Tetrahedral manganese (II) complexes—intense and unique type of mechanoluminophores

Intense and unique type of mechanoluminescence (ML) is found in tetrahedral manganese (II) complexes. During the excitation of ML by the impact of a piston onto the crystal, the ML intensity initially increases with time, attains a maximum value and then decreases. After retardation of the piston, the decay rate of ML is faster during crystal deformation; however, its value decreases after cessation of the deformation and becomes equal to the decay rate of phosphorescence. The ML disappears below the melting point. Since the crystals of tetrahedral manganese (II) complexes are centrosymmetric, the local non-centrosymmetric sites near the defects are attributed to be responsible for the mechanoluminescence excitation.     

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 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.     

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.     

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.     

Crystalloluminescence and temporary mechanoluminescence of As2O3 crystals

Crystalloluminescence and temporary mechanoluminescence of As₂O₃ crystals are investigated. The crystalloluminescence spectra are similar to the photoluminescence and mechanoluminescence (of fresh crystals, in CO₂ atmosphere) spectra. The mechanoluminescence spectra of freshly grown crystals taken in air consist of the superposition of the photoluminescence and nitrogen emissions. The mechanoluminescence spectra of old crystals of As₂O₃ consist of only the nitrogen emission. The total number of crystalloluminescence flashes is linearly related to the total mass of the crystals grown. The mechanoluminescence intensity increases with the mass of the crystals. The mechanoluminescence intensity decreases with the age of the crystals and the rate of decrease increases with increasing temperature of the crystals. Different possibilities of crystalloluminescence and mechanoluminescence excitations in As₂O₃ crystals are explored and it is concluded that crystalloluminescence and mechanoluminescence are of different origins.     

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.     

Dependence of mechanoluminescence in rochelle-salt crystals on the charge-produced during their fracture

The dependence of mechanoluminescence in rochelle-salt crystals on the charge-produced during their fracture is found to be linear up to the applied stress of 344 kg/cm². This fact is discussed on the basis of the instability of cracks in a crystal and it is concluded that the new surfaces created by mobile cracks are responsible for the appearance of mechanoluminescence in rochelle-salt crystals.     

A search for mechanoluminophors capable of pressure-induced thermal population of excited states

During the process of deforming a crystal, a high pressure is developed near the tip of mobile cracks, which may in turn produce a new ground state by thermal electron transfer. Upon sudden release of pressure, the electron can either relax to one atmosphere ground state or remain in the excited state potential well long enough to relax to one atmosphere and radiatively transfer back to the ground state. For analysing the pressure induced thermal population of the excited state, the mechanoluminescence(ML) and high pressure photoluminescence(PL) of several organic and inorganic crystals were measured. The study indicated that usual pressure coefficient of energy shift of the order of 50–100 cm⁻¹/kbar and the stress at the crack-tip of the order of 5–10 kbar, are not sufficient to cause the thermal population of the excited state. If by any means the product of pressure coefficient and stress at the mobile crack-tip can be increased by 50 to 100 times, then the thermal population of the excited states may take place. Using the pressure coefficient of energy shift and the difference in ML and PL spectra, and using independently the change in relative intensities of the vibronic peaks, the pressure at the emitting mechanoluminescent crystal sites is evaluated and it is found to be of the order of several kbar which varies from crystal to crystal.     

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.     

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.     

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.     

Emission processes accompanying deformation and fracture of metals

Present-day physical methods of investigation reveal that the fracture and plastic deformation of metals is accompanied by emission processes, in particular, by luminescence and emission of electrons. All the metals studied thus far exhibit a capability of luminescence. The intensity, duration, and spectrum of mechanoluminescence are different for different metals. The intensity is determined by the mechanical and thermal characteristics. For a given metal, the intensity depends on dislocation density in the structure and the sample loading rate. The spectrum of noble metals is governed by the electronic structure of surface states. The dynamics of mechanoluminescence and electron emission (exoemission) depends on the rate of stress variation in the sample under study. This permits one to consider the mechanoluminescence and exoemission not only as physical characteristics but also as a potential tool for probing surface states in metals and the kinetics of emergence of mobile dislocations on the surface with a high time resolution. Fiz. Tverd. Tela (St. Petersburg) 41, 841–843 (May 1999)     

应力发光材料Sr2SiO4∶Eu,Dy的光谱性质研究

采用高温固相法制备一系列Sr₂SiO₄∶Eu_0.01, Dy_x(x=0.000 1, 0.002 5, 0.005, 0.01)应力发光材料,研究了不同掺杂浓度下,Sr₂SiO₄∶Eu, Dy的光致发光和应力发光性质。研究结果表明在掺杂Dy3+浓度较低时,样品同时存在α和β两种相,当掺杂Dy3+浓度增加时,则出现β到α的相转变。由于Eu2+占据Sr2+格位的不同,样品在蓝光区486 nm(Sr1)和绿光区530 nm(Sr2)有两个峰存在。而应力发光光谱与余辉光谱类似,均只呈现出530 nm的发光,这说明二者的发光来源于占据Sr2格位的Eu2+,都是通过改变陷阱的浓度实现发光性能的变化,但Sr₂SiO₄∶Eu, Dy的应力发光强度的变化还与其结构改变有关。同时,Sr₂SiO₄∶Eu, Dy应力发光强度与所施加的力之间呈良好的线性关系,并且可用眼睛观察到明显的黄色应力发光,这为应力发光传感器准确检测物体所受应力提供依据。结合余辉、热释以及应力发光性质,推测Sr₂SiO₄∶Eu, Dy的应力发光机制应是压电产生的电致发光。     

Mechanoluminescence and lyoluminescence characterization of Li2BaP2O7:Eu phosphor

In this work mechanoluminescence and lyoluminescence properties of Li₂BaP₂O₇: Eu phosphor are reported. Phosphor was synthesized through high temperature solid state diffusion method. Analysis of phosphor was made through various characterization techniques such as mechanoluminescence (ML), lyoluminescence (LL), x-ray powder diffraction (XRD), scanning electron microscope (SEM) and photoluminescence (PL). It was observed that ML intensity showed good enhancement with variation in time, concentration of dopant Eu, mass of piston and impact velocity. Lyoluminescence intensity was also found to increase with change in time and mass of the sample. Variation in gamma doses imparted to Li₂BaP₂O₇: Eu phosphor was observed to affect both the ML and LL intensities' respectively. Both the ML and LL intensity attain a maximum value I_m at a particular time t_m but afterwards, it decreases and finally disappears. Morphology of Li₂BaP₂O₇: Eu luminescent material was also studied using scanning electron microscope technique. The average particle size in Eu doped lithium barium diphosphate phosphor was around 2 μm.     

Pulse-induced mechanoluminescence of ultraviolet-irradiated SrAl2O4:Eu,Dy phosphors

The SrAl₂O₄:Eu,Dy phosphors prepared by solid state reaction technique in a reduced atmosphere of 95% Ar+5% H₂ exhibit very intense mechanoluminescence (ML) which can be seen in daylight with naked eye. When the phosphors are deformed by the impact of a low-power electric hammer, initially the ML intensity increases with time, attains a maximum value and then decreases with time. After the threshold pressure, the peak of ML intensity I_m and the total ML intensity I_T increase with the increasing value of the impact pressure. For the ML excited by the pressure pulse of short duration, two decay times of ML are observed; however, for the ML excited by the pressure pulse of long duration, only one decay time is observed. The ML intensity decreases with successive applications of pressure on SrAl₂O₄:Eu,Dy phosphors. For the low applied pressure in the range below the limit of elasticity recovery of ML intensity takes place when the sample is exposed to ultraviolet (UV) light. This fact indicates that the vacant traps produced during the application of pressure pulses get filled during the exposure of the sample to UV light. The ML in the elastic region of SrAl₂O₄:Eu,Dy phosphors can be understood on the basis of the piezoelectrically induced detrapping model. The non-irradiated SrAl₂O₄:Eu²⁺,Dy³⁺ phosphors exhibit ML during the fracture of the compact mass of phosphors whose ML intensity is less when compared to that of the UV-irradiated compact masses. The ML induced by pressure pulses may be useful for determining the magnitude and rise time of unknown pressure pulses and to determine the lifetime of charge carriers in shallow traps.     

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.     

Luminescence induced by elastic deformation of ZnS:Mn nanoparticles

When the thin film of ZnS:Mn nanoparticles deposited on a glass substrate is elastically deformed by applying a load, then initially the mechanoluminescence (ML) intensity increases with time, attains a peak value I_m at a particular time t_m, and later on it decreases with time. The rise and decay characteristics of the ML produced during release of the load are also similar to those produced during the application of load. Similar rise, occurrence of peak and then decrease in ML intensity are also found, when the film is deformed impulsively by dropping a steel ball of small mass from a low height; however, in this case, the time durations for the occurrence of ML and decay time of ML are very short. In the cases of loading and impulsive deformation ,after t_m, initially the ML intensity decreases at a fast rate and then at a slow rate, in which the decay time of fast decrease is equal to the time-constant for rise of pressure and the decay time for slow decrease is equal to the relaxation time of the surface charges. In the case of loading, the peak intensity I_m and the total intensity I_T of ML increase quadratically with the magnitude of applied pressure; however, in the case of impulsive deformation, both the I_m and I_T increase linearly with the height through which the ball is dropped on to the sample. In the case of deformation of the samples at a fixed strain rate, I_m should increase linearly with the applied pressure. The elastico ML in ZnS:Mn nanoparticles can be understood on the basis of the piezoelectrically-induced electron detrapping model, in which the local piezoelectric field near the Mn²⁺ centres reduces the trap-depth, and therefore, the detrapping of filled electron traps takes place, and subsequently the energy released non-radiatively during the electron-hole recombination excites the Mn²⁺ centres and de-excitation gives rise to the ML. The equal number of photons emitted during the application of pressure, release of pressure, and during the successive applications of pressure, indicates that the detrapped electron-traps get filled during the relaxation of the surface charges induced by the application and release of pressure because the charge carriers move to reduce the surface charges. On the basis of the piezoelectrically-induced electron detrapping model, expressions are derived for different characteristics of the ML of ZnS:Mn nanoparticles and a good agreement is found between the theoretical and experimental results. The expressions explored for the dependence of ML intensity on several parameters may be useful in tailoring the suitable nanomaterials capable of exhibiting ML during their elastic deformation. The values of the relaxation time of surface charges, time-constant for the rise of pressure, and the threshold pressure can be determined from the measurement of the time-dependence of ML. It seems that the trapping and detrapping of charge carriers in materials can be studied using ML.     

Plasma characteristics of the discharge produced during mechanoluminescence

The conditions during light emission from the fracture of solids have been difficult to determine because such mechanoluminescence (ML) is usually weak. When ML is produced by acoustic cavitation of a liquid slurry of resorcinol crystals, however, we observe bright light emission, which makes it possible to measure plasma conditions by emission spectra: a bimodal heavy atom emission temperature profile is observed with 405+/-22 K (for 80% of emitting CH) and 4015+/-730 K (for 20%), with an electron density and energy of 1.3+/-0.13x10;{14} cm;{-3} and approximately 3.5 eV (i.e., an effective T_{e} approximately 41 000 K).     

Mechanoluminescence and thermoluminescence of BaFCl:Sm 2+ and BaFBr:Sm 2+ crystals

The alkaline-earth fluorohalide crystals MFX, where M=Ca, Sr, Ba, Pb and X=Cl, Br, I, form an important class of materials crystallizing in the PbFCl-type tetragonal structure which is also called the matlockite structure. These compounds have long been of interest because of the various defect species which can be detected by spin resonance and associated techniques. The crystals were prepared by slow cooling of the melt of a stoichiometric mixture of BaF ₂ and the corresponding chloride or bromide under 0.2 bar of ultrapure argon (5N5), often slightly fluorinated. We have studied the mechanoluminescence (ML) of BaFBr:Sm ²⁺ and BaFCl:Sm ²⁺ crystals. It is seen that after the impact of a moving piston, initially the ML intensity increases with time, attains a maximum value and then it decreases with time up to a particular minimum value, and then it increases again, attaining a peak value and finally disappears. The first peak lies in the deformation region and the second peak lies in the post-deformation region. The ML intensity of the BaFCl:Sm ²⁺ crystal is much higher than the ML intensity of the BaFBr:Sm ²⁺ crystal. For different impact velocities, the ML intensity increases with velocity; and the total ML intensity attains a saturation value for higher impact velocities. The total ML intensity increases with the increase in the applied load. It is suggested that the moving dislocation produced during deformation of crystals captures holes from hole-trapped centers (like H centers), and the subsequent radiative recombination of the dislocation holes with electron gives rise to ML. Thermoluminescence (TL) of BaFBr:Sm ²⁺ and BaFCl:Sm ²⁺ crystals was studied after exposure to ultraviolet rays with the help of a TLD reader. The peak of TL for the BaFBr:Sm ²⁺ crystal is found at ～247°C and for BaFCl:Sm ²⁺ crystals at 283°C. The TL intensity initially increases with increase in the UV radiation and then it attains saturation for higher values of UV exposure. The absorption spectrum was recorded with the help of a UV–visible spectrophotometer (Shimadzu). The band found at 275 nm was attributed to H centers.