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).     

Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial d 111 symmetry is similar to the trigonal Zr 3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial d 100 symmetry different from the orthorhombic O m center induced by X-ray irradiation. At a fluence around 10 18 e/cm 2 , both centers are bleached out near 600 v K, like the corresponding X-ray induced defects. At a fluence around 10 19 e/cm 2 , defects are much more stable, since complete thermal bleaching occurs near 1000 v K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.     

Radiation-Induced Paramagnetic Centers in the Glasses Of CaO-Ga2O3-GeO2 System

The X-band (v ? 9.4 GHz) ESR spectra of the UV-, X-, and γ-irradiated glasses of CaO-Ga₂O₃-GeO₂ system with compositions similar to Ca₃Ga₂Ge₃O₁₂, Ca₃Ga₂Ge₄O₁₄, and Ca₃Ga₂O₆ crystals have been investigated at 300 and 77 K. It was shown that X- and γ-irradiation of the Ge-contained glasses induce simultaneously electron and hole paramagnetic centers, stable at room temperature. The UV-irradiation of Ge-contained glasses leads to the generation of stable centers of electron type, whereas the X- and γ-irradiation of glasses with Ca₃Ga₂O₆ composition induces stable hole centers, exclusively. The electron centers are assigned to E′ (Ge) centers with different local environments. ESR spectrum of hole centers is ascribed to O^? centers, localized on non-bridging oxygen of the glass network. The E′ (Ge) and O^? centers show high thermal stability in the CaO-Ga₂O₃-GeO₂ glass network. The obtained ESR spectra are described by spin Hamiltonian with g-factor of axial and rhombic symmetry for the E′ (Ge) and O^? centers, respectively. The nature, electron structure and some formation peculiarities of the radiation defects in CaO-Ga₂O₃-GeO₂ glasses are discussed in comparison with other glasses as well as Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ crystals.     

Farbzentren in Ammoniumhalogeniden

Color centers produced by X-rays in ammonium halides at various temperatures between 20°K and room temperature have been investigated by means of paramagnetic resonance and by optical methods. Two kinds of paramagnetic defects were found to be predominant, the self-trapped hole (V _K-center) and another electron deficiency center involving a NH₃ ⁺-radical. The electronic structure of theV _K-center is the same as in the alkali halides, except that the orientation of the molecular axis is along [100] instead of [110]. The kinetics of the thermally activated motion of theV _K-centers and of their recombination with electrons has been studied. The electronic structure of the second center was derived from the hyperfine spectrum of the paramagnetic resonance. The rotation of the NH₃ ⁺ ion and its connection with the order-disorder transition in NH₄Cl has been studied.     

Radiation induced defects in KBr:Tl+ crystals

The defects produced in KBr:Tl⁺ crystals during x-irradiation at 77 K were studied using thermoluminescence (TL), thermally stimulated currents (TSC), and absorption and emission spectra. Three main glow peaks at 165, 193 and 258 K were observed both in the TL and in the TSC curves. A variety of irradiation induced absorption bands were observed in the UV, visible and infrared up to about 2 microns. The 165 K TL peak was found to emit only the 440 nm band assigned to thallium dimers, while the peaks at 193 and 258 K exhibited the UV bands at 310 and 365 nm as well as the 440 nm band.The defects produced during the irradiation were the V_k hole center, the Tl° and the Tl⁺₂ electron centers. Smaller concentrations of Tl²⁺ and (Tl⁺)⁺₂ centers were also produced.An analysis of the results including measurements on lightly and heavily doped crystals enabled to draw conclusions on the nature of the defects and on the recombination processes involved. A close correlation has been found between the temperatures at which changes in the various absorption bands take place and the temperatures of the TL peaks. The analysis enabled also a full classification of the absorption bands.     

The Formation of Dimeric Centers of Copper,Iron and Gadolinium in Modified Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript>

It is discovered that the electron paramagnetic resonance (EPR) spectrum of the doubly charged copper centers occurs in single crystals of Pb₅Ge₃O₁₁ doped with gadolinium or iron after annealing in an atmosphere containing chlorine and bromine. Similar annealing of the crystals doped with copper in a chlorine and fluorine atmosphere leads to redistribution of the intensities of the EPR spectra of two types of Cu²⁺ centers. The influence of annealing on the ongoing intensity of spectra of the dimeric triclinic centers Fe³⁺–A, Gd³⁺–A (where A represent Cl^?, Br^?, O^2?, F^?) was the subject of this research. Consideration is given to the mechanisms for changing the charge state and association of copper center with defects.     

EPR,thermoluminescence, and thermally stimulated conductivity in BaWO4 crystals

In BaWO₄ crystals electrons and holes trapped at WO₄ complexes are identified by electron paramagnetic resonance (EPR) after X-irradiation at T = 80 K. The thermal decay of the intrinsic hole centres at about 100 K is accompanied by a simultaneous decrease of electron traps (WO₄)^3- and glow maxima of thermoluminescence (TL) and of thermally stimulated conductivity (TSC). This connection is explained by a thermally activated hopping of the $\text{(WO}{}_4\text{)}\text{3-}\text{2}$ hole centres followed by radiative recombination with electron traps (WO₄)^3-. A qualitative kinetic calculation based upon EPR data and the shift between TL and TSC glow peak confirms this model.     

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.     

Trimers of bivalent copper impurity ions in CaF<Subscript>2</Subscript> crystals: The structure and mechanism of formation

Crystals of CaF₂: Cu (with a copper impurity content higher than 0.1 at. %) grown by the Czochralski method from a melt in a mixed helium-fluorine atmosphere are investigated using electron paramagnetic resonance (EPR) spectroscopy. It is found that the crystals contain paramagnetic centers whose magnetic properties at low temperatures are identical to those of [CuF₄F₄]^6? (S=1/2) single centers. The magnetic properties of the centers exhibit a qualitative change in the temperature range 77–300 K. These changes are described within a model according to which the center is treated as a cluster composed of three [CuF₄F₄]^6? impurity complexes involved in exchange interactions and interactions occurring in the field of Jahn-Teller lattice distortions.     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.     

Determination of the Position of the Impurity Yb3+ ion in the CsCaF3 crystals

CsCaF₃ crystals doped with Yb³⁺ ions have been studied using the electron paramagnetic resonance and optical spectroscopy methods. Several types of paramagnetic Yb³⁺ centers were found, among which a paramagnetic center in the unusual position was established. The parameters of the corresponding spin Hamiltonians and schemes of the energy levels of the observed centers were determined.     

X-ray stimulated luminescence in MgO

Studies have been made of the emission spectrum of MgO crystals induced by X-irradiation at 90 K. Two bands (half-widths ～0.8 eV) were observed to peak at 4.95 and 3.2 eV, respectively, in high purity crystals. Doping with 100 ppm or greater of Fe, Co, Cr, Cu, Mn, and Ni suppressed the luminescence, though in the MgO:Ni crystal the 2.3 eV Ni²⁺ band due to the ¹T_2g→³A_2g transition was observed. In deuterium-doped crystals the ratio of the intensity of 3.2–4.95 eV emission was found to be 1.2 as compared to 8 for the undoped crystals. Prior exposure of the pure crystals to ionizing radiation enhances the 4.95 eV band by a factor of three while not affecting the 3.2 eV band. This enhancement of intensity decays in several stages upon standing at room temperature in a way that reflects the thermal stability of the various components of the composite V-band absorption. These facts together with the observation that the 210 K thermoluminescence peak is composed entirely of 4.95 eV emission indicate that this luminescence band is associated with the recombination of an electron with a hole located in a V-type center, i.e. O?□ + e → (O²?□)1 → O²?□ + 4.95 eV, where the square indicates that the perturbing positive ion vacancy is adjacent to the oxugen ion which has captured the hole. In MgO:Li⁺, which exhibits no V-type centers upon irradiation, the 4.95 eV band was absent and a 2.9 eV emission which may be associated with recombination at the [Li]⁰ center was observe.     

Intrinsic paramagnetic defects probe superionic phase transition in Ag1−xCuxI (x=0, 0.05, 0.15 and 0.50) nanocrystals

EPR probed the zincblende (γ) to cubic (α) AgI structural phase transition in AgI at 423 K through two intrinsic paramagnetic centers: an Ag²⁺-based hole center (signal ‘A’) and an Ag⁰-based conduction electron center (signal ‘B’) associated with AgI nanocrystallites. Sudden drops in intensity (I_PP), <g>, and ΔH_PP observed at 423 K for pure AgI nanocrystals. Addition of Cu in AgI increases the thermal stability of the cation sublattice as seen from the increase in the transition temperature from 423 K (undoped AgI) to 453 K. Abrupt jumps in the number of spins (N) and reciprocal susceptibility (1/χ) observed at increased phase transition temperatures in Cu-substituted AgI relative to that in undoped AgI reflects progressively strengthened local bonding configuration of γ-AgI structure induced by Cu.     

Polar-center phase nuclei in He+-irradiated CuO single crystals

Irradiation of various single-crystal CuO faces [ac,bc,(110)] with 4.6-MeV He⁺ ions has been found to result in reduction of CuO to Cu₂O and Cu on the irradiated and unirradiated sides, lifting of forbiddenness from optical transitions in the [CuO₄]⁷⁻ electron center in the 0.7–0.95-eV energy range, a change in dichroism near the bands corresponding to transitions in the hole centers, [CuO₄]⁵⁻, and electron centers, [CuO₄]⁷⁻, as well as in a resonant increase of absorption at 0.95–1.30 eV with an unusual polarization dependence. The results of He⁺ irradiation of CuO single crystals are discussed in terms of a model of the nucleation of the phase of polar (electron and hole) centers in copper-oxygen systems. Fiz. Tverd. Tela (St. Petersburg) 40, 419–424 (March 1998)     

Luminescence in x-irradiated CaF2:Co

Photoluminescence of X-irradiated CaF₂:Co single crystals is reported. The emission spectrum shows four peaks at 505, 550, 640 and 685 nm, all of them with an excitation band at 275 nm. The same emission spectrum, plus a band at 280 nm, is found in X-ray excited luminescence measurements. Thermoluminescence of 80 K X-irradiated crystals gives a glow curve with five peaks at 100, 125, 145, 190 and 225 K. The spectral distribution of these glow peaks is similar to that of the X-ray excited luminescence. The 280 nm band is associated with electron—hole recombination. The other four bands are associated with electron transitions among excited states of Co²⁺ produced by recombination of holes and Co⁺-ions created by X-irradiation.     

Paramagnetic defects in gamma-irradiated Na/K-silicate glasses

Gamma-irradiated alkali silicate glasses of the variable composition 22xNa₂O · 22(1 ? x)K₂O · 3CaO · 75SiO₂ have been studied using the electron paramagnetic resonance (EPR) method. It has been established that, upon the successive replacement Na ?? K in the two-alkali silicate glass, the EPR spectrum of hole centers on nonbridging oxygen atoms can be represented as a superposition of signals from the oxygen centers HC ₁(Na), HC ₂(Na), HC ₁(K), and HC ₂(K), which are characteristic of single-alkali silicate systems. The concentration dependences of hole and electron paramagnetic centers do not exhibit specific features that can be interpreted as a manifestation of the ??mixed-alkali effect.?? The results obtained have been discussed taking into account the extended model of centers on nonbridging oxygen atoms.     

EPR study of radiation-induced defects in carbonate-containing hydroxyapatite annealed at high temperature

Radiation-induced (γ or UV) paramagnetic defects in carbonate-containing hydroxyapatite (HAP) annealed at high (600–950 °C) temperature were studied by EPR. The complex spectra reveal the presence of different paramagnetic species. Their contributions were found to be strongly dependent on the annealing temperature as well as microwave power, thus, by the adjustment of experimental conditions some of the components can be eliminated that allowed to record EPR spectra caused by no more than two types of paramagnetic defects. All experimental spectra were analyzed using computer simulation. The parameters of the paramagnetic defects detected were determined, and the centers models were discussed. It was found that high-temperature annealing influences essentially the formation of radiation-induced defects in HAP. The СО₃³⁻, О⁻ centers and oxygen vacancy V_O⁻ were shown to be the main stable γ-induced defects in the HAP annealed at high temperatures. New paramagnetic defect with the parameters g_|| = 2.002, g_⊥ = 2.0135 was detected and tentatively identified as an O-related radical. The γ-induced EPR response from СО₃³⁻ radicals was found to be more intense than response from CO₂⁻ in non-annealed HAP. UV-irradiation was found to create smaller amounts of paramagnetic defects in comparison with γ-rays. Besides, oxygen vacancy V_O⁻ was not observed, while two other centers (СО₃⁻ and the center of unknown nature) appear in the UV-induced EPR spectra.     

CrO43- centers in NH4Al(SO4)2.12H2 O single crystals

Electron paramagnetic resonance and optical absorption spectra of radiation damage products of undoped and CrO₄^2- doped ammonium alum are studied. On X-irradiation at room temperature several paramagnetic species like CrO₄^3-, SO₃^? and O₃^? are formed in the doped crystals. In the undoped crystals SO₃^? and O₃^? are the major radiation damage products.     

Photoinduced transition of [Fe(CN)5NO] nitroprusside anions to metastable states and electron localization in the (BEDT-TTF)4K[Fe(CN)5NO]2 molecular metal

The crystals of (BEDT-TTF)₄K[Fe(CN)₅NO]₂, representing a quasi-two-dimensional organic metal with conducting layers of bis(ethylenedithio)tetrathiofulvalene (BEDT-TTF) and nonconducting layers containing pho-tochromic nitroprusside anions [Fe(CN)₅NO]^2?, were studied by the method of electron spin resonance. Illuminated by light with a wavelength of 514.5 nm, the organic metal crystals feature the formation of localized paramagnetic centers in the conducting cation layers of BEDT-TTF. The phenomenon of electron localization in the BEDT-TTF layers is related to the light-induced formation of long-lived metastable states of nitroprusside anions.     

An EPR study of Er3+ impurities in RbTiOPO4 single crystals

An electron paramagnetic resonance (EPR) study of Er³⁺ ions in single crystals of RbTiOPO₄ (RTP) is presented. The EPR spectra show the existence of six different Er³⁺ centres. The g-matrix has been determined for these centres from the analysis of the angular dependences of the spectrum in three planes of the crystal. The study supports that erbium can enter the Rb⁺ and Ti⁴⁺ low-symmetry sites of RTP. This conclusion differs from those for KTP:Er³⁺ and RTP codoped with Nb and Er. The different occupancies found for Er in these various crystals is suggested to be due to the differences in Er concentration.