selective conversion-electron Mössbauer spectroscopy. An analysis of experimental spectra revealed that the magnetic properties of the crystal surface vary smoothly from the bulk to surface characteristics within a layer ～100 nm thick. The layers lying below ～100 nm from the surface are similar in properties to the bulk of the crystal, and their spectra consist of narrow lines. The spectral linewidths increase smoothly as one approaches the crystal surface. The spectra obtained from a ～10-nm thick surface layer consist of broad lines indicating a broad distribution of effective magnetic fields. Calculations show that the field distribution width in this layer is δ=2.1(3) T, for an average value H _eff=32.2(4) T. It has been experimentally established that, at room temperature (291 K), the effective magnetic fields smoothly decrease as one approaches the crystal surface. The effective fields in a 2.4(9)-nm surface layer of α-Fe₂O₃ crystals are lower by 0.7(2)% than the fields at the ion nuclei in the bulk of the sample. In the case of FeBO₃, the effective fields decrease by 1.2(3)% in a surface layer 4.9(9) nm thick.     

Surface effects on optical phonons and on phonon-plasmon modes

The size and shape dependence of the properties of long wave optical phonons in polar crystals is discussed. The main effect occurring due to the presence of surfaces is the appearance of a surface optical phonon band in the frequency region between the frequencies ω_t and ω_l of the long wave transverse and longitudinal bulk modes. The surface modes give rise to strong absorption peaks in the infrared absorption spectra of small samples. For very small crystallites the surface mode absorption is dominant, and as the size of the specimens is increased, the ratio of surface to bulk mode absorption decreases. It is shown that the large spread in particle sizes usually encountered in experimental work and the increased damping of the phonon modes in small samples both tend to obscure the fine structure of the absorption spectrum. The surface phonon-plasmon modes in polar crystals containing free carriers are treated in an analogous manner.     

Effects of repetitive polarization switching on the coercive voltage of Pt/Pb(Zr0.52Ti0.48)O3/Pt thin films analyzed using impedance spectroscopy

We investigated the effect of repetitive switching of polarization on the ferroelectric Pt/Pb(Zr_0.52Ti_0.48)O₃/Pt thin film capacitor by using impedance spectroscopy. From the Cole-Cole plot, the equivalent circuit is described as a combination of the bulk part (a capacitor), the interface part (the constant phase element (CPE), and a parallelly-connected resistor). The circuit parameters were analyzed at various stages of switching. An early increase and a subsequent decrease of the bulk capacitance may represent the wake-up and fatigue phenomena, respectively. The change in the interface part was characterized by an increase in resistance and the growth of n, the exponent of CPE, which may have come from a reduction of defects and the diminished inhomogeneity in the interfacial layer, respectively. The change in the resistance and the coefficient of the CPE in the interface part collectively resulted in an increase in the interfacial impedance. The coercive voltage, which may have intrinsically increased due to the repetitive switching, was even larger as a result of the increased interfacial impedance.