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.     

Die Verfestigungserholung von plastisch verformten Steinsalzeinkristallen

Cylindrical rock salt single crystals have been plastically deformed by compression in the [001]-direction at room temperature to shear stresser τ _E of 200 N/cm² and 350 N/cm², respectively. Isochronal annealing experiments reveal, that workhardening recovers at >300° C. The characteristic annealing temperature was found between 400° C and 450° C. At 600° C the residual workhardening still amounts to 15–20%. The isochronal reduction of screw dislocation density between 400 and 600° C shows qualitatively the same behaviour as recovery of workhardening. From the isothermal annealing curves of the samples deformed to 200 N/cm² the activation energy for recovery of workhardening was found to be about 1 eV. Assuming that the kinetics of recovery can be explained by processes distributed in activation energy, an approximate spectrum of activation energies (with a maximum arising at ～1 eV) has been evaluated. The results show that recovery of workhardening after low deformation (stage I of the stress strain curve) is mainly due to the dislocations.     

Point defects related to 260 K thermostimulated luminescence in α-Al2O3

Abstract

Thermo- and photostimulated processes are studied in reduced hydrogen containing α-Al₂O₃ excited by UV light. It is found that UV excitation in F absorption band at 90 K results in a ionization of the F-centers and capture of released electrons at defects thus producing an anisotropy absorption band at 4.2 eV and the dominant thermoluminescence (TL) peak at 260 K. The 260 K TSL peak is accompanied by complete bleaching of the 4.2 eV absorption band and vice versa—by light stimulation in the region of the 4.2 eV band the 260 K TSL peak disappear and released electrons recombine with F⁺-centers. Both the effect of the preliminary high-temperature thermal treatment of samples on formation of 4.2 eV-centers and the observed dichroism characteristics allows to conclude that corresponding complex defect contains hydrogen and can involve vacancy pair.     

Photo- and thermostimulated processes in α-Al2O3

We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al₂O₃ crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al₂O₃ crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above 430 K the above-mentioned broad absorption band disappears. Optical bleaching of the 2.5–3.5 eV band is accompanied by the disappearance of the 430 K TSL peak and results in F-center emission. The X-ray or UV excitation of reduced α-Al₂O₃ crystals with donor-type impurities results in the appearance of an anisotropic absorption band at 4.2 eV and the appearance of a dominant TSL peak at 260 K. Above 260 K the 4.2 eV absorption disappears and photostimulated luminescence (PSL) of the F-center recombination luminescence in the 4.2 eV region is no longer observed. Optical bleaching of the 4.2 eV absorption band is accompanied by the disappearance of the 260 K TSL peak. The successful use of reduced α-Al₂O₃ in dosimetry needs the optimization of the concentration of all components (acceptors, hydrogen, intrinsic defects) involved in the thermo- and photostimulated processes.     

Radiation stabilization of U5+ in CaO matrix and its thermal stability: Electron paramagnetic resonance and thermally stimulated luminescence studies

Electron paramagnetic resonance (EPR) evidence is presented for the radiation stabilization of pentavalent uranium in CaO matrix. From the theoretical predictions ofg value for U⁵⁺ in axial symmetries, it was concluded that U⁵⁺ at Ca²⁺ site is associated with a second neighbour charge compensating Ca²⁺ vacancy. EPR measurements also revealed the presence of Mn²⁺, Mn⁴⁺ and Cu²⁺ impurities in the samples. The thermal stability of U⁵⁺ was investigated using EPR and thermally stimulated luminescence (TSL) techniques. The TSL and EPR studies on gamma irradiated uranium doped calcium oxide samples had shown that the intense glow peak at 540 K is associated with the reduction in the intensity of EPR signal of U⁵⁺ ion around this temperature. This peak is associated with the process U⁵⁺+hole→U^6+*→U⁶⁺+hv. The activation energy for this process was determined to be 1.4eV.     

Luminescence and EPR studies of YBO3:U

Yttrium borate doped with uranium was prepared by mixing and heating yttrium oxide obtained through oxalate precipitation route, boric acid and requisite amount of nuclear-grade uranium oxide at high temperature. Photoluminescence (PL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on gamma-irradiated doped/undoped yttrium borate samples in the temperature range 300-600 K. TSL studies showed the presence of two glow peaks at 414 and 471 K. PL studies along with lifetime decay investigation suggested uranium goes in the matrix as UO₂²⁺. EPR studies showed the presence of O₂⁻radical ion along with electron trapped in defect centres, which might have been produced for charge compensation. Apart from this, CO₂⁻ radical was also observed in the system having its origin from residual oxalate ion. Temperature dependence EPR studies of the observed radical confirmed the involvement of the CO₂⁻ and dioxide radical ion in the observed glow peaks. By correlating the TSL, PL and ESR data, probable mechanism is proposed for the observed TSL glow in the system.     

Annealing of γ-ray irradiated lithium compensated p-type silicon

Abstract

Annealing behavior of electrical properties and photoluminescence spectra both at 77 °K in electron-irradiated melt-grown n-GaAs were investigated. Defects electrically active in the Hall mobility and carrier removal anneal through two stages centered at 250° and 460 °K. From the temperature dependence of carrier concentration the existence of a defect level located near 0.15 eV below the conduction band is supposed. Several emission bands are resolved at 1.51, 1.47, 1.415, 1.305 and ～1.2 eV in photoluminescence experiments. Electron irradiation (1.5–2.0 MeV) causes a remarkable decrease in emission intensity of 1.51 and ～1.2 eV bands. Recovery of emission intensity occurs remarkably when samples are annealed to 520 °K which would correspond to the 460 °K annealing stage for carrier concentration and Hall mobility. The 250 °K annealing stage is not observed in photoluminescence experiments. The 1.415 eV peak appears clearly after irradiation and grows remarkably with the 520 °K annealing, especially in Si-doped samples, resulting in large reverse annealing. This band is tentatively speculated to be a complex of Si on As site with As vacancy. Moreover, in samples doped with Te a new emission band at 1.305 eV (9500 Å) is observed after 470°–620 °K annealing.     

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.     

高温退火后非掺杂磷化铟材料的电子辐照缺陷

对不同气氛下高温退火非掺杂磷化铟(InP)材料的电子辐照缺陷进行了研究. 除铁受主外，磷化铁(FeP₂)气氛下退火后的InP中辐照前没有深能级缺陷，而辐照后样品的热激电流谱(TSC)中出现了5个较为明显的缺陷峰，对应的激活能分别为0.23 eV, 0.26 eV, 0.31 eV, 0.37 eV和0.46 eV. 磷(P)气氛下退火后InP中的热生缺陷较多，电子辐照后形成的缺陷具有复合体特征. 与辐照前相比，辐照后样品的载流子浓度和迁移率产生显著变化. 在同样的条件下，经FeP₂ 气氛下高温退火后的InP样品的辐照缺陷恢复速度较快. 根据这些现象分析了缺陷的属性、快速恢复机理和缺陷对材料电学性质的影响. 关键词： 磷化铟 电子辐照 缺陷     

退火对He注入及随后208Pb27+辐照的Al2O3单晶PL谱的影响

利用高能离子研究了110 keV 的He⁺注入Al₂O₃单晶及随后230 MeV的²⁰⁸Pb²⁷⁺辐照并在不同温度条件下退火样品的光致发光的特性. 从测试结果可以清楚地看到在375 nm，390 nm，413 nm 和450 nm 出现了强烈的发光峰. 经过600 K退火2 h后测试结果显示，390 nm发光峰增强剧烈，而别的发光峰显示不明显. 在900 K退火条件下，390 nm的发光峰开始减弱相反在510 nm出现了较强的发光峰，到1100 K退火完毕后390 nm的发光峰完全消失，而510 nm的发光峰相对增强. 从辐照样品的FTIR谱中看到，波数在460—510 cm^-1间的吸收是振动模式，经过离子辐照后，吸收带展宽，随着辐照量的增大，Al₂O₃振动吸收峰消失，说明Al₂O₃振动模式被完全破坏. 1000—1300 cm^-1之间为Al-O-Al桥氧的伸缩振动模式，辐照后吸收带向高波数方向移动. 退火后的FTIR谱变化不大.     

Thermally stimulated luminescence properties of BaY 2 F 8 :Ce Crystals

Wavelength resolved thermally stimulated luminescence (TSL) measurements were performed on BaY 2 F 8 :1.8 v mol% Ce crystals after X-ray irradiation at 10 v K and at 300 v K, in order to obtain preliminary information about both trap levels and recombination centres. After irradiation at 10 v K, the TSL glow curve shows the presence of a strong peak at 50 v K, together with additional structures at approximately 20 and 170 v K. The TSL spectrum is dominated by the characteristic doublet emission due to transitions from the lowest energy level of the 5d configuration to the spin-orbit split 2 F ground state of Ce 3+ . Above RT, the glow curve exhibits a peak at 60 v C, whose spectrum is again dominated by Ce 3+ emission. The TSL emission is in accordance with radio-luminescence (RL) spectra performed in the 10-300 v K region. Moreover, RL spectra at temperatures lower than 200 v K display an additional weak high energy band at around 4.5 v eV assigned to host lattice transitions.     

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.     

Electro-transmission spectra of Li doped NiO and MnO in the visible and near infrared — A new optical effect in 3d semiconductors

Electro-modulation transmission (ET) spectra have been observed in Li doped crystals of NiO and MnO at phonon energies ∼ 0.4–2.5 eV and T < 230 °K. In each case we observe a broad temperature- sensitive peak, centred at 0.9 and 2.1 eV respectively, which we associate with charge carriers bound to Li centres. Modulation probably occurs through a small-polaron mechanism in NiO, and field- enhanced emission in MnO, but the exact mechanism is uncertain. Similar ET spectra have been observed in a doped ferrite.     

Luminescence spectra of doped and undoped lead tungstate crystals

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

Photostimulated thermoluminescence of x-irradiated NaCl

The thermoluminescence and photostimulated thermoluminescence of X-ray coloured NaCl crystals has been studied, together with the thermal annealing of F, F′ and M centres. Three glow peaks centred at 315, 341 and 348°K are obtained in the temperature range 300–400°K. The first peak (315°K) is ascribed to electron trapping by Cu²⁺ centres formed by X-irradiation. The other peaks (314 and 348°K) are related to the thermal annealing of M and F centres, respectively.     

Recovery of low temperature electron irradiation-induced damage in n-type gaas

Undoped n-type GaAa was irradiated near 5 and 77 °K with electrons having incident energies between 0.46 and 1.30 MeV. The recovery of the electrical resistivity and the Hall coefficient upon annealing from 4 to 520 °K was monitored. Changes which occurred upon annealing below 200 °K could be reversed by ionizing radiation. A small amount of irreversible ionization-induced recovery was observed after irradiation near 5 °K. Major irreversible recovery stages were centered near 235 (stage I), 280 (stage II) and 520 °K (stage III). Recovery in stage I and II obeyed first order kinetics. The activation energies of stages I and II were determined as 0.72 and 0.83 eV, respectively. The carrier concentration changes per unit irradiation dose corresponding to the three recovery stages differed in their energy dependence indicating that the defects which are removed in stage III have the lowest threshold energy. The carrier concentration changes per unit irradiation dose corresponding to stages I and III were higher for irradiation near 5 °K than for irradiation near 77 °K.     

Cr-related centers in Gd3Ga5O12 polycrystals

The luminescence excitation spectra, emission spectra under photo- and X-ray excitation, luminescence decay kinetics and thermostimulated luminescence (TSL) of Gd₃Ga₅O₁₂ garnet (GGG) polycrystalline samples have been investigated. It was established that the spectrum of Cr³⁺ ion emission were present in all TSL peaks. The activation energies of traps that are responsible for appearance of TSL in the region 295-600 K were estimated. It is shown that delocalization of electrons from the Cr³⁺e traps leads to the appearance of thermoluminescence (TL) glow peak at 390 K. The nature of other TSL peaks is discussed. The influence of visible light on the TSL intensity of the preliminary X-ray-irradiated samples is shown.     

Photoluminescence and positron annihilation spectroscopic investigation on a H(+) irradiated ZnO single crystal

Low temperature photoluminescence and room temperature positron annihilation spectroscopy have been employed to investigate the defects incorporated by 6?MeV H(+) ions in a hydrothermally grown ZnO single crystal. Prior to irradiation, the emission from donor bound excitons is at 3.378?eV (10?K). The irradiation creates an intense and narrow emission at 3.368?eV (10?K). The intensity of this peak is nearly four times that of the dominant near band edge peak of the pristine crystal. The characteristic features of the 3.368?eV emission indicate its origin as a 'hydrogen at oxygen vacancy' type defect. The positron annihilation lifetime measurement reveals a single component lifetime spectrum for both the unirradiated (164?±?1?ps) and irradiated crystal (175?±?1?ps). It reflects the fact that the positron lifetime and intensity of the new irradiation driven defect species are a little higher compared to those in the unirradiated crystal. However, the estimated defect concentration, even considering the high dynamic defect annihilation rate in ZnO, comes out to be ～4?×?10(17)?cm(-3) (using SRIM software). This is a very high defect concentration compared to the defect sensitivity of positron annihilation spectroscopy. A probable reason is the partial filling of the incorporated vacancies (positron traps), which in ZnO are zinc vacancies. The positron lifetime of ～175?ps (in irradiated ZnO) is consistent with recent theoretical calculations for partially hydrogen-filled zinc vacancies in ZnO. Passivation of oxygen vacancies by hydrogen is also reflected in the photoluminescence results. A possible reason for such vacancy filling (at both Zn and O sites) due to irradiation has also been discussed.     

Radiation-Induced Defects in Calcium Aluminate Glasses

In this work, MgF₂ and CaF₂ doped calcium aluminate glass samples have been investigated in order to describe the intrinsic defects that are formed in UV irradiated glasses. It is well known that calcium aluminate, when UV-illuminated, changes colour from blue to green. Thermoluminescence (TL), Optical Absorption (OA) and Electron Paramagnetic Resonance (EPR) measurements have been carried out and the results obtained were associated with the structural properties of the CaO—Al₂O₂—SiO₂ system, in order to provide a defect model. Thermal treatments up to 150°C were performed for OA and TL measurements but the thermal decay curves could not be adjusted by an exponential function. The TL experimental results were fitted, according to a continuous model, with a Gaussian distribution function centred at 0.6eV and a frequency factor of 10⁹s^?1.     

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