Dissymmetrization in X-irradiated RbTiOPO4 crystal

Electron paramagnetic resonance has been used to study the hole and electron paramagnetic centers formed in X-irradiated RbTiOPO₄, the crystals of the KTP family. X-irradiation of RbTiOPO₄ crystals at 77 K produced an oxygen hole center and four different trivalent titanium electron centers I₁, II, III and IV. Theg-tensors, their principal values and axes for the defects were calculated and compared with those for KTiOPO₄ centers. X-irradiation at 300 K produced another two oxygen hole centers and three electron centers I₁, I₂ and II. EPR spectra of the center II revealed dissymmetrization, i.e., irregular distribution of growth defects, between the physically equivalent sites lowering the point group symmetry of the local environment of paramagnetic centers Ti³⁺.     

Concentration of Cr<Superscript>4+</Superscript> impurity ions and color centers as an indicator of saturation of forsterite crystals Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> with oxygen

The influence of the oxygen partial pressure P _{O 2} in the growth atmosphere on the coefficient of chromium distribution between the crystal and the melt of forsterite, the Cr³⁺ and Cr⁴⁺ ion contents in crystals, and the concentration of color centers induced by irradiation has been investigated. It has been established that the crystals grown at low oxygen partial pressures P _{O 2} (0.01–0.05 kPa) are characterized by low concentrations of Cr⁴⁺ ions and color centers. A change in the oxygen partial pressure to P _{O 2} ∼ 0.85 kPa leads to an increase in the Cr⁴⁺ center concentration by a factor of ∼10 and in the color center concentration by a factor of ∼5. A further increase in the oxygen partial pressure to P _{O 2} to 12 kPa remains the concentration of these centers almost unchanged. A model has been proposed according to which the intrinsic defects formed under conditions of a relative excess of oxygen leads to both the self-oxidation of chromium and the formation of color centers in the forsterite crystals under irradiation.     

New hole configurations in X-irradiated KTiOPO4 Crystals

Electron paramagnetic resonance has been used to study the structure and thermostability of oxygen hole centers produced in KTiOPO₄ (KTP) crystals X-irradiated at 77 K. During the annealing of KTP crystals above 160 K the redistribution of charges took place. Four hole centers were observed at 40 K after the heating of the X-irradiated KTP crystal at different temperatures. The intensity of the hole center 1 decreased and new hole configurations (center 2 and center 3) appeared in the crystals. Theg-matrices were obtained from the angular dependencies of EPR spectra. The principalg-values for center 1 were 2.0040, 2.0209, and 2.0437. The principalg-values for centers 2 and 3 were 2.0053, 2.0204, 2.0431 and 2.0035, 2.0183, 2.0628, respectively. The transformation of Ti³⁺ spectra indicated that the trivalent titanium ions were involved into the recombination process. Subsequent annealing at temperatures above 220 K led to the formation of a new hole center 4 (g _a =2.0213,g _b =2.0236,g _c =2.0370).     

Intrinsic V- and Vo centers in single crystal SrO

The intrinsic V^- center (a positive hole trapped at a cation vacancy) has been observed in single crystals of SrO following x-irradiation at 77 K. The ESR spectrum corresponds to a spin-$\text{1}\text{2}$ defect having <100> axial symmetry with g₆ = 2.0012(3) and g_⊥ = 2.0703(3). The concentration of V^- centers was enhanced significantly by heating crystals in oxygen at 1000°C and rapidly quenching. V^o centers (two holes trapped at a cation vacancy) were also observed after x-irradiation at low temperature, with g₆ = 2.0011(3), g_⊥ =2.0751(3), and D = 380.4(5) MHz.     

EPR of Mn4+ in LiF:U,Mn

A new manganese center in LiF single crystals doped with U₃O₈ and MnO₂ has been observed at room and liquid nitrogen temperatures. The trigonal EPR spectrum consists of one very anisotropic fine structure transition with six well-resolved hyperfine components. An analysis of the spectra recorded at X and Q bands shows that the zero field splitting is larger than the electronic Zeeman interaction.By comparing a theoretical calculation of the g values and the hyperfine structure with the experimental X and Q band data it was concluded that the ion is Mn⁴⁺. The presence of Mn⁴⁺ in these crystals confirms an assumption of Runciman regarding the possibility of introducing high valency ions in alkali fluorides containing uranium with an excess of oxygen.     

EPR investigation of the trivalent chromium complexes in SrTiO3

The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO₃ single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr³⁺-V_O dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr³⁺-V_O centers have been performed as function of temperature. The analysis of the trigonal Cr³⁺ centers found in SrTiO₃ indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr³⁺ in SrTiO₃ has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.     

Electron paramagnetic resonance of Gd3+ ions in Ca1 − x − y Y x Gd y F2 + x + y crystals

Electron paramagnetic resonance of Ca_{1 ? x ? y} Y _x Gd _y F_{2 + x + y} single crystals has revealed spectra that are not typical of gadolinium-doped CaF₂ crystals. These spectra have a nearly tetragonal symmetry and are most probably caused by Gd³⁺ ions localized in yttrium clusters. Weak spectra of tetragonal Gd³⁺ centers, whose parameters are close to those of a cubic gadolinium center caused by an isolated Gd³⁺ ion, have been also detected. These centers are attributed to isolated Gd³⁺ ions localized near octahedral rare-earth clusters or their associations.     

Internal oxidation of Sb impurities in silver

Oxidation of antimony implanted silver single crystals at 550 K has been studied by Mössbauer spectroscopy and ion beam analysis, using the¹⁸O(p,α)¹⁵N reaction. The depth distribution measured for¹⁸O matched the Sb implantation profile. Strong evidence was found for the existence of an inward moving oxidation front. SbO_n clusters with n=2,4 were observed, the oxygen atoms occupying octahedral interstitial sites.     

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.     

Characterization of the E1′ center in quartz: Role of aluminum hole centers and oxygen vacancies

The growth of E₁′ centers in a variety of natural and synthetic quartz crystals has been investigated by employing the electron spin resonance technique. It has been reported that the growth of E₁′ centers, formed by irradiation and subsequent annealing at 300 °C for 15 min, scale with the concentration of the aluminum hole center, [AlO₄]⁰, till a limit. Later, the E₁′ centers show saturation even when the [AlO₄]⁰-center continues to grow. For quartz with low efficiency of the formation of [AlO₄]⁰-center or irradiated with low accumulated doses, the intensity of E₁′ center was small where not all oxygen vacancies are converted to the E₁′ center. Thus, besides the availability of a number of oxygen vacancy sites, the number of holes released from the [AlO₄]⁰-center plays an important role in the formation of E₁′ centers in quartz.     

A Fe[Nb]-Li center in stoichiometric LiNbO<Subscript>3</Subscript> crystals: Mechanism of formation

A new iron center in stoichiometric lithium niobate crystals has been studied by the EPR method. The angular dependences of the EPR spectrum of the center have been used to derive the parameters of its spin Hamiltonian. The data amassed on the variation in the concentrations of two iron centers in lithium niobate crystals annealed in a Li₂CO₃ powder have provided an insight into the mechanism of formation of the new center, as well as corroborated its model proposed by us earlier. According to this model, the center represents a complex of two defects aligned with the polar axis in the crystal: the iron ion at the niobium site and an interstitial lithium ion filling the nearest structural vacancy (Fe³⁺[Nb]-Li⁺[V]). The structure of other Fe³⁺ centers revealed earlier in LiNbO₃ crystals, in which the iron ion occupies the niobium site, has been discussed.     

I.R. absorption due to H− and D− Ions in BaClF and SrClF

The i.r. absorption spectra sssociated with the vibrations of H^? and D^? ions in SrClF and BaClF have been studied in the range 600–2000cm^?1.The U centers are in fluorine sites. Because of the D_2d symmetry of the fluorine site, the triple degeneracy of the U center local mode in crystals of cubic symmetry, is split in BaClF and SrClF. In these crystals (space group D⁷_4h) unlike what happens with the cubic crystals, the symmetry types of the lattice band modes which give rise to the local mode sidebands, can be known experimentally. These band modes are almost only of E symmetry type. The E symmetry modes involve a vibration of the U center.A calculation of the local mode frequencies in BaClF:H^? from the experimental one in BaF₂:H^?, has been performed. An H^? ion shell model is more adequate than a rigid ion model to account for the frequencies and the relative intensities of the localized vibrational lines. The best agreement is obtained when the shell charge and the crystal polarizability of the H^? ion in BaF₂ are respectively ?1.3 e and 2.6 ų.     

Oxygen vacancy model for the E1′ center in SiO2

An (oxygen)^- vacancy model of the E₁^≈ center in alpha quartz, featuring an asymmetric relaxation of the two silicons adjacent to the oxygen vacancy, is presented and analyzed. This model is shown to be consistent with both theoretical calculations and experimental hyperfine data, in contrast with any model previously proposed for the E₁^≈ center.     

Magnetic resonance of exchange-coupled copper complexes in perovskite-structure crystals: The potassium tantalate and cuprate superconductors

This paper reports on parallel EPR studies of high-temperature superconductors based on the cuprate perovskites RBa₂Cu₃O_6+x (R=Y, Gd, Nd) and of KTaO₃: Cu, which also has a perovskite structure. EPR measurements performed on copper-doped KTaO₃ crystals revealed Cu²⁺-Cu²⁺ copper pair centers. The copper ions making up pairs are assumed to occupy adjacent tantalum sites. The pair centers are chains consisting of two equivalent Cu²⁺ ions and three oxygen vacancies aligned in the 〈100〉 direction. The crucial point in the model proposed is the presence of an oxygen vacancy sandwiched between two Cu²⁺ ions, whereas the outer vacancies do not necessarily occupy neighboring sites. In this structure, complete charge compensation is achieved. Ferromagnetic exchange coupling takes place between the two copper ions. An investigation of the exchange and superhyperfine interactions of copper centers in crystalline potassium tantalate has permitted the estimation of the respective interactions in crystals of the cuprate superconductors which exhibit magnetic resonance signals due to exchange-coupled copper clusters in the case of oxygen deficiency.     

Study of iron implanted MgO crystals by low-energy electron induced X-ray spectroscopy

Magnesium oxide crystals implanted with Fe⁺ ions have been studied by means of Low-Energy-Electron-Induced X-ray Spectroscopy. All the implantations were carried out with 100 or 150 keV ion energy, at doses in the range from 10¹⁵ to 10¹⁷ ions cm^?2. The structure of the Fe L_II, L_III X-ray emission bands provides information about the iron chemical state. Fe L_II/L_III band intensity ratio measurements have been performed with a 3 keV electron excitation in order to investigate the whole implanted layer. In addition, by using a filtered Fourier transform technique on observed spectra, some modifications in the oxygen K emission band can be observed in implanted MgO crystals after thermal annealings in air. The oxygen spectrum fine structure suggests that the MgO matrix, partially destroyed by iron implantation, is restored after high temperature treatments. All the implantation, is restored after high temperature treatments. All the results are discussed on the basis of previous Mössbauer Spectroscopy studies and ion channeling investigations.     

Radiation-induced electrical and optical processes in materials based on Al2O3

The irradiation of dielectrics induces electric charging of microscopic regions in the bulk, which is associated with concentration inhomogeneities in the system of traps and the differences in characteristic diffusion lengths of free electrons and holes that are produced in ion tracks and collision cascades. Experimental data on radiation-induced luminescence (RIL) give evidence of the existence of three states of oxygen vacancies in Al₂O₃: an optically inactive (electrically neutral) vacancy, its excited state (known as F ⁺ center), and a negatively charged vacancy (F center). The formation of negatively charged regions under irradiation increases the intensity of the 415-nm band of F centers of RIL of Al₂O₃ single crystals. In Al₂O₃:Cr³⁺ ceramics, a radiation-induced negative charging of grain boundaries with respect to the bulk of grains takes place, which manifests itself as an increase in the intensity of the 690-nm band of RIL of Cr³⁺ ions, whereas the intensity of this band in Al₂O₃:Cr³⁺ single crystals remains unchanged. Using data on RIL, the local-charge density in grains of Al₂O₃:Cr³⁺ ceramics and the field produced by this charge are estimated.     

Local structure and the electron paramagnetic resonance parameters for the Cr3+ ions at K+-vacancy site in Cr3+:KZnF3 laser crystal

The quantitative relationship between the electron paramagnetic resonance (EPR) parameters D,g_∥,g_⊥ and the local structure parameters of Cr³⁺ ion in KZnF₃ crystals is established. The local structure for Cr³⁺ paramagnetic center in KZnF₃:Cr³⁺ crystal has been determined from EPR parameters of Cr³⁺ ion. This work shows that the trigonal crystal field of Cr³⁺ ion in KZnF₃ crystals comes from following two origins: (1) the nearest-neighbor K⁺ vacancy caused by the charge compensation in the [1 1 1]-axis direction; and (2) the lattice distortions of the nearest-neighbor fluorine coordination caused by the K⁺ vacancy and the differences in mass, charge, and radius between Cr³⁺ ion and Zn²⁺ ion. The unified calculation of the EPR zero-field splitting and g factors, taking into account the K⁺ vacancy and the lattice distortions, has been carried out on the basis of the complete diagonalization procedure and the superposition crystal-field model, all calculation results are in excellent agreement with the experimental data. Although the main source of the trigonal crystal field comes from the K⁺ vacancy caused by the charge compensation, the contribution of the lattice distortion cannot be neglected.     

Influence of photoexcitation on the EPR spectra of Mo5+ in Li2Zn2(MoO4)3: Ce3+,Cu2+ crystals annealed in a CO2 atmosphere

The influence of recovery annealing in a CO₂ atmosphere at 700°C on the properties of Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions has been studied. The EPR investigation of Li₂Zn₂(MoO₄)₃ crystals annealed in a CO₂ atmosphere has revealed that the annealing leads to the formation of oxygen vacancies in positions adjacent to the oxygen octahedron of lithium, M3, and the oxygen tetrahedron of molybdenum, Mo1. In this case, the charge state of molybdenum becomes Mo⁵⁺ and appears in the EPR spectra in the form of one magnetically nonequivalent position. The analysis of the angular dependence of the EPR spectrum of Mo⁵⁺ made it possible to calculate the spectral parameters g _∥ = 1.862, g _⊥ = 1.933, A _∥ = 71.8 G, and A _⊥ = 34.1 G. The cross relaxation on the hyperfine structure from the molybdenum isotope ⁹⁷Mo is found in the EPR spectra. The photoexcitation of Li₂Zn₂(MoO₄)₃ crystal doped with cerium ions leads to the saturation of the EPR spectrum of Mo⁵⁺ and to the formation of the hyperfine structure from one lithium ion with a hyperfine structure constant of 14 G. For Li₂Zn₂(MoO₄)₃ crystals doped with copper ions, a very weak EPR spectrum of Mo⁵⁺ is observed in the initial crystals. As a result of the photoexcitation, an increase in the intensity of this spectrum by an order of magnitude and manifestation of the EPR spectrum of Cu²⁺ ions take place. It is assumed that such a behavior of the EPR spectra of molybdenum ions in Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions under photoexcitation is caused by different positions of the energy levels of cerium and copper ions with respect to the energy level of the molybdenum ion.     

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.     

Characterization of optical waveguide in Nd: GdVO4 by triple-energy oxygen ion implantation

We report on the optical planar waveguide formation and modal characterization in Nd: GdVO₄ crystals by triple oxygen ion implantation at energies of (2.4, 3.0, and 3.6 MeV) and fluences of (1.4, 1.4, and 3.1)  × 10¹⁴ions/cm². The prism-coupling method is used to investigate the dark-mode property at wavelength of 632.8 nm. The refractive index profiles of the waveguide are reconstructed by an effective refractive index, n_eff method. The modal analysis shows that the fields of TE modes are well restricted in the guiding region, which means the formation of nonleaky waveguide in the crystal.