Ion diffusion-controlled thermally stimulated processes in x-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF₂, BaF₂, LiBaF₃ and KBr crystals were investigated above 290 K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF₂, BaF₂, LiBaF₃ and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal show that above 290 K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.     

Ion diffusion-controlled thermally stimulated processes in X-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF 2 , BaF 2 , LiBaF 3 and KBr crystals were investigated above 290 v K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF 2 , BaF 2 , LiBaF 3 and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal evidence that above 290 v K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide 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.     

Relaxations and phase transitions phenomena in structurally related tyrosine-derived polyarylates

Abstract

A series of four tyrosine-derived polyarylates with different number of methylene groups in the backbone (y = 2, 4, 6 and 8) were studied by measuring thermally stimulated depolarization currents (TSDC). The low temperature TSDC spectra (80—240K) were analyzed at two different degrees of hydration to assess the effects of small amounts of water in the observed broad and complex β band. Higher temperature TSDC spectra (250 to 350 K) provided the α relaxation peaks associated with the glass transition temperature. The direct signal analysis (DSA) method allowed the decomposition of the complex peaks into elementary processes. The β_i components result from localized motions of molecular segments of variable length molecules whose identities were established in a prior study of polycarbonates. The changes observed in the low and high temperature polarization with the number of backbone methylene groups were interpreted as a combination of flexibility and entanglement phenomena.     

Thermally stimulated luminescence and electron paramagnetic resonance studies of actinide doped calcium chloro phosphate

Electron paramagnetic resonance [EPR] and thermally stimulated luminescence [TSL] studies were conducted on self [α]-irradiated²³⁹Pu doped calcium chloro phosphate andγ-irradiated²³⁹Pu/²³⁸UO ₂ ²⁺ doped calcium chloro phosphate to elucidate the role of the electron/hole traps in thermally stimulated reactions and to obtain trap parameters from both TSL and EPR data. TSL glow peaks around 135 K (# peak 1), 190 K (# peak 2), 435 K (# peak 5) and 490 K (# peak 7) were observed and their spectral characteristics have shown that Pu³⁺ and UO ₆ ⁶⁻ act as luminescent centres in calcium chloro phosphate with respective dopants. EPR studies have shown the formation of the radical ions H⁰, PO ₄ ²⁻ , O⁻, O ₂ ⁻ and [ClO]²⁻ under different conditions. Whereas the [ClO]²⁻ radical being stable up to 700 K, was not found to have any role in TSL processes, the thermal destruction of other centres was found to be primarily responsible for the TSL peaks observed. The trap depth values were determined both by using the TSL data and also the temperature variation of EPR spectra of these centres.     

Internal irradiation effects in239Pu doped K2Ca2(SO4)3): EPR,TSL and PAS investigations

The electron/hole trapped centres created during internal irradiation in²³⁹Pu doped K₂Ca₂(SO₄)₃ were investigated using electron paramagnetic resonance (EPR), thermally stimulated luminescence (TSL) and photoacoustic spectroscopic studies (PAS). These techniques were used to identify the defects and characterize the thermally induced relaxation processes. TSL studies of self (α)/γ-irradiated²³⁹Pu doped K₂Ca₂(SO₄)₃ revealed two glow peaks around 400 and 433K. Plutonium introduced as Pu⁴⁺ was partly reduced to Pu³⁺ due to self irradiation. This was ascertained from PAS studies. EPR studies carried out on these samples showed the formation of radical ions SO ₄ ⁻ , SO ₃ ⁻ , O ₃ ⁻ , etc. The thermal destruction of SO ₄ ⁻ ion was found to be associated with the prominent glow peak around 433K. Pu³⁺ was found to act as luminescent centre for the observed TSL glow. The trap depth for the glow peak at 433K has been determined from TSL and EPR data.     

Effect of ionic liquid on chain segment motion and charge detrapping in poly(l-lactide)/ionic liquid composites

The effect of ionic liquid on the chain segment motion and charge detrapping in poly(l-lactide) (PLA)/ionic liquid (IL) composites has been investigated by means of thermally stimulated depolarization current (TSDC), scanning electron microscopy, and differential scanning calorimetry. There are four current peaks (namely, α, ρ₁, ρ₂, and ρ₃ peaks, respectively) in TSDC spectra of PLA and PLA/IL composites. The α peak corresponds to the glass transition, the ρ₁ peak is attributed to space charge trapped in the amorphous phase, the ρ₂ peak is originated from space charge trapped in the interphase that includes PLA/IL interface and crystalline/amorphous interface of PLA, and the ρ₃ peak is originated from space charge trapped in the crystalline phase. With the increase of IL content from 0 to 5phr, ρ₂ and ρ₃ peaks gradually merge into one single peak. By analyzing the characteristic parameters of these peaks, it is found that IL can accelerate the mobility of chain segments and increase structural defects in PLA/IL composites. In addition, IL decreases the stability of trapped charge in both amorphous and crystalline phases, but not affecting the stability of trapped charge in interphase.     

The Chain Segment Motion and Traps in γ‐Irradiation Crystalline Nylon 1010

The chain segment motion, charge trapping and detrapping in γ‐irradiated nylon 1010 films (doses in the range 0–2,000 kGy were used) have been investigated by means of thermally stimulated depolarization current (TSDC). There are three current peaks (named α, ρ₁ and ρ₂, respectively) in the TSDC spectra, corrected by spontaneous current, above room temperature. By analyzing the characteristic parameters of the three peaks, it is found that the chain segment motion in the amorphous regions becomes more difficult at low irradiation dose (<100 kGy) and then becomes easier with further increasing irradiation dose. The stability of the traps at the crystalline‐amorphous interfaces increases at low irradiation dose (<500 kGy) and then decreases with further increasing irradiation dose; the irradiation promotes the creation of traps and the stability of traps in the crystalline regions.     

Interpretation of thermoluminescence and thermally stimulated conductivity experiments: Part II: Application to CdGa2S4

Results of thermally stimulated luminescence (TSL) and conductivity (TSC) experiments on CdGa₂S₄ are reported. In the lower temperature region of the TSl curve a decay of luminescence is observed that is probably due to donor-acceptor pair recombination since no accompanying conduction is measured. The TSL and TSC curves of the undoped material further consist essentially of two peaks. If trap depths are calculated with various methods from the literature it turns out that for one peak different values are obtained. These differences cannot be explained with the conventional model consisting of one trapping level and one recombination level. If the results are compared with more complex models it follows that thermal quenching, the presence of a trap distribution, thermally disconnected traps and recombination via excited states, are important. This is most clearly demonstrated in the cases with excess Ga and with Ag or In as dopant. Although this approach probably yields valuable information about CdGa₂S₄, no definite conclusions may be drawn since some essential questions remain unsolved.     

Thermally stimulated depolarization currents and ionic conductivity of cubic lead fluoride containing small rare earth ions

Abstract

This work is concerned with thermally stimulated depolarization current (TSDC) and ionic conductivity studies in lead fluoride containing the small rare earths Dy, Ho, Er and Yb. The TSDC scans from 80 to 300 K show two peaks. For Pb_1?xEr_xF_2+x one is located at 106 K, and another, which is much stronger, occurs at about 160 K. The former is associated with a dipolar defect containing at least two rare earths and the latter is attributed to the development of F^? space charge during polarization of the sample. The activation energies obtained from both the high temperature TSDC peak and the ionic conductivity are the same, which corroborates the latter assignment. In addition, the ionic conductivity is shown to be independent of concentration. Those results can be understood of rare earth clustering, which is either absent or is unobservable dielectrically for large rare earths such as lanthanum, occurs extensively even at very low concentrations of the small rare earths. The explanation is that the majority of fluorine charge compensators are trapped by clusters.     

Study of thermal currents in powder β-spodumene ceramics doped with Cuo, FeO and TiO2

Ternary-phase ceramic system of Li₂O Al₂O₃ 4SiO₂ doped with CuO, FeO and TiO₂ has been prepared and subjected to dc electrical conductivity and thermally stimulated depolarization current (TSDC) measurements as a function of temperature (30-250 °C) and field strength. The electrical conductivity results are explained by assuming both ionic and electronic conduction mechanisms coexist with different contributions over the whole temperature range of experiments. TSDC spectra have been found to be characterized by a broad intense relaxation peak, which can be attributed to an ionic charge polarization. The broad relaxation transitions are apparently a result of the nonuniform nature of this process. Activation energies are calculated for both dc electrical conductivity and TSDC according to Arrhenius equation and initial rise method, respectively.     

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.     

Liquid–Liquid Transition and Detrapping of Trapped Carriers of P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M _η～2×10⁵) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature (T _LL) of the copolymers follows a type of the Fox equation. Fitting the results gives a T _LL of 102°C for polybutyl acrylate.     

Thermally stimulated depolarization current studies of sulfonated polystyrene ionomers

A detailed study of thermally stimulated depolarization current (TSDC) was carried out to investigate dipolar relaxation and the charge storage phenomenon in films of sulfonated polystyrene (SPS) ionomers having lithium or potassium as counterions. Differential scanning calorimetry measurements were also applied as a complementary technique, mainly to follow the change of the glass transition temperature with the amount of sulfonated groups. It was observed that, since the glass transition does not change significantly with the amount of sulfonated groups, a cluster of multiplets is expected not to be formed in the range used in this work. TSDC of SPS samples polarized at temperatures higher than the glass transition temperature showed three peaks: one at lower temperature (peak β), an intermediate peak (peak α), and a third that appeared at a temperature coincident with the polarization temperature (peak ρ). Quantitative information about trapping–detrapping and dipolar relaxation and their corresponding activation energies was determined by fittings of the deconvoluted peaks with kinetic relaxation processes.     

Dielectric relaxation properties of tysonite-type solid solutions La1−xBaxF3−x

Dielectric relaxation properties of solid solutions La_1?xBa_xF_3?x (x ? 0105) have been studied by thermally stimulated depolanzation current (TSDC)- and a c. dielectric loss (DL) techniques.For x < 30 × 10^?3 the dielectric spectra show a relaxation peak which is ascribed to a simple associate of a substitutional dopant ion and a fluoride ion vacancy (Ba_LaV_F)^x in nearest-neighbour position, the vacancy being confined to the B sublattice For x values of about 1.3 × 10^?2 a relaxation peak appears which is tentatively attributed to a similar type of defect associate with the vacancy now confined to the A sublattice of the tysonite anion array One broad relaxation peak dominates the TSDC and DL spectra over the whole concentration range This peak is due to the relaxation of macroscopic space charge, i e ionic conductivity The low-temperature ion conductivity has been determined for several solid solutions, and extrapolates to the high-temperature conductivity determined previously with impedance spectroscopy Below liquid-nitrogen temperature three relaxations are observed, and ascribed to electronic transitions in cenum impurities. A computer programme has been developed to analyse TSDC relaxation peaks, taking dipole-dipole interactions into account Relaxation parameters and dipole concentrations are presented.     

Thermally Stimulated Luminescence (TSL) and Conductivity (TSC) of synthetic crystalline quartz

A comparative and simultaneous study of TSL and TSC above room temperature (20–400°C) has been performed on “as-grown” and “hydrogen-swept” synthetic quartz crystals. Following X- irradiations, TSL spectra (heating RATE = 1°C/s) feature a number of peaks: at 75°C an intense structure is observed (the well-known “100°C” peak of quartz); the analysis of this peak obtained by numerical methods has shown that it follows monomolecular kinetics, giving a value of 0.83 eV for the trap depth. Additional peaks are observed at 110°C and 160°C, followed by weaker and less resolved emissions above 200°C. TSC peaks at 80°C, 120°C and 160°C, particularly evident in as-grown samples when measured with the electric field applied along the x-axis, can be associated to the corresponding TSL peaks. However, spectra performed with the electric field applied along the z-axis evidence different features. In as-grown samples a strong and broad peak at approximately 132°C is observed, while hydrogen-swept samples are characterized by two peaks at 180°C and 275°C. Such an anisotropic character, and the fact that no TSL structures are observed in the same temperature range, support the hyporthesis of an ionic nature for the latter peaks. TSC “pre-dose” measurements of the 75°C peak show that no current enhancement is observed upon irradiational and heating treatment: this result is in accordance with previous radioluminescence and thermally stimulated exoelectron emission experiments and supports the proposed model of the dynamics of this effect.     

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.     

TSL, OSL and ESR studies in ZnAl2O4:Tb phosphor

ZnAl₂O₄:Tb phosphor was prepared by combustion synthesis. ZnAl₂O₄:Tb exhibits three thermally stimulated luminescence (TSL) peaks around 150, 275 and 350 °C. ZnAl₂O₄:Tb exhibits optically stimulated luminescence (OSL) when stimulated with 470 nm light.Electron spin resonance (ESR) studies were carried out to identify defect centres responsible for TSL peaks observed in ZnAl₂O₄:Tb. Two defect centres are identified in irradiated ZnAl₂O₄:Tb phosphor and these centres are assigned to V and F⁺ centres. V centre appears to correlate with the 150 °C TSL peak, while F⁺ centre could not be associated with the observed TSL peaks.     

Effect of Polarization Temperature on the Chain Segment Motion and Space Charge Detrapping in Polyamide 610 Film Electrets

The effect of polarization temperature on the chain segment motion and charge trapping and detrapping in polyamide 610 films has been investigated by means of thermally stimulated depolarization current (TSDC) and wide-angle X-ray diffraction (WAXD). A small part of the amorphous phase of quenched polyamide 610 changes into the crystalline state with increasing polarization temperature. There are three current peaks (named α, ρ₁, and ρ₂ peak, respectively) in the TSDC spectra. The α peak corresponds to the glass transition, the ρ ₁ peak is attributed to space charge trapped in the amorphous phase, and interphase between crystalline and amorphous phases, and the ρ ₂ peak originates from space charge trapped in the crystalline phase. By analyzing the characteristic parameters of these peaks, it was found that the increase of polarization temperature induced a decrease of the chain segment mobility and promoted the creation of structural traps in polyamide 610. The decrease of the chain segment mobility in the amorphous phase made the intensity of the α peak weak and the activation energy increased. The higher the polarization temperature, the higher the degree of crystallinity and the more charge carriers trapped in the crystalline phase. So, the increase of polarization temperature made the intensity of the ρ ₂ peak strong and increased the stability of trapped charge in the crystalline phase. The increase of polarization temperature also made the intensity of the ρ ₁ peak strong and decreased the stability of trapped charge in the amorphous phase and interphase.     

The role of alkali ions in the 190 K TSL peak in quartz

The role of alkali ions in the creation of the thermally stimulated luminescence (TSL) peak at 190 K in quartz has been investigated by wavelength resolved TSL and thermally stimulated current (TSC) measurements performed on synthetic crystals, both as grown and hydrogen swept, characterised by alkali content of about 1–3 and 0.1 ppm respectively. The 190 K peak has been efficiently produced in as-grown crystals by a double irradiation procedure consisting of a first x-ray irradiation at 90 K followed by heating in the 170–300 K temperature range and a second irradiation at 90 K; this effect has not been observed in the hydrogen swept crystal. Moreover, the study of the spectral composition of the emitted light has shown the existence of two emission bands, one peaking at 450 nm (T<150 K) and the second one evidenced for T>150 K and peaking at around 380 nm.

In as grown samples, TSC peaks at 205, 260 and at around 350 K (composite structure) have been detected: their intensities are much stronger in the as grown crystal and with the electric field oriented along the z-axis indicating that they have an ionic character. By taking into account the mechanism of formation of the [SiO₄/M⁺]⁰ (M⁺=Li⁺, Na⁺) traps (previously found to be responsible for the 190 K TSL peak), the 205 K TSC peak can be attributed to the radiation induced dissociation of alkalis from [AlO₄/M⁺]⁰ defect centres and subsequent migration near to Si sites; on the other hand, the 260 K TSC peak can be related to the subsequent disintegration of [SiO₄/M⁺]⁰ defects involving the migration of alkalis to different ionic traps.

PACS: 78.60.K–61.72.J–42.70.Ce