Spodumene and garnet luminescence excited by subnanosecond electron beams

Pulsed cathodoluminescence of spodumene and yttrium-aluminum garnet crystals activated by Mn²⁺ and Nd³⁺ ions, respectively, is investigated. The luminescence was excited upon crystal irradiation by electron beams with current densities of 35 and 100 A/cm² and average electron energy of ∼ 50 keV for 0.1, 0.25, and 0.65 ns. It is demonstrated that the electron beam duration decreased to several tenth of a nanosecond does not lead to essential changes of the mechanisms of pulsed cathodoluminescence excitation and character of its spectrum, but in this case, the intensity of luminescence of the hole centers increases compared with the intracenter luminescence.     

Luminescence in x-irradiated CaF2:Co

Photoluminescence of X-irradiated CaF₂:Co single crystals is reported. The emission spectrum shows four peaks at 505, 550, 640 and 685 nm, all of them with an excitation band at 275 nm. The same emission spectrum, plus a band at 280 nm, is found in X-ray excited luminescence measurements. Thermoluminescence of 80 K X-irradiated crystals gives a glow curve with five peaks at 100, 125, 145, 190 and 225 K. The spectral distribution of these glow peaks is similar to that of the X-ray excited luminescence. The 280 nm band is associated with electron—hole recombination. The other four bands are associated with electron transitions among excited states of Co²⁺ produced by recombination of holes and Co⁺-ions created by X-irradiation.     

Effect ofγ-radiation on the spectral luminescence characteristics of impure cadmium tungstate crystals

Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·10⁴ Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.     

Spectral separation of Cr<Superscript>3+</Superscript> optical centers in stoichiometric magnesium-doped lithium niobate crystals

The broadband luminescence of chromium optical centers with strongly overlapping spectral lines and similar emission probabilities from excited ⁴ T ₂ states of red and green Cr³⁺ centers in stoichiometric magnesium-doped lithium niobate crystals has been separated for the first time. The spectral-luminescence characteristics and parameters of intracenter interaction between red and green optical Cr³⁺ centers in stoichiometric lithium niobate have been calculated. The luminescence quantum efficiencies of red and green chromium centers are determined.     

Ultraviolet luminescence of single crystals and single-crystal films of YAlO3

The nature of intrinsic emission bands of yttrium orthoaluminate in the UV spectral region at _max=220 nm (5.63 eV) and 330 nm (4.13 eV) is studied on the basis of the luminescence of single crystals and single-crystal films of YAlO₃ and Ce: YAlO₃ excited by synchrotron radiation sources with an energy of 3–25 eV at 9 and 300 K. The single crystals and single-crystal films were obtained, respectively, from solution and solution-melt by liquid-phase epitaxy and are characterized by considerably different concentrations of substitutional and vacancy defects. It is found that only the luminescence band at 300 nm, which has the decay time τ=4.1 ns and is excited in a band shifted from the range of interband transitions by 0.25 eV, has exciton-like character. The luminescence band at 220 nm with τ=0.1 µs at 9K, which is observed only for YAlO₃ single crystals and is absent in the luminescence of single-crystal films, is associated with antisite defects of the Y _Al ³⁺ type, which are a specific type of cationic isoelectronic impurities. It is shown that the phosphors based on single-crystal films of YAlO₃ have a simpler scintillation decay kinetics than their bulk analogues due to the absence of channels of excitation energy dissipation associated with the antisite defects of Y _Al ³⁺ type and vacancy defects.     

Cooperative down-conversion of UV light in disordered scheelitelike Yb-doped NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> and NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

Concentration series of disordered scheelitelike Yb:NaGd(MoO₄)₂ and Yb:NaLa(MoO₄)₂ single crystals are grown by the Czochralski method. The actual concentrations of Yb³⁺ ions in the crystals are determined by optical-absorption spectroscopy. The luminescence of Yb³⁺ ions in these crystals in the region of 1 μm is studied under UV and IR excitation. In the case of UV excitation, this luminescence appears as a result of nonradiative excited state energy transfer from donor centers of unknown nature to ytterbium. The character of the concentration dependence of Yb³⁺ luminescence indicates that the energy transfer at high Yb concentrations occurs with active participation of a cooperative mechanism, according to which the excitation energy of one donor center is transferred simultaneously to two Yb³⁺ ions. In other words, the quantum yield of this transfer exceeds unity, which can be used to increase the efficiency of crystalline silicon (c-Si) solar cells.     

About the luminescence properties of YAG∶Nd,Ce and YAG∶Nd single crystals and their relation to laser properties

Laser excited luminescence studies of various YAGNd, Ce and YAG:Nd (with an excess of yttrium) single crystals together with a testing of laser properties of rods made from the same crystals have been investigated in this paper. It was observed that laser pulse energies increase with increasing halfwidths of the luminescence spectral bands. This dependence and other observations indicate that local structure changes or Nd³⁺ nonequivalent centres are present in the studied crystals. Various mechanisms leading to the formation of Nd³⁺ nonequivalent centres are discussed and it seems that the more probable mechanism is oxygen segregation and diffusion.     

Thermal annealing behavior of luminescence of Gd3+-doped PbWO4 single crystal in air atmosphere

The results of photoluminescence measurements on as-grown PbWO₄:Gd³⁺ show that Gd³⁺ acts as a sensitizer of luminescence in the PbWO₄ lattice. Effects of sequential annealing in air atmosphere on luminescence of PbWO₄:Gd³⁺ were investigated by means of X-ray excited luminescence and photoluminescence. The annealing experiments indicate that the essence of the annealing in air atmosphere is the exchange of oxygen components between PbWO₄:Gd³⁺ crystal and the environment to improve the defects in the lattice. Annealing at a temperature of about 640 °C could further enhance the luminescence of PbWO₄ and depress it at a higher temperature. However, PbWO₄:Y³⁺ and PbWO₄:La³⁺ crystals do not show any luminescence enhancement in the same annealing process. A tentative mechanism of luminescence enhancement due to annealing is suggested. PACS 74.62.Dh; 81.40.Tv; 78.55.-m; 82.80.Pv; 78.70.En     

New observations on the luminescence of lead molybdate crystals

UV excited luminescence of lead molybdate (PbMoO₄, PMO) single crystals grown under controlled conditions has been studied at room temperature in both spectral and temporal domains. In literature, the luminescence from PMO crystals has been investigated by exciting with UV or synchrotron radiation sources. The results presented here show that the emission spectrum is a sensitive function of the crystal composition and both green and blue emissions may be observed at room temperature in crystals possessing minor stoichiometric deviations.     

Second-harmonic generation spectroscopy on?organic?nanofibers

Optical second-harmonic generation upon nanosecond laser irradiation of nanofibers grown from nonsymmetrically functionalized para-quarter-phenylene molecules on mica surfaces is investigated in the spectral region around electronic resonances. Strong multiphoton excited luminescence appears together with the second-harmonic signal in the spectra. It is demonstrated how the two components can be separated by analyzing emission spectra recorded over a broad range of wavelengths around the second-harmonic energy. Spectra of the absolute values of the second-harmonic signals are obtained for three differently functionalized molecules. Together with supplementary measurements of the structure of the nanofiber films this forms the basis for estimation of the second-harmonic susceptibility of the fiber materials. Values of the nonlinear susceptibilities are obtained, which are comparable to those of well-known inorganic nonlinear optical crystals.     

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.     

Anti-stokes luminescence of solid AgCl<Subscript>0.95</Subscript>I<Subscript>0.05</Subscript> solutions

An anti-Stokes luminescence band with λ_max = 515 nm of microcrystals of solid AgCl_0.95I_0.05 solutions excited by a radiation flux of density 10¹³–10¹⁵ quanta/cm²·sec in the range 600–800 nm at 77 K was detected. It is shown that the intensity of this luminescence and the frequency of its excitation depend on the prior UV-irradiation of samples. Analysis of the stimulated-photoluminescence spectra and the anti-Stokes luminescence excitation spectra of the indicated microcrystals has shown that to the centers of anti-Stokes luminescence excitation correspond local levels in the forbidden band of the crystals. These states are apparently due to the atomic and molecular disperse silver particles that can be inherent in character or formed as a result of a low-temperature photochemical process. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 738–742, November–December, 2005.     

Impurity Luminescence of Alexandrite Crystals

The luminescence of alexandrite excited by a highcurrent electron beam is investigated. Its spectrum has bands of the impurity ions Cr³⁺ and of the Cr–Cr pairs and also the band at = 492–495 nm. In all of the crystals we have detected chromium ions distributed over two nonequivalent positions, differently in different crystals. It is shown that the color of the crystals and its change on illumination of the crystals with the light of different spectral composition depend mainly on the chromium ions and their distribution over crystalline positions. A noticeable effect of other impurity ions is noted for a number of crystals.     

Luminescence of defect centres in Hg2Cl2

Abstract

Luminescence in Hg₂Cl₂, crystals excited with UV light is investigated in the spectral region 0.8–2.25 eV. Measurements are performed on as-grown samples and on samples previously exposed to UV light at RT. Six emission bands are found which depend on the concentration of the photochemical entities produced by irradiation of the crystals at RT. It is concluded that infra-red (IR) luminescence of Hg₂Cl₂ originates from crystal defects. The observed emission bands are tentatively attributed to the emission of (HgCI_xBr_3?x)^? and (HgCl_xBr_4?x)^2? complexes formed with residual Br impurities. Centres responsible for IR Hg₂Cl₂ emissions are excited: (i) via excitons of Hg₂Cl₂, (ii) via excited states of isolated Hg₂Br₂ molecules, and (iii) resonantly through the excitation bands of defect centres.     

Europium luminescence in fluorite upon high-energy excitation

The reflection and luminescence excitation spectra of CaF₂ crystals containing europium ions in divalent (Eu²⁺) and trivalent (Eu³⁺) states were measured in the range from 4 to 16 eV. It was established that, in CaF₂ : Eu³⁺ crystals, luminescence of Eu³⁺ ions (the f-f transitions) is effectively excited both in the charge-transfer band (at ～8 eV) and in the region of the 4f–5d transitions (at ～10 eV) but is virtually not excited in the fundamental region of the crystal (at an energy higher than 10.5 eV). Luminescence of Eu²⁺ ions (the 427-nm band) in CaF₂ : Eu³⁺ is effectively excited in the fundamental region of the crystal; i.e., luminescence of divalent europium ions occurs through the trapping mechanism. Emission of Eu²⁺ ions in CaF₂ : Eu²⁺ crystals is characterized by the excitation band at an energy of 5.6 eV (the 4f → 5d,t _2g transitions), as well as by the exciton and interband luminescence excitations. The results obtained and data available in the literature are used to construct the energy level diagram with the basic electron transitions in the CaF₂ : Eu crystals.     

Pulsed photo- and cathodoluminescence of LiF crystals doped with tungsten oxide

We have studied the spectral and kinetic characteristics of activated photo- and cathodoluminescence of LiF-O and LiF-WO₃ crystals in the spectral range of 3.6–1.6 eV using methods of pulsed spectrometry with nanosecond time resolution in the temperature range of 15–300 K and in the range of ionizing radiation dose absorbed by crystals of 10²−2 × 10³ Gy.     

Luminescence spectroscopy of excitons and antisite defects in Lu3Al5O12 single crystals and single-crystal films

The nature of the intrinsic luminescence of the lutetium aluminum garnet Lu₃Al₅O₁₂ (LuAG) has been analyzed on the basis of time-resolved spectral kinetic investigations upon excitation of two model objects, LuAG single crystals and single-crystal films, by pulsed X-ray and synchrotron radiations. Due to the differences in the mechanisms and methods of crystallization, these objects are characterized by significantly different concentrations of Lu_Al antisite defects. The energy structure of luminescence centers in LuAG single crystals (self-trapped excitons (STEs), excitons localized near antisite defects, and Lu_Al antisite defects) has been established. For single-crystal LuAG films, grown by liquid-phase epitaxy from a Pb-containing flux, the energy parameters of the following luminescence centers have been determined: STEs in regular (unperturbed by the presence of antisite defects) sites of the garnet lattice and excitons localized near Pb²⁺ ions. The structure of the luminescence centers, related to the background emission of impurity Pb²⁺ ions, has also been established in the UV and visible ranges. It is suggested that, in contrast to the two-halide hole self-trapping, a self-trapped state similar to STEs in simple oxides (Al₂O₃, Y₂O₃) is formed in LuAG; this state is formed by self-trapped holes in the form of singly charged O^? ions and electrons localized at excited levels of Lu³⁺ cations.     

Different processes responsible for blue pumped, ultraviolet and violet luminescence in high-concentrated Er:YAG and low-concentrated Er:YAP crystals

Ultraviolet and violet upconverted luminescence in high-concentrated (8.4 at%) Er³⁺:YAG and low-concentrated (1 at%) Er³⁺:YAP crystals has been investigated under blue laser excitation of the ⁴F_7/2 multiplet. The upconversion mechanisms were studied in detail based on upconversion luminescence intensity dependence and decay curves. Upconversion luminescence was attributed to energy transfer processes in Er³⁺:YAG and excited state absorption processes in Er³⁺:YAP, respectively.     

Luminescence and electronic excitations in crystals K<Subscript>2</Subscript>Al<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> with defects

This paper reports on the results of the comprehensive study of the dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals, obtained by low-temperature luminescence vacuum ultraviolet spectroscopy with nanosecond time resolution upon photoexcitation by synchrotron radiation. For the first time, the data have been obtained on the photoluminescence (PL) decay kinetics, PL spectra with time resolution, PL excitation spectra with time resolution, and reflection spectra at 7 K; the intrinsic nature of PL at 3.28 eV has been established; luminescence bands of defects have been separated in the visible and ultraviolet spectral regions; an intense long-wavelength PL band has been detected at 1.72 eV; channels of the formation and decay of electronic excitations in K₂Al₂B₂O₇ crystals have been discussed.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.