Defect states in Lu 3 Al 5 O 12 :Ce crystals

Wavelength-resolved TSL measurements after x-ray irradiation at room temperature were performed on undoped, Ce- and (Ce, Zr)-doped Lu 3 Al 5 O 12 crystals. Several glow peaks were observed in the 20-450 v C temperature region, whose intensities and emission spectra are influenced by doping. Namely, the TSL spectra are governed by defect and trace impurity-related emissions in the undoped crystal, while only the Ce 3+ emission is detected in the doped crystals. Moreover, EPR measurements performed at 12 v K revealed typical spectra of Ce 3+ (4f 1 , S =1/2) occupying Lu 3+ substitutional positions. In situ light irradiation (250-330 v nm) of the crystals results in a step-like decrease of the Ce 3+ EPR intensity. Such a behaviour can reflect a creation of Ce 4+ ions under UV irradiation or an increase of the Ce 3+ population in the excited (5d) state.     

Site symmetry and crystal field splittings of Ce 3+ in LiLuF 4 and LiSr 0.8 Ca 0.2 AlF 6

Electron paramagnetic resonance (EPR) spectra of Ce 3+ in LiLuF 4 (LLF) and LiSr 0.8 Ca 0.2 AlF 6 (LSCAF) observed at low temperatures (<20 v K) show that the Ce 3+ centers have tetragonal and pseudo-trigonal symmetry with ( g , g )=(2.751, 1.467) and (2.14, 0.80), respectively. The EPR lines of Ce 3+ in LSCAF are inhomogeneously broadened by different Ce 3+ configurations which correspond to the random occupation of the second nearest neighbor cation sites by Ca 2+ and Sr 2+ and/or charge compensators. These EPR results indicate that the Ce 3+ centers in LLF and LSCAF are associated with substitution of Ce 3+ for Lu 3+ with eight-fold coordination and Sr 2+ /Ca 2+ with six-fold coordination, respectively. Fourier transform infrared absorption has been used to measure transitions between the 2 F 5/2 ground state and the 2 F 7/2 multiplet of Ce 3+ in LLF at 10 v K. The optical absorption and luminescence of Ce 3+ :LLF and Ce 3+ :LSCAF in the UV range are strongly polarized. The energy levels and polarization dependence of the optical transitions can be accounted for in terms of the crystal field potential experienced by the Ce 3+ ions under the action of the different point group symmetries.     

Thermally and optically stimulated radiative processes in LiBaF3 crystals

In LiBaF₃ crystals both valence–core transitions (5.4–6.5 eV) and so-called self-trapped exciton luminescence (about 4.3 eV) are important for practical application. Here, we present a study of 4.3 eV luminescence under photo- and thermostimulation after X-irradiation of undoped LiBaF₃ crystals at various temperatures. Optically stimulated luminescence as a result of electron recombination with both self-trapped holes and holes localized at some defects, were observed after X-irradiation below 130 K and that of electron recombination with defect-localized holes was observed after X-irradiation above 130 K. The spectra of thermo-stimulated luminescence (TSL) contain a broad band about 4 eV related to the electron (high-energy side) or hole (low-energy side) recombination depending on TSL peak temperature.     

EPR study of monomeric and dimeric vanadyl ions in SbVO 5

A new compound, SbVO 5 , formed in the V-Sb-O system, has been synthesized and investigated using the electron paramagnetic resonance (EPR) technique. SbVO 5 has been prepared by two methods: by heating equimolar mixtures of V 2 O 5 and f -Sb 2 O 4 in air and by oxidation of the known phase (SbVO 4.5 ) of rutile type obtained in pure argon at temperatures between 550 v C and 650 v C. At room temperature only a weak EPR signal from the powder sample of SbVO 5 was detected corroborating the absence of bulk V(IV) ions in the structure. Comparison with the CuSO 4 reference sample revealed that only 0.02% vanadium ions are EPR active. Intense EPR spectra obtained in the low temperature range, below 100 v K, showed a well resolved hyperfine structure typical of isolated vanadium ions in axial symmetry, present as VO 2+ species, and a broad line attributed to V 4+ -O-V 5+ bonds. The hyperfine structure lines could be analyzed by an axial spin Hamiltonian with g =1.9311, g =1.9425 and A =181 ‐ 10 m 4 v cm m 1 , A =54 ‐ 10 m 4 v cm m 1 . The spectrum recorded at the lowest obtainable temperature T=3.65 v K contains yet another component which is typical of a triplet state indicating the presence of two interacting VO 2+ nuclei with spin 1/2 giving a singlet S=0 and a triplet S=1 state. The appearance of a low-field line (B～1600 v Gs at g , 4) is another diagnostic for the presence of dimeric species and is attributed to the forbidden j M S = - 2 transition.     

EPR of radiation defects in LiBaF 3 crystals

EPR spectra of LiBaF 3 crystals have been investigated after X-irradiation at RT. A spectrum consisting of approximately 35 nearly equidistant EPR lines has a strong angular dependence on the line intensities. The spectrum is caused by a hyperfine interaction (hfs) of a spin S =1/2 with neighbouring groups of nuclei. The observed large number of hfs lines required Li nuclei being in the first shell and fluorine nuclei in the more distant second shell. We analysed the spectrum in the F -centre model, taking reduced hfs values of the F -centre in LiF and found qualitative explanation of the number of hfs lines. The angular dependence of the line intensities could be explained by an anisotropy of the g -tensor with its main axis along the [1 v 0 v 0] axis of the crystal.     

Trap levels in Y-aluminum garnet scintillating crystals

Point defects acting as trap levels were investigated on undoped, Ce- and (Ce, Si)-doped Y₃Al₅O₁₂ (YAG) crystals by TSL measurements performed over a wide temperature range (10–800 K). Below room temperature, a composite glow curve was observed, whose intensity strongly increased after Ce doping. Moreover, Ce doping introduced new trap levels giving rise to glow peaks in the 100–200 K range. On the other hand, Si co-doping did not influence the low T glow curve in a significant way. The spectral emission of the TSL was found to be governed by the Ce³⁺ 5d–4f radiative transition, while defect related higher energy emission bands were detected only in the undoped crystal. Above RT, the glow curve was found to be much more influenced by Si co-doping since a strong increase of a glow peak at about 250°C was noticed. Scintillation time decays of Ce- and Ce,Si-doped samples are also reported and compared with TSL data. The significance of the results and the potential impact of defect states on the scintillation properties are discussed.     

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.     

Phase transition in Cu2+-doped RbH2 PO4 as observed by EPR

The electron paramagnetic resonance (EPR) spectra of Cu²⁺-doped RbH₂ PO₄ at elevated temperatures indicate a phase transition at 358 K. The EPR-silent state at this temperature is attributed to a so-called polymeric phase transition. After the transition when the temperature is lowered to 293 K, the EPR signal does not appear; therefore, the transition is irreversible. This result seems to be in agreement with the other observations. The EPR spectra for the sample indicate the presence of two sites for Cu²⁺, and the values of EPR parameters are in accord with the literature on Cu²⁺-doped single crystals. Any other phase transitions could not to be observed at low temperatures down to 113 K.     

Optical spectroscopy of Ce 3+ ions in BaY 2 F 8 single crystals

In the present work we report on the spectroscopic properties of the Ce 3+ ion in BaY 2 F 8 single crystals. The absorption and excitation spectra of the emission centered at 340 v nm have been measured in the temperature range 15-300 v K. The 340 v nm emission consists of two broad partially overlapping bands, peaking at 324 and 347 v nm (at 15 v K), respectively. The full width at half maximum is about 0.5 v eV at room temperature. The absorption spectrum of the lowest in energy component of the f M d transition of Ce 3+ reveals at low temperature a marked vibronic structure. High resolution (0.02 v cm m 1 ) Fourier transform infrared spectroscopy in the wave number range 500-5000 v cm m 1 and in the temperature range 9-300 v K has been exploited to monitor the f level splitting. The absorption transitions from the three Stark components of the 2 F 5/2 manifold to the four of the 2 F 7/2 one, have been monitored in the wave number range 2000-3400 v cm m 1 . The wave number separation at 9 v K between the lowest level of the ground 2 F 5/2 manifold and lowest one of the 2 F 7/2 manifold is found to be 2197.47 v cm m 1 in good agreement with the splitting detected between the two components of the d M f emission.     

MCeO3：Eu^3＋（M=Sr，Ba）的合成及发光性质研究

利用高温固相反应法合成了Eu^3＋掺杂的MCeO3（M=Sr，Ba）发光粉末样品，采用X射线衍射技术和荧光光谱等测试手段分别对其物相组成和发光性质进行了研究。X射线衍射结果显示，Eu^3＋离子容易替代MCeO3晶格中M^2＋离子的位置。荧光光谱测试结果表明，Eu^3＋掺杂的SrCeO3和BaCeO3样品在紫外波段存在着非常宽的吸收带，峰值分别位于311和320nm左右，它们属于Ce^4＋-O^2-的电荷迁移带，SrCeO3和BaCeO3基质与Eu^3＋离子之间存在着能量转移。在MCeO3：Eu^3＋样品中，Eu^3＋的发射主要来自于^5D0激发态能级，其中以磁偶极跃迁^5D0-^7F1发射强度为最大；此外样品中还存在着较高的^5D1激发态能级的辐射跃迁。SrCe03：EU^3＋样品的发射强度远大于BaCeO3：EU^3＋样品。     

Gamma ray interactions with MoO3-doped lead phosphate glasses

The UV–Visible, Fourier transform infrared (FTIR) and Raman and electron spin resonance (ESR) spectra of undoped lead phosphate and MoO₃-doped glassy samples have been investigated. The UV–VIS absorption spectra were re-measured after successive gamma irradiation. Before irradiation, undoped sample exhibited strong ultraviolet absorption, which was attributed to co-absorption due to trace iron impurities (mainly Fe³⁺ ions) and lead Pb²⁺ ions. With the introduction of MoO₃ in progressive amounts, extra visible bands were recorded at about 400–440, 540, 750 and 870?nm. These bands are most likely correlated with the presence of Mo³⁺, Mo⁴⁺ and Mo⁵⁺ ions in the host glass. In the undoped specimen, gamma irradiation produced UV absorption bands that increased slightly with irradiation but no visible bands were recorded. Samples containing high MoO₃ content showed some resistance to irradiation with no bands in the visible region being observed. FTIR absorption spectra of the undoped and MoO₃-doped samples revealed the formation of metaphosphate and pyrophosphate structural units. Highly MoO₃-doped samples exhibited additional bands due to molybdate groups. Raman and ESR spectra were in agreement with UV–VIS and IR data, indicating the presence of molybdenum ions in lead phosphate glass, as Mo³⁺, Mo⁴⁺ and Mo⁶⁺ with different ratios. However, such glassy systems favor the trivalent species.     

Defect formation and VUV luminescence in BaF 2

Nominally pure BaF 2 single crystals were investigated at 77 v K with optical absorption and electron paramagnetic resonance to understand the mechanism of radiation damage. We find that X-irradiation at 77 v K of undoped BaF 2 produces V k - and F -centres having absorption bands at 3.4 and 2.3 v eV respectively.     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

Vibrational spectroscopy of oh-defects in sol-gel Ce 3+ and Gd 3+ -doped silicate glasses

Vibrational modes of OH, as stretching, bending, combination, and overtones, were monitored by means of FTIR spectroscopy in Ce 3+ - and Gd 3+ -doped silicate glasses, prepared by means of the sol-gel technique, submitted to different thermal treatments, and aimed to applications as scintillators. The dopant concentration was varied in a wide range (10 m 3 -8% m.f.) and co-doped samples were also investigated. In this framework, the effects of OH and of rare-earth (RE) clustering, i.e. two possible non-radiative decay channels, on the IR spectra in the 500-14 v 000 v cm m 1 were examined. OH was detected as belonging either to water and to silanol in samples densified at 450 and 750 v C, while in those treated at 1050 v C only Si-OH groups were present in a concentration of the order of 1% m.f., nearly regardless of the RE amount. An absorption peaking at 4250 v cm m 1 was identified as related to an OH combination mode (bending+stretching) perturbed by a Gd cluster on the basis of its amplitude dependence on the Gd concentration and rapid thermal treatment.     

Non-equilibrium effects in copper vapor laser pumped Nd3+ doped PVA film: Photo-electon paramagnetic resonance and photoacoustic spectral investigations

Photo-EPR measurements carried out on Nd³⁺ -doped polyvinyl alcohol (PVA) films have shown that nearly 100% reduction occurs in the intensity of EPR of Nd³⁺ under in situ copper vapor laser (CVL) illumination (510.5 nm and 578.2 nm). The kinetics of decay and recovery were investigated. Photoacoustic (PA) spectra, observed under CVL pump condition had shown that the CVL induced changes were not due to photoinduced valence change, and that the CVL pumping creates highly favorable conditions for non-equilibrium population distribution in the excited electronic states. The complete disappearance of EPR under CVL pumping is attributed either to the possible equalization of population of |+〈 and |−〈 Zeeman components, through the decay of many excited states in the presence of magnetic field or configurational changes around Nd³⁺ shifting the resonance frequency. The former appears less probable in view of the relatively slower recovery of EPR signal.     

Radiation effects in KMgF 3 crystals

Effects of x, g and UV irradiation on Tb 3+ and Eu 2+ doped KMgF 3 crystals were studied. Thermoluminescence (TL) excited by VUV radiation was compared to that induced by x and g rays. TL excitation spectra showed maxima at 125, 140, 155 and 180 v nm. The main TL peaks appeared after VUV irradiation at about the same temperatures and with the same thermal activation energies as after x or g irradiation, indicating that these peaks are due to the same trapping levels. In samples, which had previously been exposed to ionizing radiation, TL could also be excited with longer wavelengths that could not excite any TL in un-irradiated crystals; this is attributed to a process of phototransfer (PTTL). The x and UV excited luminescence was measured at LNT and RT and showed essentially the same main emission bands that appeared in the TL and PTTL peaks of these crystals. The dose dependence of the 730 v K TL peak in of KMgF 3 :Eu 2+ was linear up to about 2000 v Gy. The TL sensitivity of KMgF 3 :Eu 2+ was by an order of magnitude higher than that of KMgF 3 :Tb 3+ , which was by a factor of two greater than that of the known TLD-l00 phosphor.     

EPR of Gd3+ - doped CeF3 single crystal: Linewidth variation with temperature

Detailed X-band EPR study of a Gd³⁺-doped CeF₃ single crystal has been made from 4.2 to 473 K, with particular attention to EPR linewidths. In general, it is found that there are four regions over which the log-log plot of the linewidth versus temperature is linear, implying separate power-law dependences of the linewidth. Gd³⁺ spin Hamiltonian parameters in CeF₃ have been estimated at various temperatures from the line positions. From the linewidth variation with temperature the Debye temperature has determined to be about 140 K.     

Time-Resolved and Pulse EPR Study of Triplet States of Alkylketones in β-Cyclodextrin

The triplet states of deoxybenzoin (DOB) and benzophenone (BP) molecules in randomly methylated β-cyclodextrin (CD) cavity are studied by time-resolved (TR) and pulse electron paramagnetic resonance (EPR). The observed TR EPR spectrum of DOB in β-CD at 30 K is close to the spectrum measured in polar solvent trifluoroethanol, revealing strong hydration by water molecules. At the same time, TR EPR spectrum of BP in β-CD corresponds to nonpolar surrounding of the CO-group. The electron spin relaxation times T ₁ and T ₂ of triplet BP at 30 K measured by pulse EPR are found to be different in β-CD compared to nonpolar toluene glass. The observed increase of T ₂ by up to a factor of four in β-CD is caused by the lower vibration amplitude of CO-bond of BP due to the confinement in β-CD. The influence of β-CD with covalently attached nitroxide on the triplet states of DOB and BP is principally different: the excited triplet states could not be observed by TR EPR due to the efficient quenching of the excited states by nitroxide.     

Electron paramagnetic resonance of Yb<Superscript>3+</Superscript> ions in a concentrated YbRh<Subscript>2</Subscript>Si<Subscript>2</Subscript> compound with heavy fermions

The EPR signal from localized ytterbium ions was observed in an undoped YbRh₂Si₂ compound with heavy fermions in the temperature range from 1.5 to 25 K. The exponential contribution dominating the temperature dependence of EPR line width at temperatures above 15 K was shown to be caused by the random transitions from the ground to the first excited Stark sublevel of the Yb³⁺(4f¹³) ion with the activation energy Δ=115 K.     

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.