Electron paramagnetic resonance studies of photorefractive crystals II: Fe3+ doped Bi12SiO20 with copper vapour laser illumination in 10–100 K range

Photo-induced charge transfer and its kinetics were investigated in Bi₁₂SiO₂₀ in 10–300 K temperature range, using EPR of Fe³⁺ centre, underin situ illumination with copper vapour laser (CVL). The decay kinetics was found to follow double exponential behaviour. Relaxation of the photo-induced electron transfer to the preillumination condition occurred even at 10 K. Shallow traps were, therefore, associated with the electron trapping, leading to a better understanding of the fast photorefractive response of BSO.     

Radiation stabilization of U5+ in CaO matrix and its thermal stability: Electron paramagnetic resonance and thermally stimulated luminescence studies

Electron paramagnetic resonance (EPR) evidence is presented for the radiation stabilization of pentavalent uranium in CaO matrix. From the theoretical predictions ofg value for U⁵⁺ in axial symmetries, it was concluded that U⁵⁺ at Ca²⁺ site is associated with a second neighbour charge compensating Ca²⁺ vacancy. EPR measurements also revealed the presence of Mn²⁺, Mn⁴⁺ and Cu²⁺ impurities in the samples. The thermal stability of U⁵⁺ was investigated using EPR and thermally stimulated luminescence (TSL) techniques. The TSL and EPR studies on gamma irradiated uranium doped calcium oxide samples had shown that the intense glow peak at 540 K is associated with the reduction in the intensity of EPR signal of U⁵⁺ ion around this temperature. This peak is associated with the process U⁵⁺+hole→U^6+*→U⁶⁺+hv. The activation energy for this process was determined to be 1.4eV.     

Electron paramagnetic resonance of Mn2+ and Gd3+ in Pr2Zn3(NO3)12.24 H2O single crystals

The electron paramagnetic resonance of Mn²⁺ and Gd³⁺ doped in Pr₂Zn₃(NO₃)₁₂.24H₂O single crystals has been studied at X-band. Mn²⁺ substitutes for two Zn²⁺ sites, while Gd³⁺ substitutes for single type of Pr³⁺ sites. The spin-Hamiltonian analysis of the EPR spectra is presented at 298 K as well as 77 K.     

Electron paramagnetic resonance parameters and local structure for Gd3+ in KY3F10

The electron paramagnetic resonance parameters, zero-field splittings (ZFSs) b₂⁰, b₄⁰, b₄⁴, b₆⁰, b₆⁴ and the g factors for Gd³⁺ on the tetragonal Y³⁺ site in KY₃F₁₀ are theoretically studied from the superposition model for the ZFSs and the approximation formula for the g factor containing the admixture of the ground ⁸S_7/2 and the excited ⁶L_7/2 (L=P, D, F, G) states via the spin-orbit coupling interactions, respectively. By analysing the above ZFSs, the local structure information for the impurity Gd³⁺ is obtained, i.e., the impurity-ligand bonding angles related to the four-fold (C₄) axis for the impurity Gd³⁺ center are found to be about 0.6° larger than those for the host Y³⁺ site in KY₃F₁₀. The calculated ZFSs based on the above angular distortion as well as the g factors are in reasonable agreement with the observed values. The present studies on the ZFSs and the local structure would be helpful to understand the optical and magnetic properties of this material with Gd dopants.      

Surface acoustic wave distribution and acousto-optic interaction in proton exchanged LiNbO3 waveguides

The efficiency of acoustooptic (AO) interaction in YZ-cut proton exchanged (PE) LiNbO₃ waveguides is theoretically analysed by determining the overlap between the optical and acoustic field distributions. The present analysis takes into account the perturbed SAW field distribution due to the presence of the PE layer on the LiNbO₃ substrate determined by the rigorous layered medium approach. The overlap is found to be significant upto very high acoustic frequencies of the order of 5 GHz, whereas in the earlier analysis by vonHelmolt and Schaffer [6] for diffused waveguides, it was shown that the overlap integral rolls down to nearly zero at this high frequency range.     

Spectral line intensities of Yb3+ ion in LiNbO3 crystals

Optical spectra of absorption and luminescence of LiNbO₃:Yb³⁺ crystals are investigated experimentally and theoretically. Within the framework of the point charge approximation of crystal field, the Stark problem is solved: crystal field parameters and wave functions of Stark states are determined. Line strengths due to indirect electric-dipole and magnetic-dipole inter-Stark transitions are calculated and values of the Judd-Ofelt parameters are determined. Values of the branching ratios of luminescence. Einstein coefficients and, lifetime of the excited sublevel are calculated. A satisfactory agreement of calculated results with experimental data is obtained.     

Non-equilibrium effects in copper vapor laser pumped Nd3+ doped PVA film: Photo-electon paramagnetic resonance and photoacoustic spectral investigations

Photo-EPR measurements carried out on Nd³⁺ -doped polyvinyl alcohol (PVA) films have shown that nearly 100% reduction occurs in the intensity of EPR of Nd³⁺ under in situ copper vapor laser (CVL) illumination (510.5 nm and 578.2 nm). The kinetics of decay and recovery were investigated. Photoacoustic (PA) spectra, observed under CVL pump condition had shown that the CVL induced changes were not due to photoinduced valence change, and that the CVL pumping creates highly favorable conditions for non-equilibrium population distribution in the excited electronic states. The complete disappearance of EPR under CVL pumping is attributed either to the possible equalization of population of |+〈 and |−〈 Zeeman components, through the decay of many excited states in the presence of magnetic field or configurational changes around Nd³⁺ shifting the resonance frequency. The former appears less probable in view of the relatively slower recovery of EPR signal.     

Electron spin resonance studies of Cu2+ doped in cadmium maleate dihydrate single crystals

Electron spin resonance studies have been carried out on Cu²⁺ ion doped in single crystals of cadmium maleate dihydrate at 303 and 77K. It has been found that Cu²⁺ enters this lattice interstitially. The spin Hamiltonian parameters have been evaluated and the ground state wave function is found to be predominantly |X ² −Y ²〉 with a slight admixture of |3Z ² −r ²〉.     

Electron paramagnetic resonance of NH 3 + radical in potassium sulphate

Room temperature EPR spectra of (NH₄)₂SO₄ doped K₂SO₄ monocrystals irradiated with x-rays show the presence of NH₃ ⁺ radicals. The EPR parameters areg ‖=2.0037 andg ⊥ = 2.0068;¹⁴NA _XX=13.75;A _YY=24.5;A _ZZ=25.5 gauss;¹HA _XX=A _YY=22 andA _ZZ=25 gauss. From the¹⁴N and¹H coupling constants it has been inferred that at room temperature the planar NH₃ ⁺ radical undergoes rotation about theC ₃ axis which corroborates with the equivalence of the protons, but the radical itself is in an asymmetric crystal field environment. The 77K spectra indicate a considerable reduction in the motion of the radical with the free motion almost completely stopped. Part of Ph.D. work of the second author     

Theoretical explanation of g factors for Ti ions in LiNbO3 and LiTaO3 crystals

The EPR g factors g_// and g_⊥ for Ti³⁺ ions at the trigonal octahedral Li⁺ sites of LiNbO₃ and LiTaO₃ crystals are calculated from the third-order perturbation formulas of g factors for 3d¹ ion in trigonal symmetry. In the calculations, the crystal-field parameters are obtained from the structural data by using the superposition model. The calculated values are in reasonable agreement with the observed values. The results are discussed.     

Electron paramagnetic resonance study of exchange coupled Ce3+ ions in Lu2SiO5 single crystal scintillator

The Ce³⁺ ions incorporation inside lutetium oxyorthosilicate (Lu₂SiO₅) single crystals was studied by electron paramagnetic resonance. Already known Ce1 and Ce2 centers originating from the lattice peculiarity allowing two lutetium sites coordinated by different number of the oxygen ions were detected. Remarkably, for the Ce2 center, the determined g² tensor is asymmetric and could not be diagonalized as compared to the Ce1 center, for which the three principal values and corresponding axes orientation have been determined and reported previously. Besides, the much weaker resonance lines found in spectra close to those coming from the Ce1 and Ce2, and following them under crystal rotation with respect to the direction of an external magnetic field, have been revealed as well. They were classified as doublets produced by the exchange coupled Ce³⁺ ions, creating the Ce1–Ce1, Ce2–Ce2 and Ce1–Ce2-like dimers. The corresponding spin–spin coupling constants were estimated. They are in the range 0.04–0.4 cm⁻¹. The Ce1, Ce2 and total dimer centers populations were calculated as 89%, 4.5% and 6.5%, comparing integral intensities of corresponding resonance lines.     

Electron paramagnetic resonance parameters of Mn<Superscript>4+</Superscript> ion in h-BaTiO<Subscript>3</Subscript> crystal from a two-mechanism model

The EPR parameters (g factors g _‖, g _⊥ and zero-field splitting D) of Mn⁴⁺ ion in h-BaTiO₃ crystal are calculated from the complete high-order perturbation formulas based on a two-mechanism model for the EPR parameters of 3d ³ ions in trigonal symmetry. In the model, not only the widely used crystal-field mechanism, but also the charge-transfer mechanism (which is not considered in crystal-field theory) are included. The calculated results are in reasonable agreement with the experimental values. The relative importance of charge-transfer mechanism to EPR parameters and the defect structure of Mn⁴⁺ centre in h-BaTiO₃ crystal obtained from the calculations are discussed.      

Experimental evidence of photoinduced valence change of Fe3+ in BaTiO3 and mechanism for growth of new grating in depleted pump condition: An EPR investigation

With a view to understanding the role of photo-induced valence changes of impurities in BaTiO₃ in the phenomena of photorefraction, EPR experiments were conducted under in situ He-Ne laser illumination. These experiments gave evidence for photoinduced valence change of Fe in BaTiO₃ at room temperature. The EPR signal due to trivalent iron was found to reduce in intensity with laser illumination The kinetics of the valence change has been investigated. Under large fringe width condition, the time constant of the decay is identified as the dielectric relaxation time τ_d. The changes in line shape on laser illumination to Dysonian form, appeared most predominantly in mechanically poled crystal compared to electrically poled single domain crystals. This demonstrated the possible role of domain walls and the defects there, as source or sinks of charge carriers on photo excitation. It is observed, that there is transient growth of Fe³⁺, when the laser illumination was put on, before its decay. This was attributed to charge transfer between electrons in oxygen vacancies and Fe⁴⁺. This predicted the growth of a transient grating under depleted pump condition in a two beam coupling experiment. This was experimentally proved by following the diffracted signal of the reading beam under the depleted pump condition.     

Electron paramagnetic resonance study of impurities and point defects in oxide crystals

In this topic review the results of the X-band electron paramagnetic resonance (EPR) measurements of Mn, Co, Cr, Fe ions in YAlO₃ (YAP) crystals and Fe ions in LiNbO₃ (LNO) crystals and of chromium doped Bi₁₂GeO₂₀ (BGO) and Ca₄GdO(BO₃)₃ single crystals, are presented. It is well known that the oxide crystals (for example:YAP, LNO, BGO) are one of the most widely used host materials for different optoelectronic applications. The nature of point defect of impurities and produced in the oxide crystal after irradiation by bismuth ions and after irradiation by the ²³⁵U ions with energy 9.47 MeV/u and fluency 5?×?10¹¹?cm^?1 is discussed. The latter is important for applications of these oxide crystal as laser materials.     

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⁺.     

Local structure of the trigonal defect center for Cr3+ ions in KMgF3 crystals

Abstract

The zero-field splitting D, the anisotropic g-factors g _∥, Δg(=g _∥ ? g _⊥) and the first excited state splitting Δ(² E) for the trigonal Cr³⁺–V_K center in KMgF₃: Cr³⁺ crystals have been studied from Macfarlane's high-order perturbation formulas. From the studies, the local structure of the trigonal center is obtained. The local lattice distortions (i.e., the displacement directions of the ions in the center) are consistent with the expectation based on the electrostatic interaction.     

Photoinduced changes in photorefractive PVA films doped with Cr3+ and VO2+: EPR and PAS investigations

In order to understand the mechanism of optical image storage in photorefractive polyvinyl alcohol (PVA) films, photo-EPR and photoacoustic spectral investigations were carried out on PVA films doped with Cr³⁺ and VO²⁺. The EPR spectrum of Cr³⁺ has shown reduction in intensity onin situ illumination with copper vapor laser (CVL). The decay and recovery of Cr³⁺ signal, with and without CVL illumination respectively, was monitored at different temperatures in 10–300 K region. These were found to obey a double exponential, with one time constant independent of temperature, and the other showing significant temperature dependence. From Τ(T), activation energy for the charge carrier transport in one of the processes was estimated to be 0.016 eV. The PA spectra showed shift towards lower wavelength side on consecutive runs. On the other hand, VO²⁺ doped PVA film has not shown any significant changes in intensity on laser illumination. These observations suggest (i) interaction of PVA matrix with excited Cr³⁺ and (ii) predominant non-radiative relaxation in VO²⁺: PVA system with no change in the oxidation state.     

Theoretical studies of the defect structures and spin Hamiltonian parameters for manganese(II) and nickel(II) doped Zn(en)3(NO3)2 single crystals

The spin Hamiltonian parameters (g factors, hyperfine structure constants and zero-field splittings D and E) and local structures for Mn²⁺ and Ni²⁺ in [Zn(en)₃](NO₃)₂ single crystal are theoretically investigated from the perturbation calculations for trigonally distorted 3d⁵ and trigonally (or orthorhombically) distorted 3d⁸ cluster. The trigonal Mn²⁺ and Ni²⁺ centres are found to undergo the moderate angular variations Δβ of 4.5° and 5.2°, respectively, related to host Zn²⁺ site due to size mismatch. The orthorhombic Ni²⁺ centre shows the relative axial elongation ratio ρ (≈ 2.5%) and the relative perpendicular bond length variation ratio τ (≈0.2%). For Mn²⁺ centre, the contributions to g-shifts Δg_CT (or hyperfine structure constants A_CT and zero-field splitting D_CT) from charge-transfer (CT) mechanism are opposite in sign and five times (or 5% and 8%) in magnitude compared with those from crystal-field (CF) mechanism. For the trigonal Ni²⁺ centre, Δg_CT (or D_CT) are the same (or opposite) in sign and 17% (or 2%) in magnitude related to those from CF mechanism. For the orthorhombic Ni²⁺ centre, Δg_CT and E_CT (or D_CT) are same (or opposite) in sign and 16% and 48% (or 442%) in magnitude with respect to those from the CF mechanism. The signs and magnitudes of the trigonal distortion angles δβ (≈ ?0.3 and 0.4°) related to an ideal octahedron and the local angular variations Δβ related to the host bond angle are suitably illustrated by those of the axial distortion degree (ADD) and the angular variation degree (AVD) of the systems, respectively.     

Unified calculations of the optical and electron paramagnetic resonance spectral data for Ce ion in Y3Ga5O12 crystal

Seven crystal field energy levels (obtained from the optical spectra) and three g factors g_x, g_y and g_z (obtained from electron paramagnetic resonance (EPR) spectra) for Ce³⁺ ion in Y₃Ga₅O₁₂ crystal are calculated together by diagonalizing a complete energy matrix. The Hamiltonian of this energy matrix includes all the interactions for 4f¹ ion Ce³⁺ in rhombic crystal field and under an external magnetic field, and so the optical and EPR data can be studied in a unified way. The calculated crystal field energy levels are in better agreement with the experimental values than the calculated values in the previous paper, and the g factors (which have not been calculated previously) are explained reasonably. The results are discussed.