Kinetic phenomena in non-crystalline materials studied by thermal analysis

The structural relaxation and viscosity behavior of Ge₃₈S₆₂ glass has been studied by thermomechanical analysis. The relaxation response to any thermal history is well described by the Tool-Naraynaswamy-Moynihan model. The apparent activation energy of structural relaxation is very close to the activation energy of viscous flow (Eη=478±12 kJ mol^-1). However, the activation energy of crystal growth obtained by optical microscopy is about one half of this value. Similar result has been obtained from isothermal DSC measurement (Ea=220±20 kJ mol^-1). The kinetic analysis of these data reveals interface controlled crystal growth with zero nucleation rate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Homopolar bonds in Se-rich Ge-As-Se chalcogenide glasses

We have prepared three groups of Ge–As–Se glasses in which the Se content is 5.5 mol%, 10 mol%, and 20 mol%rich, respectively. We explored the possibility of suppressing the formation of the Ge–Ge and As–As homopolar bonds in the glasses. Thermal kinetics analysis indicated that the 5.5 mol% Se-rich Ge_(11.5)As_(24)Se_(64.5) glass exhibits the minimum fragility and thus is most stable against structural relaxation. Analysis of the Raman spectra of the glasses indicated that the Ge–Ge and As–As homopolar bonds could be almost completely suppressed in 20 mol% Se-rich Ge_(15)As_(14)Se_(71) glass.     

Electrical properties of MWCNT-composite (Se80Te20)100−xAgx (0 ≤ x ≤ 4) chalcogenide glasses

This article describes the preparation of multi-walled carbon nanotube (MWCNT) chalcogenide glass composite by the melt-quenching technique. MWCNT composite (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples are characterized by the XRD, SEM and EDX. The electrical measurements were carried out in the temperature range of the 308-388 K. Cole–Cole plot has been used to determine the electrical conductivity at room temperature. It has been observed that MWCNT chalcogenide composite have higher value of electrical conductivity than pure glass. The results have been discussed on the basis of increased ionic conductivity (Ag⁺ ions) in MWCNT doped (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples.     

中红外高保偏硫系玻璃双芯光子晶体光纤耦合特性研究

设计了一种中红外硫系玻璃双芯光子晶体光纤,利用多极法和模式耦合基本理论研究了这种光纤的耦合特性.数值模拟发现,空气孔间距Λ = 5.4 μm,空气孔半径为r = 1.35 μm,空气填充率d/Λ = 0.5的光纤,在归一化波长λ/Λ = 2.04 μm处双折射可以达到0.551×10^-2,在归一化波长λ/Λ = 0.93 μm处x偏振方向的耦合长度为145.32 μm,y偏振方向的耦合长 关键词： 双芯光子晶体光纤 硫系玻璃 双折射 耦合长度     

Structural analysis of xCsCl(1−x)Ga2S3 glasses by means of DFT calculations and Raman spectroscopy

The alkali metal halide doping of gallium‐sulfide glasses yields improvements in the optical, thermal and glass forming properties. To understand these improvements, the short‐range order of xCsCl(1 − x)Ga₂S₃ glasses was probed by Raman spectroscopy. Raman spectra have been interpreted using density functional theory (DFT) harmonic frequency calculations on specific clusters of GaS₄H₄ and/or GaS₃H₃Cl tetrahedral subunits. The assignment of the observed vibrational bands confirms the main structural conclusions obtained with X‐ray and neutron diffraction experiments and gives some new insights into the gallium‐network present in the xCsCl(1 − x)Ga₂S₃ glasses. At the lowest concentration, the observed spectrum may be interpreted with small clusters such as dimers and trimers connected by corner‐sharing (CS) GaS₄H₄ tetrahedral subunits. The vibrational fingerprints of tri‐clusters with three‐fold coordinated sulfur atoms have also been identified; however, no Raman signature of chlorine‐doped subunits has been found to be caused by their insufficient intensity. For higher CsCl concentrations, distinct spectral features corresponding to chlorine‐doped clusters appear and are increasing in intensity with x. In other words, undoped and Cl‐doped tetrahedra coexist in the xCsCl(1 − x)Ga₂S₃ glasses. The added chlorine atoms induce a fragmentation of the glass network and replace the sulfur atoms in the CS tetrahedral environment. The comparison of the observed spectra with theoretical predictions and diffraction data favoured one‐fold coordinated chlorine atoms in the glass network. Copyright © 2009 John Wiley & Sons, Ltd.     

Controlled synthesis of ferromagnetic MnSe_x particles

The MnSe_x(x = 1,2) nanoparticles were synthesized under hydrothermal condition,by reaction of the reduced selenium and Mn~(2+) ion in the presence of hydrazine and acetic acid.By precisely controlling the pH value of the solution,a series of MnSe_x particles were synthesized.The structure and morphology of as-prepared particles were examined with x-ray diffractometer(XRD),transmission electron microscopy(TEM),and scanning electron microscopy(SEM).The average sizes of as-prepared particles varied from nanoscale to microscale with pH value increase.Furthermore,the nucleation and growth mechanism associated with pH values were discussed,which can be applied to the hydrothermal synthesis of metal chalcogenide in general.Finally,the optical and magnetic properties of as-prepared particles were measured.All as-made particles exhibit a ferromagnetic behavior with low coercivity and remanence at room temperature.     

非晶态As2S8半导体薄膜的光致结构变化效应研究

实验研究了非晶态As2S8半导体薄膜在光照、退火-光照和退火-光照-退火-光照关连作用下的光折变效应及淀积态与退火态两种膜系光致体积变化现象.采用棱镜耦合技术、Raman光谱和X线衍射测试技术,确认了As2S8薄膜经紫外光辐照后薄膜密度增高、折射率增大的现象.实验表明,淀积态As2S8薄膜经紫外光照后,折射率变化的最大增量可达到0.06,而退火态As2S8薄膜经紫外光照射后,其折射率最大变化比前者要小一个数量级,约为0.005 7.淀积态和退火态两种膜系紫外光照后,体积缩小,这与As2S3非晶态薄膜的情况不同,体积变化率分别为－3.5%和－2.1%.实验还显示,退火态的As2S8薄膜存在折射率完全可逆现象.     

GeS2-Ga2S3-CsI硫系玻璃的析晶行为及其组成依赖研究

硫系玻璃晶化过程中析出晶相的控制是硫系玻璃陶瓷制备中的一个重要环节. 在制得的65GeS₂·25Ga₂S₃·10CsI(GGC25)和70GeS₂·20Ga₂S₃·10CsI(GGC20)玻璃和玻璃陶瓷基础上, 利用可见—近红外透过光谱, SEM, XRD, Raman光谱等测试技术表征了其透过性能、晶粒尺寸、晶相类型等信息. 研究发现在这两组玻璃样品中少量的组分差别就能导致其显著的析晶行为改变: GGC20玻璃在热处理过程中析出的是GeS₂晶体; GGC25样品则拥有两步析晶过程, 其率先析出Ga₂S₃, 而后才有GeS₂晶体出现. 此外, 研究讨论了这种析晶行为与组成的依赖关系及其与玻璃网络结构之间联系, 可为今后硫系玻璃的可控晶化研究提供实验依据和理论指导.     

Amorphous to crystalline phase transition in glassy Se65Te20Ag15 alloy

In the present work, the amorphous to crystalline phase transition of chalcogenide glass Se₆₅Te₂₀Ag₁₅ has been studied using differential scanning calorimetric (DSC) measurements. The heating rate dependence of crystallization peaks has been used for the determination of activation energies of glass transition (E _g) and crystallization (E _c). Different non-isothermal methods have been used for this purpose. Other useful kinetic parameters such as the order parameter (n), the numerical factor of crystallization mechanism (m) and the frequency factor (K _o) of the rate constant (K) have been also determined.     

Lead telluride nanocrystalline thin films: Structure,optical characterization and a broadband dielectric spectroscopy study

Nanocrystalline PbTe thin films were deposited on a glass substrate by thermal evaporation technique with two thicknesses namely, 45 and 250 nm. The structural studies revealed that the films have nanocrystalline cubic structure and the particle size was found to be 11 and 20.7 nm, for low and high thicknesses respectively. The FE-SEM study shows that the surface grains increase for higher thickness film. This indicates that samples lying under the strong regime of confinement for PbTe thin films. The optical properties confirm the occurrence of confinement process as the optical band gap are 1.67 and 0.9 eV for 45 and 250 nm films, respectively. The dielectric results indicated that the conductivity increases by about two orders of magnitude with increasing the thickness from 45 to 250 nm. Moreover, the permittivity shows a higher dispersion step at lower frequencies in both samples due to the hopping conduction mechanism in addition to the interfacial polarization in such heterogeneous structures. Another small dispersion step is noticed in case of the lower thickness. It is attributed to the polarization of the accumulated charge carriers near the grain boundaries interfaces. No indication of any electrode phenomena in both samples is shown here.