Luminescence and relaxed excited state origin in CsI:Pb crystals

Emission and excitation spectra, luminescence polarization and decay kinetics have been studied for CsI:Pb crystals in the 0.36-300 K temperature range. The origin of the excited states responsible for the optical characteristics has been discussed. It has been concluded that the doublet ≈3.70 eV absorption (excitation) band is caused by the electronic transitions into the Pb²⁺ triplet state split due to the presence of a cation vacancy near a Pb²⁺ ion, while the higher-energy bands are of the charge-transfer origin. Like in CsI:Tl, four emission bands of CsI:Pb have been found to belong to the main luminescence centres. Two emission bands, peaking at 3.1 and 2.6 eV, are suggested to arise from the triplet relaxed excited state of a Pb²⁺ ion. Two visible emission bands, peaking at 2.58 and 2.23 eV, are interpreted as the luminescence of an exciton localized near the Pb²⁺ ion.     

Emission and decay time studies on Pb2+ centers in KBr,RbBr, and RbCl

The emission spectra and the luminescence decay times of KBr, RbBr, and RbCl crystals doped with Pb²⁺ and excited in the A-absorption band have been studied in the temperature range 5–300 K. The emission-lineshape spectra have been analysed in terms of skew-Gaussian bands. New bands have been observed in RbCl and RbBr at very low temperatures. While the luminescence decay of KBr:Pb²⁺ and RbBr:Pb²⁺ show only a single component with a decay time τ ～ 20 ns, RbCl:Pb²⁺ shows a short and a long component. The reason for the missing long component in KBr:Pb²⁺ and RbBr:Pb²⁺ is tentatively attributed to an anomaly in the structure of the adiabatic potential energy surface (APES) of the excited states.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Photoluminescence studies of γ-irradiated CaF2:Dy:Pb:Na single crystals

The optical absorption (OA) and photoluminescence (hereafter referred to as luminescence) studies were made on CaF₂:Dy:Pb:Na single crystals (Dy—0.005 at%, Pb—0.188 at% and Na—0.007 at%) before and after γ-irradiation. The unirradiated crystal exhibited a strong OA band around 6.36 eV attributed to the ‘A’ band absorption of Pb²⁺ ions. The γ-irradiated crystal exhibited OA bands around 2.06, 3.28, 3.75 (broad shoulder) and 2.48 eV. The first three bands could be tentatively attributed to M_Na centre when compared with that of the coloured CaF₂:Na. The origin of 2.48 eV band was not explicitly known. Luminescence emission and excitation of Pb²⁺ and Dy³⁺ ions were negligible in the unirradiated crystal. Irradiated crystal exhibited a strong excitation spectrum with overlapping bands, due to different colour centres, in the UV-vis region for the 2.15 eV emission characteristic of Dy³⁺ ion. When excited, the absorbed energy (may be a part) was transferred from a colour centre to nearby Dy³⁺ ions and Dy³⁺ characteristic emission was observed. Exciting the irradiated crystal around 3.28 eV yielded emission at 2.56, 2.15 and 1.76 eV. The first two emission bands were due to Dy³⁺ ions. The excitation spectrum for the 1.76 eV emission showed two prominent bands around 2.02 and 3.08 eV and hence the emission was attributed to the M_Na centre. The luminescence mechanism was described.     

The impurity-induced luminescence of RbMnF3

The impurity-induced luminescence of RbMnF₃ has been studied in the temperature range, 4–120 K. Multimagnon sidebands of impurity-induced Mn²⁺ emission lines have been detected spanning the spectral range, 5515–5960 Å. The broad emission bands, which peak at 5750 Å and 6440 Å, have been attributed to phonon-assisted transitions from two impurity-induced Mn²⁺ traps of different depths. Pulsed luminescence measurements indicate that the quenching of the shallow trap emission is by a thermal activation to the E1 exciton level whereas the quenching of the deeper trap emission is by a multiple phonon decay. The coupling between Mn²⁺ ions is strong enough to support a detectable transfer of excitation between these two traps.The results of this research also include the observation in absorption of the E1 exciton line and its 1-magnon and possible 2-magnon sidebands.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

Low-temperature X-ray and photoluminescence of lead halide crystals

The emission spectra of PbF₂, PbCl₂ and PbBr₂ monocrystals are measured under optical and X-ray excitation at liquid helium temperature. Certain emission bands are attributed to the radiative transitions in the self-trapped cation exciton (excited Pb²⁺ion). The increase of trapped exciton via electron-hole recombination is discussed.     

Luminescence properties and radiation response of sodium borate glasses scintillators

We examined basic luminescence properties and radiation response of sodium borate glass scintillators activated with Pb²⁺, Cu⁺, Ti⁴⁺, V⁵⁺, W⁶⁺ and Yb³⁺ ions, respectively. These glasses had more than 80% transparency for emission wavelength range, and strong absorption bands due to the charge transition of the ions were observed. In the photoluminescence spectra, all glasses demonstrated intense emission peak in visible region, which are corresponding to the ions with s² (Pb²⁺), d¹⁰ (Cu⁺) and d⁰ (Ti⁴⁺, V⁵⁺, W⁶⁺) configuration. Additionally charge transfer emission was observed in Yb³⁺-doped glass. When ²⁴¹Am 5.5 MeV alpha-ray excited the glasses, they showed weak emission intensity because of low energy transfer efficiency from host lattice to emission center. By ²⁴¹Am irradiated pulse height spectra, Cu⁺-doped glass demonstrated the highest scintillation output in the glasses.     

+3价离子掺杂钨酸铅晶体发光性能和微观缺陷的研究

通过透射光谱、x射线激发发射光谱（XSL）的测试，研究了Bridgman法生长的几种不同+3价离子掺杂钨酸铅晶体的发光性能，并利用正电子湮没寿命谱（PAT）和x光电子能谱（XPS）的实验手段，对不同钨酸铅晶体的微观缺陷进行研究.实验表明，不同的+3价离子掺杂，对钨酸铅晶体发光性能的改善不同，并使得晶体中正电子俘获中心和低价氧的浓度发生不同变化.其中掺镧晶体的正电子俘获中心和低价氧浓度均上升，而掺钇和掺铋晶体的正电子俘获中心和低价氧浓度均下降，掺锑晶体则出现了正电子俘获中心浓度上升、低价氧浓度下降的情况.提 关键词： 钨酸铅晶体 +3价离子掺杂 正电子湮没寿命谱 x光电子能谱     

Luminescence spectroscopy and energy transfer in Eu2+/Mn2+-doped KCaPO4 phosphors

Eu²⁺/Mn²⁺-doped KCaPO₄ phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), SEM, photoluminescence excitation, and emission spectra, and the luminescence decay curves were measured. Mn²⁺ singly doped KCaPO₄ shows the weak origin-red luminescence band peaked at about 590 nm. The Eu²⁺/Mn²⁺ co-doped phosphors emit two distinctive luminescence bands: a blue one centered at 480 nm originating from Eu²⁺ ions and a broad red-emitting one peaked at 590 nm from Mn²⁺ ions. The luminescence intensity from Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ ions. The efficient energy transfer from Eu²⁺ to Mn²⁺ was verified by the photoluminescence spectra together with the luminescence decay curves. The resonance-type energy transfer via a dipole–quadrupole interaction mechanism was supported by the decay lifetimes. The emission colors could be tuned by changing the Mn²⁺-doping concentration.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

Luminescence studies of thallium co-doped KBr:Eu2+ powder phosphors

In this study, photoluminescence (PL) and photostimulated luminescence (PSL) properties in KBr:Eu²⁺, Tl⁺ powder phosphors are reported. PL emission spectra of these Tl⁺ co-doped KBr:Eu²⁺ phosphors show four overlapping bands around 310, 325, 360 and 375 nm in addition to the characteristic of Eu²⁺ ions at 420 nm. These additional short wavelength bands were attributed to centres involving Tl⁺ ions. The decrease in PSL intensity of γ-irradiated KBr:Eu²⁺, Tl⁺ powder phosphors with Tl⁺ concentration and the absence of thallium emission bands in PSL were attributed to the efficient electron trapping by Tl⁺ ions during irradiation.     

Radiative energy transfer from Pb2+ to Eu2+ ions in NaCl,Kcl, and KBr single crystals

In the present work, the emission and excitation spectra of NaCl, KCl, and KBr doubly doped with europium and lead ions were investigated. In all cases, excitation with light lying in the A-band of the Pb²⁺ ions produces in addition to the ³P₁ → ³S_o Pb²⁺ emission, the 4f⁶ 5d (^t2g) → 4f⁷ europium emission. This fact indicates that energy transfer occurs from Pb²⁺ to Eu²⁺ ions. From the data obtained, it was determined that the energy transfer process is of a radiative nature and that it is more efficient in KCl than in either of NaCl or KBr. A possible explanation for this fact is given.     

Luminescence of Tb3+ ions in silicate glasses

The optical absorption and photoluminescence emission spectra of terbium doped sodium and lithium aluminium silicate glasses have been measured as a function of terbium concentration. Optical absorption has been measured over the wavelength range from 250 nm to 40 μm and the absorption bands attributed to Tb³⁺ ions have been identified. Luminescence emission occurs in two groups of bands in the blue and in the green. The green ⁵D₄ → ⁷F_J emission is more intense than the blue ⁵D₃ → ⁷F_J. The green luminescence is enhanced at the expense of the blue when the Tb³⁺ ion concentration reaches 0.5 molar%, which corresponds to an ion separation of 20 Å. The green emission is quenched when the Tb³⁺ ion concentration exceeds 5 molar%, corresponding to an ion separation of 9.5 Å. It is concluded that energy transfer from ⁵D₃ to ⁵D₄ levels begins at Tb³⁺ ion separations of 20 Å, and that the process is multipolar. Exchange dipole processes set in at 9.5 Å and quench the green emission. The ion separations at which the two processes occur in silicate glasses are much larger than those at which similar processes set in crystalline material. This enhancement of energy transfer processes in silicate glass is attributed to inhomogeneous broadening of the absorption and emission bands. The detailed structure of the emission bands, particularly that of the ⁵D₄ → ⁷F_6,5,4 doublets, is used to suggest that the Tb³⁺ ions occupy two different sites with rhombohedral and cubic symmetries.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

Fluorescence of Mn2+ in CaCO3

The fluorescence of Mn²⁺ ion as impurity in CaCO₃ has been investigated. Emission bands from the ⁴D(E_g), ⁴D(T_2g) and ⁴G(T_1g) levels have been observed. The analysis of excitation and emission spectra has allowed to obtain the values of field strength (Dq) for the excited energy levels of Mn²⁺ in CaCO₃ lattice. The temperature dependence of excitation and emission spectra yield an activation energy for thermal quenching of luminescence very close to theoretical calculation. The behaviour of luminescence lifetime with temperature has also been obtained.     

Synchrotron and laser excitation of luminescence in PbWO<Subscript>4</Subscript>:Tb crystals at different temperatures

The effect of temperature on the spectral luminescence characteristics of PbWO₄:Tb³⁺ crystals with synchrotron and laser excitation is studied. If PbWO₄:Tb³⁺ is excited by synchrotron radiation with λ = 88 nm at 300 K, a faint recombination luminescence of the impurity terbium is observed against the matrix luminescence. When the temperature is reduced to 8 K, the luminescence intensity of PbWO₄:Tb³⁺ increases by roughly an order of magnitude and the characteristic luminescence of the unactivated crystal is observed. Excitation of PbWO₄:Tb³⁺ by a nitrogen laser at 300 K leads to the appearance of emission from Tb³⁺ ions. At 90 K, a faint matrix luminescence is observed in addition to the activator emission. The formation of the luminescence excitation spectra for wavelengths of 60–320 nm is analyzed and the nature of the emission bands is discussed.     

Photoluminescence from deep centers in GaAs

Sharp line structure attributable to phonon assisted radiative emission has been observed in the 6 K photoluminescence spectra from deep centers in bulk samples of chromium doped GaAs. Two luminescence bands at 0.56 and 0.8 eV have been observed and both bands exhibit evidence of phonon assisted radiative recombination. An exploration of these luminescence bands in terms of excited state to ground state transitions of Cr³⁺ and Cr²⁺ ions is proposed.     

氟化物、氟磷酸盐和磷酸盐玻璃中Er3+离子的发光研究

测定了氟化物、氟磷酸盐和磷酸盐玻璃中Er³⁺离子的吸收、荧光和激发光谱,解释了基质玻璃对Er³⁺离子发光的影响。进一步研究了在这三种基质玻璃中Er³⁺离子发光的浓度效应和温度效应,讨论了Er³⁺离子内和离子间的能量转移过程。 关键词：     

Effect of Pb2+ ions on the photoluminescence characteristics of Mn2+-doped Zn2SiO4

Zn₂SiO₄ single-doped and co-doped with Mn²⁺ ions and Pb²⁺ ions has been prepared by a sol–gel process. The luminescent properties of the samples have been investigated. From the excitation and emission spectral analysis, it was found that the emission peaks vary with the change of the excitation wavelength. An enhanced luminescent characteristic of Mn²⁺ ions (in blue and green spectral zones) has been observed, due to the energy transfer from the Pb²⁺ ion to the Mn²⁺ ion. The emission peaks originate from the d–d transitions of the Mn²⁺ ion. However, the relative intensities of the peaks show a dependence on the concentration of the Pb²⁺ ion. PACS 81.05.Je; 78.55.Hx; 61.72.Ww