Optical and dosimetric properties of variously doped SrF2 crystals

Optical properties and irradiation effects of Nd³⁺-, Pr³⁺-, Tb³⁺- and Tm³⁺-doped SrF₂ crystals and their possible application to solid-state dosimetry were studied and compared to those induced in pure SrF₂ crystals. Optical absorption, thermoluminescence (TL), X- and light-induced luminescence (XL and PL) as well as optically stimulated luminescence and phototransferred TL (OSL and PTTL) were measured in the various samples. Special attention was given to effects of monochromatic vacuum ultraviolet (VUV) radiation. TL was excited in the pure and doped samples by X and β rays as well as by VUV radiation. TL peaks appeared after VUV irradiation at the same temperatures and with the same thermal activation energies as after X or β irradiation, indicating that they are due to the same processes. The VUV excitation spectra showed two maxima at about 145 and 130 nm. Comparison of the TL sensitivities of the various TL materials, showed that the sensitivity of SrF₂:Pr³⁺ was by more than an order of magnitude higher than that of the known LiF:Mg,Ti (TLD-100) phosphor. The sensitivity of pure and of the Nd, and Tb-doped SrF₂ were by a factor of 2–4 higher than that of the TLD-100 and that of SrF₂:Tm was slightly lower. The main emission bands of SrF₂:Pr³⁺ are located in a convenient spectral region between 460 and 640 nm, where most of the standard photomultipliers are sensitive. The dose dependence of the 460 K TL peak in SrF₂:Pr³⁺ is nearly linear in a wide range up to above 27 000 Gy.     

Decay kinetics of the green emission in tungstates and molybdates

Luminescence characteristics of a number of undoped and variously doped PbWO₄ crystals were studied at 0.4–400 K by the time-resolved spectroscopy and compared with those of ZnWO₄,CdWO₄ and PbMoO₄ crystals. Two types of green emission centres are detected in PbWO₄ crystals. The centres of the first type are responsible for the low-temperature 2.3–2.4 eV emission observed under excitation around 3.90–3.95 eV. The structure and parameters of their relaxed excited states were determined. It was concluded that the origin of defects responsible for the green emission of the first type could vary for different crystals. The centres of the second type with the emission around 2.5 eV appear in crystals containing oxygen vacancies after the thermal destruction of Pb⁺-WO₃ centres at T>180 K. Decomposition of the exciton and various defect-related states was also studied, and activation energies of this process were calculated.     

两种新型芴衍生物的合成、晶体结构及光谱性能

合成了两种新型芴衍生物:2,7-二（3,5-二（三氟甲基）苯基）-9,9-二乙基芴（1）和2,7-二（4-氟苯基）-9,9-二乙基芴（2）。通过元素分析、红外光谱（IR）、核磁共振氢谱（¹H NMR）以及单晶X射线衍射对其结构进行了表征。化合物1属于单斜晶系,P2₁/c空间群;化合物2属于三斜晶系,P-1空间群。通过紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明:在CH₂Cl₂溶液和固态薄膜中,化合物1、2在350～400 nm波段有吸收峰,归属于π-π^*电荷跃迁;化合物1、2的光学带隙E_g分别为3.31 eV和3.30 eV,并且均有强烈的蓝色荧光发射现象（激发波长为330 nm）,在二氯甲烷中的荧光量子效率分别为0.62和0.61,固态荧光寿命分别为6.39 ns和9.00 ns。     

Emission properties of Ta-centres in KCl

Electrolytic colouration at about 600°C and 350 V/cm, for KCl crystal containing Pb²⁺ and for KCl:Pb²⁺ crystals co-doped with Li⁺, Na⁺ and Rb⁺ has been undertaken. Several absorption bands were observed in both doped and co-doped crystals in the visible-UV region. Excitation into these bands gives rise to the same 0.86 eV emission band except for the Li⁺-co-doped crystal which gives rise to a 0.80 eV emission band. These absorption bands are due to the same T_a-centre related to Pb⁻. The observed infrared emission intensity of the crystal with F-centres is higher than of without F-centres.     

Intensities and spectral features of the ~4I_(13/2)-~4I_(15/2) potential laser transition of Er~(3+) centers in CaF_2-CeF_3 disordered crystal

A CaF_2-CeF_3 disordered crystal containing 1.06% of Er~(3+) ions was grown by the temperature gradient technique.Optical absorption and emission spectra recorded at room temperature and at 10 K, luminescence decay curve recorded at room temperature, and extended x-ray-absorption fine structure spectra were analyzed with an intention to assess the laser potential related to the ~4I_(13/2)→~4I_(15/2) transition of Er~(3+). In addition, the thermal diffusivity of the crystal was measured at room temperature. The analysis of room-temperature spectra revealed that the ~4I_(13/2) emission is long-lived with a radiative lifetime value of 5.5 ms, peak emission cross section of 0.73 × 10~(-20) cm~2, and large spectral width pointing at the tunability of the emission wavelength in the region stretching from approximately 1480 nm to 1630 nm. The energies of the crystal field components for the ground and excited multiplets determined from low-temperature absorption and emission spectra made it possible to predict successfully the spectral position and shape of the room-temperature ~4I_(13/2)→~4I_(15/2) emission band. Based on the correlation of the optical spectra and dynamics of the luminescence decay, it was concluded that in contrast to Yb~(3+) ions in heavily doped CaF_2 erbium ions in the CaF_2-CeF_3 crystal reside in numerous sites with dissimilar relaxation rates.     

Time-resolved luminescence of complex wide-gap oxide crystals under inner-shell excitation

In order to investigate the soft X-ray energy transformation in oxide detectors the optical spectra of several wide-gap oxide crystals were analyzed. The time-resolved luminescence (2.5–10.5 eV) and luminescence excitation spectra (50–200 and 500–630 eV) as well as decay kinetics of luminescence at 10 and 295 K were recorded using the synchrotron radiation from BW3 channel (HASYLAB, DESY). Several analogous features were discovered in the excitation spectra of both intrinsic self-trapped exciton luminescence and recombination luminescence for BeO, BeAl₂O₄, Be₂SiO₄ and AlPO₄ crystals under inner-shell excitation. Simultaneously, the excitation of Ce³⁺-luminescence in scintillating Be₂La₂O₅-Ce crystals significantly differs.     

Radioluminescence (RL) behaviour of Al2O3:C-potential for dosimetric applications

The radioluminescence (RL) of carbon doped aluminium oxide (Al₂O₃:C) TL dosimeter material (TLD-500) was investigated using a ¹³⁷Cs conversion electron source (which also emits β and γ) for simultaneous irradiation and luminescence excitation. Furthermore, RL dosimetry characteristics of this material were studied. The main RL emission occurs at 420 nm. That matches the known main TL and OSL emissions for this material as well as an emission that was investigated in earlier RL studies, excited at higher energies (4 MeV electrons) and very high pulse delivered doses (≈800 kGy·s⁻¹). Furthermore, the saturation dose for the main peak is reached at the dose level of ≈80 Gy as known from TL and earlier RL investigations. Other peaks at 700 and 790 nm and broad emission bands at photon energies higher than 3.00 eV and others between 2.00 and 2.50 eV were observed. The 700 nm emission shows growth also at higher dose levels, and saturates at an estimated dose of ≈800 Gy. The 790 nm emission reaches its maximum intensity at ≈10 Gy absorbed dose. The reported results give an outlook to the usability and the potential of Al₂O₃:C combined with RL measurements for radiation dosimetry as well as for beta source calibration, using radioluminescence.     

Conversion of VUV to UV and visible in K5Li2LnF10 containing rare-earth from cerium group (Ln=La, Ce, Pr, Nd)

The potential of single crystals K₅Li₂LnF₁₀, for applications as VUV excited phosphors has been examined. The crystals were doped with lanthanide ions (Ce³⁺–Nd³⁺) with concentrations up to 100 at%. The self-quenching of luminescence is strongly reduced in this material. Luminescence spectra in the 50,000–10,000 cm⁻¹ range and excitation spectra in the 40,000–250,000 cm⁻¹ spectral range have been recorded at room and low temperature. Intense visible emission has been observed for Nd³⁺ and Pr³⁺. For the Pr³⁺ ions strong the ¹S₀–¹I₆ transition has been recorded only for concentrated crystals. Efficient conversion of VUV excitation to UV–VIS emission was observed in crystals doped with 3 and 100 at% of cerium. In both cerium-activated crystals the lifetimes of f–d transitions were equal to 32 ns.     

Charge-transfer bands in crystals of alkaline earth fluorides with Eu<Superscript>3+</Superscript> and Yb<Superscript>3 + 1</Superscript>

The absorption, luminescence, and excitation spectra of CaF₂, SrF₂, and BaF₂ crystals with EuF₃ or YbF₃ impurity have been investigated in the range 1–12 eV. In all cases, strong wide absorption bands (denoted as CT₁) were observed at energies below the 4f ⁿ -4f ^{n ? 1}5d absorption threshold of impurity ions. Weaker absorption bands (denoted as CT₂) with energies 1.5–2 eV lower than those of the CT₁ bands have been found in the spectra of CaF₂ and SrF₂ crystals with EuF₃ or YbF₃ impurities. The fine structure of the luminescence spectra of CaF₂ crystals with EuF₃ impurities has been investigated under excitation in the CT bands. Under excitation in the CT₁ band, several Eu centers were observed in the following luminescence spectra: C _4v , O _h , and R aggregates. Excitation in the CT₂ bands revealed luminescence of only C _4v defects.     

Effects of type of radiation on glow curve and thermoluminescence emission spectrum of CaF2:Tm

Thermoluminescence emission spectra of CaF₂:Tm (TLD-300) samples irradiated with 48 keV X-rays ⁶⁰Co gamma rays, 4.5 MeV alpha particles and 15 MeV neutrons were measured in the 300–650 K temperature region. Seven emission bands were observed of which the one in the infrared (at 803 nm) is very intense. The emission bands can be assigned to ¹D, ¹G, ³F and ³H levels characteristic for Tm³⁺ de-excitation in a cubic field. All observed lines in the spectrum are due to 4f-4f transitions. The spectra undergo remarkable changes in intensity when the temperature is raised from room temperature up to 350°C, while the number of the emission bands remains constant. The glow curve structure is both dependent on emission wavelength and the type of radiation. Evidence has been found that the trapping structures responsible for glow peaks 2 and 3 alter under the influence of high LET () radiation. For glow peaks 4–6 the filling of the traps alters with the type of radiation. The observations can be explained assuming a TL process involving several hole trapping centres but with only one luminescent centre (Tm³⁺) active at all temperatures.     

M2SiO4：Re(M=Mg,Ca,Ba;Re=Ce3+,Tb3+)的发光性能

合成了系列M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)样品,研究了样品在真空紫外区域的激发光谱和发射光谱。从激发谱可以看出:M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)在147,172nm有很强的吸收带。用Mg,Ca完全取代Ba₂SiO₄:Tb³⁺中的Ba,相对应的晶体的晶格参数逐渐增大,晶场的能量逐渐减少,其激发光谱随着碱土离子半径的增加向长波方向移动。在172nm真空紫外光激发下,观察到M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Tb³⁺和M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)特征发射;在真空紫外激发下,随着M₂SiO₄:Re(M=Mg,Ca,Ba;Re=Ce³⁺,Tb³⁺)中Ce³⁺含量的增加,M₂SiO₄:Re的特征发射明显减弱,并分析讨论了相关发光现象的成因。     

Cubic and tetragonal Ce ions in strontium fluoride

Optical absorption spectra in the vacuum ultraviolet, and high resolution emission and absorption spectra in the ultraviolet region of cubic and tetragonal Ce³⁺ centres in SrF₂ crystals were measured. Cubic centres are characterised by the zero phonon line at 33250 cm⁻¹ and a sharp phonon line is spaced from the zero phonon line by 410 cm⁻¹. The decay times of the luminescence from the cubic or tetragonal centres are equal to 32 ns. A comparison of the cubic and tetragonal spectra allows us to determine the influence of the charge compensating interstitial fluorine ion on the f and d levels of the Ce³⁺ ions.

Unrestricted Hartree–Fock calculations of Ce states in molecular clusters of alkaline-earth fluorides were performed. To make the calculated transitions coincide with the experimental one it is necessary to take into account the shift of the Ce³⁺ and interstitial F⁻ ions toward each other by 10% of initial distance.     

Absorption and emission spectra of yttria-stabilized zirconia and magnesium oxide

We have investigated the luminescence and absorption spectra of doped and undoped ZrO₂-Y₂O₃ and MgO crystals at room- and low temperatures. The crystals used are partly doped with the transition metals Ni, Co, Cr and the rare earth Pr. The emission spectra were obtained under laser excitation at different wavelengths. The observed optical emission and absorption bands of the MgO crystals doped with Ni, Co and Cr correspond to transitions between spin-orbit split crystal field levels of the transition metals. Luminescence and absorption bands of undoped yttria-stabilized zirconia (YSZ) crystals are due to color centers, absorption bands of the doped YSZ correspond to the well known transitions of the Ni²⁺, Co²⁺ and Pr³⁺ ions, respectively. The emission spectra of the doped YSZ obtained under various laser excitations can be explained by an energy transfer process between the color center and the doping materials. The influence of annealing on the absorption and emission of Pr³⁺/Pr⁴⁺ is investigated.     

Thermoluminescence mechanism of Mn, Mg and Sr doped calcite

In this work, the thermoluminescence properties of synthetic crystals of doped calcite were studied. Samples were doped with Mn²⁺, Mg²⁺ or Sr²⁺, either individually or simultaneously with more than one of these impurities. TL glow curves, partial heating measurements, isometric curves, emission spectra and thermal treatment were performed, in order to investigate the role played by the impurities in the TL glow peaks of calcite. We conclude that the crystals doped with Mn²⁺ show five TL peaks with emission spectra due only to the Mn²⁺. The relative intensity of these peaks is closely related to the other divalent dopant added in the solution (Sr²⁺ or Mg²⁺). These results suggest that although Sr²⁺ and Mg²⁺ act as TL activators stabilising slightly different electron traps, they are not directly connected to the Mn²⁺ luminescence centre.     

YAG：Ce发光材料合成的助熔剂研究

采用高温固相法合成YAG:Ce荧光粉时,传统的以硼酸为助熔剂的产物硬度很大,处理过程中容易破坏晶体形貌,影响发光性能.采用氟化物助熔剂(MgF₂、CaF₂、SrF₂、BaF₂、AlF₃)及它们与H₃BO₃混合助熔剂来制备YAG:Ce,研究了助熔剂种类及其浓度对制得的粉体发光性能的影响,比较了它们的晶体形貌与物相组成.结果表明,采用不同助熔剂合成的YAG:Ce的激发光谱及发射光谱基本相同,而BaF₂、AlF₃、SrF₂及它们与H₃BO₃的混合助熔剂系列,可在一定程度上降低产品硬度、提高产品发光亮度;其中H₃BO₃~SrF₂系列、H₃BO₃~BaF₂系列的晶化程度与粒度分布均有改善;H₃BO₃~BaF₂系列的物相组成比较纯,除Y₃Al₅O₁₂主相外基本无杂相.     

高气压直流辉光CH4/H2等离子体的气相过程诊断

对高气压(约100 Torr) 直流辉光碳氢等离子体的气相过程进行了光谱和质谱原位诊断. 在高气压下, 等离子体不同区域光发射特性存在明显差异. 正柱区存在着以C₂和CH为主的多个带状谱和分立谱线, 阳极区粒子发射谱线明显减少, 而在阴极区则出现大量复杂的光谱成分, 表明高气压情形下等离子体与阴极间强烈的相互作用将导致复杂的原子分子过程. 从低气压到高气压演变过程中, 电子激发温度降低而气体分子转动温度升高. 在高气压下, 高甲烷浓度导致C₂, C₂H₂及C₂H₄增多而C₂H₆减少. 表明在高气压条件下, 气体温度对气相过程的影响作用显著增强. 关键词： 高气压直流等离子体 光发射谱 质谱     

Luminescence of defect centers in yttrium–aluminum garnet crystals

Spectral–kinetic properties of the 2.38 eV emission in neutron-irradiated and as-received yttrium aluminum garnet (Y₃Al₅O₁₂) crystals are investigated. This luminescence band as well as its lifetime and the temperature dependence are analyzed. It is suggested that the 2.38 eV luminescence band is due to the strongly allowed transition of the F⁺-center in garnet crystals. Possible reasons that may explain the observed temperature dependence of this emission intensity are discussed.     

Luminescence study of pure and Fe- or Mo-doped ZnWO4 crystals

ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals were investigated by the methods of time-resolved spectroscopy in the temperature range of 4.2–300 K. It is shown that the Mo and Fe impurities significantly reduce the light yield of ZnWO₄. The main 2.5 eV emission of ZnWO₄ and the 1.77 eV emission band of ZnWO₄:Mo are shown to originate from the triplet excited state of the WO₆ and MoO₆ complex, respectively. In ZnWO₄:Fe,Mo the MoO₆ emission band is shifted to lower energies due to the perturbing influence of the iron impurity. No perturbing effect of Fe or Mo ions was observed for the main emission of ZnWO₄:Fe and ZnWO₄:Mo. The creation spectrum of self-trapped holes was measured for ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals in the energy region of 4–30 eV.     

Gd3+/Y3+共掺对Nd:CaF2晶体光谱性能的影响

通过坩埚下降法生长了系列共掺Nd,Gd:CaF₂和Nd,Y:CaF₂晶体, 研究了Gd³⁺/Y³⁺共掺对Nd³⁺光谱性能以及Nd:CaF₂晶体晶胞参数的影响规律. 对于0.5 at.%Nd, x at.%Gd(x=2,5,8,10):CaF₂系列晶体, 当调控Gd³⁺掺杂浓度为2 at.%时, 具有最大的荧光寿命499 μs; 当Gd³⁺掺杂浓度为5 at.%时, 具有最大的吸收截面1.47×10^-20 cm², 最大的发射截面1.9×10^-20 cm²; 当Gd³⁺掺杂浓度为8 at.%时, 具有最佳的发射带宽29.03 nm. 对于0.6 at.%Nd, xat.%Y(x=2, 5, 8, 10):CaF₂系列晶体, Y³⁺掺杂浓度为5 at.%时, 有最大的吸收截面2.41×10^-20 cm², 最大的发射截面3.17×10^-20 cm²; 当Y³⁺掺杂浓度为10 at.%时, 具有最长的荧光寿命359.4 μs,并且具有最大发射带宽26 nm.     

Congruent Sr 0.61 Ba 0.39 Nb 2 O 6 doubly doped with Ce and Cr: PHoto- and thermoluminescence investigations

Congruent Sr x Ba 1 m x Nb 2 O 6 (SBN, x=0.61) doped with Ce or Cr ions exhibits enhanced photorefractive properties and new spectral features like increased red sensitivity. Here special emphasis is placed on the luminescence features of doubly doped Ce+Cr SBN crystals. The luminescence excitation and emission spectra combined with the absorption of the impurities allow to draw conclusions about the origin of the charge carriers und their recombination. The well separated thermo-luminescence peaks detected and their spectral line shape in emission point to specific recombination processes following the thermal liberation of light-induced electron trapping centers: Nb 4+ polarons and VIS-centers created at low temperature under light irradiation. The thermal activation energy for the hopping motion of Nb 4+ polarons and of VIS-centers are estimated to be 0.18 - 0.02 v eV and 0.30 - 0.05 v eV respectively. Possible excitation and recombination mechanisms in SBN:Ce+Cr are discussed.