Submillimeter electron-nuclear excitation spectra in CsCdBr3:Ln3+ (Ln=Tm, Ho) crystals

The ESR spectra of single and pair impurity centers of thulium and holmium ions in CsCdBr₃:Tm³⁺ and CsCdBr₃:Ho³⁺ crystals are measured in the frequency range 160-400 GHz. Analysis of the characteristic features of the hyperfine structure of the ESR lines and analysis of the variations in the spectra as a function of the temperature and external magnetic field shows that the Ln³⁺ ions substitute for Cd²⁺ ions and predominantly form symmetric pair centers of the type Ln³⁺-(vacancy at a neighboring Cd²⁺ site)-Ln³⁺. The ESR spectra of CsCdBr₃: Ln³⁺ crystals are used to make a positive identification of the optical spectra of selective laser excitation. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 7, 535–540 (10 April 1997)     

Paramagnetic defects in BaTiO3 and their role in light-induced charge transport — Optical studies

On the basis of a previous identification of paramagnetic defects in nominally undoped as grown BaTiO₃ single crystals, we have investigated the changes of the concentrations of these centers and their optical absorptions under illumination with light of varying wavelengths. The most pronounced charge transfers occur by hole ionization of Fe⁴⁺ and — to a lesser extent — of Cr⁵⁺ and Cr⁴⁺. At low temperatures the created holes are trapped in the form of O^–-ions next to Al³⁺ or unknown acceptor defects. Corresponding Fe⁴⁺ and O^– absorptions have been identified.     

Self-compensation characteristics of Eu ions in BaTiO3

In order to clarify whether the mixed valence of Eu²⁺/Eu³⁺ exists in a self-compensation mode in Eu-doped BaTiO₃, the site occupation and valence state of Eu ions in barium titanate were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), Raman spectroscopy (RS), and dielectric measurements. The results indicate that Eu ions may enter both Ba- and Ti-sites as Eu³⁺, forming a self-compensation mode with the amphoteric behavior. Self-compensation characteristics of Eu ions in BaTiO₃ are reflected by an expansion in unit cell volume, evolution of the 830 cm^− 1 Raman band, strong diffusion of the dielectric peak, disappearance of the Eu²⁺ ESR broad signal, and a g = 2.004 signal independent of temperature.     

Infrared and ESR spectroscopy of KTaO3 : Er

Infrared reflection and ESR spectra of KTaO₃ : Er³⁺ single crystals have been investigated. The frequency of the lowest optical phonon mode TO₁ has been found to increase as compared to undoped KTaO₃ crystals, which indicates the suppression of the ferroelectric instability of the system. The ESR spectra have revealed the presence of two Er³⁺ centers of different (cubic and non-cubic) symmetries in KTaO₃ : Er³⁺.     

Vibronic Frenkel exciton in a soft-mode crystal

The pair electron-hole Jahn-Teller effect, which is realized on degenerate states of a vibronic Frenkel exciton (VFE) in soft-mode crystals, is considered. It is shown that the vibronic effect in a VFE can be significantly enhanced in crystals having soft lattice modes. The occurrence of strong local order-disorder fluctuations in this situation is predicted. The manifestations of VFEs localized at impurities in soft matrices (Cr³⁺ in SrTiO₃, Fe⁵⁺ in KTaO₃, and Mn⁵⁺ in TbVO₄ and TbPO₄) are considered. The possibility of fluctuation effects related to VFEs in nominally pure soft-mode crystals (SrTiO₃ and BaTiO₃) is discussed.     

Pressure induced effects in forsixrite monitored by ESR

Summary

Chromium doped single crystals of Forsterite where investigated directly under the influence of uniaxial pressure in situ by ESR. The two Cr³⁺ centres M₁ and M₂ exhibit distinct response to the action of pressure on the crystal as a whole. The pressure effects are manifested in remarkable changes of the line width of the fine structure transitions. Uniaxial pressure in the MPa range induces nearly symmetrical distribution of distortions of the coordination polyhedra of the Cr³⁺ centres accompanied by reorientation effects.     

Thermoluminescence and ESR phenomena in X-ray irradiated mixed alkaline-alkaline earth metal sulfates—I

Abstract

Thermoluminescence (TL) and ESR phenomena induced by X-ray irradiation of the mixed samples of K₂SO₄ and alkaline earth metal sulfate (MgSO₄ or BaSO₄) were investigated in terms of the reactivities and the crystallogrpahic properties. A high intensive TL resulted from the diffusion of a small amount of Mg²⁺ into K₂SO₄ crystals. The amount formed of K₂Mg₂(SO₄)₃, langbeinite, compound had a maximum at the stoichiometric composition. From the ESR measurements, SO^? ₃ radicals were found to be easily formed in the langebeinite by excitation. Both the TL and the ESR phenomena were hardly observed in the K₂SO₄–BaSO₄ system due to little diffusion of Ba²⁺ with much larger radius than Mg²⁺. The results were mainly discussed on the basis of the radii of the component cations in these systems. In addition, the fundamental data as to the application to the ESR dosimetry were obtained.     

ESR of Fe3+ -Rhombic,Fe2+ -Vo and Fe1+ -Vo complexes in SrTiO3

Three new Fe-defect complexes have been identified by ESR in Fe doped crystals of SrTiO₃. These are an Fe³⁺ center with rhombic fine structure in the “as-grown” crystals, and the vacancy associated complexes Fe²⁺ -V_o and Fe¹⁺ -V_o in “reduced” crystals. Photo-excited charge transfer effects are observed for these centers.     

Impurity mediated mechanism of photorefractive effect in BaTiO3: A combination of sangster and piezoelectric effects

An impurity mediated mechanism of photorefractive effect in BaTiO₃ is proposed. The photoinduced changes in the relative concentration of Fe³⁺ in BaTiO₃ results in an electro-optic coupling through a combination of the Sangster and piezoelectric effects. This is based on the examination of the extensive results on the EPR of Fe³⁺ in the BaTiO₃ lattice. This model explains the improved photorefractive behavior of BaTiO₃ on doping with Co²⁺.     

Valence states of cobalt in BaTiO3: An EPR study

A study by means of the Electron-Paramagnetic-Resonance (EPR) technique of the valence states of the cobalt ion in oxidized and reduced BaTiO₃ is presented. As a result, the identification of high-spin Co⁺ in reduced crystals was possible. The Co²⁺ centre is also discussed.     

Effects of Gd<Superscript>3+</Superscript> doping on structural and dielectric properties of PZT (Zr:Ti = 52:48) piezoceramics

The purpose of this research is to study the effect of doping Gd into Pb(Zr_0.52Ti_0.48)O₃ ceramics prepared by solid state reaction. X-ray diffraction patterns show that all PGZT samples are of tetragonal structure and the highest doping should be no more than 2 mole % Gd at which the unreacted oxides start to appear. The electron spin resonance (ESR) spectra of PGZT's indicate that Gd³⁺ can enter both A site of the perovskite structure instead of only A site as widely believed. The ESR peaks resonance shift towards low fields as the concentration is higher, which is due to the change in crystal field experienced by Gd³⁺ ions. At x =0.001, 0.005 and 0.01 dopings, two sets of powder ESR signals arising from Gd³⁺ (4f⁷, spin 7/2) ions at A site. The first set shows some fine structure having strong absorption peaks centered at 76.26 mT (g = 8.550). The second is a seven-peak spectrum centered at 206.01 mT (g = 3.165), which belongs to the Gd³⁺ ions at B sites. Furthermore, the overlapped ESR strong absorption peaks from 309.17 mT to 314.49 mT (g = 2.2818-2.1087) belong to Gd³⁺ of unreacted Gd₂O₃. The local environments of Gd³⁺ ions were verified from the calculated ESR spectra using appropriate spin Hamiltonian parameter, i.e. gyromagnetic tensor g, zero-field splitting D and hyperfine tensor A.     

ESR study of rare-earth ions with the effective spin of 1/2 in LiNbO3 crystals

Rare-earth ions of Nd³⁺ and Er³⁺ in nearly stoichiometric and MgO-doped LiNbO₃ crystals, respectively, have been investigated by employing an X-band electron spin resonance (ESR) spectrometer. The grown crystal was heated in Li-rich powder at 1100°C in order to make it nearly stoichiometric by the vapor transport equilibrium technique. Due to the fact that the ESR linewidth is much narrower in the stoichiometric crystal than in the congruent LiNbO₃, we were able to determine the hyperfine constants of¹⁴³Nd and¹⁴⁵Nd at 4 K. By codoping MgO into LiNbO₃, a new Er³⁺ center has been observed with a differentg-tensor. We propose that the new Er³⁺ center in Mg-doped LiNbO₃ occupies the niobium site due to the local excessive Mg²⁺ ion at the lithium site, whereas Nd³⁺ and Er³⁺ in congruent crystals reside at the lithium site. The proposal is consistent with theg-value anisotropy.     

The structure of trapped hole centres in Al-doped TiO2

In rutile single crystals the ESR signals of holes are observed, trapped near [Al]^- and [Al-Al]^- centers upon u.v. excitation with the 405 nm Hg-line. The different centers can be thermally populated and quenched during warm-up of the crystals. Their charge state seems connected with charge transfer processes at other (e.g. Fe³⁺ impurities causing the photochromic behaviour of rutile.     

ESR study of the ferrimagnetic spinel selenide CuCr2Se4

Ferrimagnetic spinel selenide CuCr₂Se₄ has been investigated by the electron spin resonance (ESR) spectroscopy. Experimental results reveal that ESR signals originate from the localized d-shell electrons of Cr³⁺ ions. In addition, the ESR linewidth ΔH _PP increases linearly with decreasing temperature. It is suggested that the spin-orbit coupling may be one of the contributions to the broadening of ΔH _PP . Our ESR results support the model of the ferrimagnetic hybridization between localized 3d ³ electrons of Cr³⁺ with delocalized holes of Se 4p band.     

Electron spin resonance of copper pair centers in crystals with perovskite structure

Copper pair centers, which could be of interest for obtaining quantitative information about exchange interactions in superconductors based on cuprate perovskites, are observed in crystals with the perovskite structure by the ESR method. Such centers are investigated in KTaO₃:Cu and K_1−x Li_xTaO₃:Cu crystals. A model consisting of a chain of two equivalent Cu²⁺ ions and three oxygen vacancies, extending along the 〈 100〉 axis, is proposed for the centers. The exchange interaction in the pairs is ferromagnetic. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 12, 890–894 (25 June 1999)     

Impurity centers in a barium titanate ceramic doped with rare-earth ions

The ceramic BaTiO₃ doped with rare-earth ions Y, La, Nd, Sm, Lu, and Dy to 0.1–0.5 at. % was studied in the temperature range 160<T<480 K by ESR. Several ESR spectra were observed. The most intense spectra have g factors close to 5.5 and 1.96. The dependences of their intensity, g factor, and width on the concentration of rare-earth ions and temperature were studied. Analysis of the data obtained made it possible to determine the critical concentration of the rare-earth ions x _c =0.2–0.3 at. %. It is characterized by the fact that for x<x _c or x>x _c all rare-earth ions, except Lu, replace predominantly Ba⁴⁺ or Ti⁴⁺, respectively. Models of paramagnetic centers were established: Fe³⁺-V _O (g≈5.5) and Ti³⁺-Ln³⁺ (g≈1.96), where V _O is an oxygen vacancy and Ln is a rare-earth ion. An abrupt change in axial symmetry to cubic for a Fe₃₊-V _O center at a phase transition from the tetragonal into the cubic phase was observed for the first time. The role of new centers in the appearance of the posistor effect is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 1838–1842 (October 1999)     

BaTiO3和Ce:BaTiO3单晶的高温喇曼散射研究

从室温至180℃测量了BaTiO₃和Ce:BaTiO₃单晶的偏振喇曼谱,在X(ZZ)Y几何配置下发现了三条频率分别为986,1204和1480cm^-1的新谱线.根据喇曼散射截面的温度依赖关系,确认这些新谱线对应二阶喇曼散射,而A₁(TO)谱中位于275和514cm^-1处的非对称宽峰则属于一阶喇曼散射.在此基础上,对立方相BaTiO₃的喇曼谱和结构相变机制进行了讨论.通过比较B     

Crystal field narrowing and relaxation rates in the ESR spectra of CePd3:Gd intermediate valence compound

The mechanisms that are responsible for the thermal behaviour of the ESR lines CePd₃:Gd are examined. A complete fitting of the ESR spectra, both for single crystals and powdered samples is obtained. The mechanisms considered in this work are the narrowing of the fine structure of Gd³⁺ in low temperatures, the excitation energy of the 4f⁰ to 4f¹ configurations of Ce, and the possible existence of an hybridization hole. Complete fitting of the ESR spectra is obtained in the whole range of temperatures.     

Nanocrystalline BaTiO3, doped with Eu and Cr: Fluorescence spectroscopy and spontaneous ordering effects

The results of optical studies of Cr³⁺ and Eu³⁺ ions doped nanocrystalline ferroelectric BaTiO₃ produced by the sol-gel process (particle size 20-40 nm) are reported. The Cr³⁺ impurity ions ²E-⁴A₂ (R-lines) fluorescence spectra in BaTiO₃ revealed significant differences from that reported in literature for the bulk material. At least three types of Cr³⁺ centers were found in the spectra. The temperature dependence of optical second harmonic generation in nanocrystalline BaTiO₃: Eu³⁺ shows a strong hysteresis in C_4v-O_h ferroelectric phase transition region, which was explained by the ordering effects in the system of electric dipole moments of dipole nanocrystals. The temperature dependencies of radiative lifetime of Eu³⁺⁵D₀ excited level reveal some hysteresis too. The possibility of influence of the ordering in the system of BaTiO₃:Eu³⁺ nanocrystals on the effective index of refraction of the medium and thus on the Eu³⁺⁵D₀ radiative lifetime, due to the local field effects is discussed.     

Experimental studies of electrical conduction mechanism of H2-reduced BaTiO3

ESR, resistivity and Seeback coefficient measurements have been performed on both ceramics and single crystals of reduced semiconducting BaTiO₃.From the results that the observed temperature dependence of the Seeback coefficient can be explained by the temperature dependence of carrier concentration estimated from the electric resistivity making use of the data of electron mobility, it is concluded that the electric conduction in reduced BaTiO₃ is due to the band conduction rather than to the hopping process. From the measurement of the temperature dependence of the ESR intensity of the F-center, the number of electrons trapped at the F-centers decreases exponentially with temperature, while the number of conduction electrons increases. This temperature dependence can not be simply explained as that of the unionized donors in semiconductor. Therefore, the ESR signal considered as that of the F-center may not be due to simple donors, even though some of the conduction electrons may be originated in them.