A phototropic center and distribution of the chromium impurity in rare-earth garnet crystals

Crystals of two types, namely, Gd₃Sc₂Al₃O₁₂ doped by Ca²⁺ and Cr³⁺ ions and Gd₃Sc₂Ga₃O₁₂ doped by Nd³⁺ and Cr³⁺, are studied using x-ray diffraction. In order to elucidate how an impurity is embedded in the lattice, its effect on the electron density distribution and microstrains of the crystal lattice is investigated. It is shown that chromium ions can occupy the lattice sites located predominantly in the octahedral environment of the oxygen ligands.     

Multisites Cr3+ in GGG and GSGG garnets

The emission and excitation spectra of Cr³⁺ -doped Gd₃Ga₅O₁₂ (GGG) and Gd₃Sc₂Ga₃O₁₂ (GSGG) are explained in the light of multisite effects. The situation is particularly complicated in the case of GSGG, where the different sites have²E energy levels near each other which overlap with the⁴A₂ →⁴T₂ absorption bands. The spectra obtained under selective excitations are interpreted on the multisite assumption.     

Multisites Cr3+ in GGG and GSGG garnets

The emission and excitation spectra of Cr³⁺ -doped Gd₃Ga₅O₁₂ (GGG) and Gd₃Sc₂Ga₃O₁₂ (GSGG) are explained in the light of multisite effects. The situation is particularly complicated in the case of GSGG, where the different sites have²E energy levels near each other which overlap with the⁴A₂ ⁴T₂ absorption bands. The spectra obtained under selective excitations are interpreted on the multisite assumption.     

Temperature dependence of the lifetime of Cr3+ luminescence in garnet crystals

The coexistence of sharp R-lines from the ² E state and the broad band from the ⁴ T ₂ state in the photoluminescence spectra of Cr³⁺:Gd₃Sc₂Ga₃O₁₂ (GSGG) and Cr³⁺:Y₃Ga₅O₁₂ (YGG) is observed at low temperature (10K). The decay lifetimes of the broad emission bands of Cr³⁺ in GSGG and YGG are very close to those of the R-lines being, respectively, 0.23 ms and 2.5 ms. These results are explained in terms of the extent of the mixing of the ⁴ T ₂ vibronic wavefunction with that of the ² E lowest excited state by tunnelling.     

Nonlinear optical properties of Cr<Superscript>3+</Superscript>-doped laser crystals

The nonlinear optical properties in six Cr³⁺-doped laser crystals LiCaAlF₆, LiSrGaAlF₆, Gd₃Ga₅O₁₂, Gd₃Sc₂Ga₃O₁₂, LaMgAl₁₁O₁₉ and Alexandrite are investigated with the help of the Z-Scan technique at λ = 532 nm in the CW regime. The data reported here include particularly the excited state absorption cross section and the third-order nonlinear susceptibilities. It is found that the three first systems only exhibit both refractive and absorptive nonlinear effects, whereas the three others have only absorptive effects. Gd₃Ga₅O₁₂ shows the best nonlinear potentialities. The excited state absorption cross section corresponding mainly to the ⁴T₂ →   ⁴T₁ transition is found to be ranging between 8.9 × 10⁻²² cm² in LiSGaF and 3.1 × 10⁻²⁰ cm² in LaMgAl₁₁O₁₉. The calculated ratio of the third order nonlinear susceptibility to the ground state absorption coefficient is found to be largest in GGG with a value of 146 × 10⁻⁶ esu.cm and smallest in Alexandrite (0.6 × 10⁻⁶ esu.cm).     

Gamma-ray irradiation effect on the absorption and luminescence spectra of Nd:GGG and Nd:GSGG laser crystals

Laser crystals Nd³⁺:Gd₃Ga₅O₁₂ (Nd:GGG) and Nd³⁺:Gd₃Sc₂Ga₃O₁₂ (Nd:GSGG) were grown by Czochralski method. The influence of gamma-ray irradiation on their absorption and luminescence spectra has been investigated. Two additional absorption (AA) bands induced by gamma-ray irradiation appear in the spectra of Nd:GGG crystal while only a very weak AA band appears for the Nd:GSGG crystal. This indicated that Nd:GSGG crystal has stronger ability to resist the color center formation by irradiation. The intensity of the excitation and emission spectra of Nd:GGG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, a luminescence strengthening effect was observed in Nd:GSGG crystal after exposure to the same irradiation dose. The results showed that the Nd:GSGG crystal is a promising candidate used under radiation environments such as in outer space.     

Timing characteristics of the scintillation response of Gd3Al2Ga3O12:Ce and Gd3Al2.6Ga2.4O12:Ce single crystal scintillators

The timing characteristics of scintillation response of Czochralski-grown Gd₃Al₂Ga₃O₁₂:Ce and Gd₃Al_2.6Ga_2.4O₁₂:Ce single crystals were compared. The photoelectron yield, scintillation decay times, and coincidence time resolution were measured. At 662 keV γ-rays, the photoelectron yield of 6200 phe MeV⁻¹ obtained for Gd₃Al₂Ga₃O₁₂:Ce is higher than that of 4970 phe MeV⁻¹ obtained for Gd₃Al_2.6Ga_2.4O₁₂:Ce, while an inferior energy resolution of the former (7.2% vs. 5.6%) is observed. Scintillation decays are approximated by sum of exponentials with the dominant fast component decay time and its relative intensity of 89 ns (73%) for Gd₃Al₂Ga₃O₁₂:Ce and 136 ns (69%) for Gd₃Al_2.6Ga_2.4O₁₂:Ce. The coincidence time resolution obtained for Gd₃Al₂Ga₃O₁₂:Ce is superior than that of Gd₃Al_2.6Ga_2.4O₁₂:Ce. The normalized time resolution was also discussed in terms of a number of photoelectrons and decay characteristics of the light pulse.     

Intensities of hypersensitive transitions in garnet crystals doped with Er<Superscript>3+</Superscript> ions

We examine the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of yttrium-aluminum, scandium-containing, and gallium garnet crystals doped with Er³⁺ ions. A comparative analysis of the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of garnets with different contents of Al³⁺ and Sc³⁺ ions (Gd_2.4Er_0.5Sc_1.8Al_3.3O₁₂, Gd_2.4Er_0.5Sc_1.9Al_3.2O₁₂, Gd_2.4Er_0.5Sc_2.0Al_3.1O₁₂) is performed, as a result of which the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of these crystals are shown to have close values. We find that Ca₃(NbGa)₅O₁₂ crystals doped with Er³⁺ ions are characterized by highest values of the oscillator strengths for hypersensitive transitions and of the intensity parameter Ω₂ of Er³⁺ ions compared to the values of these quantities in the examined garnet crystals, which is determined by the fact that the symmetry of the local environment of Er³⁺ ions in these crystals is C ₁, C ₂, or C _2ν. We reveal that, as the concentration of Er³⁺ ions in these crystals increases from 1 to 39 at %, both the oscillator strength of the hypersensitive transition ⁴ I _15/2 → ² H _11/2 of Er³⁺ ions and their intensity parameter Ω₂ tend to decrease, which can be related to an increase in the relative fraction of Er³⁺ ions with higher symmetry of the local environment.     

Optical absorption by Nd<Superscript>3+</Superscript> and Gd<Superscript>3+</Superscript> ions in epitaxial films grown on Gd<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> substrates from a lead-containing solution melt

Epitaxial films of composition (Gd,Nd)₃Ga₅O₁₂ or (Gd,Y,Nd)₃Ga₅O₁₂ with a neodymium content varying from 0.3 to 15 at. % are grown by liquid-phase epitaxy from a supercooled PbO-B₂O₃-based solution melt on Gd₃Ga₅O₁₂(111) substrates. The optical absorption spectra of the epitaxial films grown are measured in the wavelength range 0.2–1.0 µm. The results of interpreting the absorption bands observed in the spectra are used to construct the energy level diagrams of Nd³⁺ and Gd³⁺ ions in the matrices of the epitaxial films.     

Morin transition in annealed iron implanted garnets

Y₃Fe₅O₁₂, Y₃Al₅O₁₂ and Gd₃Ga₅O₁₂ single crystal granets were implanted with 10¹⁷iron.cm⁻². Complementary techniques: CEMS, TEM and XRD at glancing angles have allowed to follow the behavior of implanted iron during thermal annealings. For Y₃Fe₅O₁₂ large α-Fe₂O₃ particles are formed after annealings and at 1200°C occurs a low temperature regime of the Morin transition at room temperature. For Y₃Al₅O₁₂, due to aluminium substitution in the precipitates, the Morin transition is only detected after an annealing at 1300°C whereas in Gd₃Ga₅O₁₂ no Morin transition is observed.     

Phase-matched second-harmonic generation at 440 nm in a LiNbO3 -Gd3Ga5O12 waveguide with a tunable stimulated Raman source

Using a tunable stimulated Raman source, we have observed second-harmonic generation in the blue in a sputtered LiNbO₃ film deposited on Gd₃Ga₅O₁₂. With the choice of Gd₃Ga₅O₁₂ as a substrate, it becomes possible to both phase-match a large range of fundamental wavelengths as well as have an excellent epitaxial quality surface. The SHG efficiency for the TM^ω₀ → TM^2ω₂ phase matched conversion process is estimated to be ～ 10^-4.     

Theoretical explanation of optical absorption spectra and covalent effect of Ni2+ ions in octahedral sites of Ca3Sc2Ge3O12 crystal

The optical absorption spectra (d-d transition bands) and covalent effect of Ni²⁺ ions in octahedral sites of Ca₃Sc₂Ge₃O₁₂ crystal have been investigated by the full energy matrix based on the two spin–orbit coupling parameters model. The bond length of octahedral site is R_i?=?2.19 Å, which can be determined by the cubic crystal-field parameter and optical spectral data. The lattice distortion of the Ni²⁺ center in Ca₃Sc₂Ge₃O₁₂ crystal is also obtained from the calculations. In addition, the result has shown that the covalent effect of Ni²⁺ ion in the octahedral site of Ga₃Sc₂Ge₃O₁₂ is obvious and cannot be ignored. The calculated d-d transition bands agree well with that of the experimental findings, suggesting that the present methods can explain reasonably the optical spectral data and covalent effect of 3d⁸ ions in octahedral lattices.     

Sc2－xGaxW3O12体系负热膨胀性能研究

通过固相反应法,在1100 ℃下成功制备出了系列Ga掺杂Sc_2-xGa_xW₃O₁₂（x=0, 0.05, 0.1, 0.2, 0.3, 0.5, 0.8）固溶体.X射线粉末衍射结构精修表明,Ga以替代Sc的形式成功进入Sc_2-xGa_xW₃O₁₂晶格,但不能获得端元组分Ga₂W₃关键词： 负热膨胀 热膨胀系数 Rietveld结构精修     

Axial parameter D of octahedral S-state ions in garnets

The values of the spin-hamiltonian parameters are reported for systems Fe³⁺:Ca₃Sc₂Ge₃O₁₂, Fe³⁺:Na₃Sc₂V₃O₁₂ and Mn²⁺:Na₃Sc₂V₃O₁₂. The values of the axial parameterD together with the values ofD compiled from literature are used in the discussion of the origin ofD. A close correlation ofD with the trigonal deformation of the octahedron of S-state ion indicates the importance of the covalency effects. On the other hand, it is shown thatD can be hardly understood on the basis of the relativistic model only.We are indebted to Dr. B. V.Mill of Moscow State University (USSR) for supplying the single crystals of Na₃Sc₂V₃O₁₂ and Ca₃Sc₂Ge₃O₁₂ garnets.     

Phase stability and elasticity of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> at high pressure

An investigation into the high-pressure behavior of Sc₂O₃ was conducted using first-principle calculations based on density functional theory within the generalized gradient approximation. Nine candidate phases were considered and simulated, C-, B-, A-RES, Rh₂O₃(II), Gd₂S₃, U₂S₃, Al₂Er₃, corundum and PPv respectively. Our results demonstrate phase transitions of Sc₂O₃ from C- to B-RES phase at 15 GPa, then to Gd₂S₃ phase at 18 GPa. Elastic constants of Sc₂O₃ present softening from about 270 GPa to 337 GPa, associated with a semiconductor-to-metal crossover. The Gd₂S₃-type Sc₂O₃ is both mechanically and dynamical stable at least up to 302 GPa supported by the mechanically stable criteria and the phonon spectrum.     

Epitaxial films (Bi,Gd)3(Ga,Pt)2Ga3O12 grown by liquid-phase epitaxy

Single-crystal films of complex composition (Bi,Gd)₃(Ga,Pt)₂Ga₃O₁₂ on Gd₃Ga₅O₁₂(111) substrates are synthesized by liquid-phase epitaxy from a supercooled solution-melt based on Bi₂O₃-B₂O₃ flux. Optical absorption of Bi³⁺ and Pt³⁺ ions in these films is investigated in the wavelength range from 200 to 860 nm.     

Liquid-phase epitaxy and optical absorption of gadolinium-gallium garnet films grown from a PbO-B2O3 solution melt on Gd3Ga5O12 substrates

The optical absorption due to impurity ions was studied in gadolinium-gallium garnet single crystal films with a stoichiometric composition Gd₃Ga₅O₁₂ grown by liquid-phase epitaxy from a supercooled PbO-B₂O₃ solution melt on (111)-oriented Gd₃Ga₅O₁₂ substrates.     

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.     

GSAG and YSAG: a study on isomorphism and crystal growth

The composition of gadolinium-scandium-aluminium (GSAG) and yttrium-scandium-aluminium (YSAG) garnet crystals grown by the Czochralski method and by floating zone melting was analysed. It is shown that Sc³⁺ and Al³⁺ ions in GSAG and Y³⁺, Sc³⁺ and Al³⁺ ions in YSAG can simultaneously occupy two types of sites in the lattice. The congruent melting composition of GSAG is {Gd_2.88Sc_0.12} [Sc_1.77Al_0.23] (Al₃)O₁₂. The homogeneity range of GSAG is rather narrow. In the Y₂O₃-Sc₂O₃-Al₂O₃ system a wide range of garnet-structured solid solutions exist. However, there is no ternary garnet that melts congruently. Distribution coefficients of components in YSAG are slightly varied from unity in the whole concentration range, and as the melt composition approaches YAG they tend to unity. Cr³⁺ and Nd³⁺ distribution coefficients in GSAG and YSAG are presented.

     

Electrical transport properties of gadolinium scandium gallium garnet

Electrical conductivity and thermoelectric power are measured on a single crystal of Gd_3.0Sc_1.8Ga_3.2O₁₂ (GSGG) between 1273 and 1673 K. The measurements are made both in air and in controlled atmospheres, and P_O2 varies from 10^?1.68 to 10^?5.6 MPa. The data indicate GSGG may well be a mixed conductor in this temperature and P_O2 range, with n-type electronic conductivity and ionic transport on the oxygen sublattice. Changes in temperature induce long-lived disequilibrium in electrical conductivity of GSGG (over 30 h at T < 1373 K) that can be explained by temperature dependent cation redistribution. The effective activation energy for equilibrium electrical conductivity is E_a = 2.40 ± 0.05 eV, as opposed to values of E_a between 1.8 and 2.2 eV during actual temperature changes. An additional contribution in the equilibrium E_a, due to thermally activated cation redistribution, can account for the higher value seen.