Ultrafast Optical Switches and Wavelength Division Multiplexing (WDM) Amplifiers Based on Bismuth Oxide Glasses

Glasses with a high refractive index exhibit interesting properties. All optical switching and broadband amplification performances have been demonstrated using glasses based on bismuth oxide (Bi₂O₃). Optical Kerr shutter (OKS) switching and degenerated four-wave mixing experiments for nonresonant-type Bi₂O₃–B₂O₃–SiO₂ glasses have been performed using femtosecond lasers. This glass exhibits an ultrafast response (<150 fs) in OKS operation. Moreover, terahertz-range (THz-range) optical switching has been successfully performed with this glass, using a 1.5-THz pulse train. Erbium-doped bismuth-based oxide glasses also have been prepared for wavelength division multiplexing (WDM) amplifiers. These glasses exhibit broadband emission and negligible concentration quenching, which indicates that the bismuth-based glass is suitable for broadband amplifiers and highly doped short-length fiber applications for metro use.     

Role of Nd3+ ions on the nucleation and growth of PbS quantum dots (QDs) in silicate glasses

The influence of Nd₂O₃ addition on the precipitation kinetics of lead chalcogenide (PbS) quantum dots (QDs) in silicate glasses was investigated. Energy dispersive X‐ray spectroscopy (EDS) indicated that the Nd³⁺ ions are preferentially located inside the PbS QDs rather than in the glass matrix. Changes in diameter (D) of PbS QDs exhibited smaller time dependencies (i.e., D≈t^{0.270‐0.286}) than that predicted by the classical Lifshitz–Slyozov–Wagner (LSW) theory. This is due to the limited concentrations of Pb²⁺ and S^2? ions and the large diffusion distance inside the glass matrix. In addition, extended X‐ray absorption fine structure (EXAFS) results indicated that the formation of PbS QDs was retarded due to the presence of Nd₂O₃ in the glasses, as the large NdO_x polyhedra interrupt the diffusion of Pb²⁺ and S^2? ions. We believe that these Nd³⁺ ions are primarily located in PbS QDs in the form of Nd–O clusters, and that the PbS QDs are built on top of these clusters.     

Thermal, Dielectric, and Optical Properties of Neodymium Borosilicate Glasses for Thick Films

Because of their thermal, dielectric, and optical properties, new glass compositions and thick-filmed transparent dielectrics containing neodymium oxide (Nd₂O₃) were studied as a source of purer images in plasma display panels. In the present study, PbO–B₂O₃–SiO₂ and PbO–B₂O₃–SiO₂–ZnO–Al₂O₃ were used as starting glass compositions, to which up to 25 wt% of Nd₂O₃ then was added. Increased amounts of Nd₂O₃ increased the glass transition temperature and dielectric constant of the bulk glasses and decreased the coefficient of thermal expansion. The fired thick films (around 30 μm) allowed selectively visible light to penetrate and showed deep absorption properties at 585 nm that were related to an extraneous gas from neon discharge.     

Molecular‐Like Ag Clusters and Eu3+ Co‐Sensitized Efficient Broadband Spectral Modification with Enhanced Yb3+ Emission

AgNO₃/EuF₃/YbF₃ tri‐doped oxyfluoride glass was prepared by a melt‐quenching method, in which a high‐efficient broadband spectral modification can be realized due to the simultaneous energy‐transfer processes of Eu³⁺→Yb³⁺, molecular‐like Ag (ML‐Ag) clusters→Yb³⁺, and ML‐Ag clusters→Eu³⁺→Yb³⁺. The spectral measurements indicated that besides the F‐center brought by the fluorides, the formation of the ML‐Ag clusters and the evolution of silver species within the glass matrix were also closely related to the introduction of Eu³⁺ and Yb³⁺ ions and which in return greatly affected the luminescence properties of these rare‐earth ions. As the UV‐visible irradiation in the wavelength region of 250–600 nm can be efficiently converted into near‐infrared emission around 1000 nm in the AgNO₃/EuF₃/YbF₃ tri‐doped glass, which thus has promising application in enhancing the photovoltaic conversion efficiency of the silicon solar cell.     

Synthesis and Unique Photoluminescence Properties of Eu2Ti2O7 and Eu2TiO5

The europium titania materials, pyrochlore Eu₂Ti₂O₇ and orthorhombic Eu₂TiO₅, were synthesized from a mixture of Eu₂O₃ and TiO₂ using the solid‐state reaction method. The structural and optical properties of these titania materials were investigated using X‐ray diffraction analysis, photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and diffuse reflectance spectroscopy. Temperature dependence of the PL intensity was measured between T = 20 and 450 K and analyzed on the basis of various theoretical models. A remarkable increase in the PL intensity with increasing T was observed in these titania materials at higher temperatures, above ~140 K, and well explained by a trap/reservoir model. Interestingly, a dramatic decrease in the electric‐dipole emission component relative to the magnetic‐dipole one was observed in Eu₂Ti₂O₇ above T ~ 140 K. The schematic energy‐level diagram for Eu³⁺ in the Eu₂Ti₂O₇ host was proposed for the sake of a better understanding of the PL and PLE processes in this type of phosphorescent material.     

Nd3+‐Doped Silicate Glasses as an Efficient Color Filter to Improve the Color Gamut of a White LED

Nd³⁺‐doped silicate glass (Nd‐glass) was employed as a color filter for a white LED based on red and green phosphor (RG‐LED), to manipulate the photoluminescence spectral shape and thus to provide a wider color gamut. The hypersensitive transition of Nd³⁺:⁴I_9/2→⁴G_5/2,²G_7/2 was adjusted via glass composition and Nd concentration, and improved absorbance as well as reduced the absorption bandwidth. The effective absorption of the Nd‐glass at ~580 nm reduced the spectral linewidth of the green and red emissions, improving the color reproduction range. The color gamut of the RG‐LED was improved from 75.3% to 81.6% NTSC by the introduction of Nd‐glass as a color filter. Reliability under high operating current and high temperature were also examined and discussed.     

Highly Transparent Lu-α-SiAlON

Novel Lu-α-SiAlON ceramics were produced by hot pressing mixtures of Si₃N₄, Lu₂O₃, AlN, and Al₂O₃ at 1950°C for 2 h in a nitrogen atmosphere. The resultant SiAlON was fully dense and possessed a uniform, equiaxed microstructure with a grain size of ∼1 μm, which resulted in a high hardness of >19 GPa. In addition to high hardness, the sample showed very high optical transparency in the visible light region, with >70% transmission at higher wavelengths. This high transparency was attributed to the uniform, dense microstructure and lack of residual grain-boundary phase.     

Structure and physical properties of Ba(PO3)2–AlF3–BaSO4 fluoro-sulfo-phosphate glasses

Alkali-earth-metaphosphate-based fluoro-sulfo-phosphate M(PO₃)₂–AlF₃–MSO₄ (MPFS, M = Ca, Sr, Ba) glasses have been developed via simultaneously incorporating fluoride and sulfate into metaphosphate glass. Their glass-forming regions were efficiently determined under the guidance of thermodynamic calculation method. The physical and structural properties of BaPFS glass were investigated in detail. Furthermore, near-infrared spectroscopic properties of Er³⁺-doped BaPFS (Er–BaPFS) glass were studied. Physical parameters, such as Abbe's number ν_d (55-75) and nonlinear refractive index n₂ (1.17-1.86 × 10⁻¹³ esu), of BaPFS glass are strongly depended on P/F/S ratio. The structure of BaPFS glass gradually depolymerizes and tends to become multianionic when Ba(PO₃)₂ is substituted by AlF₃ and BaSO₄. Anion-substitution strategy effectively modulates the property and structure of glass, providing a scheme to derive glass materials. In addition, enhanced emission at ~1.5 μm has been observed from Er–BaPFS glass along with large emission cross section (5.0-5.5 × 10⁻²¹ cm²) and long lifetime (6.7-7.3 ms), resulting in large figure of merit (3.46-3.84 × 10⁻²³ cm²·s), which is a promising candidate for solid-state laser.     

纳米二氧化锆的制备及其光学性能研究

纳米二氧化锆是飞机隐身涂料的重要原料,经稀土原位掺杂制得的纳米二氧化锆又是隐形防伪油墨的发光组分。本研究以氧氯化锆为原料,氨水为沉淀剂,经沉淀法制备了具有红外吸收及其红外激发荧光功能纳米级二氧化锆粒子。研究了锆盐浓度、溶剂种类、分散剂相对分子质量、分散剂加入量、干燥方式、煅烧温度等条件对产物粒径的影响,并对产物进行了透射电镜、X射线衍射分析,结果表明:采用无水乙醇作溶剂,真空干燥,600℃煅烧等反应条件可制备粒径20~30 nm的纳米二氧化锆粒子。在氧氯化锆溶液中加入Er3 盐和Yb3 盐得到的稀土掺杂纳米二氧化锆在远红外下可发出荧光。     

Tunable white light and energy transfer of Eu2+-Tb3+-Eu3+ tri-activated glasses synthesized in air

An ever increasing demand for white light-emitting diodes (W-LEDs) results in the gradual growth of research on functionalized luminescent glasses. In this paper, single-composition tunable white-emitting Eu²⁺-Tb³⁺-Eu³⁺ tri-activated glasses were synthesized by melt quenching method without additional reducing atmosphere. The coexistence of Eu²⁺ and Eu³⁺ was confirmed by ultraviolet-visible transmission spectra, photoluminescent spectra, fluorescence decay curves, and X-ray photoelectron spectroscopy. Tb³⁺ can act as bridge to connect Eu²⁺-Eu³⁺ luminescent centers by energy transfer. Tone-tunable white light can be achieved by coupling the emission centered at 412, 541, and 612 nm contributed from Eu²⁺, Tb³⁺, and Eu³⁺, respectively. By adjusting the relative content of Eu²⁺/Tb³⁺/Eu³⁺, ideal chromaticity coordinates of (0.33, 0.33) can be achieved under excitation of ultraviolet light. High thermal stability and tiny chromaticity shift were exhibited in samples. These results suggest that Eu²⁺-Tb³⁺-Eu³⁺ tri-activated glasses have great potential application in ultraviolet-driven W-LEDs.     

Elastic Properties and Molar Volume of Rare-Earth Aluminosilicate Glasses

The elastic properties, molar volume, and glass transition temperature ( T _g) of rare-earth-containing aluminosilicate glasses were investigated in the compositions of SiO₂–LnAlO₃ and SiO₂–Ln_3/4Al_5/4O₃, where Ln is Y, La, Nd, Eu, or Yb. The molar volume decreased with decreased ionic size of the Ln³⁺ ion, and T _g and elastic moduli increased in the same order. The Yb-containing glasses showed the highest Young's modulus among all the oxide glasses, even higher than the highest value ever known for glass containing Y₂O₃, as expected from the smaller ionic radius of Yb³⁺ than that of Y³⁺. The bulk modulus was found to be almost proportional to the inverse four-thirds power of the molar volume of glasses in each composition, indicating that Ln³⁺ ions can substitute for each other without changing the glass structure except for the size of the local structure around themselves. From the comparison of these properties, the structural role of rare-earth ions in these glasses is discussed.     

Optical Amplification at 1.3 μm in a Praseodymium-Doped Sulfide-Glass Fiber

Praseodymium-doped glasses were prepared in the Ga-Na-S (GNS) system and their optical properties were studied. A single-mode fiber with an attenuation loss of 1.2 dB/m at a wavelength of 1.31 μm was fabricated using an extrusion method, and the amplification characteristics were measured in the bidirectional pumping configuration. We demonstrated a gain coefficient of 0.81 dB/mW at a wavelength of 1.34 μm, which is the highest we have ever reported, and achieved a net gain of 32 dB for a pump power of 90 mW. Highly efficient optical amplification at a wavelength of 1.3 μm was demonstrated in the praseodymium-doped GNS fiber.     

Optical and Mechanical Properties of α/β Composite Sialons

Two-phase α/β composites have been produced with a combination of high hardness, fracture toughness, and strength. Compared with a single-phase α-sialon, the composite showed around a twofold increase in both fracture toughness and bending strength, with only minimal reduction in hardness. Despite being a two-phase material, the optical properties of the composite were very good, showing transparency in sections of around 0.5 mm thickness. The optical properties were in fact better for the composite than for the single-phase α-sialon. Work to date on transparent sialons has focused on single-phase α-materials, which have inherently low fracture toughness unless elongated microstructures are developed. However, this microstructural development appears to adversely affect optical transparency. In this work it has been shown that good combination of mechanical properties can be achieved while maintaining optical transparency in two-phase composite sialons. The development of such materials should widen their range of application.     

Physical Properties and Structure of Silica-Alumina-Europium Oxide Glasses

SiO₂–Al₂O3–Eu₂O₃ glasses were prepared for the composition 50siO₂·(50 – x )Al₂O_3·xEu₂O₃, and their density, sound velocity, and elastic modulus were measured. The chemical shift of the AIK a band emission spectra and the isomer shift of ¹⁵¹Eu by Mössbauer effect were obtained to determine the coordination states of Al³⁺ and Eu³⁺ ions in these glasses. It was found that the coordination number of Eu³⁺ ions was 12 and that the average coordination number of A1³⁺ ions was almost 5 in these glasses. By introducing Eu₂O₃, the packing of constituent ions was strongly enhanced and the elastic modulus increased in this system. The compositional dependence of the molar volume and elastic modulus were explained by these states of high coordination number for Eu³⁺ and low coordination number for Al³⁺ ions compared with those in the corresponding M₂O₃ crystals.     

Toward tunable and bright deep‐red persistent luminescence of Cr3+ in garnets

Garnet structure (A₃B₂C₃O₁₂) with three different cation sites is a very flexible host material widely used for w‐LEDs, solid‐state lasers, scintillators, and so on. In this work, we have successfully developed six different Cr³⁺‐doped garnets: Y₃Ga_4.99Cr_0.01O₁₂ (YGG:Cr), Gd₃Ga_4.99Cr_0.01O₁₂ (GGG:Cr), Lu₃Ga_4.99Cr_0.01O₁₂ (LuGG:Cr), Y₃Sc_1.99Cr_0.01Ga₃O₁₂ (YSGG:Cr), Gd₃Sc_1.99Cr_0.01Ga₃O₁₂ (GSGG:Cr), and Lu₃Sc_1.99Cr_0.01Ga₃O₁₂ (LuSGG:Cr), which exhibit persistent luminescence (PersL) due to Cr³⁺ emission matching well with both the response curve of the Si detector and the wavelength region of the first biological window (NIR‐I, 650‐950 nm). The main emission band of Cr³⁺ in these garnets can be easily tunable from the sharp R‐line emission due to the ²E (²G)→⁴A₂ (⁴F) transition in the strong crystal field to the broad band emission due to the ⁴T₂ (⁴F)→⁴A₂ (⁴F) transition in the weak one when Lu³⁺ in the A site and Ga³⁺ in the B site are, respectively, replaced by larger cations, Y³⁺/Gd³⁺ and Sc³⁺. Furthermore, based on the knowledge of 4f energy levels of 15 lanthanide ions in the host‐referred binding energy (HRBE) diagram, we took the GSGG host as a typical example to discuss the feasibility of four trivalent lanthanides (Sm³⁺, Eu³⁺, Tm³⁺, Yb³⁺) as potential sensitizers for enhancing Cr³⁺ PersL.     

Sol–Gel Synthesis of Cadmium Telluride-Microcrystal-Doped Silica Glasses

The sol–gel process has been applied to the preparation of small-sized CdTe-doped silica glasses. Gels synthesized by the hydrolysis of a complex solution of Si(OC₂H₅)₄, Cd(CH₃COO)₂· 2H₂O, and Te were heated from 350° to 600°C in a H₂─N₂ atmosphere to form fine cubic CdTe crystals. The size of CdTe crystals, determined from the line broadening of X-ray diffraction pattern, increases from 4 to 9 nm in diameter with increasing heat-treatment temperature. The optical absorption edge shifts to the higher-energy side as the size of the CdTe crystals decreases. This phenomenon is interpreted in terms of a quantum confinement effect of electron and hole in the CdTe microcrystals.     

米粒状纳米硫化银的制备及其光学性能

以月桂酸银、硫化钠为原料,聚乙烯吡咯烷酮为保护剂,室温下仅0.5 h即合成了平均长度约35 nm的米粒状硫化银颗粒。研究表明,聚乙烯吡咯烷酮和硫化钠的存在是形成米粒状特征的必要条件;且相对较高的硫化钠浓度可缩短米粒状特征形成的时间。与大块硫化银相比,所得米粒状纳米硫化银的紫外-可见吸收光谱中吸收边明显蓝移,直接禁带宽度达到4.4 eV,表现出明显的量子尺寸效应。     

Synthesis of Eu3+‐doped BaBi2Ta2O9 based glass‐ceramic nanocomposites: Optical and dielectric properties

In this paper we report for the first time synthesis of Eu³⁺‐doped transparent glass‐ceramics (TGC) with BaBi₂Ta₂O₉ (BBT) as the major crystal phase using the glass system SiO₂–K₂O–BaO–Bi₂O₃–Ta₂O₅ by melt quenching technique followed by controlled crystallization through ceramming heat treatment. DSC studies were conducted in order to determine a novel heat‐treatment protocol to attain transparent GCs by controlling crystal growth. The structural properties of the BBT GCs have been investigated using XRD, FE‐SEM, TEM and FTIR reflectance spectroscopy. Optical band gap energies of the glass‐ceramic samples were found to decrease with respect to the precursor glass. An increased intensity of emission along with increase in the average lifetime of Eu³⁺ was observed due to incorporation of Eu³⁺ ions into the low‐phonon energy BBT crystal site. The local field asymmetric ratios of all the samples were observed greater than unity. The dielectric constant (ε_r), dielectric loss, and dissipation factor values of both the base glass and ceramized samples were found to decrease with increase in frequency.     

The Red-Shift of Ultraviolet Spectra and the Relation to Optical Basicity of Ce-Doped Alkali Rare-Earth Phosphate Glasses

The ultraviolet absorption and emission spectra of Ce³⁺ doped phosphate glasses based on gadolinium and sodium phosphates are studied in the present work. Compared with the cerium-free phosphate glass matrixes, CePO₄ doping shifts the ultraviolet absorption edge of glasses into the longer wavelength because of the 4f–5d absorption transition of Ce³⁺. The emission spectra correlate such red-shift with glass compositions. Explanations are based on variation in the optical basicity of glasses, which corresponds not only to the alkali content but also to the O/P ratio. The latter is proportional to the number of nonbridging oxygen in the oxyanion unit (PO₄), and most likely plays an overwhelming role in the overall optical basicity of glasses.     

Properties of Calcium, Strontium, and Barium Galliosilicate Glasses

Glasses in three alkaline-earth (Ca, Sr, and Ba) galliosilicate systems were prepared, and the density, viscosity, thermal expansion coefficient, and glass transformation temperature were measured. All glasses contain 30 mol% alkaline-earth oxide. It is suggested that alkaline-earth ions can play a role in the glass structure which is similar to that of an intermediate ion.