Ga对新型远红外Te基硫系玻璃光学性能的影响

用传统熔融淬冷法制备了新型远红外Te基硫系玻璃(100-x)(GeTe₄)-xGa (x=0, 5, 10 mol%).利用差热分析(DTA)、可见/近红外吸收光谱、红外透射光谱等技术,在GeTe₄玻璃的基础上,通过引入较高配位金属Ga, 研究其对玻璃组成、结构和性能的影响,利用经典的Tauc方程计算了样品光学带隙允许的直接跃迁、允许的间接跃迁及Urbach能量.分析结果表明:在GeTe₄玻璃中引入 关键词： 光学材料 硫系玻璃 光学带隙 红外光谱     

新型远红外Ge-Ga-Te-KBr硫系玻璃性能研究

用传统的熔融淬冷法制备了远红外Te基硫系玻璃(Ge15Ga10Te75)100-x(KBr)x(x=2、4、6、8mol%).利用X射线衍射仪、差示扫描量热仪等设备测试玻璃的结构和物化性质,分析了引入KBr对Te玻璃的结构、化学和物理热稳定性等方面的影响;利用分光光度计、红外光谱仪等光学方法研究了该类Te玻璃的光谱性质,分析了KBr对该类玻璃的短波吸收和红外透过光谱的影响;利用Tauc方程估算了玻璃样品直接和间接的光学带隙.实验结果表明:随着KBr含量的增加,玻璃的短波截止边发生红移,而红外截止边基本没有发生变化,该组玻璃始终保持较宽的红外透过范围.     

新型远红外Ge-Te-I硫系玻璃性能研究

采用传统的熔融-淬冷法制备了系列Ge20Te80－xIx(x=2,4,6,8 mol%) 玻璃样品.利用X射线衍射仪、扫描电子显微镜、差热分析仪等设备系统测试了玻璃结构和物化性质,分析了卤素I对玻璃形成及稳定性的影响|利用分光光度计、红外光谱仪等研究了玻璃光谱性质,分析了I对玻璃的短波吸收及红外透过光谱的影响|利用Tauc方程计算了样品的直接和间接光学带隙.实验结果表明:I的引入,降低了Te的金属性,提高了Te基硫系玻璃的成玻能力|随着卤素I含量的增加,玻璃的密度减小,摩尔体积增大,且短波吸收截止边发生红移,光学带隙减小|I的引入提高了玻璃的热稳定性,其中玻璃组分为Ge20Te72I8样品热稳定性最好,其特征温度（ΔT）达到121℃|各Ge-Te-I玻璃样品均具有良好的红外透过性能,其红外透过范围为1.8~25 μm.     

TeO2-Nb2O5-BaCl2玻璃的结构及光学性能研究

用传统熔融法制备了一种新型的氧氯碲酸盐玻璃:（90-x）TeO₂-10Nb₂O₅-xBaCl₂（x=10,20,30）,用密度比重天平、显微拉曼光谱仪、红外-可见-紫外分光光度计和棱镜耦合仪研究了组分变化对玻璃密度、结构、光学性质、折射率和色散的影响.研究结果表明:随玻璃中BaCl₂含量增加,玻璃密度出现了先增大后减小的现象;玻璃结构中双三角锥体[TeO₄]量减少,三角棱锥体[TeO₃]量增加;玻璃的折射率逐渐减小.新型的氧氯碲酸盐玻璃具有较高的线性折射率n_max=2.02259,非线性折射率N₂=6.8×10^-12esu与三阶非线性极化率χ^（3）=3.7×10^-13esu.制备的新型碲酸盐玻璃在可见和中红外光谱区具有高透过,在近紫外光谱区具有明显的吸收截止波长,且随BaCl₂含量增加吸收截止波长发生了明显的蓝移现象.利用经典的Tauc方程计算了玻璃样品的直接跃迁光学带隙和间接跃迁光学带隙,玻璃的光学带隙随BaCl₂含量增加而增大.     

远红外Ge-Te-I高卤硫系玻璃的制备及其光学性能的研究

为获得高质量的远红外硫系玻璃,采用传统的真空熔融淬冷法配合真空低温固化技术制备了高卤素含量的Te硫系玻璃(卤素Imax =40 at.％),并分析了该系列Ge20Te80-xIx(x-10、15、20、25、30、35、40)硫卤玻璃样品.采用分光光度计和傅里叶红外光谱仪等光学仪器分析该玻璃的可见/近红外吸收光谱和红外透射光谱等频谱性质,利用Raman光谱仪和X射线衍射仪分析了玻璃的内部微观结构.研究表明,随着卤素Ⅰ元素的增加,可见/近红外吸收光谱的短波截止边持续发生蓝移,光学带隙持续增大,从近红外的1 μm一直到远红外波长25μm都保持透光性;Ge20Te65I15玻璃的转变温度最大,在138℃附近,其红外透过率最高,达到50％.     

远红外Ge-Te-Ⅰ高卤硫系玻璃的制备及其光学性能的研究

为获得高质量的远红外硫系玻璃,采用传统的真空熔融淬冷法配合真空低温固化技术制备了高卤素含量的Te硫系玻璃(卤素Imax=40at.%),并分析了该系列Ge20Te80-xIx(x=10、15、20、25、30、35、40)硫卤玻璃样品.采用分光光度计和傅里叶红外光谱仪等光学仪器分析该玻璃的可见/近红外吸收光谱和红外透射光谱等频谱性质,利用Raman光谱仪和X射线衍射仪分析了玻璃的内部微观结构.研究表明,随着卤素I元素的增加,可见/近红外吸收光谱的短波截止边持续发生蓝移,光学带隙持续增大,从近红外的1μm一直到远红外波长25μm都保持透光性;Ge20Te65I15玻璃的转变温度最大,在138℃附近,其红外透过率最高,达到50%.     

Ge-Se基硫系玻璃在通信波段的三阶非线性与光谱特性研究

在Ge-Se二元体系中引入相同摩尔比的Ga, Sn, Sb, Te四种元素, 使用熔融淬冷法制备了一系列硫系玻璃. 利用吸收光谱获得了不同元素引入下硫系玻璃能带结构的变化, 并结合拉曼光谱详细研究了产生光学特性变化的微观表征. 使用Z扫描方法测试了各个硫系玻璃样品在1550 nm波长下的三阶非线性参数, 发现加入Sn的玻璃的三阶非线性折射率n₂最大, 达到了6.36×10^-17 m²/W, 且其品质因子大于23, 表明Sn引入能够增强硫系玻璃在通信波段的三阶非线性, 这一研究结果为以后的高性能红外器件的设计及制备提供了一种环保且性能优良的候选材料.     

GeS2-In2S3硫系玻璃的物化性质与晶化行为研究

认识玻璃组成-性能-结构之间关系是玻璃科学中经久不衰的研究课题之一. 在制得(100-x) GeS₂-xIn₂S₃ (x=10, 15, 20, 25或30 mol%) 系列玻璃和玻璃陶瓷样品的基础上, 利用可见-近红外透过光谱, DSC, XRD和Raman光谱等测试技术表征了随组份变化的光学带隙, 玻璃转变温度以及晶化行为等, 并结合GeS₂-Ga₂S₃玻璃研究结果探讨了Ga, In 元素及其形成的网络结构对玻璃性质的影响.研究发现, 在硫系玻璃中In比Ga对光学带隙和玻璃转变温度等性质的影响要大. 它们所形成玻璃的晶化行为也截然不同, 但与其各自的材料相图有着密切的联系. 利用偏振拉曼光谱获得玻璃网络中的基本结构单元信息.最后, 结合材料相图, 玻璃随组成变化的物化性质和晶化行为以及基本网络结构单元的认识, 探讨了玻璃的化学拓扑与网络拓扑之间的联系, 为今后研究提供一种新的研究思路.     

反应磁控溅射法制备的氟化类金刚石薄膜的XPS结构研究

采用射频反应磁控溅射法用高纯石墨作靶、三氟甲烷(CHF₃)和氩气(Ar)作源气体制 备了氟化类金刚石（FDLC）薄膜，通过XPS光谱结合拉曼光谱、红外透射光谱和紫外 可见光光谱研究了源气体流量比等工艺条件对薄膜中键结构、sp2/sp3杂化比以及光学带隙等性能的影响.结果表明在低功率(60W)、高气压(2.0Pa)和适当的流量比(Ar/CHF₃=2∶ 1)下利用射频反应磁控溅射法可制备出氟含量高且具有较宽光学带隙和超低介电常数的FDLC薄膜. 关键词： 反应磁控溅射 氟化类金刚石薄膜 红外透射光谱 XPS光谱     

电子回旋共振等离子体增强沉积氟化非晶碳薄膜的光学性质

用紫外可见光透射光谱(UV-VIS)并结合键结构的X射线光电子能谱(XPS)和红外谱(FTIR)分析,研究了电子回旋共振等离子体增强化学气相沉积法制备的氟化非晶碳薄膜的光吸收和光学带隙性质.在微波功率为140—700W、源气体CHF₃∶C₆H₆比例为1∶1—10∶1条件下沉积的薄膜,光学带隙在1.76—2.85eV之间.薄膜中氟的引入对吸收边和光学带隙产生较大的影响,吸收边随氟含量的提高而增大,光学带隙则主要取决于CF键的含量,是由于强电负 关键词： 氟化非晶碳薄膜 光吸收与光学带隙 电子回旋共振等离子体     

Optical absorption and thermoluminescence studies on LiF-Sb2O3-B2O3 glasses doped with Ni ions

20LiF-(30−x)Sb₂O₃-50B₂O₃:xNiO glasses with the value of x (ranging from 0 to 1.0 mol% in steps of 0.2) were prepared. A number of studies, viz. differential scanning calorimetry, optical absorption, magnetic susceptibility and thermoluminescence, on these glasses were carried out as a function of nickel ion concentration. An anomaly has been observed in all the properties of these glasses when NiO concentration is about 0.6 mol%. The results of these studies were analysed in the light of different environments of nickel ions in the glass network.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

Ion implantation effects in glasses

Abstract

Ion implantation can be used to introduce network damage and to alter the chemical composition in glasses. Structural changes can be inferred from IR measurements near 1000 cm^?1 and by optical absorption near 2150 Å. Implantation-induced damage decreases the implanted volume in fused silica with consequent changes in the refractive index, the near-surface hardness, and the tensile surface stress. Prior work in these areas is reviewed. Implantation into alkali silicate glasses depletes the alkali content in the implanted region. These changes allow preferential surface crystallization in Li₂O-2SiO₂ glasses. Crystallization of amorphous SiO2 can be induced by implantation of Li. Insight into the crystallization process is obtained by following the associated ion movement by elastic recoil detection (ERD) and optical techniques. Implantation of 20keV H shows that saturation of implanted H-sites in fused silica occurs at about 2.2 × 10²¹ H/cm³ in agreement with free volume estimates of the maximum number of available interstitial sites. Details of H and D interactions in fused silica were studied as a function of fluence and temperature. Results are of interest in studies of corrosion in glasses considered for nuclear waste encapsulation and for components in fusion reactors.

IV Summary     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.     

Crystallization behavior of GeSe2-Ga2Se3-CsI glasses studied by Differential Thermal Analysis

GeSe₂-Ga₂Se₃-CsI chalcohalide glasses had been prepared by the melt-quenching technique. With the addition of CsI, the short wavelength cut-off edge of the glasses shifts to the short wavelength gradually, while the long wavelength cut-off edge located at ∼16 μm is nearly unchanged. Thermal properties were measured by Differential Thermal Analysis (DTA). From the heating rate dependence of crystallization temperature, the activation energy for crystallization (E) and the order parameter (n) were calculated by the Kissinger equation. The results show that the activation energy of crystallization decreases dramatically with increasing of CsI content, and the most probable crystallization mechanism is volume controlled one-dimensional growth.     

Influence of valence states and co-ordination of cobalt ions on dielectric properties of PbO-Bi2O3-As2O3:CoO glass system

The glasses of the composition (40−x) PbO-15Bi₂O₃-45As₂O₃-xCoO, with 0≤x≤0.6 mol% in the steps of 0.1 were synthesized. The dielectric properties viz., dielectric constant, loss and ac conductivity over moderately larger ranges of frequency and temperature were investigated. The results were analyzed with the aid of the data on optical absorption and IR spectra. The analysis indicated that there is an increase in the insulating strength of the glasses with increase in the concentration of CoO up to 0.4 mol%.     

Second-order optical nonlinearity in Sb2S3 microcrystal doped glasses by electron beam irradiation

With Maker fringe measurements, the prominent second harmonic generation was observed in the sol-gel-derived Sb₂S₃ doped silica glasses irradiated by electron beam, which was related to the space-charge electrostatic field that makes the glasses poled and broken the centrosymmetry of the glasses. By sides, the interface of nanoparticles contributed to the second harmonic intensity as well. The second harmonic intensity increased with the increasing of the irradiating current, accelerating voltage and the concentration of the dopant due to the enhanced built-in electrostatic field. The poled region was located in the surface of the sample about several microns by the TSDC measurements. The second harmonic intensity is almost 10 times larger than that of the base glass due to the existence of microcrystal.     

Spectroscopical splitting of Cu ion energy levels in magnesium lead fluoro silicate glasses

Homogeneous 40.0 MgO-(10-x) PbF₂-50.0 SiO₂: x CuO glasses were prepared using melt-quenching technique under controlled conditions. Spectroscopic studies (UV-vis absorption, ESR, FT-IR) are carried out for these glasses. One broad characteristic visible absorption band is observed around 700-850 nm in these glasses, the optical band gap decreases as the content of the CuO increases in the glass network up to 0.7 mol % then reversal trend is observed. ESR spectra of all these glasses show resonance peaks characteristic of Cu²⁺ ions and hyperfine splitting is resolved with increasing the CuO content in the glass network. From the observed ESR spectra, the spin-Hamiltonian parameters have been evaluated and indicate that Cu²⁺ ions have octahedral coordination with a strong tetragonal distortion in these glasses. By correlating ESR and optical absorption data, the molecular orbital coefficients have been evaluated. FT-IR spectra give important information about the nature of bonds in the glass matrix. The density of the glasses is also measured and is found to decrease with the increase CuO contents in the glass matrix. The physical parameters along with spectroscopic parameters are measured.     

Fluorescence features of Sm ions in Na2SO4-MO-P2O5 glass system—Influence of modifier oxide

Na₂SO₄-P₂O₅:Sm³⁺ glasses mixed with three different alkaline earth modifier oxides viz., MgO, CaO and BaO were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature; the Judd-Ofelt theory was successfully applied to characterize these spectra. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r, for various emission levels in the spectra of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies in the change of scenario for modifying oxides in the glass network.     

Radiation-Induced Paramagnetic Centers in the Glasses Of CaO-Ga2O3-GeO2 System

The X-band (v ? 9.4 GHz) ESR spectra of the UV-, X-, and γ-irradiated glasses of CaO-Ga₂O₃-GeO₂ system with compositions similar to Ca₃Ga₂Ge₃O₁₂, Ca₃Ga₂Ge₄O₁₄, and Ca₃Ga₂O₆ crystals have been investigated at 300 and 77 K. It was shown that X- and γ-irradiation of the Ge-contained glasses induce simultaneously electron and hole paramagnetic centers, stable at room temperature. The UV-irradiation of Ge-contained glasses leads to the generation of stable centers of electron type, whereas the X- and γ-irradiation of glasses with Ca₃Ga₂O₆ composition induces stable hole centers, exclusively. The electron centers are assigned to E′ (Ge) centers with different local environments. ESR spectrum of hole centers is ascribed to O^? centers, localized on non-bridging oxygen of the glass network. The E′ (Ge) and O^? centers show high thermal stability in the CaO-Ga₂O₃-GeO₂ glass network. The obtained ESR spectra are described by spin Hamiltonian with g-factor of axial and rhombic symmetry for the E′ (Ge) and O^? centers, respectively. The nature, electron structure and some formation peculiarities of the radiation defects in CaO-Ga₂O₃-GeO₂ glasses are discussed in comparison with other glasses as well as Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ crystals.