Refractive indices of laser nanocrystalline ceramics based on Y3Al5O12

Refractive indices of the nanocrystalline Y₃Al₅O₁₂ ceramic and a garnet single crystal of the same composition have been measured. In the visible and near IR range (0.4–1.064 μm), the prism method was used; in the medium IR range (2–6.2 μm), the interference method with the use of thin plates was applied. The refractive indices of these crystalline materials are practically the same over the entire spectral range studied and are described by the approximate formula proposed earlier for a single crystal. The parameters of the continuos-wave lasing in the nanocrystalline Y₃Al₅O₁₂ ceramic doped with Nd³⁺ and Yb³⁺ ions measured recently are presented.     

New data on the physical properties of Y3Al5O12-based nanocrystalline laser ceramics

Microhardness and fracture toughness of highly transparent Y₃Al₅O₁₂-and Y₃Al₅O₁₂: Nd³⁺-based nanocrystalline ceramics are measured for the first time. For the Y₃Al₅O₁₂: Nd³⁺ laser ceramics, the use of a longitudinal scheme with a diode-laser pumping at a wavelength of 1.3186 mm (⁴ F _3/2 → ⁴ I _13/2 channel) enabled one to attain an output power of continuous-wave lasing of ～3.7 W with 35% efficiency.     

Nd3+:Y3Al5O12 laser ceramics: Influence of the size of yttrium oxide particles on sintering

The influence of the size of Y₂O₃ powder particles on the structure formation and densification of Nd³⁺:Y₃Al₅O₁₂ laser ceramics has been studied. It is shown that the use of 50- and 100-nm yttrium oxide particles makes it possible to synthesize single-phase yttrium aluminum garnet at temperatures of 1200 and 1500°C, respectively, whereas in the case of 5000-nm yttrium oxide particles 2-h exposure at a temperature of 1500°C yields only 80 wt % of the Nd³⁺:Y₃Al₅O₁₂ phase. Bulk swelling of pressed samples during sintering of 2.94Y₂O₃-0.06Nd₂O₃-5Al₂O₃ powders with the size ratio of the initial particles R(Al₂O₃/Y₂O₃) ～ 5 is observed. The application of different-sized powders (R ～ 2.5) provides quantitative ratios between phases in the 3Y₂O₃-5Al₂O₃ system at which shrinkage in a temperature range of 20–1500°C is dominant. Laser ceramics 0–2 at % Nd³⁺:Y₃Al₅O₁₂ have been obtained by the solid-phase sintering of oxide powders (R ～ 2.5). The slope efficiency for 1 at % Nd³⁺:Y₃Al₅O₁₂ laser ceramics is found to be 33%.

     

Microhardness and fracture toughness of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>-based nanocrystalline laser ceramics

The microhardness and fracture toughness of laser nanocrystalline ceramics based on the cubic oxides Y₂O₃ and Y₃Al₅O₁₂ are determined experimentally. It is shown by comparative measurements that the fracture toughness and microhardness of Y₂O₃ ceramics exceed the corresponding parameters of Y₂O₃ single crystals by factors of 2.5 and 1.3, respectively. The fine morphology of grains and grain boundaries in fractures is investigated. It is ascertained that changes in the mechanical properties of the nanocrystalline ceramics under study are related to both the sizes and structure of grains and the structure of grain boundaries. It is suggested that twinning processes determine the mechanisms of formation of nanocrystalline ceramics.     

Fabrication of Cr4+,Nd3+:YAG transparent ceramics for self-Q-switched laser

Transparent 0.1 at.%Cr,1.0 at.%Nd:YAG (Y₃Al₅O₁₂) ceramics were fabricated by a solid-state reaction and vacuum sintering with CaO as a charge compensator and tetraethyl orthosilicate (TEOS) as a sintering aid using high-purity powders of Al₂O₃, Y₂O₃, Nd₂O₃ and Cr₂O₃. The mixed powder compacts were sintered at 1800 °C for 5 h and 30 h under vacuum. The optical transmittance of the Cr,Nd:YAG ceramics sintered at 1800 °C for 5 h and 30 h is ∼63% and ∼78% in the infrared wavelengths, respectively. The two samples exhibit pore-free structures and the average grain size is about 10 and 20 μm. For the sample sintered at 1800 °C for 5 h, the dominant fracture mechanism is the transgranular fracture. With increase of holding time up to 30 h, the ratio of intergranular fracture surfaces increase and more Cr³⁺ ions in the Cr,Nd:YAG ceramic transform to Cr⁴⁺. High-quality Cr⁴⁺,Nd³⁺:YAG transparent ceramics may be a potential self-Q-switched laser material.     

Luminescence properties of Y3Al5O12:Eu3+-coated submicron SiO2 particles

Silica submicron spherical particles coated with an yttrium aluminum garnet (Y₃Al₅O₁₂, YAG) layer doped with Eu³⁺ were prepared by the sol–gel method. The structure and morphology of samples determined by the X-ray powder diffraction measurements and transmission electron microscope images, respectively, indicated that well-crystallized garnet nanocrystallites were formed with successive coating cycles. Similar trends were deduced from the evolution of the luminescence spectra. The ratio of integrated intensities of the ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁ transitions was used to analyze the structural variations in the surroundings of the Eu³⁺ ion. The effect of coating was analyzed by comparing the luminescence properties of the Y₃Al₅O₁₂:Eu³⁺ nanocrystalline powders and composite Y₃Al₅O₁₂:Eu³⁺/SiO₂ materials.     

Spectroscopy of Rare-Earth Elements in Single-Crystal Films of Yttrium-Aluminium Garnets (YAG)

The utilization of liquid-phase epitaxy for growing thin yttrium-aluminium garnet films is discussed. By transfer method from lead solvents films were obtained with a composition Y₃Al₅O₁₂: Nd³⁺ on substrates with composition Y₃Al₅O₁₂, and films Y₃Al₅O₁₂: Er³⁺, Y₃Al₅O₁₂: Er³⁺, Ga³⁺ (about 40 wt% of erbium) on substrates Y₃Al₅O₁₂: Nd³⁺ Characteristics are given for simultaneous induced emission generation of the system film-substrate at 77 K Er³⁺ ion (λ_gen = 1.6602 μ) being a component of the film, and Nd³⁺ ion, being a component of the substrate (λ_gen = 1.061 μm). The results obtained are discussed.     

Effects of yttrium codoping on fluorescence lifetimes of Er3+ ions in SiO2–Al2O3 sol–gel glasses

In order to find a new glass host and optimize erbium doping for IR glass optical amplifiers in photonic applications, a study on the optimization of the emission of erbium ions in the SiO₂–Al₂O₃ glass by codoping with Y₂O₃ is performed. It is first attempted to make a new sol–gel glass host based on SiO₂, Al₂O₃, and Y₂O₃ doped with Er³⁺ ions of the composition (1−x)SiO₂–xAl₂O₃–yY₂O₃:0.65Er₂O₃ (in mol%), x varies from 0 to 65, and y from 0 to 4. The optimal proportion in mol% of SiO₂ and Al₂O₃ for the Er³⁺ emission (at a fixed optimal concentration of 0.65) was 65 – 35. The effect of Y₂O₃ content on photoluminescence, decay curve profiles and lifetime of the ⁴I_13/2 level of Er³⁺ in SiO₂–Al₂O₃ glass is observed. The largest quantum efficiency and the higher emission intensity are observed in the sample with 65Al₂O₃ and 4Y₂O₃. The emission intensity at 1530 nm is two times higher than in glasses without Y₂O₃. A shift of 3 nm to shorter wavelengths is observed. The emission spectral profiles are flatter and broader for the glasses containing Al and Y (bandwidth of 59.5 nm). The decay curves show strong difference profiles for the different samples. The increase of the lifetime value τ (about ms) of the ⁴I_13/2 level of Er³⁺ in the SiO₂–Al₂O₃ with the Y₂O₃ is discussed.     

Effect of annealing and gamma irradiation on undoped and Eu3+-doped Y2SiO5 single crystals

The absorption spectra of the undoped Y₂SiO₅ and Eu³⁺-doped Y₂SiO₅ crystals grown by the Czochralski technique were compared before and after annealing and, similarly, the unannealed and annealed crystals after γ-ray irradiation. The absorption bands of Eu²⁺ ions with peaks at 300 and 390 nm were observed in the as-grown Y₂SiO₅:Eu³⁺ crystal. These peaks were more intense in H₂-annealed and irradiated Y₂SiO₅:Eu³⁺ crystals. The additional absorption peaks at 260 and 320-330 nm which were attributed to F color centers and O⁻ hole centers were observed in irradiated undoped Y₂SiO₅ and Y₂SiO₅:Eu³⁺ crystals, respectively.     

The luminescence of Pr3+ ions doped in Y4Al2O9 by sol–gel synthesis

The Pr³⁺-doped Y₄Al₂O₉ powders were synthesized by sol–gel method. Powder X-ray diffraction and SEM techniques were used to check for Y₄Al₂O₉ powders. The Li⁺ co-doping with Pr³⁺ has an influence on the sintering temperature and morphology of the Y₄Al₂O₉ powders produced from the gel. The emission spectra under different excitations, e.g., the 488 nm line of an argon-ion laser, X-ray and UV light, were investigated. The luminescence intensity of Y₄Al₂O₉:Pr³⁺ could be increased with Li⁺ co-doping. Luminescence properties of Pr³⁺ ions in the two samples have some difference. In the Y₄Al₂O₉:Pr³⁺, the emission at 490 nm from ³P₀ is dominant, while, the Y₄Al₂O₉:(Pr³⁺ + Li⁺) system was characterized by a red emission at 607 and 610 nm corresponding to the ¹D₂ → ³H₄ inner transition of Pr³⁺ ions; and these two emissions show different excitation band from the 4f5d state.     

Colour centre in YAG: Cr3+ crystals

YAG crystals doped with 0.01 wt% Cr were grown by Czochralski method using 98% Ar + 2% H₂ protective atmosphere. Four colour varieties of the crystals were prepared in the dependence of the Al₂O₃ :Y₂O₃ ratio in the melt and the sign of electrical potential above the melt level. New absorption bands were attributed to the O⁻ centre (400 to 480 nm), F centre (357, 500, and 833 nm) or Cr³⁺ at another site than octahedral (455, and 612 nm).     

Growth and properties of Lu3Al5O12-RE3+ single crystals

Optically transparent garnet single crystals were grown from Lu₃Al₅O₁₂ melts containing different RE³⁺ ions. The distribution coefficient of Nd³⁺ ions is found to be a function of the growth rate. Lu₂O₃–Al₂O₃ system studies have been partially carried out. Measurements of the lattice data, absorption spectra and comparison with some properties of Y₃Al₅O₁₂ single crystals have also been made.     

Gd3Ga5O12:Nd3+ crystals for a continuous-wave diode-pumped laser operating in 4F3/2 → 4I11/2 and 4F3/2 → 4I13/2 channels

Garnet crystals of the composition Gd₃Ga₅O₁₂:Nd³⁺ (concentration series C_Nd = 1–10 at. %) were grown from flux. In terms of spectroscopy, these crystals, unlike those grown from melts, form medium with a single activator center. For the first time, continuous-wave lasing was excited by diode pumping with the use of Gd₃Ga₅O₁₂:Nd³⁺ crystals at the wavelengths λ₃ = 1.3315 and λ₄ = 1.3370 μm of the ⁴F_3/2 → ⁴I_13/2 channel and also the simultaneous generation at two wavelengths, λ₁ = 1.0621 and λ₂ = 1.0600 μm, of the ⁴F_3/2 → ⁴I_11/2 channel.     

Luminescence of Y2O3:Eu and Gd2O3:Eu Depending on Precursor and Activation Temperature

The activation of Y₂O₃, Gd₂O₃and (Y_0.7,Gd_0.3)₂O₃ with Eu³⁺ ions at temperatures lower than 1000 °C is studied using different starting compounds. The activator ions are introduced during the crystallization or precipitation of the precursor. Phosphors prepared from hydroxides and activated at 900 °C exhibit luminescence with high efficiency under 254 nm Hg-line excitation. Strong emission is observed even in samples activated at 700 °C. Luminescence intensity, emission and excitation spectra are compared to these of Y₂O₃:Eu produced by the industry.     

Kinetics of luminescence of CsI single crystals scavenged by Y3+

CsI single crystals were grown from the melt scavenged by Y³⁺ (YCl₃) addition in 6.7·10⁻⁴–6.7·10⁻³ mol·kg⁻¹ range. The addition of the scavenger amounts comparable with the total concentration of the oxygen‐containing admixtures in molten CsI results in complete destruction of the latter. Because of this, the intensity of the band with a maximum at 2.8 eV in radioluminescence spectra caused by the oxygen‐containing admixtures (anion vacancies) considerably decreases, and the fraction of the slow 2μs‐component corresponding to these admixtures becomes lower than 0.01 (0.007). The addition of larger quantities of YCl₃ leads to the appearance of a wide band with a maximum at 2.8 eV caused by cation vacancies, and the intensity of the slow 2μs‐component increases to 0.02. The maximum ratio of two faster components with the decay constants equal to 7 and 30 ns reaches 0.65:0.33 at Y³⁺ concentration in CsI melt equal to 6.7·10^‐3 mol·kg^‐1, the effective luminescence time of fastest components is ca 14 ns. The dependence of the ‘Fast/Total ratio’ on Y³⁺ concentration passes through its maximum (0.81) corresponding to the equivalence of Y³⁺ and O²⁻ concentrations in the growth CsI melt.     

Optics and spectroscopy of a Pb3Ga2Ge4O14:Nd3+ crystal, a new representative of the langasite family

Absorption and luminescent properties of a Pb₃Ga₂Ge₄O₁₄:Nd³⁺ crystal have been studied. The refractive indices are measured in the range from 0.405 to 1.064 μm, and the molecular refraction is calculated.     

Luminescence characteristics of Yb, La codoped yttrium oxide nanopowders

Luminescence characteristics of Yb³⁺, La³⁺ codoped yttrium oxide nanopowders were investigated. The grain size and the crystallinity of (Yb_0.05Y_0.90La_0.05)₂O₃ nanopowders increase with the increase of calcination temperature. The average grain size of the nanopowders calcined at 1100 °C is 66 nm and its cooperative up-conversion luminescence centered at 498 nm was detected due to nanometer size effect and perfect crystallinity. However, the cooperative up-conversion luminescence of (Yb_0.05Y_0.90La_0.05)₂O₃ transparent ceramics was not detected.     

Tb3+ luminescence enhancement of YAG:Tb3+ nanocrystals embedded in silica xerogel

The luminescence behavior of composite materials consisting of nanocrystals of Y_3?xAl₅O₁₂:Tb (YAG:Tb³⁺) embedded into silica xerogel has been studied. Blue and green luminescence of the materials is due to a cross-relaxation effect in Tb³⁺ ions doped into a YAG lattice. The materials with YAG:Tb³⁺ nanocrystals immobilized in silica exhibit enhancement of Tb³⁺ luminescence in comparison with the macrocrystalline YAG:Tb³⁺ powder. The Tb³⁺ luminescence intensity of a composite material dried at room temperature can be improved when higher aliphatic alcohols are applied in a one-pot procedure during a sol–gel synthesis. On the other hand, the Tb³⁺ luminescence is quenched in the presence of Ag nanoparticles in the material. The composite material (YAG:Tb³⁺ in silica) exhibits thermal stability at higher temperatures and achieves the highest emission intensity after having been annealed at 700 °C.     

Growth of (Er,Yb):YAl3(BO3)4 laser crystals

(Er,Yb):YAl₃(BO₃)₄ single crystals of optical quality, up to 15 × 10 × 10 mm³ in size, have been grown from a (Er_0.023Yb_0.116Y_0.862)Al₃(BO₃)₄ solution in a Y₂O₃-B₂O₃-K₂Mo₃O₁₀ melt. The initial borate concentration was 17 wt %, and the flux cooling rate increased from 0.08 to 0.12°C/h in the range 1060–1000°C. The physical properties of the single crystals grown are good enough that they can be used as laser elements in systems with diode pumping and radiation near 1.5 μm.     

Determination of Concentration of Rare Earth Ions Yb3+, Er3+, Tb3+, Ho3+, Tm3+ in Monocrystals of Yttriumaluminum Garnets on Basis of Magnetic Susceptibility

Crystals of solid solutions (R_xY_1-x)₃Al₅O₁₂ (where R is rare earth ion Er³⁺, Yb³⁺, Tb³⁺, Ho³⁺, Tm³⁺) with garnet structure were grown. The temperature dependencies of magnetic susceptibility for these crystals were obtained. On the basis of measurement of magnetic susceptibility a non-destructive technique for determining the concentration of rare earth ions in yttrium-aluminum garnets was developed.