Photoinduced oxygen-vacancy related centers in PbWO 4 : Electron spin resonance and thermally stimulated luminescence study

Using electron spin resonance (ESR) and thermally stimulated luminescence (TSL) three different electron traps based on regular W sites perturbed by oxygen vacancies have been identified in PbWO 4 . Analysis of ESR spectra parameters ( g -factor values and principal axes orientations) has shown that revealed centers are (WO 3 ) m vacancy containing complex anions associated with a defect in Pb sublattice: (WO 3 ) m m A Pb complexes. One of the centers (W 1 ) is thermally stable up to 350-370 v K, while the other two (W 2 and W 3 ) only to 270-290 v K. Above these temperatures trapped electrons become free and recombine with localized holes, giving rise to TSL glow peaks at T\approx 323\,\hbox{K} and 365\,\hbox{K} . Using the initial rise method the 323\,\hbox{K} TSL peak-shape was fitted allowing the first order recombination kinetic that gives trap parameters E = 0.88\,\hbox{eV} and s\simeq 5\ast 10^{12}1/\hbox{s} .     

Neutron-induced defects in the lithium tetraborate single crystals

The X-band ( x ; 9.4 v GHz) electron spin resonance (ESR) spectra of the un-doped isotopically enriched lithium tetraborate (LTB) Li 2 B 4 O 7 single crystals, irradiated by thermal neutrons (fluences | n =2.74 ‐ 10 15 1 1.79 v ‐ 10 18 v cm m 2 ) were investigated at 300 and 77 v K. The LTB crystals of high chemical purity and optical quality with different isotope compositions ( 6 Li 2 10 B 4 O 7 , 6 Li 2 11 B 4 O 7 , 7 Li 2 10 B 4 O 7 and 7 Li 2 11 B 4 O 7 ) were grown by Czochralski technique. The thermal neutrons (the total quantity >90%) with fluence near 10 18 v cm m 2 induce at least 4 different types of stable paramagnetic centers in the Li and B isotopically enriched LTB crystals. The ESR spectra, electron structure and efficiency of generation for centers, induced by thermal neutrons, essentially depend on neutron fluence and isotope composition of the LTB crystals. The local symmetry and the spin Hamiltonian parameters of the observed paramagnetic centers were determined and their electron structure were established. The possible models and formation mechanism of the radiation defects, induced by thermal neutrons in the LTB lattice, are proposed.     

Thermoluminescence of nominally pure KTaO 3 crystals

After an exposure to ultraviolet light ( u <350 v nm) at 12 v K, weak thermoluminescence of nominally pure KTaO 3 crystals was observed within the temperature region from 13 to 65 v K for the first time. An analysis of the glow curves of integral thermoluminescence revealed five glow peaks with markedly sample-dependent intensities. Three glow peaks near 26, 31, and 58 v K at the heating rate of 0.155 v K/s correspond to thermoluminescence spectrally very similar to broad-band visible photoluminescence. The glow peaks near 26 and 31 v K were assigned to the electron release from photoinduced Ta 4+ -OH m and Ta 4+ - V O centers and the glow peak near 58 v K to the hole release from photoinduced O m centers. The glow peaks near 34 and 41 v K are connected with the structureless emission band peaking near 714 v nm at 15 v K that was observed in the emission spectra of KTaO 3 crystals for the first time.     

Discovery of a self-trapped-electron center in α-TeO 2

Electron spin resonance (ESR) studies show that electron irradiation of an f -TeO 2 single crystal followed by 330-nm UV illumination at ～10 v K generates a new spin-1/2 paramagnetic center having C 2 symmetry, like the Te lattice sites, that is attributed to a self-trapped charge on a Te. Identification is facilitated by a strong hyperfine interaction with 125 Te at a central Te site and weaker 125 Te superhyperfine interactions with three different equivalent pairs of neighboring Te cations. The irradiations also produce the diamagnetic V_{O}^{\times} center and the paramagnetic V_{O}^{\bullet} and V_{O}^{\prime} centers. From measurements of concentration changes of the paramagnetic centers due to thermal annealing of the new center it is deduced that the self-trapped charge is a self-trapped electron. It is designated as a \hbox{TeO}_{2}^{\prime} center. This assignment is consistent with its low thermal stability since it anneals quickly at temperatures above 40 v K. ESR characteristics of this new center are described.     

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.     

Radiation-induced electronic and ionic charge storage and release in sapphire

Radiation-induced thermally stimulated relaxation (TSR) processes in the reduced f -Al 2 O 3 (sapphire) crystal were investigated at 290-650 v K by means of the TS current (TSC), ionic depolarisation current (TSDC) and electron emission (TSEE) techniques. After thermal (ionic) polarisation of sapphire wide (～75 v K) and asymmetric ionic dipolar TSDC peak at T max , 590 v K (disorientation of the anion vacancy-related dipoles) was detected. This peak correlates with the wide TSEE peak at T max , 615 v K, the radiation-induced electrical degradation (RIED) yield rise above 550 v K ( T max , 745 v K) and the chromium emission line broadening in ruby. Above 450-500 v K the anion vacancy hopping (migration) starts. This can lead to lattice dynamic disordering and anion vacancy diffusion-controlled processes in sapphire (especially in vacuo near the sample surface, grain boundaries, dislocations) in various TSR (TSC, TSDC, TS heat release and bleaching) and RIED phenomena. Surface structure and impurity content, surrounding atmosphere (vacuum or air) and electric fields determine these phenomena.     

Transient color centers in GGG crystals

Electron pulse induced absorption and their decay kinetics have been investigated in samples of GGG crystals with different starting absorption spectra. It is shown that for all samples there appears a wide transient absorption (TA) band with two maxima in the region 14,000-17,000 v cm m 1 and 22,000-26,000 v cm m 1 . TA decay kinetics measurements in 14,000 v cm m 1 and 22,000 v cm m 1 are two-exponential (with half-time order several tens and several hundreds ns). Analyzing the obtained results, we can suppose that low and high energy TA bands are connected with the F + (or O m ) and F transient color centers (TCC) respectively.     

The ground state of metallic nano-structures in heavily irradiated NaCl-KBF 4

ESR, NMR and static magnetic susceptibility measurements of heavily irradiated NaCl-K and NaCl-KBF 4 are reported. Up to 10% of the NaCl-molecules are transformed into metallic Na nanoparticles and Cl 2 precipitates. In addition, there are paramagnetic F- and F-aggregates, which are coupled by exchange interactions to the conduction electrons in the nanoparticles. Above 160 v K the NMR and ESR signals of NaCl-K and NaCl-KBF 4 show Pauli paramagnetism and the properties of the Na nanoparticles are similar to bulk sodium. A single ESR line is observed revealing exchange interaction between conduction electrons in the nano-particles and F-aggregates. The observed decrease of the ESR susceptibility with decreasing temperature is due to a metal-insulator transition. The conduction electrons are localized below 40 v K and the above mentioned F-aggregate centers contribute significantly to the overall ESR signal. For NaCl-KBF 4 we observed that with decreasing temperature the ESR line shifts towards lower fields due to antiferromagnetic ordering and internal magnetic fields.     

Effects of pre-irradiation treatment on EPR,optical absorption and TL of albite

In the present work pre-irradiation annealing effect was investigated in albite, NaAlSi 3 O 8 , a silicate crystal. Albite powder samples were heated at 500, 600, 700, 800 and 900 v C for 40 minutes, and then submitted to n -irradiation. Results show that first TL peak (around 160 v C) decreases with annealing temperature, while higher temperature peaks strongly increase. EPR signal around g factor 2, attributed to Al-O m -Al centers, increase with annealing temperature too, as well as optical absorption bands that appear in the crystal after relatively strong n -dose irradiation (of some kGys).     

Thermally Stimulated Electron–Hole and Ionic Processes in Zinc Oxide Crystals

The principal results of the investigation of thermally stimulated electron–hole and ionic processes in hydrothermal and gas-phase ZnO single crystals preexcited at low temperatures, based on simultaneous study of photo-EPR and thermoluminescence (TL), are presented. The nature of the traps determining the TL peaks at 17, 24, 40, 53, 90–110, 140–150, and 160–200 K is discussed. In particular, it has been established that the lithium paramagnetic centers (Li_Zn ⁺–O^I) play the role of hole traps in ZnO giving green and red TL in the temperature range 160–200 K and, in the case of association with small-sized donors, also TL in the temperature range 90–110 K. The other traps are electronic in character, and in the presence of acceptor lithium in the crystals, they form yellow-orange TL. Optical quenching of TL has been evaluated, and it has been found that there is a difference E 0.75 eV between the thermal and optical energies of ionization of lithium acceptors. Irreversible ionic processes associated with the healing of cationic vacancies at T 360–420 K have been revealed.     

Correlated ESR, PL and TL studies on Sr5(PO4)3Cl:Eu thermoluminescence dosimetry phosphor

Electron spin resonance (ESR), thermoluminescence and photoluminescence studies in Eu²⁺ activated Sr₅(PO₄)₃Cl phosphor are reported in this paper. The Sr₅(PO₄)₃Cl:Eu²⁺ phosphor is twice as sensitive as the conventional CaSO₄:Dy phosphor used in thermoluminescence dosimetry of ionizing radiations. It has a linear response, simple glow curve, emission peaking at 456 nm. The defect centers formed in the Sr₅(PO₄)₃Cl:Eu²⁺phosphor are studied by using the technique of ESR. A dominant TL glow peak at 430 K with a smaller shoulder at 410 K is observed in the phosphor. ESR studies indicate the presence at three centers at room temperature. Step annealing measurements show a connection between one of the centers and the dominant glow peak at 430 K. The 430 K TL peak is well correlated with center I, which is tentatively identified as (PO₄)²⁻ radical.     

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.     

Thermoluminescence and low-temperature luminescence of beryllium oxide

Beryllium oxide in the forms of either single crystals (pristine, additively-colored) or hot-pressed ceramic samples was studied in the energy range of 1.2–6.2 eV using both the thermoluminescence (TL) and steady-state X-ray induced luminescence (XRL) techniques. The XRL emission spectra were recorded at 6 and 293 K, whereas TL glow curves were studied after X-ray exposure at T₀ = 6 K upon linear heating in the temperature range from 6 to 293 K. A search for TL manifestations of shallow trapping centers was carried out using a sensitive channel for TL registration in the range of more than six decades of change in intensity. The participation of shallow trapping centers in the process of recombination luminescence excitation at 6–293 K; branching electronic excitations between different recombination channels; the dominance of the self-trapped exciton and F-center emissions in spectra of the low-temperature recombination luminescence in BeO at 6–293 K were discussed.     

Enhancement of the electron mobility with infrared photoexcitation in Si: Te at low temperatures

Hall measurements on Te-doped silicon (N _Te 10¹⁶ cm^–3) have been performed in the temperature range between 10 K and 300 K with infrared photoexcitation of electrons into the conduction band. The samples exhibit electron Hall mobilities which are increased by approximately 50% compared to measurements in the dark. The increased electron mobility can be correlated with an increased electron population of shallow donor levels by photoexcitation. Coulomb scattering due to charged shallow donor centers is converted into less efficient dipole scattering (Te-acceptor pairs) by the light-induced redistribution of electrons.     

Trapping centers and their distribution in Tl2Ga2Se3S layered single crystals

Thermally stimulated current (TSC) measurements with current flowing perpendicular to the layers were carried out on Tl₂Ga₂Se₃S layered single crystals in the temperature range of 10-260 K. The experimental data were analyzed by using different methods, such as curve fitting, initial rise and isothermal decay methods. The analysis revealed that there were three trapping centers with activation energies of 12, 76 and 177 meV. It was concluded that retrapping in these centers was negligible, which was confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. The capture cross section and the concentration of the traps have been also determined. An exponential distribution of electron traps was revealed from the analysis of the TSC data obtained at different light illumination temperatures. This experimental technique provided values of 10 and 88 meV/decade for the traps distribution related to two different trapping centers.     

Luminescence spectra of doped and undoped lead tungstate crystals

TL spectra of undoped lead tungstate crystals exhibit glow peaks at 30 v K and 85 v K centred at 440 v nm, plus a peak at 50 v K at 530 v nm in an annealed sample. Annealing adds a 170 v K peak. Trivalent dopants of La 3+ and Y 3+ reduce the green luminescence, and Nb 5+ introduces a peak near 100 v K centred at 530 v nm; Sb introduces features between 40 v K and 90 v K and 150 and 180 v K. The luminescence emissions around 50 v K may be attributed to complex intrinsic defect centres, including (WO 4 ) m 3 . Of the four dopants studied in the present research, Sb +5 has the highest luminescence intensity. CL spectra show interesting anomalies near 170 v K which are linked to a phase change of water/ice nanoparticles trapped at dislocations.     

Thermally stimulated current and high temperature resistivity measurements of 4H semi-insulating silicon carbide

High purity semi-insulating 4H SiC single crystals have potential applications for room temperature radiation detectors because of the wide band gap and radiation hardness. To control carrier lifetime, a key parameter for high performance radiation detectors, it is important to understand the nature of the deep traps in this material. For this purpose, we have successfully applied thermally stimulated current (TSC) and high temperature resistivity measurements to investigate deep level centers in semi-insulating 4H SiC samples grown by physical vapor transport. High temperature resistivity measurements showed that the resistivity at elevated temperatures is controlled by the deep level with an activation energy of 1.56 eV. The dominant traps revealed by TSC measurements were at 1.1-1.2 eV. The deep trap levels in 4H-SiC samples, the impurity and point defect nature of TSC traps peaked at ∼106 K (0.23 eV), ∼126 K (0.32 eV), ∼370 K (0.95 eV), ∼456 K (1.1-1.2 eV) are discussed.     

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.     

Luminescence sensitivity changes of quartz by bleaching,annealing and UV exposure

The sensitivities of quartz luminescence signals to dose were studied after ionizing irradiation, ultraviolet (UV) exposure and different annealing conditions. The relationship between the 110 v °C thermoluminescence (TL) and optically stimulated luminescence (OSL) were studied on the same aliquot by looking at the ratio of both signals created by a test dose. It is suggested that the sensitivity changes of both signals are closely related, but not identical. Significant differences are observed when annealing to temperatures higher than 500 v °C. A modified model was proposed to interpret the observations. The similarity is interpreted as the same R hole centers are shared by both signals, whereas 110 v °C TL only uses additional R hole centers. Dramatic changes in luminescence sensitivity for quartz relate to the phase changes.