Mechanoluminescence response to the plastic flow of coloured alkali halide crystals

The present paper reports the luminescence induced by plastic deformation of coloured alkali halide crystals using pressure steps. When pressure is applied onto a γ-irradiated alkali halide crystal, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value and later on it decreases with time. The ML of diminished intensity also appears during the release of applied pressure. The intensity I_m corresponding to the peak of ML intensity versus time curve and the total ML intensity I_T increase with increase in value of the applied pressure. The time t_m corresponding to the ML peak slightly decreases with the applied pressure. After t_m, initially the ML intensity decreases at a fast rate and later on it decreases at a slow rate. The decay time of the fast decrease in the ML intensity is equal to the pinning time of dislocations and the decay time for the slow decrease of ML intensity is equal to the diffusion time of holes towards the F-centres. The ML intensity increases with the density of F-centres and it is optimum for a particular temperature of the crystals. The ML spectra of coloured alkali halide crystals are similar to the thermoluminescence and afterglow spectra. The peak ML intensity and the total ML intensity increase drastically with the applied pressure following power law, whereby the pressure dependence of the ML intensity is related to the work-hardening exponent of the crystals. The ML also appears during the release of the applied pressure because of the movement of dislocation segments and movements of dislocation lines blocked under pressed condition. On the basis of the model based on the mechanical interaction between dislocation and F-centres, expressions are derived for the ML intensity, which are able to explain different characteristics of the ML. From the measurements of the plastico ML induced by the application of loads on γ-irradiated alkali halide crystals, the pinning time of dislocations, diffusion time of holes towards F-centres, the energy gap E_a between the bottom of acceptor dislocation band and the energy level of interacting F-centres, and work-hardening exponent of the crystals can be determined. As in the elastic region the strain increases linearly with stress, the ML intensity also increases linearly with stress, however, as in the plastic region, the strain increases drastically with stress and follows power law, the ML intensity also increases drastically with stress and follows power law. Thus, the ML is intimately related to the plastic flow of alkali halide crystals.     

Mechanoluminescence induced by elastic and plastic deformation of coloured alkali halide crystals at fixed strain rates

Mechanoluminescence (ML) emission from coloured alkali halide crystals takes place during their elastic and plastic deformation. The ML emission during the elastic deformation occurs due to the mechanical interaction between dislocation segments and F-centres, and the ML emission during the plastic deformation takes place due to the mechanical interaction between the moving dislocations and F-centres. In the elastic region, the ML intensity increases linearly with the strain or deformation time, and in this case, the saturation region could not be observed because of the beginning of the plastic deformation before the start of the saturation in the ML intensity. In the plastic region, initially the ML intensity also increases linearly with the strain or deformation time, and later on, it attains a saturation value for large deformation. When the deformation is stopped, initially the ML intensity decreases at a fast rate; later on, it decreases at a slow rate. The decay time for the fast decrease of the ML intensity gives the relaxation time of dislocation segments or pinning time of the dislocations, and the decay time of the slow decrease of the ML intensity gives the diffusion time of holes in the crystals. The saturation value of the ML intensity increases linearly with the strain rate and also with the density of F-centres in the crystals. Initially, the saturation value of the ML intensity increases with increasing temperature, and for higher temperatures the ML intensity decreases with increasing temperature. Therefore, the ML intensity is optimum for a particular temperature of the crystals. From the ML measurements, the relaxation time of dislocation segments, pinning time of dislocations, diffusion time of holes and the energy gap between the bottom of the acceptor dislocation band and interacting F-centre level can be determined. Expressions derived for the ML induced by elastic and plastic deformation of coloured alkali halide crystals at fixed strain rates indicates that the ML intensity depends on the strain, strain rate, density of colour centres, size of crystals, temperature, luminescence efficiency, etc. A good agreement is found between the theoretical and experimental results.     

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.     

Mechanoluminescence induced by elastic deformation of coloured alkali halide crystals using pressure steps

During the elastic deformation of coloured alkali halide crystals, the bending segments of dislocations capture F-centre electrons lying in the expansion region of edge dislocations, to the states of dislocation band. After the separation from interacting F-centres, the captured electrons move together with the bending segments of dislocations and also drift along the axis of dislocations and subsequently the radiative electron–hole recombinations, owing to both the processes of captured-electron movement, give rise to the light emission. The generation rate of electrons in the dislocation band and the mechanoluminescence (ML) intensity initially increase with time, attain maximum value at a particular time, and then they decrease with time. The intensity I_m corresponding to the peak of ML intensity versus time curve and the total intensity I_T of ML increase with the applied pressure and also with the density of F-centres in the crystals. At low temperature, both I_m and I_T increase with temperature and at higher temperature they decrease with increasing temperature due to the thermal bleaching of F-centres and also due to the decrease in luminescence efficiency. Thus, both I_m and I_T are optimum for a particular temperature of the crystals. For longer time duration, the ML intensity decreases exponentially with time in which the decay time is equal to the lifetime of interacting F-centres. Expressions derived for the different characteristics of ML are able to explain the experimental results. It is shown that the time constant for rise of pressure, lifetime of the interacting F-centres or damping time of dislocation segments, and the activation energy can be determined from the ML measurements.     

Dynamics of the mechanoluminescence induced by elastic deformation of persistent luminescent crystals

When a composite of suitable dimension formed by mixing the microcrystalline or nanocrystalline persistent luminescent materials in epoxy resin is deformed at a fixed pressing rate, then the elastico mechanoluminescence (EML) emission takes place after a threshold pressure, in which the EML intensity increases linearly with the applied pressure. When the applied pressure is kept constant or decreased linearly, then the EML intensity decreases with time, in which depending on the prevailing condition, the EML intensity initially decreases at a fast rate and then at a slow rate or sometimes it decreases exponentially having only one decay time. When a small ball is dropped from a low height onto the film of a persistent luminescent material, then initially the EML intensity increases with time, attains a peak value and then it decreases initially at a fast rate and later on at a slow rate. In this case, both the peak EML intensity and the total EML intensity increase linearly with the height through which the ball is dropped onto the film. Considering the piezoelectrically induced detrapping model based on successive detrapping of exponentially distributed traps a theoretical approach is made to the dynamics of light emission induced by elastic deformation of persistent luminescent crystals and thin films. It is shown that the EML intensity depends on several parameters such as pressure, pressing rate or strain rate, temperature, density of filled electron traps, piezoelectric constant near defect centers, etc. Both, in the case of slow deformation and impact stress, the fast decay time is related to the time-constant for the decrease of pressing rate of the samples and the slow decay time of EML is related to the lifetime of electrons in the shallow traps lying in the normal piezoelectric region of the crystals. Both, the EML produced during the release of pressure and the EML produced during the successive applications of pressure take place due to the detrapping of retrapped electrons in the vacant electron traps near activator ions, in which retrapping is caused by the thermally released electrons from the filled shallow traps lying in the normal piezoelectric region of the crystals, which get filled during the detrapping of stable traps at the time of increase of pressure. On the basis of the proposed model, the dependence of EML intensity on different parameters, dynamics of EML and physical concepts of the threshold pressure, characteristic piezoelectric field for detrapping, coefficient of deformation detrapping, nonlinear increase of the EML intensity of some crystals at high pressure and higher EML intensity in the crystals having higher coefficient of deformation detrapping can be satisfactorily understood. A good agreement is found between the theoretical and experimental results. It is shown that the present study may be helpful in tailoring the intense persistent elastico mechanoluminescent materials having long lasting time.     

Mobile interstitial model and mobile electron model of mechano-induced luminescence in coloured alkali halide crystals

A theoretical study is made on the mobile interstitial and mobile electron models of mechano-induced luminescence in coloured alkali halide crystals. Equations derived indicate that the mechanoluminescence intensity should depend on several factors like strain rate, applied stress, temperature, density of F-centres and volume of crystal. The equations also involve the efficiency and decay time of mechanoluminescence. Results of mobile interstitial and mobile electron models are compared with the experimental observations, which indicated that the latter is more suitable as compared to the former. From the temperature dependence of ML, the energy gaps between the dislocation band and ground state of F-centre is calculated which are 0.08, 0.072 and 0.09 eV for KCl, KBr and NaCl crystals, respectively. The theory predicts that the decay of ML intensity is related to the process of stress relaxation in crystals.     

Dislocation unpinning model of acoustic emission from alkali halide crystals

The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constantτ _s for surface annihilation of dislocations and the pinning timeτ _p of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.     

Mechanoluminescence excitation in alkali halide crystals and colouration decay in microcrystalline powders

The mechanoluminescence (ML) of NaCl, NaBr, NaF, LiCl and LiF crystals ceases at 105, 58, 170, 151 and 175°C respectively. Both the temperatureT _c at whichML disappears and the temperatureT _s required to induce a particular percentage of colouration decay in a given time, decreases with increasing nearest neighbour distance in alkali halide crystals. This perhaps suggests that similar processes cause the disappearance ofml in alkali halide crystals and the colouration decay in their microcrystalline powders. It is shown that mobile dislocations may cause the leakage of surface charge and the decay of colouration in microcrystalline powders.     

Specific features of the temperature quenching of luminescence of self-trapped excitons in alkali halide crystals under low-temperature deformation

The activation energy of temperature quenching of luminescence of self-trapped excitons in alkali halide crystals subjected to low-temperature uniaxial deformation is evaluated experimentally. It is found that an increase in the activation energy is observed in the following series of crystals: KBr → NaCl → KI → NaBr → CsBr → RbI. The effect of enhancement of intrinsic luminescence of alkali halide crystals due to the lowering of the symmetry of the crystal lattice under low-temperature uniaxial deformation is interpreted by analyzing the observed increase in the activation energy that characterizes the height of the potential barrier separating channels of radiative and nonradiative decay (with the formation of radiation defects) of self-trapped excitons.     

On the mechanisms of thermoluminescence and deformation luminescence in gamma-irradiated KCl

Thermoluminescence (TL) and deformation luminescence (DL) studies in KC1 γ-irradiated at room temperature are reported. The roles that F-centres and their higher conglomerates on the one hand, and V₂- and V₃-centres as recombination centres on the other hand, play in these processes are specified. Two peaks at 2.5 eV and 3 eV are observed in the emission spectra of both TL and DL. The close relationship between TL and DL is confirmed.     

Persistent mechanoluminescence induced by elastic deformation of ZrO2:Ti phosphors

ZrO₂:Ti phosphors show such a strong mechanoluminescence (ML) that it can be seen in day light with naked eye. When a pellet of ZrO₂:Ti phosphor mixed in epoxy resin is deformed in the elastic region at a fixed strain rate using a testing machine, ML intensity increases linearly with time, and when the deformation is stopped, ML intensity decreases exponentially with time. For a given strain rate, ML intensity increases linearly with pressure, and for a given pressure, ML intensity increases linearly with the strain rate. The total ML intensity, in the deformation region, increases quadratically with pressure; however, the total ML intensity in the post-deformation region increases linearly with pressure. ML intensity decreases with successive number of pressings, whereby the reduced ML intensity can be recovered by UV-irradiation of the sample. ML intensity increases linearly with density of filled electron traps and it is optimum for a particular concentration of Ti in ZrO₂. ML intensity should change with increasing temperature of the phosphors. Although ZrO₂ is non-piezoelectric as a whole, it seems that the local structures near the Ti ions in ZrO₂ crystals are in the piezoelectric phase. The elastico ML in ZrO₂ phosphors can be understood on the basis of the localized piezoelectrification-induced detrapping model. According to this model, the localized piezoelectric field near Ti ions causes detrapping of electrons and subsequently the detrapped electrons moving in the conduction band are captured by the energy state of excited Ti⁴⁺ ions, whereby excited Ti⁴⁺ ions are produced and consequently the decay of excited Ti⁴⁺ ions gives rise to the light emission. The expressions derived on the basis of this model are able to explain satisfactorily the characteristics of ML. The relaxation time of localized piezoelectric charges and the threshold pressure for the ML emission can be determined from ML measurements. The long decay of elastico ML indicates the possibility of exploring persistent elastico ML, which may be useful for the fabrication of dim light sources capable of operating without any external power.     

Correlation between deformation bleaching and mechanoluminescence in coloured alkali halide crystals

The present paper reports the correlation between deformation bleaching of coloration and mechanoluminescence (ML) in coloured alkali halide crystals. When the F-centre electrons captured by moving dislocations are picked up by holes, deep traps and other compatible traps, then deformation bleaching occurs. At the same time, radiative recombination of dislocation captured electrons with the holes gives rise to the mechanoluminescence. Expressions are derived for the strain dependence of the density of colour centres in deformed crystals and also for the number of colour centres bleached. So far as strain, temperature, density of colour centres, E _a and volume dependence are concerned, there exists a correlation between the deformation bleaching and ML in coloured alkali halide crystals. From the strain dependence of the density of colour centres in deformed crystals, the value of coefficient of deformation bleaching D is determined and it is found to be 1.93 and 2.00 for KCl and KBr crystals, respectively. The value of (D+χ) is determined from the strain dependence of the ML intensity and it is found to be 2.6 and 3.7 for KCl and KBr crystals, respectively. This gives the value of coefficient of deformation generated compatible traps χ to be 0.67 and 1.7 for KCl and KBr crystals, respectively.     

Transient behaviour of the mechanoluminescence induced by impulsive deformation of fluorescent and phosphorescent crystals

When a crystal is fractured impulsively by the impact of a moving piston, then initially the mechanoluminescence (ML) intensity increases quadratically with time, attains a peak value and later on it decreases with time. Considering that the solid state ML and gas discharge ML are excited due to the charging and subsequent production of electric field near the tip of moving cracks, expressions are derived for the transient ML intensity I, time t_m and intensity I_m corresponding to the peak of ML intensity versus time curve, respectively, the total ML intensity I_T, and for fast and slow decays of the ML intensity. It is shown that the decay time for the fast decrease of the ML intensity after t_m, is related to the decay time of the strain rate of crystals, and the decay time of slow decay of ML, only observed in phosphorescent crystals, is equal to the decay time of phosphorescence. The value of t_m decreases with the increasing impact velocity, I_m increases with the increasing impact velocity, and I_T initially increases and then it tends to attain a saturation value for higher values of the impact velocity. The values of t_m, I_m and I_T increase linearly with the thickness, area of cross-section and volume of the crystals, respectively. So far as the rise, attainment of ML peak, and fast decay of ML are concerned, there is no any significant difference in the time-evolution of solid state ML, gas discharge ML, and the ML emission consisting of both the solid state ML and gas discharge ML. From the time-dependence of ML, the values of the time-constant for decrease of the surface area created by the movement of a single crack, the time-constant for the decrease of strain rate of crystals, and the decay time of phosphorescence of crystals can be determined. A good agreement is found between the theoretical and experimental results. The importance of fracto ML induced by impulsive deformation of crystals is discussed.     

Mechanoluminescence by impulsive deformation of γ-irradiated Er-doped CaF2 crystals

An impulsive technique has been used for mechanoluminescence (ML) measurements in γ-irradiated Er doped CaF₂ crystals. When the ML is excited impulsively by the impact of moving piston on to γ-irradiated CaF₂:Er crystals, two peaks are observed in ML intensity with time and it is seen that the peak intensities of first and second peaks (I_m1 and I_m2) increase with increasing impact velocity. However the time corresponding to first and second peaks (t_m1 and t_m2) shifts towards shorter time values with increasing impact velocity. It is also seen that the total ML intensity I_Total initially increases with the impact velocity and then it attains a saturation value for higher values of the impact velocity. We have presented a theoretical explanation for the observed results.     

On the pressure dependence of the effective ionic charge of cesium halides

The importance of temperature effects in the use of the second Szigeti relation to calculate the volume dependence of the effective ionic charge of cesium halide crystals is studied. The effect obtained is larger than the one for alkali halide crystals of the NaCl structure. Positive values of (? ln s/? In v) are obtained using low temperature experimental data with the Grüineisen parameter γ_t(T → 0K) calculated using the generalized first Szigeti relation. Values of γ_t are also obtained with a rigid ion model and they differ little from the previous ones.     

γ-Radiolysis of LiF

Abstract

Data are reported of optical absorption, magnetic susceptibility, mass and mass density measurements, which were carried out on γ-irradiated single crystals of lithium fluoride. The results show that the radiation damage in the γ-irradiated samples is strikingly similar to that in the neutron-irradiated specimens. A quantitative observation, however, reveals differences which give experimental evidence for the statement that the F-centres occur in a more aggregated form in the γ^? than in the neutron-irradiated crystals.     

Dislocation models of mechanoluminescence in γ- and X-irradiated alkali halides crystals

The mechanoluminescence appears in the elastic, plastic and fracture regions of γ- and X-irradiated KCl and NaCl crystals. A linear relation is found between the mechanoluminescence intensity and the newly created dislocations. Four models are proposed for the mechanoluminescence excitation during the movement of dislocations. These models are: dislocation unpinning model, dislocation interaction model, dislocation defect stripping model, and dislocation innihilation model. The dislocation annihilation model seems to be a dominating process for the M.L. excitation in γ- and X-irradiated alkali halide crystals.     

Electrical and thermoluminescence properties of γ-irradiated La2CuO4 crystals

Abstract

Measurements of the electrical properties of unirradiated as well as γ-irradiated La₂CuO₄ crystals were carried out at different temperatures in the frequency range of 0.1-100 kHz. Thermoluminescence (TL) studies were also performed on such crystals in the temperature range of 300-600K. The conductivity of the unirradiated La₂CuO₄ crystals were found to obey the power law frequency dependence at each measured temperature below the transition temperature (T_c = 450K). The activation energies for conduction and dielectric relaxation time have been calculated. The TL response and the dc resistance were found to increase with γ-irradiation dose up to 9-10 kGy. The results showed that the ferroelastic domain walls of La₂CuO₄ crystal as well as its TL traps are sensitive to γ-raditaion. This material can be used in radiation measurements in the range 225 Gy-10 kGy.     

Charged dislocations in ionic crystals

Experiments and theories concerning charged dislocations in alkali halide crystals are reviewed in detail, with particular attention to the way in which the experiments should be interpreted and to the range of applicability of the sweep-up and various forms of thermal-equilibrium models. Possible effects on mechanical properties and internal friction are analysed. The transient and steady-state effects of plastic deformation on ionic conductivity are described and new interpretations involving charged dislocations are proposed. A survey of results on the scattering of light by alkali halide single crystals leads to the conclusion that charged dislocations do not play an important role.

Evidence about charges on surfaces and on dislocations in AgCl and AgBr is reviewed and compared with that for alkali halides. Comparisons are also made with MgO, the CsCl and CaF₂ structures, semiconductors and ice.     

Evolution of Anion and Cation Excitons in Alkali Halide Crystals

The manifestations of the existence of free anion excitons, the processes of their self-trapping, and the coexistence of mobile and self-trapped excitons (STEs) in wide-gap alkali halide crystals are reviewed. The radiative channel of decay of anion excitons, yielding luminescence, and a particular type of nonradiative channel with the creation of elementary Frenkel defects (FDs) are considered. We analyzed the criteria for the efficiency of this channel for defect formation, possible mechanisms for the decay of self-trapped excitons with the production of neutral and charged anion Frenkel defects, and the processes of multiplication of electronic excitations in alkali halide crystals. Particular attention is paid to the decay of cation excitons, including from the point of view of the possibility of the low-temperature creation of elementary Frenkel defects in the cation sublattice of alkali halide crystals.