Synthesis and characterization of Cr4+-doped CaO–GeO2–Li2O–B2O3(Al2O3) transparent glass-ceramics

Synthesis and devitrification behavior of Cr-doped CaO–GeO₂–Li₂O–B₂O₃(Al₂O₃) glasses have been studied. A range of glass compositions was found to yield transparent glass-ceramics after devitrification. The size of crystallites is below 1 μm. Glass-ceramic samples exhibit 1050–1600 nm broad-band emission with a maximum around 1260 nm, very similar to the emission of Cr⁴⁺:Ca₂GeO₄ bulk crystals. X-ray diffraction measurements indicate that the structure of crystallites exhibiting near infrared emission in glass-ceramics may be assigned to Cr⁴⁺:Ca₂GeO₄ with increased lattice parameters.     

EPR spectra of Cr3+-doped LuNbO4 crystals

Ferroelastic LuNbO₄ single crystals containing 0.3 at. % Cr³⁺ ions have been grown by the floating zone technique, and their EPR spectra have been studied at a frequency of 9.8 GHz at room temperature. The lines on the spectra are due to the transitions caused by three paramagnetic centers formed as a result of the replacement of one isovalent position of a Lu₃₊ ion and two nonisovalent positions of Nb₅₊ions by Cr₃₊-ions. As a result of twinning, the line number is doubled and four principal directions arise along which the same spectra are obtained. The spectra of these centers were described by a spin Hamiltonian with S = 3/2, the D and E parameters ranging from 0.024 to 0.17 cm^?1, and the g-factors g ∥ = 1.75–2.20 and g ⊥ = 1.90–2.13.     

Preparation of transparent lithium-mica glass-ceramics

In order to fabricate transparent and machinable mica-type glass-ceramics, parent glasses having chemical compositions corresponding to Li_(1+x)Mg₃AlSi_3(1+x)O_10+6.5xF₂ (x = 0.15, 0.5, 0.65, 1.0 and 1.2) were crystallized. Lithium-micas were precipitated in all the specimens as the main crystal at 650 °C though the content was little. And the micas were changed from trisilicic type to tetrasilicic type as the x increased. After the precipitation of the micas, a large amount of β-eucryptite solid solution was precipitated as the main crystal at higher temperatures and even at 650 °C after a certain period of time. The parent glasses having the spinodal phase separation, of which the x was 1.0 and 1.2, were transparent and colored in light blue. And at 650 °C, the fine mica crystals with size of about 20 nm were precipitated in one continuous glass phase of the spinodal phase separation, which made the phase separation structure become finer. Consequently, the heated specimens showed higher transmittance of visible ray and became colorless. Moreover, because the mica crystals formed the continuous phase, the specimens showed the machinability.     

CdSe晶体及掺Cr2+激光器的研究进展

以CdSe晶体光参量振荡器为代表的中红外激光器在生物、医疗和军事等诸多领域有着广泛的应用前景.本文总结了生长CdSe单晶的工艺方法包括熔体法、熔剂法和气相法等,其中常用的为气相法,近年来高压垂直梯度冷凝(HPVGF)技术也逐渐被采用.国内外将本征CdSe晶体用于光参量振荡器件(OPO),适用于多种激光器泵浦源,且输出功率不断提高.而Cr2+的掺杂能有效提高泵浦效率,实现波长的连续可调.     

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.     

Sol-gel synthesis of erbium-doped yttrium silicate glass-ceramics

Yttrium silicate glasses and glass-ceramics were prepared by the sol-gel process. Yttrium nitrate was added to tetraethyl orthosilicate in amounts representing between 0.2 and 20 mol%, as well as amounts corresponding to the disilicate composition. Some samples were doped with erbium acetate. The solutions underwent gellation in 2-7 days and were dried for 2 weeks. Differential thermal analysis was used to design a multi-step heat treatment to 1000 °C to densify samples to transparent or translucent monoliths. Above 1000 °C, samples crystallized to yttrium disilicate and cristobalite. Phase separation before crystallization influenced the formation of the crystal phases.     

Studies of Er doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

An erbium doped germanate-oxyfluoride glass 60GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (GPOF) and a tellurium-germanate-oxyfluoride glass 30TeO₂ · 30GeO₂ · 20PbO · 10PbF₂ · 10CdF₂ (TGPOF) were prepared in the bulk form. By appropriate heat treatment of the as-prepared glasses above, transparent glass-ceramics were obtained with the formation of β-PbF₂ nanocrystals in the glass matrix confirmed by X-ray diffraction. Optical absorption and photoluminescence measurements were performed on as-prepared glass and glass-ceramics. The luminescence of Er³⁺ ions in transparent glass-ceramics revealed sub-band splitting generally seen in a crystal host. The intensity of red and near infrared luminescence significantly increased in transparent glass-ceramic compared to that in as-prepared glass. Two luminescence bands at 758 nm from ⁴F_7/2 → ⁴I_13/2 and at 817 nm from ²H_11/2 → ⁴I_13/2 transitions were observed from transparent glass-ceramic but cannot be seen from the corresponding as-prepared glass. These results are attributed to the change of ligand field of Er³⁺ ions and the decrease of effective phonon energy when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

Leaching of some lithium silicate glasses and glass-ceramics by HCl

The leaching of some binary and ternary lithium silicate glasses and their respective glass-ceramics by HCl is reported.The leaching rate of lithium silicate glasses gradually decreases with the decrease of the percentage of Li₂O or by the introduction of small amounts of a third component, e.g. Al₂O₃, MgO, ZnO or B₂O₃. With a further increase in the proportions of B₂O₃ or ZnO the rate of leaching increases. The rate of leaching is also substantially modified by the conversion of glasses into glasses-ceramics.The results obtained are discussed in terms of the effects of the different ions on the rate of the interdifussion of the lithium and hydrogen ions in the glass and the leached layer, the phase separation developed in the glass, the type and concentration of crystalline phases developed in glass-ceramics and the composition of the residual glass phase.     

Preparation and spectral properties of Nd3 +-doped transparent glass ceramic containing Ca5(PO4)3F nanocrystals

A Nd^3 +-doped transparent oxyfluoride glass ceramic containing Ca₅(PO₄)₃F nanocrystals was prepared by thermal treatment at the crystallization temperature for the precursor glass. The transmittances of the precursor glass and the glass ceramic with a thickness of about 2 mm are up to 84.7% and 77.4% in the visible range. The volume fraction of Ca₅(PO₄)₃F nanocrystals in the glass ceramic is about 19% and the ingress fraction of Nd^3 + ions into the Ca₅(PO₄)₃F nanocrystals is about 32%. The peak absorption cross-section increases to 224% at 807 nm and the full width at half maximum for the 807 nm band decreases from 17.5 to 3.5 nm after the crystallization process. The peak stimulated emission cross-section increases from 1.89 × 10^? 20 to 2.42 × 10^? 20 cm² at 1062 nm and the effective width of the emission line for the 1062 nm band decreases from 34 to 29 nm after the crystallization process. The improvement of spectroscopic properties indicates that the glass ceramic is potentially applicable as the 1.06 μm laser material.     

Preparation and luminescent properties of Eu-doped transparent glass-ceramics containing SrF2 nanocrystals

Transparent glass-ceramics containing SrF₂ nanocrystals were fabricated by melt-quenching and subsequent heating of glass with a composition of 50SiO₂–10Al₂O₃–20ZnF₂–20SrF₂. X-ray diffractometry, transmission electron microscopy, and energy dispersive spectroscopy were used to investigated the microstructure of the SrF₂ glass-ceramics. Results show that SrF₂ nanocrystals were homogeneously precipitated among the aluminosilicate glass matrix, and the mean size of the SrF₂ nanocrystals was about 20 nm, and Eu³⁺ ions partition mainly into the precipitated SrF₂ nanocrystals after crystallization. The glass-ceramics exhibited intense red emission corresponding to the ⁵D₀ → ⁷F_J (J = 0–4) transitions of Eu³⁺ ions under 393 nm excitation. A significant Eu³⁺ luminescence enhancement by a factor of about nine times was observed after crystallization. Besides, the obvious stark splitting emissions, the low forced electric dipole ⁵D₀ → ⁷ F₂ transition, and the long decay lifetimes of Eu³⁺ ions also revealed the partition of Eu³⁺ ions into low phonon energy SrF₂ nanocrystals. Our results indicate the SrF₂ based fluorosilicate glass-ceramics is an excellent host for trivalent lanthanide ion doping and may find applications in photonics.     

Growth and some properties of Ce3+-doped LiYbF4 single crystals

LiYbF₄ single crystals, nominally pure and doped with Ce³⁺ ions, of optical quality and up to 60 mm in diameter, have been grown by vertical directed crystallization. The optical and mechanical properties of the crystals have been studied. The refractive index dispersion for LiYbF₄ in the range of 0.4–0.6 μm can be described by the dependence n ²(λ) − 1 = Aλ²/(λ² − λ ₀²), where A = 1.14 and 1.21 and λ₀ = 0.074 and 0.080 μm for n _o and n _e, respectively. The sample microhardness exceeds 2.6 GPa. LiYbF₄ crystals are transparent in the range of 0.17–9 μm and have an absorption band in the range of 0.9–1.2 μm. It is shown that LiYbF₄ crystals doped with Ce³⁺ ions can be used as optical cut-off UV filters in the operating range λ = 0.25−0.28 μm.     

Er3+掺杂钨酸铅晶体的发光和光谱特征

本试验测试了Er3 掺杂钨酸铅晶体(PbWO4:Er3 )的吸收光谱,依据J-O理论,首次计算报道了光谱项特征:J-O强度参数、量子荧光效率、荧光分支比等,Ω2=3.75×10-20cm2,Ω4=0.67×10-20cm2,Ω6=0.41×10-20cm2。计算证实,PWO:Er3 中几乎有80%的激发能量非辐射跃迁转移致4I13/2能级,4I13/2的计算寿命是5200μs,J-O计算显示,在PWO中产生4I13/2→4I15/2和发射1.53μm.有高的几率。讨论了不同浓度Er3 掺杂对于吸收系数和PbWO4晶体光学吸收边的影响,讨论了Er3 掺杂PbWO4晶体的光致发光和X射线激发发光光谱,PbWO4:Er3 晶体中存在着从PbWO4基质到Er3 离子的能量传递,发光光谱的分析表明,这种能量传递是共振能量传递。     

Photoluminescence of Sm3+, Dy3+, and Tm3+-doped transparent glass ceramics containing CaF2 nanocrystals

Photoluminescence properties of Sm³⁺, Dy³⁺, and Tm³⁺-doped transparent oxyfluoride silicate glass ceramics containing CaF₂ nanocrystals were reported. Emission bands of ⁴G_5/2 → ⁶H_5/2 (562 nm), ⁴G_5/2 → ⁶H_7/2 (598 nm), ⁴G_5/2 → ⁶H_9/2 (645 nm) and ⁴G_5/2 → ⁶H_11/2 (706 nm) for the Sm³⁺: glass and glass ceramic, with an excitation at ⁶H_5/2 → ⁴F_7/2 (402 nm) have been recorded. Of them, ⁴G_5/2 → ⁶H_7/2 (598 nm) has shown a bright orange emission. With regard to the Dy³⁺: glass, a bright fluorescent yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) and blue emission at 481 nm (⁴F_9/2 → ⁶H_15/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 386 nm (⁶H_15/2 → ⁴I_13/2 + ⁴F_7/2) wavelength. Emission bands of ¹G₄ → ³F₄ (650 nm) and ¹G₄ → ³H₅ (795 nm) transitions for the Tm³⁺: glass and glass ceramic, with an excitation at ³H₆ → ¹G₄ (467 nm) have been observed. Of them, ¹G₄ → ³F₄ (650 nm) has shown bright red emission. Decay lifetime measurements were also carried out for all the observed Sm³⁺, Dy³⁺, and Tm³⁺-doped glass and glass ceramic emission bands.     

Broadband infrared luminescence of Ni-doped silicate glass-ceramics containing lithium aluminate spinel nanocrystals

Transparent Ni²⁺-doped SiO₂-Al₂O₃-Ga₂O₃-Li₂O (LGAS) glass-ceramics embedding lithium aluminate spinel nanocrystals was prepared. After heat treatment, LiAl₅O₈ crystallite was precipitated in the glasses, and its size was about 3 nm. It was confirmed from the absorption spectra that the ligand environment of Ni²⁺ ions changed from the trigonal bi-pyramid fivefold sites in the as-made glass to the octahedral sites in the glass-ceramics. Upon excitation at 980 nm, broadband infrared luminescence centered at around 1250 nm with full width at half maximum (FWHM) more than 250 nm was observed originating from the ³T₂(³F) → ³A₂(³F) transition of Ni²⁺ in octahedral sites. The broadband near-infrared (NIR) emission from Ni²⁺-doped glass-ceramics can be as host materials for broadband optical amplifier.     

Cr~(4+)∶Ca_2GeO_4多晶料的合成与表征

采用固相法合成Cr4+∶Ca2GeO4晶体原料,通过XRD分析确定了合成Cr4+∶Ca2GeO4多晶料的最佳温度,计算了Cr4+∶Ca2GeO4多晶料的晶格参数。XPS和荧光光谱分析表明多晶料中含有Cr4+。Cr4+∶Ca2GeO4多晶料具有宽的室温荧光光谱,光谱范围为1000~1600 nm,最强荧光发射峰位于1257 nm,这是Cr4+的3T2→3A2能级跃迁导致的荧光发射。     

GdAl3（BO3）4及其Yb^3＋激活激光晶体的研究

采用顶部籽晶法从K2Mo3O10-B2O3助熔剂体系中生长出尺寸达到20 mm的GdAl3(BO3)4(简称GAB)和Yb3 激活的晶体.测试了GAB晶体的<100>和(001)轴向热膨胀系数,确定了透光波长范围,计算了有效倍频系数和相位匹配角随波长的变化,结果表明GAB晶体在整个透光范围内均可实现相位匹配.测定了Yb3 :GAB晶体在室温下的偏振吸收和荧光光谱,进行了光谱计算,测试了晶体的激光性能,在1046 nm处实现了2.1 W激光输出,斜率效率达到58%.