Radiation and thermally induced effects in YAlO3:Mn crystals

We have studied effects induced by γ-radiation and temperature in Mn-doped YAlO₃ crystals. The studies have been performed by means of optical spectroscopy that include measuring of optical absorption changes induced by γ-radiation and elevated temperature as well as thermally stimulated luminescence (TSL). It has been shown that under γ-irradiation of YAlO₃:Mn crystals, along with the ionization of Mn_Al⁴⁺ ions (Mn_Al⁴⁺→Mn_Al⁵⁺+e⁻), some additional coloration processes take place. This additional coloration is characterized by a wide intense band centered at 26,000- that is ascribed to color centers intrinsic to YAlO₃ lattice. This coloration is removed by the way of crystal warming at , while the coloration caused by Mn_Al⁵⁺ ions is removed at higher temperature . The observed TSL glow of irradiated crystals reveals three peaks near 360, 400 and that correspond to three types of traps. Parameters of the traps have been determined. The TSL emission corresponds to intra-center luminescence of Mn_Al⁴⁺ and Mn_Y²⁺ ions. The possible ionization and trapping mechanisms in YAlO₃:Mn crystals are discussed.     

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.     

Luminescence of F + and F centers in YAlO3

In YAlO₃ crystals grown in vacuum or reduced by annealing at low oxygen pressure, the luminescence of F centers in the band at 420 nm, with τ=30 ms at 9 K, excited in the bands at 212 and 242 nm, as well as the luminescence of F ⁺ centers in the band at 355 nm, with τ=2.7 ns, excited in the main band at 220 nm and weaker bands at 190 and 288 nm, was detected. On the basis of the results obtained and data in the literature, the behavior of the emission of F ⁺ and F centers in oxides of the Al₂O₃-Y₂O₃ system is analyzed on the example of the compounds α-Al₂O₃, YAlO₃, and Y₃Al₅O₁₂. The role of antisite defects in the stabilization of F-like luminescence and absorption centers in multisublattice oxides is discussed.     

Luminescence of Bismuth‐Activated Ceramics of Yttrium and Scandium Oxides

The luminescence spectra of Y₂O₃:Bi and Sc₂O₃:Bi ceramics have been investigated. The spectra have been resolved into elementary components by the Alentsev–Fock method. It has been established that the luminescence is attributed to emission centers of three types, two of which are due to the replacement of Y³⁺ (or Sc³⁺) by Bi³⁺ at the nodes of the crystal lattice of Y₂O₃ (or Sc₂O₃) with the point symmetry C ₂ and C _3i . The emission center Bi³⁺ in the position C_3i leads to the appearance of blue luminescence with maxima at 3.03 eV for Y₂O₃:Bi and at 3.05 eV for Sc₂O₃:Bi; this luminescence is attributed to the transition ³ P ₁–¹ S ₀. The emission center Bi³⁺ in the position C ₂ initiates green luminescence (which is also related to the ³ P ₁–¹ S ₀ transition in Bi³⁺) with a maximum in the region of 2.40 eV in Y₂O₃:Bi and in the region of 2.46 eV in Sc₂O₃:Bi. The red luminescence band with maxima at 1.85 eV in Y₂O₃:Bi and at 1.95 eV in Sc₂O₃:Bi is related to the presence of structural defects.     

Irregular Ceand defect-related luminescence in YAlO3 single crystal

Using the methods of time-resolved and steady-state luminescence spectroscopies, the luminescence and defects creation processes were studied at 4.2-300 K under excitation in the 3.0-10.5 eV energy range for an YAlO₃:Ce crystal with very low concentration of Ce³⁺ ions. The results were compared with those obtained at the study of YAlO₃:Ce crystals with large Ce³⁺ content coming from the same technological laboratory. Three irregular Ce³⁺ centers were found and two intrinsic defect luminescence centers related to the cation and oxygen vacancies were evidenced. The origin and structure of luminescence centers are discussed.     

Influence of lead-related centers on luminescence of Ce3+ and Pr3+ centers in single crystalline films of aluminium perovskites and garnets

Luminescence characteristics of Ce³⁺- and Pr³⁺-doped aluminium perovskite (LuAlO₃, YAlO₃) and garnet (Lu₃Al₅O₁₂, Y₃Al₅O₁₂) single crystalline films, prepared by the liquid phase epitaxy method with the use of the PbO-based flux, were investigated by the time-resolved spectroscopy methods in the 80–300 K temperature range. The influence of various lead-related centers on the characteristics of the Ce³⁺- and Pr³⁺-related luminescence centers was studied. It was found that the presence of lead-related centers in the single crystalline films results in a decrease of the quantum efficiency and appearance of undesirable slow components in the luminescence decay kinetics. The possibilities of improving the scintillation characteristics of the single crystalline films were considered.     

Infrared excited-state absorption and stimulated-emission cross sections of Er3+-doped crystals

Detailed spectra of the excited-state absorption and the stimulated-emission cross-sections of Er³⁺ -doped Y₃Al₅O₁₂, YAlO₃, LiYF₄, and KYF₄ crystals are analyzed in the infrared wavelength regions from 700 to 2100 nm. The spectra were measured with a pump and probe technique employing a double modulation scheme. For Er (2%): Y₃Al₅O₁₂ also the stimulated emission at 3 µm and the reabsorption due to excited-state absorption from the lower laser level are investigated.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

Luminescence of excitons in single-crystal garnets

Comparative studies of the luminescence of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and their volume analogues—Y₃Al₅O₁₂ and Y₃Al₅O₁₂:Ce single crystals, excited by synchrotron radiation with energy E=120–150 eV, have been performed. The films were grown from melt-solution by liquid-phase epitaxy and the crystals were grown from melt. The single-crystal films and single crystals studied are characterized by different degrees of structural order, in particular, different concentrations of substitutional defects of the Y _Al ³⁺ and LU _Al ³⁺ types. It was ascertained that the bands at 260 and 250 nm in the intrinsic luminescence spectra of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and single crystals are due to the emission of self-trapped excitons. The luminescence band with λ_max=300 nm and τ=0.36 μs, which is present in the luminescence spectrum of single crystals and absent in the spectra of single-crystal films, is due to the recombination of electrons with holes localized at Y _Al ³⁺ centers. It is shown that an efficient energy transfer by excitons to activator ions occurs in Y₃Al₅O₁₂ and Lu₃Al₅O₂ single-crystal films doped with Ce³⁺ ions.     

Luminescence of Sc3+ and La3+ isoelectronic impurities in Lu3Al5O12 single-crystal films

The time-resolved luminescence and luminescence excitation spectra, and luminescence decay kinetics at 8 and 300 K of Lu₃A₁₅O₁₂ (LuAG) single-crystal films doped with Sc³⁺ and La³⁺ isoelectronic impurities and excited by synchrotron radiation are investigated. It is established that the La³⁺ isoelectronic impurity in the ?ub;c?ub; positions of the garnet lattice forms La _Lu ³⁺ luminescence centers emitting in the band with λ_max = 280 nm and the decay time of the main component τ = 300 ns at 300 K. The Sc³⁺ isoelectronic impurity located in the ?ub;c?ub; and (a) positions of the LuAG lattice forms two luminescence centers, Sc _Lu ³⁺ and Sc _Al ³⁺ , emitting in the bands with λ_max = 290 nm and τ = 240 ns and λ_max = 335 nm and τ = 375 ns, respectively, at 300 K. It is shown that the luminescence excitation of the La³⁺ and Sc³⁺ isoelectronic impurities in LuAG single-crystal films occurs through radiative decay of excitons localized near La _Lu ³⁺ , Sc _Lu ³⁺ , and Sc _Al ³⁺ centers. The energies of formation of these excitons are determined to be 6.8, 6.88, and 7.3 eV, respectively. It was found that the excited state of the excitons genetically related to the La _Lu ³⁺ , Sc _Lu ³⁺ , and Sc _Al ³⁺ enters has two radiative levels with different transition probabilities. This configuration leads to the presence of fast (2.3–8.4 ns) and slow (150–375 ns) main components in the luminescence of the centers formed by isoelectronic impurities in garnets.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Photoluminescence properties of Y0.75-xGdxAl0.10BO3:Eu3+0.10, 0.05R3+ (R= Sc, Bi) (0.00≤x≤0.45)

Y$_{0.75 - x}$Gd_xAl_0.10BO$₃:Eu$^{3+}_0.10, 0.05R³⁺ ($R$=Sc, Bi) ($0.00 ≤ x ≤ 0.45$) powder samples are prepared by solid-state reaction and their luminescence properties are investigated. With the replacement of Y³⁺$ ions by Sc³⁺$ (or Bi³⁺)$ and Gd³⁺$ ions in (Y,Al)BO$₃:Eu, the intensities of emission at 254 and 147~nm are remarkably improved, because Sc³⁺$ ions can absorb UV light and transfer the energy to Eu³⁺$ ions efficiently. Moreover, Gd³⁺$ and Bi$^{3 + }$ ions act as an intermediate ``bridge' between the sensitizer and the activator (Eu³⁺)$ in energy transfer to produce light in the (Y, Gd)BO$₃:Bi³⁺$, Eu³⁺$ system more effectively. After doping an appropriate concentration of Gd³⁺$ into Y$_{0.50}$Gd$_{0.25}$Al_0.10BO$₃:Eu³⁺_{0.01}$, Bi$^{3+}_{0.05}$, the emission intensity reaches its maximum, which is nearly 110{\%} compared with the red commercial phosphor (Y,Gd)BO$₃:Eu and better chromaticity coordinates (0.650, 0.350) are obtained.     

Luminescence properties of Y3Al5O12:Ce nanoceramics

Comparative analysis of the luminescent properties of Y₃Al₅O₁₂:Ce (YAG:Ce) transparent optical ceramics (OС) with those of single crystal (SC) and single crystalline film (SCF) analogues has been performed under excitation by pulsed synchrotron radiation in the fundamental absorption range of YAG host. It has been shown that the properties of YAG:Ce OC are closer to the properties of the SCF counterpart, where Y_Al antisite defects are completely absent, rather than to the properties of SC of this garnet with large concentration of Y_Al antisite defects. At the same time, the luminescence spectra of YAG:Ce OC show weak emission bands in the 200-470 nm range related to Y_Al antisite defects and charged oxygen vacancies (F⁺ and F centers). YAG:Ce ОС also possesses significantly larger contribution of slow components in the Ce³⁺ luminescence decay under high-energy excitation in comparison with SC and SCF of this garnet due to the involvement of antisite defects, charged oxygen vacancies as well as boundaries of grains in the energy transfer processes from the host to the Ce³⁺ ions.     

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.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Luminescence of Donor‐Acceptor Pairs in Compounds of Yttrium and Scandium Oxides

The luminescence spectra of Sc₂O₃, Y₂O₃, and Y₂GeO₅ ceramics and thin films exposed to laser and cathode excitation were investigated. The investigation of the properties of longwave luminescence bands in Sc₂O₃ with maxima at 2.65, 2.35, and 2.05 eV, in Y₂O₃ with maxima at 2.60, 2.35, and 2.10 eV, and also in Y₂GeO₅ with maxima at 2.55, 2.25, and 2.00 eV point to the fact that they are caused by radiative recombination of the excited donoracceptor pairs Sc³⁺ (or Y³⁺)O^2–.     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

High Pressure Spectroscopy of Ti Doped Al2O3 and YAIO3 Host Crystals

We report high-pressure luminescence spectroscopy studies of Ti^3? in Al₂O₃ and YAlO₃. High-pressure luminescence spectra were measured for Al₂O₃:Ti^3? up to 90kbar and for YAlO₃:Ti^3? up to 181 kbar. In both cases, a blue shift of the luminescence peak with pressure was observed and is attributed to an increase in the octahedral crystal-field strength (10 Dq) with pressure. In the case of YAlO₃;Ti^3?, an additional luminescence peak was observed at 181 kbar and below ～ 200 K, and is attributed to a metastable state. The metastability of the ²E excited state was induced by pressure that removes the equivalency of three energy minima of the ²E state coupled to the ? mode.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Tunable room-temperature laser action of Cr4+-doped Y3ScxAl5−xO12

A new class of tunable room-temperature Cr⁴⁺ lasers is presented: Cr⁴+-doped Y₃Sc_xAl_5–xO₁₂ garnets. With increasing scandium content the emission shifts to longer wavelengths due to the weakening of the crystal field. Free running laser wavelengths are 1440, 1498, 1548 and 1584 nm for x = 0, 0.5, 1.0 and 1.5, respectively. Continuous tunability is obtained from 1309 to 1628 nm.