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.     

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.     

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.     

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.     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000     

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.     

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.     

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.     

Gd3Ga5O12:Ag薄膜电致发光材料的制备及其发光性质

研究了Gd₃Ga₅O₁₂:Ag材料的制备及其发光性质.Gd₃Ga₅O₁₂:Ag材料通过固相反应法制得,采用X射线衍射法分 析了材料的结晶度及成分.用电子束蒸发将该材料制备成交流的薄膜电致发光器件,得到了 较好的蓝紫色发光,发光峰分别位于397和467nm.通过对材料的光致发光和激发光谱的研究 和比较,得出397和467nm分别来自于氧空位和Ag⁺的发光.     

Spectroscopic analysis of Cr,Er:Gd3Ga5O12 crystals as candidates of potential xenon lamp pumped ~ 2.7 μm laser

A series of Cr,Er:Gd₃Ga₅O₁₂ crystals with high concentrations of Er^3 + were grown by Czochralski method. The absorption spectra, the up-conversion, near infrared (NIR) and mid-infrared (Mid-IR) luminescence spectra as well as the luminescence decay curves of Er: ⁴I_13/2 and ⁴I_11/2 levels were measured at room temperature. The spectroscopic properties of Cr,Er:Gd₃Ga₅O₁₂ crystals and Cr–Er energy transfer processes were investigated. The spectroscopy of the Er^3 +:⁴I_11/2 → ⁴I_13/2 transition was centralized to discuss, and the important optical parameters including luminescence lifetimes and the Cr–Er energy transfer efficiency are presented. Based on the comprehensive spectral analyses, 0.6 at.%Cr/50 at.%Er:GGG crystal is preferred as candidate of potential xenon lamp pumped ~ 2.7 μm laser in this work.     

Disorder and the shape of the R-lines in Cr3+-doped garnets

This paper describes measurements of the R-line emission from Cr³⁺ ions in Y₃Ga₅O₁₂, Gd₃Sc₂Ga₃O₁₂, and Gd₃Sc₂Al₃O₁₂. Discrete splittings of the lines are interpreted as due to disorder on the cation sublattices. Assuming statistical distributions of the cations on the different cation sublattices enables estimates to be made of the degree of non-stoichiometry in the crystals.     

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.     

Energy levels fitting and crystal-field calculations of Nd3+ doped in GYSGG crystal

The single crystal Nd³⁺-doped in GdY₂Sc₂Ga₃O₁₂ (Nd³⁺:GYSGG) was grown by Czochralski method successfully, and its absorption spectra was analyzed in a wider spectral wavelength range at 7.6 K and 300 K, respectively. The free-ions and crystal-field parameters were fitted to the experimental energy levels at 7.6 K and 300 K with the root mean square deviation of 11.25 and 12.48 cm^?1, respectively. According to the crystal-field calculations, 116 levels of Nd³⁺ at 7.6 K and 114 levels of Nd³⁺ at 300 K were assigned. The fitting results of free-ions and crystal-field parameters were compared with those already reported of Nd³⁺:GSGG and Nd³⁺:YSAG. The results indicated that the free-ions parameters are similar to those of the Nd³⁺ in GYSGG, GSGG and YSAG crystals, and the crystal-field interaction of GSGG and YSAG is stronger than that of GYSGG, which results in the dual-wavelength properties of Nd³⁺:GYSGG crystal.     

The effect of relative plasma plume delay on the properties of complex oxide films grown by multi-laser, multi-target combinatorial pulsed laser deposition

We report the effects of relative time delay of plasma plumes on thin garnet crystal films fabricated by dual-beam, combinatorial pulsed laser deposition. Relative plume delay was found to affect both the lattice constant and elemental composition of mixed Gd₃Ga₅O₁₂ (GGG) and Gd₃Sc₂Ga₃O₁₂ (GSGG) films. Further analysis of the plasmas was undertaken using a Langmuir probe, which revealed that for relative plume delays shorter than 200 μs, the second plume travels through a partial vacuum created by the first plume, leading to higher energy ion bombardment of the growing film. The resulting in-plane stresses are consistent with the transition to a higher value of lattice constant normal to the film plane that was observed around this delay value. At delays shorter than 10 μs, plume propagation was found to overlap, leading to scattering of lighter ions from the plume and a change in stoichiometry of the resultant films.     

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).     

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.     

Cr,Mg:GSGG 晶体生长、光谱性能及Cr4+形成机理的研究

采用传统提拉法单晶生长技术成功生长出了Cr,Mg:GSGG晶体, 并对生长出的晶体样品进行了氧化气氛和还原气氛退火处理. 通过对比分析退火处理前后样品吸收光谱的变化, 推断出晶体中四面体配位Cr⁴⁺离子的形成机理为: 晶体生长和高温氧化气氛退火的过程中, 四价Cr⁴⁺离子首先在八面体格位上形成, 然后在热激发作用下与邻近四面体格位上的Ga³⁺离子发生置换反应, 从而形成一定浓度的四面体配位Cr⁴⁺离子. 实验结果还表明, 随着电荷补偿离子Mg²⁺离子浓度的增大, 更有利于提高四面体配位Cr⁴⁺离子的浓度.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.