Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

Austauschwechselwirkungen,Intrabandschwingungen und Ti3+-Kristallfeldaufspaltung in dotiertem Al2O3

The absorption spectra of ruby with various Cr concentrations have been studied in the wavelength region between 50 μ and 1 mm at liquid helium and nitrogen temperatures. At liquid helium temperatures two strong absorptions have been found at 37.7 and 106 cm^?1 and weak absorptions at 18.8, 30.7, 33.2 and 43.0 cm^?1. These lines depend on the Cr concentration and vanish at N₂ temperatures. The two strong absorptions have also been observed in Al₂O₃ crystals doped with Ti or V. Sapphire did not show any of these absorptions. The origin of the two strong absorptions in Al₂O₃ crystals doped with Ti, V or Cr are discussed by consideration of magnetic dipole transitions of exchange coupled Cr³⁺ - pairs, the crystal field splitting of Ti³⁺ impurities and impurity — induced lattice modes. The weak absorption lines, on the other hand, may be assigned to transitions between the exchange levels of the second-nearest and fourth-nearest Cr³⁺ pairs if one makes use of the data obtained from the EPR and fluorescence spectra. For the second-nearest Cr³⁺ pairs group theory of the exchange interaction predicts transitions withΔS=2, whereas for the fourth-nearest neighbours no restriction forΔS exists.     

Luminescence of Mn ions in ordered and disordered LiAl5O8

The phosphorescence and excitation spectra of Mn ions in the ordered and disordered phases of LiAl₅O₈ have been measured. In both phases Mn²⁺ ions substitute for Al³⁺ ions in two different tetrahedral sites of the LiAl₅O₈ lattice. In both sites in the ordered phase, sharp zero-phonon transitions have been observed in the low temperature phosphorescence and excitation spectra - these transitions were considerably broadened in the disordered phase due to crystal field inhomogeneity in that phase. The deviation from neutrality caused by the Mn²⁺ ions in the ordered phase is largely compensated by Mn⁴⁺ ions occupying octahedral Al³⁺ sites. On disordering, a large proportion of Mn⁴⁺ is reduced to Mn²⁺, while the remainder takes up a site with a higher proportion of Li⁺ ions as next nearest neighbours. This leads to an increase in the ionicity of the Mn⁴⁺ site in the disordered phase and hence to a larger value of the Racah parameter B.     

Crystal field splittings and luminescence properties for Nd3+, Er3+ and Dy3+ in yttrium orthoaluminate (YAlO3)

This report contains information appropriate for a theoretical analysis of the optical spectra of triply ionized lanthanides in YAlO₃. Starting with the best-fit crystal field parameters, the crystal field splitting schemes, multiplet-to-multiplet line strengths, radiative lifetimes, branching ratios, line-to-line square matrix elements and g-factors for the triply ionized Nd, Er and Dy in YAlO₃ have been calculated. In this paper detailed discussions were made on the luminescence properties of the principal transitions of Nd-doped YAlO₃ emanating from the metastable ⁴F_{$\text{3}\text{2}$} state to Stark components of multiplets of the ground ⁴I_J term and compared to similar results of Y₃Al₅O₁₂ (YAG). The line-to-line branching ratios were calculated including J-mixing effects. In the calculations, only electric dipole transitions were considered because of odd-parity. The results predicted some interesting differences in the optical behavior of Nd³⁺ in these two host materials. It has been observed that there is a reasonable agreement between the theoretical data and those reported experimentally for YAlO₃ and YAG. The theoretical studies undertaken here were chosen to supplement or extend the optical data for these two host materials.     

Solvothermal synthesis and luminescence properties of the novel aluminum garnet phosphors for WLED applications

The color rendering index (CRI) and structural stability of cerium doped yttrium aluminum garnet (YAG:Ce) based phosphors have been enhanced by replacing Y³⁺ ions by larger radius ions (Tb³⁺, Gd³⁺, Eu³⁺, and Sm³⁺) at the dodecahedral site and replacing Al³⁺ ions by larger ones (Ga³⁺, Y³⁺, Tb³⁺, Gd³⁺, and Sm³⁺) at the octahedral site. These aluminum garnet crystalline powders were prepared by solvothermal reaction method at 300 °C for 48 h. The lattice constant values of synthetic aluminum garnet crystalline powders are larger than that of YAG and the emission wavelength of Ce³⁺ ion of these samples is longer than that of YAG:Ce. FESEM and TEM studies revealed that the Ln₃Ga₂Al₃O₁₂ and Ln₃Al₂Al₃O₁₂ crystalline powders have 3-dimensional star-like morphology with submicron size and good crystallinity, while, Ln₃(LnAl)Al₃O₁₂ garnet crystalline powders were cubic crystalline phases and shaped as cubes with the round edge having an approximate diameter of about 200–400 nm. All the prepared powders were grown along (100) direction and crystallized into single crystal. Also, the effects of treatment time and reaction temperature on the structure of aluminum garnet crystalline powders have been investigated.     

Spectroscopic properties of alexandrite crystals II

Several aspects of the optical spectroscopic properties of alexandrite crystals not previously investigated are reported here. For Cr³⁺ ions occupying the Al³⁺ lattice sites with mirror symmetry in BeAl₂O₄, the positions of the zero-phonon lines for absorption transitions to the ²T_1g and ⁴T_2g levels are identified, and vibronic transition peaks in the fluorescence spectrum are compared to transitions appearing in the Raman spectrum and Stokes excitation spectrum. In addition, the effects of radiation trapping are shown to lengthen the fluorescence lifetime of the ²E_g - ⁴A_2g transition for ions in these sites at low temperatures. For Cr³⁺ ions occupying the Al³⁺ lattice with inversion symmetry, the ground state splitting of the ²E_g - ⁴A_2g transition is reported and the decrease of the fluorescence lifetime with temperature is shown to be due to the increase in vibronic emission probability as well as increased probability of direct radiationless decay.     

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.     

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.     

Luminescent properties and energy transfer of Y3Al5O12:Ce3+, Ln3+ (Ln=Tb,Pr) prepared by polymer-assisted sol–gel method

Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and Y₃Al₅O₁₂:Ce³⁺, Tb³⁺ nano-particles have been synthesized by polymer-assisted sol–gel method. Crystal structure, luminescent properties and energy transfer of the phosphors are analyzed. XRD study of polycrystalline powders shows that all the samples are of YAG phase without impurity. Photoluminescence (PL) emission and excitation spectra illustrate that in YAG:Ce, Pr phosphors, energy transfer occurs mutually between Ce³⁺ and Pr³⁺, while in YAG:Ce, Tb systems, only one-way path energy transfer of Tb³⁺→Ce³⁺ is observed.     

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.     

Magnetic circular dichroism of transition metal ions in solids-I. MgO:Cr3+

Absorption and magnetic circular dichroism (MCD) spectra of MgO: Cr³⁺ have been studied over the temperature range 5–300 °K and with magnetic fields up to 77 kG. A theory for intensity calculation using a weak field coupling scheme is discussed. Spin-forbidden transitions to ²E and ²T₁, are observed in MCD and are interpreted as magnetic dipole zero-phonon lines. The spin allowed bands ⁴T₂ and ⁴T₁ are found to be vibration-induced electric dipole transitions in which the t_1u lattice modes are the dominant contributors to the intensity.     

Scintillation properties of Er-doped Y3Al5O12 single crystals

Er-doped Y₃Al₅O₁₂ single crystals with different Er concentrations of 0.1, 1.0, 10, 30, and 50% were grown by the micro-pulling down method. There were several absorption lines due to the Er³⁺ 4f-4f transitions in the transmittance spectra and these lines correspond to the transitions from the ground state of ⁴I_15/2 to the excited states. The photo- and radio-luminescence spectra showed Er³⁺ 4f-4f emissions. Relative light yield under 5.5 MeV alpha-ray irradiation of Er 0.1%:Y₃Al₅O₁₂ was estimated to be 63% of that of Bi₄Ge₃O₁₂.     

Role of Al2O3 in upconversion and NIR emission in Tm and Er codoped calcium fluoro phosphorous silicate glass system

In this study, the principal role of Al₂O₃ on the features of the photoluminescence spectra of Tm³⁺ ion and upconversion phenomenon in Tm³⁺ and Er³⁺ codoped CaF₂−Al₂O₃−P₂O₅−SiO₂ glass system has been investigated. The concentration of Al₂O₃ is varied from 2 to 10 mol% while that of Er³⁺ and Tm³⁺ is fixed. IR and Raman spectral studies have indicated that there is a gradual increase in the degree of disorder in the glass network with increase in the concentration of Al₂O₃ up to 6.0 mol%. This is attributed to the presence of Al³⁺ ions in octahedral positions in larger proportions. When the glasses are doped with Tm³⁺ ions, the blue and red emissions were observed, whereas in Er³⁺ doped glasses blue, green and red emissions were observed. When the glasses are codoped with Tm³⁺ and Er³⁺ ions and excited at 790 nm, all the three emission lines were observed to be reinforced, especially in the glasses mixed with 6.0 mol% of Al₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄→³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to codoping. The reasons for enhancement in the intensity of various emission bands due to codoping have been identified and discussed with the help of rate equations for various emission transitions.     

Energy response of the TL detectors based on YAlO3:Mn crystals

This study demonstrates the energy response of thermoluminescent (TL) detectors based on YAlO₃:Mn crystals. Experimental results of the relative sensitivity of YAlO₃:Mn²⁺ detectors to various kinds of photon radiation (from ⁶⁰Со, ¹³¹Cs, ¹⁹²Ir, and ¹³⁷Cs isotopes; X-ray from 220 kVp; and photon radiation from a linear accelerator (LINAC) at 5, 10, and 15 MV) agree with the theoretical energy response from Monte Carlo simulation. In addition to YAlO₃ (YAP), energy response was calculated for other yttrium-containing oxides such as Y₂O₃, Y₃Al₅O₁₂ (YAG), and Y₄Al₂O₉ (YAM). A possibility of filtering (modification) of the energy response of high atomic number (Z) materials by the metallic filters was shown.     

Photoluminescence in MgxSr1−xAl2O4:Eu, Ndand electron-vibrational interaction in the Eu 5d states

Green phosphor compositions Mg_xSr_1−xAl₂O₄:Eu, Nd (with x=0.05-0.25) were prepared by solid state reaction method. The effect of Mg substitution on photoluminescence characteristics was investigated. The photoluminescence show intense green emission for MgSrAl₂O₄:Eu²⁺, Nd³⁺ with long persistence. This green emission corresponds to transitions from 4f⁶5d¹ to 4f⁷ of Eu²⁺ ion. Comparative analysis of the excitation and emission spectra were used to evaluate the crystal field splitting of the 5d states of Eu²⁺ and the parameters of electron-vibrational interaction, such as Huang-Rhys factor, effective phonon energy, and zero-phonon line position.     

Luminescence of impurity 3d and 4f metal ions in different crystalline forms of Al2O3

The ² E-⁴ A ₂ luminescence spectra of Cr³⁺ ions in Al₂O₃ are investigated in the course of transitions between the structural forms γ-δ-θ-α. The spectral lines observed are assigned to Cr³⁺ ions in these structural forms, which are identified by an X-ray powder diffraction analysis. The lifetimes of the Cr³⁺ excited states in transient forms of Al₂O₃ are measured. Investigations of the luminescence spectra of Al₂O₃: Eu³⁺ demonstrate that the Eu³⁺ ions can form regular centers only in α-Al₂O₃ and, unlike the Cr³⁺ ions, give no rise to similar centers in moderately ordered θ-Al₂O₃.     

Intensities of f-f transitions in Pr3+ and Dy3+ in glasses in the near-IR spectral range

The absorption spectra of Pr³⁺ and Dy³⁺ ions in three glass matrices (SiO₂-P₂O₅-GeO₂, Al₂O₃-B₂O₃-SiO₂, and LiB₃O₅) are thoroughly studied in the near-IR spectral range (4600–14 300 cm^?1). The temperature dependences of the intensity, the width, and the location of the absorption bands observed are investigated for the first time. It is shown that the f-f transitions in the studied glasses are allowed by static odd distortions in the environment of the rare-earth ions and these distortions decrease with an increase in temperature. A comparative analysis of the absorption band parameters and their temperature behavior in different materials makes it possible to determine the differences in magnitudes, symmetries, and dispersions of the distortions in the nearest environment of rare-earth ions in different glasses.     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al₂O₃透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱，发现在Al₂O₃六配位的八面体结构中，Cr⁴⁺的荧光发射也处在1100—1600nm波段的红外区间，荧光发射峰位于1223nm附近，类似Cr⁴⁺在四面体中的发光行为.同时由于氧化铝晶格常数较小，晶体场强较强，使Cr⁴⁺:Al₂O_{3< 关键词： 4+')" href="#">Cr⁴⁺ 2}O₃透明陶瓷')" href="#">Cr:Al₂O₃透明陶瓷 光谱性质 八面体     

Cr3+ doped Al2O3 nanoparticles: Effect of Cr3+ content in intensifying red emission

Cr³⁺-doped α-Al₂O₃ nanoparticles (Al_2−xCr_xO₃, 0.005 ≤ x ≤ 0.05) were synthesized by co-precipitation method. X-ray diffraction (XRD) patterns of Cr³⁺:Al₂O₃ nanoparticles revealed the crystallite size of ∼53 nm and electron microscopy (SEM & TEM) confirmed the spherical nanoparticle formation. Diffuse reflectance spectra (DRS) displayed peaks at 406 and 558 nm corresponding to the Cr³⁺ transitions which became prominent with the increase in Cr³⁺ concentration which was also evidenced by the gradually increasing pink coloration of the samples. Photoluminescence (PL) studies showed the sharp red emission at 694 nm (ruby line) which was observed for all samples. The Dq/B value for all samples was found to be greater than 2.3 confirming the presence of Cr³⁺ ions in the octahedral sites. Chromaticity diagrams displayed the maximum red appearance for the sample with x = 0.01 and a lifetime of 4 ms. The synthesized Cr³⁺:Al₂O₃ nanoparticles with smaller crystallite sizes and narrow near monochromatic emission can be used in various applications including sensing, lasing, and bioimaging applications.