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.     

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.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

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.     

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.     

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.     

Single-crystalline films of Ce-doped YAG and LuAG phosphors: advantages over bulk crystals analogues

Luminescent properties of phosphors based on single-crystalline films (SCF) of Y₃Al₅O₁₂:Ce (YAG:Ce) and Lu₃Al₅O₁₂:Ce (LuAG:Ce) garnet have been analyzed in comparison with single-crystal (SC) analogues. It has been shown that the main peculiarity of luminescent properties of YAG:Ce and LuAG:Ce SCF as compared to SC is determined by the extremely low concentration of Y_Al³⁺ and Lu_Al³⁺ antisite defects (AD) in SCF. The advantages of phosphors based on YAG:Ce and LuAG:Ce SCF are caused by the absence in these SCF the additional channels for dissipation of excitation energy connected with AD and vacancy-type defects.     

Luminescent properties of LuAG:Yb and YAG:Yb single crystalline films grown by Liquid Phase Epitaxy method

In this work, investigation of the spectroscopic parameters of the luminescence of Yb³⁺ ions in single crystalline films of Lu₃Al₅O₁₂ and Y₃Al₅O₁₂ garnets was performed using the synchrotron radiation excitation with the energy in the range of Yb³⁺ charge transitions (CT), exciton range and the onset of interband transitions of these garnets. The basic spectroscopic parameters of the Yb³⁺ CT luminescence in LuAG and YAG hosts were determined and summarized with taking into account the differences in the band gap structure of these garnets.     

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.     

Preparation, Luminescence Properties, and Application of Scintillators Based on Lu3Al5O12:Ce Single‐Crystal Films

The possibility of obtaining scintillators with a high effective atomic number of the element Z _ef based on Lu₃Al₅O₁₂:Ce³⁺ singlecrystal films (SCF) on doping with La³⁺ and Sc³⁺ ions on Y₃Al₅O₁₂ substrates has been investigated. It is established that the SCF of (LuLaY)₃Al₅O₁₂:Ce³⁺ (Z _ef = 58.9 and = 6.67 g/cm²) does not rank below those of Y₃Al₅O₁₂:Ce³⁺ (Z _ef = 29 and = 4.52 g/cm²) in the conversion efficiency of radiation at the band with _max = 515 nm. This allows their use as screens of xray images with a space resolution of 0.75–1.00 m. It is suggested that in the SCF of Lu₃Al₅O₁₂ the isoelectronic impurities of lanthanum and scandium form radiative recombination centers of the type La_Lu, Sc_Lu, and ScAl as well as the centers Lu as a consequence of the effect of replacement of some Lu³⁺ ions by the La³⁺ ions to octanodes of the garnet lattice. The low efficiency of Ce³⁺ radiation in the SCF of (LuSc)₃(AlSc)₅O₁₂:Ce is explained by substantial losses due to excitation of the recombination luminescence in the UV region of the centers formed by the isoelectronic impurities of scandium and to the possible existence of the channel of energy excitation dissipation related to the transitions between extrema of the allowed energy bands and activator levels.     

Investigation of structural features of the Y3Al5O12: Ce3+/Lu2O3 crystal phosphors formed by the colloidal chemical method

The specific features of the crystal structure of crystal phosphors Y₃Al₅O₁₂: Ce³⁺/Lu₂O₃ (Lu₂O₃: Ce) synthesized by the colloidal chemical method have been investigated by neutron diffraction at room temperature. The influence of the method used for introducing Lu₂O₃ into the system on the structure and luminescence properties of the samples has been analyzed. The investigation has revealed that the spectra of the samples prepared under the most nonequilibrium conditions are characterized by the Stokes shift and high photoluminescence intensity. This has been explained by the disorder of their crystal structure due to the formation of stable associates of defects.     

Effect of composition disorder on the electron paramagnetic resonance spectrum of the thermally populated excited state of Er<Superscript>3+</Superscript> ions in YLuAG mixed garnets

The results of investigation of electron paramagnetic resonance of Er³⁺ ions in the thermally populated first excited state in (Y_{1 − x} Lu _x )₃Al₅O₁₂ (YLuAG) mixed yttrium-lutetium garnet single crystals (0 ≤ x ≤ 1) are considered. In composition-disordered YLuAG, a number of new (as compared to Y₃Al₅O₁₂ (YAG)) Er³⁺ paramagnetic centers are detected; these centers appear due to a change in the crystal field symmetry and magnitude upon isomorphic substitution of Lu³⁺ for Y³⁺ in the yttrium sublattice of garnets. The origin of new paramagnetic centers is established and their formation probability is calculated.     

Luminescence properties of phosphors based on Tb<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> (TbAG) terbium-aluminum garnet

The processes of excitation energy transfer in phosphors based on single-crystal Tb₃Al₅O₁₂:Ce (TbAG:Ce) and Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet films have been investigated. These films are considered to be promising materials for screens for X-ray images and luminescence converters of blue LED radiation. The conditions for excitation energy transfer from the matrix (Tb³⁺ cations) to Ce³⁺ and Eu³⁺ ions in TbAG:Ce and TbAG:Ce,Eu phosphors have been analyzed in detail. It is established that a cascade process of excitation energy transfer from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions and from Ce³⁺ ions to Eu³⁺ ions is implemented in TbAG:Ce,Eu via dipole-dipole interaction and through the Tb³⁺ cation sublattice.     

Synthesis and electrical properties of new perovskite-like <Emphasis Type="Italic">A</Emphasis>Mn<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript> (A = Ca,Ce, and Sm) compounds

AMn₃V₄O₁₂ (A = Ca, Ce, and Sm) compounds with a perovskite structure are synthesized at high pressures and temperatures. The crystalline structure of these compounds (space group \(Im\bar 3\)Z = 2) is determined via X-ray analysis. If ions in the A sublattice are changed in the order Ca²⁺–Sm³⁺–Ce³⁺, the valence is redistributed from Ca²⁺Mn₃²⁺V₄⁴⁺O₁₂ to Sm³⁺Mn₃²⁺V₄^3.75+O₁₂, and to Ce³⁺Mn₃²⁺V₄^3.75+O₁₂. The temperature dependences of the electrical resistivity are studied.     

Luminescent and scintillation properties of the Pr3+ doped single crystalline films of Lu3Al5−xGaxO12 garnet

The Pr³⁺ d–f luminescence was investigated in the single crystalline films (SCF) of Lu₃Al_5−xGa_xO₁₂:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B₂O₃ flux. The shape of CL spectra and decay kinetics of Pr³⁺ ions in Lu₃Al_5−xGa_xO₁₂ SCFs strongly depend on the total gallium concentration x and distribution of Ga³⁺ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu₃Al_5−xGa_xO₁₂:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 2–2.5 range.     

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.     

Growth and luminescence properties of Pr3+-doped single crystalline films of garnets and perovskites

Peculiarities of growth of single crystalline films (SCF) of Pr³⁺ doped Y₃Al₅O₁₂ and Lu₃Al₅O₁₂ garnets and YAlO₃ and LuAlO₃ perovskites by the liquid phase epitaxy method from melt-solutions based on PbO–B₂O₃ flux as well as luminescent and scintillation properties of these SCFs were studied in this work. Dependence the intensity of the Pr³⁺ d-f and f-f-luminescence on the activator concentration and influence of Pb²⁺ flux dopant on the light yield of SCFs of the mentioned garnets and perovskites were analyzed.     

Lu2SiO5:Ce and Y2SiO5:Ce single crystals and single crystalline film scintillators: Comparison of the luminescent and scintillation properties

The paper is dedicated to development of scintillators based on the single crystalline films of Ce³⁺ doped Lu₂SiO₅ (LSO:Ce) and Y₂SiO₅ (YSO:Ce) orthosilicates grown by Liquid Phase Epitaxy method onto YSO substrates from melt-solutions based on the PbO–B₂O₃ flux. We also compare the luminescent and scintillation properties of Ce doped LSO:Ce and YSO:Ce single crystalline films with those of their single crystal counterparts, grown by the Czochralski method.     

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.     

Nature of radiation resistance of LFS oxyorthosilicate crystals doped with Ce,Sc, Ca,and Y ions

Optical and luminescence characteristics of Lu_2+2ySi_1-yO_5+y (LFS) scintillation crystals are studied before and after irradiation with doses to 45 Mrad from a ⁶⁰Co source. LFS crystals were doped with Ce³⁺, Sc³⁺, Ca²⁺, and Y³⁺ ions with various concentrations. The dependence of the radiation resistance of LFS crystals on Ce ion concentration is detected. For the crystal of composition Ce:Sc:Ca:Y:LFS, it was found that its optical transmission (OT) and pulsed cathodoluminescence (PCL) spectra before irradiation do not differ from the spectra measured after irradiation with a dose of 45 Mrad within experimental error. The nature of the radiation resistance of rare-earth lutetium oxyorthosilicates (LFS) is discussed.