Upconversion Luminescence in Er3+ Doped and Yb3+/Er3+ Codoped Yttria Nanocrystalline Powders

Y_1.9Er_0.1O₃ and Y_1.7Yb_0.2Er_0.1O₃ nanocrystalline powders were prepared via a reverse-strike coprecipitation method using nitrates and ammonia as raw materials. The obtained powders were of cubic-phase structure of Y₂O₃ and the particle size was in the range of ∼60–80 nm. Strong red (⁴F_9/2–⁴I_15/2) and green (²H_11/2/⁴S_3/2–⁴I_15/2) upconversion luminescence were observed in all the samples when excited with a 980-nm continuous wave diode laser. The possible upconversion mechanisms in Y_1.9Er_0.1O₃ and Y_1.7Yb_0.2Er_0.1O₃ were discussed. Power studies indicated that two-photon processes are responsible for the green and red upconversion luminescence in these systems. The codoping of Yb³⁺ greatly enhanced the red (⁴F_9/2–⁴I_15/2) upconversion emission.     

Upconversion Luminescence in γ-AlON:Yb3+,Tm3+ Ceramic Phosphors

Upconversion emission properties of γ-AlON:Yb³⁺,Tm³⁺ phosphors were investigated under single-wavelength diode laser excitation of 980 nm. Blue (479 nm) and red (653 nm) emission bands were observed which correspond to the transitions of ¹G₄→³H₆ and ¹G₄→³F₄ of Tm³⁺ ions, respectively. The upconversion spectra show a concentration-dependent luminescence intensity, reaching its peak at a concentration of 1.2 mol% Yb and 0.5 mol% Tm. Pump power dependence of the upconversion emission intensity ( P – I ) revealed that a two-photon process was involved in the blue and red emissions.     

2.0 μm Emission Properties and Energy Transfer between Ho3+ and Tm3+ in PbO—Bi2O3—Ga2O3 Glasses

Emission properties of 2.0 μm fluorescence and the energy transfer between Ho³⁺ and Tm³⁺ in 57PbO·25Bi₂O₃·18Ga₂O₃ (mol%) glass codoped with Ho³⁺ and Tm³⁺ were investigated. Cross-relaxation rates in Tm³⁺ increased approximately 5 times when the Tm₂O₃ concentration was increased from 1.0 to 1.5 wt%. Coefficients of the forward Tm³⁺→ Ho³⁺ energy transfer were about 15 times larger than those of the Tm³⁺← Ho³⁺ backward transfer. Analysis of the energy transfer and gain spectra indicated that the highest gain at the 2.0 μm wavelength region could be achieved from the glass with 1.5 wt% of Tm₂O₃ and 0.3 wt% of Ho₂O₃.     

Fabrication and Luminescent Properties of Nd3+-Doped Lu2O3 Transparent Ceramics by Pressureless Sintering

The fabrication of transparent Nd³⁺ ion-doped Lu₂O₃ ceramics is investigated by pressureless sintering under a flowing H₂ atmosphere. The starting Nd-doped Lu₂O₃ nanocrystalline powder is synthesized by a modified coprecipitant processing using a NH₄OH+NH₄HCO₃ mixed solution as the precipitant. The thermal decomposition behavior of the precipitate precursor is studied by thermogravimetric analysis and differential thermal analysis. After calcination at 1000°C for 2 h, monodispersed Nd³⁺:Lu₂O₃ powder is obtained with a primary particle size of about 40 nm and a specific surface area of 13.7 m²/g. Green compacts, free of additives, are formed from the as-synthesized powder by dry pressing followed by cold isostatic pressing. Highly transparent Nd³⁺:Lu₂O₃ ceramics are obtained after being sintered under a dry H₂ atmosphere at 1880°C for 8 h. The linear optical transmittance of the polished transparent samples with a 1.4 mm thickness reaches 75.5% at the wavelength of 1080 nm. High-resolution transmission electron microscopy observations demonstrate a "clear" grain boundary between adjacent grains. The luminescent spectra showed that the absorption coefficient of the 3 at.% Nd-doped Lu₂O₃ ceramic at 807 nm reached 14 cm⁻¹, while the emission cross section at 1079 nm was 6.5 × 10⁻²⁰ cm².     

Fabrication and Photoluminescence Characteristics of Eu3+-Doped Lu2O3 Transparent Ceramics

A novel co-precipitation process was adopted for the preparation of highly sinterable europium-doped lutetia powders using ammonium hydroxide (NH₃·H₂O) and ammonium hydrogen carbonate (NH₄HCO₃) as the mixed precipitant. The resultant powders calcined at 1000°C for 2 h showed good dispersity and excellent sinterability. Highly transparent polycrystalline lutetia ceramics with a relative density of ∼99.9% were fabricated by pressureless sintering in flowing H₂ atmosphere at 1850°C for 6 h without any additives. The average grain sizes of the transparent material were estimated to be 50–60 μm. Optical in-line transmittance in the visible wavelength region for Lu₂O₃ ceramics (1 mm in thickness) reached 80%. The luminescence and decay behavior of the obtained transparent plate and the corresponding nanophosphors were also investigated.     

Processing and Properties of in Situ-Reinforced α-SiAlONs Stabilized with Y2O3 and Lu2O3

α-SiAlONs with equiaxed and elongated microstructures stabilized with Y₂O₃ and Lu₂O₃ were produced by hot pressing, and the phase structure and room- and high-temperature mechanical properties were assessed. Additional liquid added to the starting composition in the form of 5 wt% rare-earth monosilicate resulted in the formation of elongated microstructures and improvements in room-temperature strength and fracture toughness. The elongated grain growth was promoted by the additional liquid phase, which crystallized to form a secondary grain-boundary phase thought to be J ' (Re₄Si_{2– x} Al _x O_{7+ x} N_{2– x} ). For the equiaxed and the elongated samples, those sintered with Lu₂O₃ showed higher hardness than the comparable Y₂O₃-sintered materials, and, at elevated temperature, the strength retention of the elongated Lu₂O₃ SiAlON was much higher than that of the Y₂O₃ sample, which was attributed to properties of the residual grain-boundary phase associated with the difference in the cationic radius of the stabilizing cation.     

La2O3-Al2O3-SiO2 Glasses for High-Power, Yb3+-Doped, 980-nm Fiber Lasers

Single-mode semiconductor pumps have failed to keep pace with the increasing power requirements of Er-doped fiber amplifiers (EDFAs), so there is a need for high-powered 980-nm sources. Yb³⁺-doped tapered fiber lasers can provide high-power output by conversion of a low-brightness, high-powered, 920-nm, multimode broad stripe laser diode to a high-brightness, 980-nm, single-mode output. The tapered fiber laser requires a fiber with high numerical aperture (NA) (>0.4), a rectangular core, and good Yb³⁺ spectroscopy for efficient operation. CVD-based fiber fabrication methods are incapable of delivering fibers with an NA > ∼0.3 or with good efficiency at 980 nm so a new method of high-NA fiber fabrication was developed. The core glass composition is critical for maintaining a high-NA fiber with good power extraction while avoiding phase separation, loss, and clustering. The SiO₂ level controlled the NA and interdiffusion between core and clad, while the Al₂O₃/La₂O₃ ratio controlled phase separation. A La₂O₃-Al₂O₃-SiO₂ glass was developed that is compatible with a pure SiO₂ cladding glass and has a laser slope efficiency of 70% at 980 nm. The optimized fiber composition yielded 450 mW of 980-nm power in a single-mode fiber.     

Effects of Sm2O3 and Gd2O3+ Nd2O3 on Electromechanical Properties of PbTiO3 Ceramics

The electromechanical properties of PbTiO₃ ceramics, modified by substitution of Sm or Gd + Nd (same average atomic radius as Sm) for Pb, were studied in the range of 6% to 14% substitution. The modified PbTiO₃ ceramics were stable, and the Curie temperature decreased linearly over this composition range. The 10% Sm composition had a large anisotropy in the coupling factor ratio, k _t / k _p , and a similar, but weaker, effect developed for 12% (1/2 Gd + 1/2 Nd). This indicates that other than average ion size may influence the electromechanical coupling factor ratio.     

Synthesis and Properties of CaAl2O4-Coated AI2O3 Microcomposite Powders

Novel microcomposite powders, consisting of inert cores (αAL-Al₂O₃) surrounded by reactive cement-based coatings (CaAl₂O₄), were synthesized by a modified Pechini process. The evolution of the crystalline CaAl₂O₄ phase during calcination was studied using multiple analytical techniques, including DRIFTS,¹³C and ²⁷AlMAS FT-NMR, and XRD, for both pure CaAl₂O₄ and CaAl₂O₄-coated Al₂O₃ precursor powders. In both powders, decomposition proceeded via hydrocarbon chain scission and removal of ester groups at low temperatures ( T < 450°C), followed by the formation of inorganic carbonates at higher temperatures ( T > 450°C). These decomposition processes were accelerated by the underlying Al₂O₃ cores. Transmission electron microscopy (TEM) of the fully calcined powders showed that the inert αAL-Al₂O₃ particles were surrounded by relatively uniform CaAl₂O₄ coatings ranging in thickness from approximately 10 to 100 nm.     

Populations and Emission Properties of the 5I6 and 5I7 Levels in Ho3+ Doped into PbO–Bi2O3–Ga2O3 Glasses

Emission properties of PbO–Bi₂O₃–Ga₂O₃ glasses doped with Ho³⁺ were investigated for fiber-optic amplification at the 1.18 μm wavelength region. When the glasses were doped with Ho³⁺ ions only, there was a weak emission at 1.18 μm with a lifetime of ∼200 μs. However, when Yb³⁺ ions were codoped, the lifetime of the 1.18 μm emission increased to 630 μs together with a significant increase in intensity. A similar enhancement in the intensity and lifetimes was realized for the 2.05 μm emission. These effects are due to energy transfer from the Yb³⁺:²F_5/2 to the Ho³⁺:⁵I₆ level. Devitrification of the ternary PbO–Bi₂O₃–Ga₂O₃ glasses was efficiently suppressed by adding 10 mol% GeO₂. Optimum Ho³⁺ concentration was ∼0.4 mol%, whereas Yb³⁺ ions can be added up to the solubility limit.     

Synthesis of Er3+ Doped Y2O3 Nanophosphors

The synthesis and characterization of yttrium hydroxyl carbonate (Y(OH)CO₃²⁻) and yttrium nitrate hydroxide hydrate (Y(OH)NO₃H₂O) precursor materials as well as Y₂O₃ nanoparticles are reported. The resultant precursor particle size is about 10–12 nm with a narrow size distribution by the enzymatic decomposition method, whereas the particle size was smaller than those acquired by the homogeneous and alkali precipitation methods. The formation of Y(OH)CO₃²⁻ and Y(OH)NO₃H₂O species was also evident from the fourier-transform infrared spectrometry (FT-IR) analysis. Precipitated Y(OH)CO₃²⁻ precursors have an amorphous nature whereas Y(OH)NO₃H₂O precursors have a crystalline nature, which was manifested from the XRD analysis. Moreover, precipitated Y(OH)NO₃H₂O precursors were found in the agglomerated form and Y(OH)CO₃²⁻ was established in the monodispersed form, as determined from the FE-SEM, TEM and DLS measurements. It was demonstrated that calcination of precursor materials at 900°C eventually removed the inorganic anions from the precursors and consequently produced crystalline Y₂O₃ nanoparticles, which was evident from the XRD and FT-IR analysis. The EDS analysis confirms Er³⁺ doping in the Y₂O₃ nanoparticles. The morphology and the size of the Y₂O₃ nanoparticles are almost unchanged before and after the calcination.     

Thermal Stability of Nanocrystalline Sm2O3 and Sm2O3–MgO

Nanocrystalline Sm₂O₃ and Sm₂O₃–MgO powders have been prepared by spray pyrolysis of aqueous precursor solutions containing citric acid as a complexant. Synthesized powders consist of hollow spheres with thin shells. The two-phase samples exhibit an improved microstructural stability compared with pure Sm₂O₃. The microstructure before and after various heat treatments has been investigated by high-resolution transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, and X-ray diffraction.     

Preparation and Properties of Nitrogen-Containing Na2O-B2O3 Glasses

Up to 3.3 wt% nitrogen can be incorporated into Na₂O-B₂O₃ glass melts. The melting procedure is described, and structure models are given. In contrast to N-containing silicate glasses, the borate glasses were transparent; however, micrographs of their fracture surfaces showed some crystallinity. Properties were determined as a function of the N and Na₂O contents of the glasses. Compared with N-containing silicate glasses, the properties of borate glasses are much less changed by the nitrogen introduced.     

Thermal Expansion of CeO2, Ho2O3, and Lu2O3 from 100° to 300°K by an X-Ray Method

Thermal expansion of CeO₂, Ho₂O₈, and Lu₂O₃ was determined from 100° to 300°K by a back-reflection X-ray technique. The variation of thermal expansion with temperature is the same as that of specific heat for CeO₂ and Ho₂O₃; these oxides obey the Grueneisen model of thermal expansion in the temperature range studied.     

Hot-Pressed Silicon Nitride with Lu2O3 Additives: Oxidation and Its Effect on Strength

The oxidation behavior and effect of oxidation on room-temperature flexural strength were investigated for hot-pressed Si₃N₄ ceramics, with 3.33 and 12.51 wt% Lu₂O₃ additives, exposed to air at 1400° and 1500°C for up to 200 h. Parabolic oxidation behavior was observed for both compositions. The oxidation products consisted of Lu₂Si₂O₇ and SiO₂. The Lu₂Si₂O₇ grew out of the surface silicate in preferred orientations. The morphology of oxidized surfaces was dependent on the amount of additive; Lu₂Si₂O₇ grains in the 3.33 wt% composition appeared partially in a needlelike type, compared with a more equiaxed type exhibited in the 12.51 wt% case. The high resistance to oxidation shown for both compositions was attributed to the extensive amounts of crystalline, refractory secondary phases formed during the sintering process. Moreover, after 200 h of oxidation at 1400° and 1500°C, the strength retention displayed by the two compositions was 93%–95% and 85%–87%, respectively. The strength decrease was associated with the formation of new defects at the interface between the oxide layer and the Si₃N₄ bulk.     

Spectroscopic Properties and Laser Performance Assessment of Yb3+ in Borophosphate Glasses

Absorption and emission properties of Yb³⁺ in borophosphate glasses of the (55- x )P₂O₅· x B₂O₃·10ZnO·10BaO·20SrO·5Nb₂O₅·1Yb₂O₃ series ( x = 0, 11, 22, 33, 44, and 55) have been investigated. To avoid the problem arising from the radiation trapping effect, the reciprocity method is employed to calculate the emission cross section. It is found that the spectroscopic properties of Yb³⁺ in our borophosphate glasses are sensitive to the Yb³⁺ site environments. In addition, the laser performance of the Yb³⁺-doped borophosphate glasses has been assessed. And the borophosphate glasses with values of x = 33 and 55 appear to be superior to the phosphate glasses as Yb-grain media.     

Stable and Metastable Equilibria in the Systems Y2O2-Al2O3, and Gd2O3-Fe2O3

The phase equilibrium relations in the systems Y₂O₃-Al₂O₃ and Gd₂O₃-Fe₂O₃ were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd₂O₃-Fe₂O₃ but only metastable in the system Y₂O₃-AI₂O₃. This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O₃. A new 2:1 molar ratio cubic phase has been found in the system Y₂O₃-A1₂O₃. Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination.     

Phases in the Binary Systems PbO—La2O3, Gd2O3, and Sm2O3

In the binary system PbO–La_zO₃ only one compound, 4PbO.La₂O₃, exists; it is flanked by two eutectics. The structure of the compound, although of lower symmetry, is intimately related to the C modification of the rare earths. Below 800° to 1000°C, metastable solid solutions are formed from oxide mixtures coprecipitated from mixed solutions of the nitrates, the cubic parameter a = 5.66 A, if extrapolated to pure La₂O₃, corresponding to half the a parameter of the C form of La₂O₃. The solid solutions existing between the compositions La₂O₃–2Pb0 and pure La₂O₃ have a cubic face–centered lattice and obey Vegard's rule. The systems of PbO with Sm₂O₃ and Gd₂O₈ are quite similar to that with La₂O₃. The compound Sm₂O₃.4Pb0 decomposes at 1000°C with evaporation of PbO; Sm₂O₃ remains in the B modification.