GexSb20Se80-x玻璃的拉曼光谱和X射线光电子能谱

用拉曼散射光谱和X射线光电子能谱研究了Ge_xSb₂₀Se_80-x(x=5 mol%, 10 mol%, 15 mol%, 17.5 mol%, 20 mol%和25 mol%)玻璃的结构. 通过对拉曼光谱和X射线光电子能谱(Ge 3d, Sb 4d 和Se 3d谱)进行分解, 发现当硫系玻璃处于富Se状态下时, 玻璃结构中会出现Se–Se–Se结构单元, 其数量随着Ge含量的增加而迅速减少, 并最终在Ge₁₅Sb₂₀Se₆₅玻璃结构中消失; Ge和Sb原子分别以GeSe_4/2 四面体和SbSe_3/2三角锥结构单元在玻璃结构中出现, GeSe_4/2四面体结构单元的数量会随着Ge浓度的增加而增加, 而SbSe_3/2三角锥结构单元的数量基本保持稳定. 另一方面, 在缺Se的硫系玻璃中, 玻璃会有Ge–Ge和Sb–Sb同极键产生, 随着Ge含量的增大, 这种同极键的数量会越来越多; 而GeSe_4/2四面体和SbSe_3/2三角锥结构的数量则相应减少. 在所有玻璃样品的结构中均有同极键Se–Se的存在. 当玻璃组分越接近完全化学计量配比时, 异质键Ge–Se和Sb–Se将占据玻璃结构中的主导地位, 同极键Ge–Ge, Sb–Sb和Se–Se 的比例降为最小.     

Glass formation and vibrational properties in the (Ge,Sn) system

The glass forming tendency and infrared reflectance spectra are investigated in the (Ge, Sn) system. It is found that the glass formation of the SnSe system is much more difficult than that of the Ge system. This is mainly ascribed to the ionicity difference between GeSe and SnSe bonds. Infrared spectra in the glassy Ge_1-xSe_x system at the composition 0.67<x<1.0 indicate the presence of clusters within which the atomic connectivity is similar as in the glassy GeSe₂. The vibrational modes caused by the $\text{SnSe}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}$ tetrahedron are found in the glassy (Ge, Sn)-Se system. It is suggested that tin atoms are mainly incorporated into the clusters. Importance of the medium range order is discussed in the formation of the glasses.     

Evidence for insulator–metal transition in amorphous chalcogenide Se–Ge–Te films

The temperature dependence of the dc conductivity and thermoelectric power was determined for five different amorphous chalcogenide Se–Ge–Te films, with Ge?=?3.0–22?at.%, Se?=?0–97?at.% and Te?=?0–97?at.%. The films were prepared by thermal evaporation of GeSe₄, GeTe₄ and GeSe₂Te₂ quenched bulk materials. Values of the activation energy calculated from the temperature dependence of both electrical conductivity and thermoelectric power showed a decrease with increasing Ge content in the Se–Ge films as well as with replacement of Te for Se in the Se–Ge–Te films. The results showed an Anderson transition, with the conductivity showing insulating behaviour on the Ge–Se side to metallic behaviour at the binary composition Ge–Te. The radius of localization was obtained for the different compositions investigated. The wave function associated with the charge carriers at the composition Ge_3.3Te_96.7 is non-localized. A minimum metallic conductivity of 237?±?5?(Ω?cm)^?1 was found.     

Large core, multimode, chalcogenide glass fibre coupler by side-polishing

A novel method for obtaining a multimode optical coupler in chalcogenide glass fibre is described. The fibres used had a large $\text{ Ge }_{17}\text{ As }_{18}\text{ Se }_{65}$ Ge 17 As 18 Se 65 core comprising about 74 % of the total cross-sectional area with an optical cladding of $\text{ Ge }_{17}\text{ As }_{18}\text{ Se }_{62}\text{ S }_{3}$ Ge 17 As 18 Se 62 S 3 . A single arc-shaped U-groove was formed in each of two silicate glass blocks. A length of fibre was embedded into each groove and glued in place. The centre of each fibre length was subsequently side-polished. Finally two such embedded fibres were glued together in close contact to form the coupler, whilst monitoring the coupling ratio at the output.     

Ag–Ge–Se glasses: a vibrational spectroscopy study

Ag_x(Ge_0.25Se_0.75)_100−x glasses with x varying from 0 to 25 have been shown to exhibit a conductivity threshold around x ~8–10. In this work, the structural changes induced by introduction of Ag in Ge₂₅Se₇₅ glass have been investigated using Raman and infra‐red spectroscopies. In ambient conditions, changes are observed in position, width and intensity for vibrations assigned to Ge–Se bonds, showing that the tetrahedral network is relaxed and gains flexibility as Ag is introduced. High pressure experiments on two glasses containing 5 and 25 at.% Ag confirm that Ag‐rich (25%) glasses clearly exhibit higher compressibility than Ag‐poor (5%) glasses. Copyright © 2013 John Wiley & Sons, Ltd.     

石墨炉原子吸收法测定麦芽粉中的锗和硒

本文叙述了平台石墨炉原子吸收法测定麦芽粉中的锗和硒，采用Ｐｄ＋Ｎｉ和Ｐｄ基体改进剂，使锗和硒的灰化温度分别提高到１４００和１２００℃，有效地消除了基体干扰。方法特征量为３１ｐｇ（Ｇｅ）和２３ｐｇ（Ｓｅ），检出限为２８ｐｇＧｅ和６２ｐｇＳｅ（３σ）。对含２２￣１１０μｇ／ｇＧｅ和１８￣３５μｇ／ｇＳｅ的样品测定，相对标准偏差为Ｇｅ３．７￣５．６％（ｎ＝９），Ｓｅ４．３￣６．５％（ｎ＝９），回收率在９     

Ge/SiO2纳米晶玻璃的制备及其荧光性质

以正锗酸乙酯和正硅酸乙酯为原料 ,合成了Ge/SiO2 纳米晶玻璃。探索了用溶胶凝胶法合成GeO2 /SiO2 玻璃 ,进而在高温 70 0℃下用氢气将其还原成Ge/SiO2 纳米晶玻璃的全过程。研究了Ge/SiO2 纳米晶玻璃的紫外吸收光谱、X射线衍射谱及荧光光谱。紫外吸收光谱显示由GeO2 /SiO2 玻璃向Ge/SiO2 纳米晶玻璃转变中有组成和结构的改变。X射线衍射谱明显显示有立方相Ge晶体颗粒在玻璃中析出。荧光光谱显示其具有荧光发射效应。根据其荧光发射峰值计算出Ge晶体颗粒平均大小为 3nm     

新型硫族化合物在中红外非线性光学晶体方面研究进展

利用红外非线性光学晶体材料对已有的成熟的激光光源进行频率转换是获得3~5μm和8~12μm"大气窗口"红外激光的主要方法。传统的红外非线性光学晶体存在缺陷,不能满足应用要求,需要探索新型的红外材料。综述了以硫族化合物为研究对象,寻找新型中红外非线性光学晶体材料的研究进展。介绍了Li MQ2(M=Ga,In;Q=S,Se,Te),BaGa4S7,BaGa4Se7,BaGa2MQ6(M=Si,Ge;Q=S,Se)及Li2In2MQ6(M=Si,Ge;Q=S,Se)的研究进展。     

偶偶Ge和Se同位素核的形变HF态及负宇称带研究

将具有负宇称的fp轨道空间扩大到包含具有正宇称的1g_9/2轨道,采用修正的表面δ相互作用,对⁶⁴Ge,⁶⁶Ge,⁶⁸Ge,⁷⁰Se,⁷²Se和⁷⁴Se等6个偶偶核做了形变HF计算.得到了基态和一些激发态的解.同时,还用近似角动量投影形变Hartree-Fock(PDHF)方法,对⁶⁴Ge和⁷⁴Se进行了能谱计算,得到其正、负宇称带的解,计算结果与实验谱基本一致.     

原子核的反常宇称能谱研究

将具有负宇称的 fp 空间扩大到包含1g9/2 轨道, 采用修正的表面相互作用(MSDI), 对64Ge, 66Ge, 68Ge, 70Se, 72Se, 74Se, 76Kr 和 78Kr等偶偶核作了形变Hartree Fock计算, 得到了基态和一些激发态的解. 同时, 还用近似角动量投影形变Hartree Fock（PDHF）方法对偶偶核64Ge, 74Se和奇A核79Kr进行了能谱计算, 得到其正、 负宇称带的解, 计算结果与实验谱基本一致.Using modified surface delta interaction, enlarging the fp configuration space to include the 1g9/2 orbit with the abnormal parity, the deformed Hartree Fock calculations for the eight nuclei: 64Ge, 66Ge, 68Ge, 70Se, 72Se , 74Se, 76Kr and 78Kr are performed. The ground state and some particle hole excited configurations are obtained. The approximate angular momentum projected deformed Hartree Fock (PDHF) method is applied to even even nuclei 64Ge and 74Se and odd A nuclus 79Kr. Both of their normal and abnormal parity bands are obtained. The calculated energy spectra are consistent well with experimental spectra.     

Influence of the selenium content on thermo-mechanical and optical properties of Ge–Ga–Sb–S chalcogenide glasses

A number of Ge₁₇Ga₄Sb₁₀S_69−xSe_x (x = 0, 15, 30, 45, 60, and 69) chalcogenide glasses have been synthesized by a melt-quenching method to investigate the effect of the Se content on thermo-mechanical and optical properties of these glasses. While it was found that the glass transition temperature (T_g) decreases from 261 to 174 °C with increasing Se contents, crystallization temperature (T_c) peak only be observed in glasses with Se content of x = 45. It was evident from the measurements of structural and physical properties that changes of the glass network bring an apparent impact on the glass properties. Also, the substitution of Se for S in Ge–Ga–Sb glasses can significantly improve the thermal stability against crystallization and broaden the infrared transmission region.     

Structural investigations of Ge(5)As(x)Se(95-x) and Ge(15)As(x)Se(85-x) glasses using x-ray diffraction and extended x-ray fine structure spectroscopy

The structure of Ge(5)As(x)Se(95-x) (x?=?10, 20, 30, 38?at.%) and Ge(15)As(x)Se(85-x) (x?=?10, 25, 34?at.%) glasses has been investigated by high-energy x-ray diffraction and extended x-ray absorption fine structure measurements. The experimental datasets have been modelled using the reverse Monte Carlo simulation technique. The model atomic configurations have been analysed in detail. It has been found that the homonuclear Ge-Ge, As-As, Se-Se and heteronuclear Ge-As bonds play an important role in the structure formation of the Ge-As-Se glasses. The total number of these bonds decreases quite slowly with the mean coordination number similarly to the nonlinear refractive index.     

Raman scattering and bond structure in chalcogenide glasses (SeGe system)

The Raman Scattering from amorphous SeGe is studied in the whole range of germanium content up to 80%. The result suggests an appearance of three-fold coordinated bond between Se and Ge above the germanium con- content of 40%.     

Ge30Sb8Se62硫系玻璃的制备及其10.6μm低损耗空芯光子带隙光纤的设计

硫系玻璃光子晶体光纤在中远红外激光传输领域具有广阔的应用前景。制备了红外波段具有优良透过特性的Ge30Sb8Se62硫系玻璃,并以此为基质材料设计了一种适合于高功率中红外激光传输的带隙型光子晶体光纤。利用平面波展开法和有限元法分析了不同结构下该光纤的光子带隙、模场面积和限制损耗特性。通过优化光纤的结构参数,获得了在10.6μm处限制损耗小于0.1dB/m的大模场(模场面积大于100μm2)光子晶体光纤。     

Thermally induced effects in amorphous GeSe2 and GeSe films studied by ultraviolet photoelectron spectroscopy

During thermal annealing, the changes in the valence states of amorphous GeSe₂ and GeSe films deposited on the substrates held at 77 K were observed by UPS. The experimental results are explained in terms of the four (Ge)-two (Se) fold coordination for amorphous GeSe₂ and the three(Ge)-three(Se) fold one for amorphous GeSe.     

Effect of replacement of Se by S on structural and physical properties of Ge–Sb–As–Se–S chalcogenide glasses

In the present study, the structural and opto-mechanical properties of Ge–Sb–As–Se–S chalcogenide glasses have been investigated. For this purpose, different bulk glasses of Ge₂₀Sb₅As₁₅Se_60?xS_x (0 ≤ x≤50) were prepared by conventional melt quenching technique in quartz ampoule and different characteristics of prepared glasses such as glass transition temperature, density, hardness, transmittance, optical band gap energy and refractive index were determined. The value of hardness and glass transition temperature of prepared glasses were found to increase with increasing the sulfur content as a result of formation of GeS₄ tetrahedral units and increasing the network connectivity and average bonding energy. The optical energy gap (according to Tauc’s relation), transmittance and refractive index of prepared glasses are in direct relation with sulfur content. In this study, the highest value of transmittance (about 70%) and lowest value of refractive index (2–2.3) was achieved in Ge₂₀Sb₅As₁₅Se₄₀S₂₀ and Ge₂₀Sb₅As₁₅Se₁₀S₅₀ glasses, respectively.     

Anomalous behaviour of the knightshift on impurity atoms in glass-forming alloys

TDPAD (time dependent Perturbation of Angular distribution) technique has been used to measure the Knightshift of^69mGe in liquid Ge and the solute Knightshift for^73mAs in solid and liquid Germanium and the Ge alloys Ge−As, Ge−Se and Ge−Te. In the Ge−Te alloy the As Knightshift could hardly be explained by the magnetic properties of the alloy. The anomaly is discussed taking the glass forming properties of the Ge−As−Te system into account. This work was supported by DFG through Sfb 161 and Kernforschungszentrum Karlsruhe     

Self-trapping of single and paired electrons in Ge2Se3

We report the theoretical prediction of single and paired electron self-trapping in Ge(2)Se(3). In finite atomic cluster, density functional calculations, we show that excess single electrons in Ge(2)Se(3) are strongly localized around single germanium dimers. We also find that two electrons prefer to trap around the same germanium dimer, rupturing a neighboring Ge-Se bond. Localization is less robust in periodic, density functional calculations. While paired electron self-trapping is present, as shown by wavefunction localization around a distorted Ge-Ge dimer, single-electron trapping is not. This discrepancy appears to depend only on the boundary conditions and not on the exchange-correlation potential or basis set. For single- and paired-electron trapping, we report the adiabatic barriers to motion and we estimate hopping rates and freeze-in temperatures. For the single trapped electron, we also predict the (73)Ge and (77)Se hyperfine coupling constants.     

Der Zerfall des77Kr

⁷⁷Kr (T _1/2=1.2 h) was produced by bombarding⁷⁶Se with 48 MeV-α-particles. After irradiation the radioactive⁷⁷Kr gas was collected in glass ampoules filled with charcoal and cooled by liquid air. The decay of⁷⁷Kr has been investigated using Ge(Li)-counters and a Ge(Li)-Ge(Li)-coincidence circuit. 27 γ-transitions, 13 of them unknown up to the present, have been found and their relative intensities have been determined. A level scheme for⁷⁷Kr→⁷⁷Br having 14 levels is proposed. This accounts for all the observed γ-transitions.     

Structural investigation of Te-based chalcogenide glasses using Raman spectroscopy

Structural changes of metals (Zn, Sb, In, Ga) and metal halides (AgI, ZnI₂, CdI₂, PbI₂, BiI₃) modified GeTe₄ glasses were investigated with the aid of Raman spectroscopy. The Raman spectra of these glasses in the frequency region between 100 cm^?1 and 300 cm^?1 display four main bands at about 124, 140, 159 and 275 cm^?1 which are contributed by Ge–Te, Te–Te, Te–Te and Ge–Ge vibration modes. The intensity of 159 cm^?1 and 275 cm^?1 bands vary with the addition of different glass modifiers. While the relative intensity of the 124 cm^?1 and 140 cm^?1 bands are insensitive to composition changes. Glass modifiers like Zn, In and Sb act as glass network unstabilizer which will disorganize the glass network by opening up the chain structures of Ge–Te and Te–Te. In the case of Ga and metal halides, Ga can open up Ge–(Te–Te)_4/2 tetrahedra and form Ga–(Te–Te)_3/2 triangle. Iodine can form covalent bonds with tellurium and decrease the tendency of microcrystal formation. Thus both Ga and iodine ultimately act as glass network stabilizer.