Influence of random electric fields on luminescence yield and kinetics of insulators

In the present work we investigate theoretically the influence of random electric fields on electron-hole recombination in wide bandgap crystals. Effective Onsager radius and, therefore, electron-hole recombination rate are significantly modified by external electric fields. Electric field distribution functions for point defects and charged dislocations are evaluated analytically. Electron-hole recombination rate decreases with concentration of point defects and dislocations. In simple case of random fields created by charge carriers in highly excited regions the recombination rate is proportional to n 2/3 rather than n , where n is the concentration of excitations. Therefore modification of luminescence kinetics is most pronounced at initial stages of relaxation of highly excited regions.     

Annealing of color centers in LiBaF 3

Results of the glow rate technique to analyze the activation energy of thermostimulated annealing of X-ray created F -type color centers in LiBaF 3 crystals are presented, showing pure and containing oxygen centers. It is shown that depending on the impurity composition two alternative mechanisms are involved in the annealing of color centers. It is proposed that either the anion vacancy governed migration of F -centers resulting in recombination with complementary defects, or the thermal delocalization of radiation created fluorine ( F i ) interstitials captured by anti-structure defects followed by recombination with all kinds of complementary F -type centers are responsible for the recombination of radiation defects above RT.     

Non-steady-state tunnelling recombination in insulating solids,controlled by defect diffusion and rotation

Abstract

The experimental data for KCl—Ag, KBr, NaCl—Ag and KCl—SO₄ crystals as well as Na₂O.3SiO₂—Tb³⁺ glass are summarized which demonstrate the delayed increase (decrease) of the intensity of the thermally stimulated tunnelling recombination of radiation defects after step-wise defrosting (frosting) of their mobility. Both theory and experiment presented here allow to distinguish the cases when the recombination kinetics is controlled by the rotation of an anisotropic defects or their diffusion respectively. It can be achieved studying the non-steady-state stages of kinetics. The effect of relative spatial defect distribution upon the kinetics under study is considered; it is argued that the {F, V _k } recombination in KBr occurs within spatially correlated pairs.     

Lyoluminescence mechanism of gamma and additively coloured alkali halides in pure water

The light emitted on dissolution of gamma and additively coloured crystals of NaCl, NaBr, KCl, KBr, CsCl and CsBr in pure water is studied. Experiments on gamma irradiated crystals have proved that the light emission originates from the recombination of released F-centres with trapped holes (V₂-centres) at the water-solid interface. Exceptionally pure additively coloured crystals having only F-centres produced no light when dissolved in pure water. However, relatively impure crystals emit light on dissolution due to the recombination of F-centres with traces of impurity ion centres in these crystals.     

Deformation-induced excitation of the luminescence centres in coloured alkali halide crystals

The present paper reports the deformation-induced excitation of the luminescence centres in coloured alkali halide crystals. The peaks of the mechanoluminescence (ML) in γ-irradiated KCl, KBr, KI, NaCl and LiF crystals lie at 455, 463, 472, 450 and 485 nm, i.e. at 2.71, 2.67, 2.62, 2.75 and 2.56 eV, respectively. From the similarity between the ML spectra and the thermoluminescence (TL) and afterglow spectra, the ML of KCl, KBr, KI, NaCl and LiF crystals can be assigned to the deformation-induced excitation of the halide ions in V₂-centres or any other hole centres. For the deformation-induced excitation of the halide ions in V₂-centres, or in other centres, the following four models may be considered: (i) free electron generation model, (ii) electron–hole recombination model, (iii) dislocation exciton radiative decay model and (iv) dislocation exciton energy transfer model. The dislocation exciton energy transfer model is found to be suitable for the coloured alkali halide crystals. According to the dislocation exciton energy transfer model, during the deformation of solids the moving dislocations capture electrons from the F-centres and then they capture holes from the hole centres and consequently the formation of dislocation excitons takes place. Subsequently, the energy released during the decay of dislocation excitons excites the halide ions of the V₂-centres or any other hole centres and the light emission occurs during the de-excitation of the excited halide ions, which is the characteristic of halide ions. The mechanism of ML in irradiated alkali halide crystals is different from that of the TL in which the electrons released form F-centres due to the thermal vibrations of lattices reach the conduction band and the energy released during the electron–hole recombination excites the halide ions in V₂-centres or in any other hole centres. It is shown that the phenomenon of ML may give important information about the dislocation bands in coloured alkali halide crystals.     

Luminescence of defect centres in Hg2Cl2

Abstract

Luminescence in Hg₂Cl₂, crystals excited with UV light is investigated in the spectral region 0.8–2.25 eV. Measurements are performed on as-grown samples and on samples previously exposed to UV light at RT. Six emission bands are found which depend on the concentration of the photochemical entities produced by irradiation of the crystals at RT. It is concluded that infra-red (IR) luminescence of Hg₂Cl₂ originates from crystal defects. The observed emission bands are tentatively attributed to the emission of (HgCI_xBr_3?x)^? and (HgCl_xBr_4?x)^2? complexes formed with residual Br impurities. Centres responsible for IR Hg₂Cl₂ emissions are excited: (i) via excitons of Hg₂Cl₂, (ii) via excited states of isolated Hg₂Br₂ molecules, and (iii) resonantly through the excitation bands of defect centres.     

Ionic,electronic and ion-diffusion controlled relaxation processes in CaF2, BaF2 and LiBaF3 crystals

Abstract

The ionic, electronic and anion-diffusion controlled thermally stimulated relaxation (TSR) processes at 80—700 K in CaF₂ BaF₂ and LiBaF₃ crystals (X-ray irradiated or non-irradiated) have been investigated by means of ionic conductivity, ionic thermally stimulated (TS) depolarization current (TSDC); as well as current (TSC), luminescence (TSL) and bleaching (TSB) techniques. Above 250—290 K broad and overlapping anion TSDC peaks and correlated TSB stages are detected. The TSB kinetics is initiated and controlled by anion detrapping and interaction with the localized charges, i.e., the anion-diffusion controlled TSR processes take place in fluorides. The TSL and TSC data for LiBaF₃ indicate that the lifetime and drift of electrons at 80—250 K is very small because of deep retrapping. The main TSL peaks at 132K, 170K and 220 K are caused by V_k center detrapping and hole-diffusion controlled tunnel recombination within pairs like {D_n e^?…V_k }.     

Crystalline properties and colour centres in alkali halide thin films

Abstract

Thin films of KCl, KBr, RbCl have been obtained by thermal evaporation on amorphous substrates with different deposition parameters. The crystalline structure and orientation have been determined, and the films resulted to be policrystals with high uniformity of orientation. Production of colour centres, achieved by irradiation with low-energy electrons, leads to F center concentrations barely observed in large crystals. The colouration kinetics is similar to that in the bulk, and shows after a maximum an exponential decay at high doses because of centre aggregation coupled to thermal effects. The films exhibit a bleaching process of the colour centres at room temperature, whose kinetics depends on the irradiation damage.     

ODMR investigations of recombination processes in ZnSe:Cu

New ODMR signals have been observed in ZnSe:Cu crystals by monitoring the Cu-green, Cu-red and the i.r. emissions. The results are interpreted in terms of direct D-A recombination involving Cu_Zn and Cu-X centres and indirect recombination via excited states of these centres.     

Recombination kinetics in nonlinear defective LiB3O5 crystals

A study of recombination kinetics in LiB₃O₅ (LBO) crystals by time-resolved luminescence and absorption spectroscopy is reported. An investigation of the kinetics of transient optical absorption (TOA) and luminescence under ns-scale electron-beam excitation performed within a broad temperature range of 77–500 K and a 1.2–5-eV spectral interval has established that the specific features in the recombination kinetics observed in LBO involve electronic, B²⁺, and hole, O⁻, trapping centers. The TOA and luminescence kinetics, as well as their temperature dependence, are interpreted by a model of competing hole centers. Relations connecting the kinetics parameters and the temperature dependence to the parameters of the main LBO point defects are presented. Fiz. Tverd. Tela (St. Petersburg) 40, 2008–2014 (November 1998)     

Ultraviolet luminescence of single crystals and single-crystal films of YAlO3

The nature of intrinsic emission bands of yttrium orthoaluminate in the UV spectral region at _max=220 nm (5.63 eV) and 330 nm (4.13 eV) is studied on the basis of the luminescence of single crystals and single-crystal films of YAlO₃ and Ce: YAlO₃ excited by synchrotron radiation sources with an energy of 3–25 eV at 9 and 300 K. The single crystals and single-crystal films were obtained, respectively, from solution and solution-melt by liquid-phase epitaxy and are characterized by considerably different concentrations of substitutional and vacancy defects. It is found that only the luminescence band at 300 nm, which has the decay time τ=4.1 ns and is excited in a band shifted from the range of interband transitions by 0.25 eV, has exciton-like character. The luminescence band at 220 nm with τ=0.1 µs at 9K, which is observed only for YAlO₃ single crystals and is absent in the luminescence of single-crystal films, is associated with antisite defects of the Y _Al ³⁺ type, which are a specific type of cationic isoelectronic impurities. It is shown that the phosphors based on single-crystal films of YAlO₃ have a simpler scintillation decay kinetics than their bulk analogues due to the absence of channels of excitation energy dissipation associated with the antisite defects of Y _Al ³⁺ type and vacancy defects.     

The role of residual technological impurities in the formation of radiative recombination centres in irradiated germanium

A comparison study of the photoluminescent (PL) spectra in pure and ultra-pure irradiated and annealed germanium has been performed. Some radiative recombination centres including impurities have been found. The spectra of samples bombarded by neutrons were found to include, along with the lines from intrinsic defects (Z, Y, X, W, V), the centres due to hydrogen and oxygen impurities (the lines T₁, T₂, U). A considerable number of the lines (A₁-A₃, B₁, B₂, C, D₁, D₂) in the PL spectra of crystals exposed to gamma-quanta and electrons were identified with the centres including carbon atoms. Such a great set of lines, presumably, results from the transformation of the above mentioned complexes in the course of annealing. The observed differences in the PL spectra within 0.72 to 0.74 eV range probably indicate a contribution of several types of intrinsic defects and other impurities, along with carbon, to complexing.     

On the radioluminescent emission of BaF2

Summary The luminescence of barium fluoride excited by X-rays has been recordedvs. wavelength. The spectrum shows two components due to recombination of excitons bound to Frenkel defects and to luminescent centres also active in the thermoluminescent process. The results are interpreted by means of a model based on the Prener and Williams recombination scheme.     

NMR probe of bulk electronic structures in H+ beam irradiated Bi2Te3 topological insulator

We report a nuclear magnetic resonance (NMR) study on H⁺ beam irradiated Bi₂Te₃ powdered single crystals. In this work, we demonstrate that the beam creates defects within its penetration range giving rise to delocalized charge carriers, thereby making further ¹²⁵Te NMR Knight shift and line broadening. Upon increasing temperature, the NMR line narrowing manifests the activated motions of thermally excited charge carriers in the irradiated sample. In contrast, it reveals that in the unirradiated sample the free-charge carriers at the Fermi level dominantly contribute to the Knight shift. Our results show that the orbital contribution to the Knight shift in the bulk state of Bi₂Te₃ becomes predominant in the system with the higher density of defects, as evidenced by modified electronic structures induced by the beam irradiation.     

Electric field effect on the mechanisms of recombination in KI doped with divalent ions

In KI crystals doped with divalent ions (Eu²⁺, Sr²⁺, Mn²⁺) a strong influence of the electric field is observed, after irradiation, on the carriers (electrons and holes) recombination kinetics. The phenomena are similar whether the electrons, distributed on traps bound to divalent ions, are excited by IR at 4 K, and recombine with trapped holes (V_k centers) or whether the holes are made thermally mobile at T>77 K. It is suggested that this is due to the recombination mechanism: the kinetics are simultaneously controlled by diffusion and tunneling. The tunneling range is a function of the applied field.     

Systematic features of diffusion and aggregation of intrinsic defects in dielectric crystals

It has been shown that the kinetics of reactions involving mobile intrinsic defects in the crystal is described by the exponential dependence in many cases. Based on this dependence and the fact that random-walk diffusion occurs in the cases under consideration, the distribution of diffusion paths traveled by mobile defects before entering into the reaction has been found. An expression for the arithmetic mean of these paths has been obtained. For lithium fluoride crystals irradiated with gamma-rays, the pre-exponential factors in the temperature dependences of the diffusion coefficients of F ₂ ⁺ color centers and anion vacancies have been determined and the diffusion coefficients of these types of defects have been estimated.     

Defects and radiation induced electronic processes in magnesium aluminate spinel of different compositions

The time dependence of the formation and decay of irradiation-induced optical absorption centers in magnesium aluminate spinel single crystals of different compositions (MgO - 1.0Al 2 O 3 and MgO - 2.5Al 2 O 3 ) was investigated. The kinetics of accumulation of X-ray irradiation-induced absorption bands is consistent with the mechanism of trap filling with free charge carriers through the conduction band. The model includes Coulomb blocking effects on spatially correlated defects. The observed two-stage decay of absorption bands after termination of X-ray irradiation is explained by electron hole recombination between centers of two different distances and/or different potential barriers. UV-irradiation confirms the existence of charge exchange between complex spatially correlated defects.     

Bleaching of color centers in NaCl crystals with laser pulses

Abstract

Bleaching of F centers in gamma irradiated NaCl crystals at room temperature and elevated temperatures using laser pulses from pulsed laser systems is studied in this paper. The rate of decay of F centers is monitored and the decay constants are evaluated. A comparison on the decay kinetics is made for CW and pulsed bleaching with a He-Cd laser. F center to C center conversions using a thermo-optic scheme are carried out with nanosecond dye laser pulses in gamma irradiated NaCl crystals.     

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.     

Dislocations used to probe the defect state of an ionic crystal lattice excited by a pulsed magnetic field

This paper presents the results of an investigation into the effect of a pulsed magnetic field on the state of linear and point defects in ionic crystals. For different amplitudes (1–7 T) and pulse lengths (3×10⁻⁵ to 10² s) of the pulsed field the kinetics of the transformation of defects into a new state and their relaxation after the field is turned off are studied in the temperature range 77–400 K. It is found that the relaxation of the states of point defects is mainly through recombination, and the change of state of the dislocations and of the point defects contribute nonadditively to the change in the dislocation mobility. The exposure of the crystal to a magnetic field leads to an increase in the dislocation mobility when the sample is mechanically stressed and to a decrease in the dislocation displacement with a second field pulse. Fiz. Tverd. Tela (St. Petersburg) 39, 634–639 (April 1997)