A. C. conductivity due to intimate pairs of charged defect centres

The influence of the association of charged defects into intimate pairs on a.c. conduction is discussed in the light of the fundamental mechanism being that of the simultaneous hopping of two electrons over the barrier separating two oppositely charged defect centres, the barrier height being correlated with the intersite separation via the Coulomb interaction. The behaviour of chalcogenide glasses is discussed in terms of the present theory, and it is concluded that the existence of two classes of a.c. conductivity behaviour into which these materials generally fall can be simply explained by the predominance of either intimate pairs or non-intimate pairs of charged defect states according to the conditions of preparation.     

非晶态半导体的缺陷态化学键的量子化学研究

用量子化学的半经验自洽场分子轨道方法CNDO/2研究硫属玻璃中的各种缺陷态,包括带正电荷、负电荷和中性的三配位硫原子簇的化学键。从原子簇能量、原子净电荷、键级函数(双原子能量)等方面作了比较,取得了与Kastner相一致的结果,验证了K-A-F的换价对(VAP)理论。探讨了孤对电子对于缺陷态化学键的影响,证实了孤对电子在硫属玻璃中的重要作用。 关键词：     

Chalcogenide glasses as a medium for controlling ultrashort IR pulses: Part I

Chalcogenide glasses are ideal materials for developing fiber lasers and amplifiers, remote sensors, high-speed switches, and other devices that operate in the IR range of 1–10 μm. The nonlinear refractive index of chalcogenide glasses may exceed that of quartz glass by a factor of 100–1200 or even more. The data on the dispersion properties of some chalcogenide glass compositions in the IR range are presented. The possibility of forming waveguide structures with specified dispersion properties (in particular with a fixed wavelength at which the group velocity dispersion is zero) from these glasses is numerically investigated. It is shown by the example of completely glassy periodic waveguide structures with planar geometry that the use of photonic band gap modes makes it possible the change the position of zero dispersion in a wide wavelength range. In the calculations the contrast of waveguide structures was varied using parameters of glasses of different composition.     

Compositional Trends of Radiation-Induced Effects in Ternary Systems of Chalcogenide Glasses

The effect of γ-irradiation on the optical transmittance spectra of pseudobinary stoichiometric and non-stoichiometric cuts of ternary systems of chalcogenide glasses was studied. The application of chemical-bond approach is proposed to explain the features of compositional dependencies of radiation-induced effects in these materials. It is shown that free volume concept must be taken into consideration at the presence of different radiation-sensitive structural units. The creation processes of coordination defects connected with the formation of free volume and coupled with the capability of the constituent atoms to passivation are the main factors determining the magnitude of the radiation-induced effects in chalcogenide glasses.     

The relation between static disorder and photoluminescence quenching law in glasses: A numerical technique

Photoluminescence (PL) quenching, which usually obeys empirical Street law for glassy solids, is analyzed taking into account the fact that the quenching of each particular emission center is statistically described by the known Mott law. A numerical technique for retrieving energy distributions of luminescent centers from PL quenching measurements is proposed. Mathematical treatment procedure is established and tested for reliability. Calculation results for chalcogenide, quartz and lead-silicate glasses demonstrate the possibility for obtaining both ordinary and polymodal energy distributions of centers and also a good promise for application in PL spectroscopy of disordered solids.     

硫系玻璃在无热化长波红外广角镜头中的应用

设计了一种工作波段为8~12μm、有效焦距为5mm、F数为2、视场角为110°的无热化长波红外广角镜头.根据红外无热化光学设计的基本原理,用了常规红外材料硫化锌、硒化锌和硫系玻璃材料制备的六片镜片,通过合理地分配各个镜片的光焦度以及相互间空气间隔等参量,在全视场角为110°的范围内实现接近衍射极限的成像效果.为了更好地控制系统像差,设计利用了硫系玻璃易于精密模压制备非球面的优点,在两片硫系玻璃镜片上设计了3处非球面.设计结果显示:系统在-40℃~60℃的温度范围内均可实现品质良好的红外成像,光学调制函数全视场内均大于0.4,同时在110°视场角时畸变控制在5%以下;实现了在较大视场角条件下控制红外广角镜头的畸变以及系统无热化等设计要求.该系统体积紧凑、质量较轻,整体设计符合民用红外车载镜头的使用要求.     

Superionic and ion-conducting chalcogenide glasses: Transport regimes and structural features

Chalcogenide glasses are essentially known as amorphous semiconductors with interesting electronic and optical properties. In contrast to vitreous oxide systems which belong mostly to ionic insulators and/or conductors, the ion transport is not common for chalcogenide glasses and was observed for the first time in the seventies. Nevertheless, a higher polarisability of sulphur, selenium or tellurium compared to oxygen and respectively a higher ionic mobility and diffusivity, makes appropriate chalcogenide glassy systems favourable candidates for both fundamental research and practical applications in the field of solid-state ionics. The observed drastically different ion transport regimes that are closely related to the mobile cation distribution in the structure of silver and copper chalcogenide and chalcohalide glasses will be discussed in the present contribution which represents a compilation of recent results obtained by the author.     

New type of charged defect in amorphous chalcogenides

We report on density-functional-based tight-binding simulations of a series of amorphous arsenic sulfide models. In addition to the charged coordination defects previously proposed to exist in chalcogenide glasses, a novel defect pair, [As(4)](-)-[S(3)](+), consisting of a fourfold coordinated arsenic site in a seesaw configuration and a threefold coordinated sulfur site in a near-planar trigonal configuration, was found in several models. The valence-alternation pairs [S(3)](+)-S-1 are converted into [As(4)](-)-[S(3)](+) pairs under HOMO-to-LUMO electronic excitation. This structural transformation is accompanied by a decrease in the size of the HOMO-LUMO band gap, which suggests that such transformations could contribute to photodarkening in these materials.     

Three-dimensional mid-infrared photonic circuits in chalcogenide glass

We report the fabrication of single-mode buried channel waveguides for the whole mid-IR transparency range of chalcogenide sulphide glasses (λ ≤ 11 μm), by means of direct laser writing. We have explored the potential of this technology by fabricating a prototype three-dimensional three-beam combiner for future application in stellar interferometry that delivers a monochromatic interference visibility of 99.89% at 10.6 μm and an ultrahigh bandwidth (3-11 μm) interference visibility of 21.3%. These results demonstrate that it is possible to harness the whole transparency range offered by chalcogenide glasses on a single on-chip instrument by means of direct laser writing, a finding that may be of key significance in future technologies such as astrophotonics and biochemical sensing.     

Photoinduced changes in optical and contact properties of chalcogenide glasses

Photoinduced changes in optical and contact properties in thin films of glasses of As-Se and As-S systems are studied experimentally. The changes detected in the optical constants and parameters of the potential barrier at the interface between a metal and a chalcogenide vitreous semiconductor are explained by the rearrangement of the glass host under the action of radiation.     

Hot-embossing fabrication of chalcogenide glasses rib waveguide for mid-infrared molecular sensing

Chalcogenide glasses have shown promise in fabricating mid infrared(MIR) photonic sensing devices due to their excellent optical properties in MIR. In addition, the glass transition temperature of chalcogenide glasses are generally low,making them ideal to create the high-throughput patterns of micro-scale structures based on hot embossing that is alternative to the standard lithographic technology. In this paper, we outline the research progress in the chalcogenide waveguide based on the hot embossing method, and discuss the problems remaining to be solved and the possible solutions.     

The dependence of photosensitivity on composition for thin films of Ge x As y Se1–x–y chalcogenide glasses

We have prepared twelve Ge–As–Se chalcogenide glass films with different chemical compositions and investigated their stability to exposure with near bandedge light. The evolution of two key parameters, the refractive index at 1550 nm and the bandgap with increasing fluence were fitted with stretched-exponential functions. While most of the films showed photo-bleaching (or photodarkening) behavior, we found that for films with a mean coordination number (MCN) around ≈2.45–2.50, neither the bandgap nor the refractive index changed upon irradiation, demonstrating that photostable glasses exist with a particular chemical composition corresponding to the strongest glass formers. Such photostable glasses are the best choice for applications in photonics.     

Variable angle spectroscopic ellipsometry and its applications in determining optical constants of chalcogenide glasses in infrared

The principle of variable angle spectroscopic ellipsometry(VASE) and the data analysis models, as well as the applications of VASE in the characterization of chalcogenide bulk glasses and thin films are reviewed. By going through the literature and summarizing the application scopes of various analysis models, it is found that a combination of various models, rather than any single data analysis model, is ideal to characterize the optical constants of the chalcogenide bulk glasses and thin films over a wider wavelength range. While the reliable optical data in the mid-and far-infrared region are limited, the VASE is flexible and reliable to solve the issues, making it promising to characterize the optical properties of chalcogenide glasses.     

Luminescence in amorphous semiconductors

A review of the luminescence properties of amorphous semiconductors is presented. The materials covered are chalcogenide glasses, silicon and arsenic. Luminescence spectra, excitation spectra, temperature dependences and lifetimes are described.

The radiative transition in chalcogenides is the recombination of an electron in the conduction band tail and a trapped hole. A strong electron-phonon coupling distorts the lattice near the trapped hole, lowering its energy. This interaction is responsible for the broadness of the luminescence band and its position at about half the band gap energy. The recombination centre is thought to be a charged dangling bond with density 10¹⁷ cm^-3 in arsenic chalcogenides and 10¹⁶ cm^-3 in selenium. The same centre is observed in the hole drift mobility, and thermally stimulated conductivity.

Luminescence in amorphous silicon also originates from recombination between the band tails and deep centres, with three separate transitions identified. In contrast to chalcogenides the electron-phonon coupling is not strong. The shape and intensity of the spectra are very sensitive to sample preparation and treatment, and correlate with other electrical and optical properties of Si.     

Radiation-Induced Coordination Topological Defects in Chalcogenide Glasses

The radiation-induced (γ-quanta of ⁶⁰Co source) coordination topological defect formation in chalcogenide glasses of quasi-binary AS₂S₃—GeS₂ system is studied using experimental techniques of IR Fourier spectroscopy and positron annihilation lifetime measurements. The new model of open-volume microvoids connected with negatively charged under-coordinated defects is developed at the basis of the obtained results.     

Photoinduced stable second-harmonic generation in chalcogenide glasses

We report on photoinduced second-harmonic generation (SHG) in chalcogenide glasses. Fundamental and second-harmonic waves from a nanosecond pulsed Nd:YAG laser were used to induce second-order nonlinearity in chalcogenide glasses. The magnitude of SHG in 20G?20A?60S glass was 10(4) larger than that of tellurite glass with a composition of 15Nb(2)O (5) 85TeO(2) (mol.%). Moreover, no apparent decay of photoinduced SHG in 20G?20A?60S glass was observed after optical poling at room temperature. We suggest that the large and stable value of chi((2)) is due to the induced defect structures and large chi((3)) of the chalcogenide glasses.     

Tm~(3+)掺杂Ge-Ga-S玻璃微球-石英光纤锥耦合系统的荧光回廊模特性

以熔融淬冷法自制了Tm~(3+)掺杂Ge-Ga-S硫系玻璃,并以此为基质材料,用漂浮粉料熔融法制备了直径分布为50—200μm的高品质因数(Q10~4)的有源硫系玻璃微球谐振腔.在显微镜下优选出一颗表面质量好、球形度较高、直径为72.84μm的微球,与氢氧焰扫描拉锥法制备的一根腰锥直径为1.93μm的石英光纤锥进行近场耦合.根据基质材料的吸收光谱特性,选用808 nm的半导体激光器作为抽运源.实验测得光纤锥倏逝波场激发出了掺Tm~(3+)硫系玻璃微球在1460 nm附近的荧光回廊模式,其典型共振峰间隔为4.39 nm.实验测得的荧光回廊模式与米氏散射理论计算结果符合度较高(最大误差仅为0.047%),验证了本文提出的掺Tm~(3+)硫系微球制备及耦合工艺的可行性.     

Concentration dependence of radiation-induced changes in the optical properties of Ge<Subscript>x</Subscript>As<Subscript>40−<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>60</Subscript> films

Radiation-induced changes in the optical properties of chalcogenide glasses in the Ge-As-S system are investigated as a function of the concentration. Theoretical calculations are performed with due regard for possible constraints on the range of variation in the number of homobonds and heterobonds upon their switching in the structural network of chalcogenide glasses. The experimental data are obtained upon irradiation of Ge_xAs_40?xS₆₀ thin films with fast electrons (6 MeV). The possible mechanism of structural transformations responsible for the specific features in the concentration dependence of the change in the band gap of chalcogenide glasses is discussed.     

Effect of primary oxygen ion implantation on SIMS depth profiling in glasses

The influence of the primary oxygen ion implantation on SIMS in-depth profiles in halide and chalcogenide glasses was examined. Various behaviours of particular profiles were generally explained in terms of the chemical affinity of analysed reactants and modifications of the glass structure induced by primary ions.     

Nonlinear Integrated Optical Waveguides in Chalcogenide Glasses

This paper reports on the study and measurement of the third order optical nonlinearity in bulk sulfide-based chalcogenide glasses; The fabrication process of the ultrafast laser deposited As-S-(Se)-based chalcogenide films and optical waveguides using two techniques: wet chemistry etching and plasma etching.