Ultrafast non-linear optical properties of Ge20As25Se55 chalcogenide films

The non-resonant third-order non-linear optical properties of amorphous Ge₂₀As₂₅Se₅₅ films were studied experimentally by the method of the femtosecond optical heterodyne detection of optical Kerr effect. The real and imaginary parts of complex third-order optical non-linearity could be effectively separated and their values and signs could be also determined, which were 6.6 × 10⁻¹² and −2.4 × 10⁻¹² esu, respectively. Amorphous Ge₂₀As₂₅Se₅₅ films showed a very fast response in the range of 200 fs under ultrafast excitation. The ultrafast response and large third-order non-linearity are attributed to the ultrafast distortion of the electron orbitals surrounding the average positions of the nucleus of Ge, As and Se atoms. The high third-order susceptibility and a fast response time of amorphous Ge₂₀As₂₅Se₅₅ films makes it a promising material for application in advanced techniques especially in optical switching.     

Ge20Sb15Se65薄膜的热致光学特性变化研究

采用磁控溅射法制备了Ge₂₀Sb₁₅Se₆₅薄膜, 研究热处理温度(150—400 ℃)对薄膜光学特性的影响. 通过分光光度计、X射线衍射仪、显微拉曼光谱仪对热处理前后薄膜样品 的光学特性和微观结构进行了表征, 并根据Swanepoel方法以及Tauc公式分别计算了薄膜折射率色散曲线和光学带隙等参数. 结果表明当退火温度(T_a)小于薄膜的玻璃转化温度(T_g)时,薄膜的光学带隙(E_g^opt)随着退火温度的增加由1.845 eV上升至1.932 eV, 而折射率由2.61降至2.54; 当退火温度大于薄膜的玻璃转化温度时,薄膜的光学带隙随退火温度的增加由1.932 eV降至1.822 eV, 折射率则由2.54增至2.71. 最后利用Mott和Davis提出的非晶材料由非晶到晶态的结构转变模型对结果进行了解释, 并通过薄膜XRD和Raman光谱进一步验证了结构变化是薄膜热致变化的重要原因. 关键词： 20Sb₁₅Se₆₅薄膜')" href="#">Ge₂₀Sb₁₅Se₆₅薄膜 热处理 光学带隙 折射率     

Photosensitive post tuning of chalcogenide Te20As30Se50 narrow bandpass filters

We present an experimental study on the photosensitive properties of narrow bandpass filters based on a chalcogenide Te₂₀As₃₀Se₅₀ (TAS) spacer. The transmittance curve of single TAS layer was shifted towards long wavelength direction after 2 h exposure by Xenon arc lamp. The refractive index and extinction coefficient were both increased together with a red shift of optical gap. A maximum 1.7% photo-induced effect was observed. Narrow band filters constituted by TAS and cryolite were manufactured by electron beam deposition. The transmittance spectrum of the filter during the exposure by a wide band source was in situ measured and the resonant wavelength was observed to turn longer gradually till saturation. A spatially localized central wavelength change up to 5.7 nm was finally obtained. The stability of the photo-induced effect was studied and some comments were given at the end of this paper.     

Effect of heat treatment on the optical and electrical transport properties of Ge15Sb10Se75 and Ge25Sb10Se65 thin films

The effect of heat treatment on the optical and electrical properties of Ge₁₅Sb₁₀Se₇₅ and Ge₂₅Sb₁₀Se₆₅ thin films in the range of annealing temperature 373-723 K has been investigated. Analysis of the optical absorption data indicates that Tauc's relation for the allowed non-direct transition successfully describes the optical processes in these films. The optical band gap (E_g^opt.) as well as the activation energy for the electrical conduction (ΔE) increase with the increase of annealing temperature (T_a) up to the glass transition temperature (T_g). Then a remarkable decrease in both the E_g^opt. and ΔE values occurred with a further increase of the annealing temperature (T_a>T_g). The obtained results were explained in terms of the Mott and Davis model for amorphous materials and amorphous to crystalline structure transformations. Furthermore, the deduced value of E_g^opt. for the Ge₂₅Sb₁₀Se₆₅ thin film is higher than that observed for the Ge₁₅Sb₁₀Se₇₅ thin film. This behavior was discussed on the basis of the chemical ordered network model (CONM) and the average value for the overall mean bond energy 〈E〉 of the amorphous system Ge_xSb₁₀Se_90−x with x=15 and 25 at%. The annealing process at T_a>T_g results in the formation of some crystalline phases GeSe, GeSe₂ and Sb₂Se₃ as revealed in XRD patterns, which confirms our discussion of the obtained results.     

Effect of sulfur atom substitute with selenium on stability of glassy Ge20As14SxSe52-XI14 chalcohalides

The paper presents results of the research carried out with the aim of establishing the effect of sulfur atom substitute with selenium on thermal and chemical stability of glasses of the Ge₂₀As₁₄S_xSe_52-xI₁₄ type.Chemical stability of glasses was estimated on the basis of their dissolution rate in potassium hydroxide of different concentrations. It was found that the rate of dissolving in KOH solutions increases with the increase of the percentage of sulfur content in the glass. The dissolving rate also depends on concentration of basic solution. It was found that the functional dependence of the rate of their dissolution could be described by an exponential function.Values of the glass transition point, as well as the temperature of the beginning of thermomechanical deformation were determined by the methods of thermomechanical analysis.It was established that characteristic temperatures increase insignificantly as sulfur content increases in investigated system.     

Fabrication and phase variation in annealed Cu3Se2 nanowire arrays

We have found for the first time that Cu₃Se₂ nanowired products encased inside the alumina pores by electrodeposition demonstrate the promising nonlinear optical properties in UV-vis-NIR spectra region. Furthermore, the annealing of these products results in the formation of Cu_2−xSe with x depending on the annealing temperature. Optical nonlinearities of as-grown and thermally treated copper selenide nanowire arrays were evidenced using the standard open-aperture Z-scan and laser pump-probe techniques.     

Temperature dependence of luminescence from ZnS0.11Se0.89 random and ordered alloys

Temperature dependence of the luminescence spectra was investigated for a ZnS_0.11Se_0.89 random alloy and a (ZnSe)₁/(ZnS_0.22Se_0.78)₁ ordered alloy with equivalent mean sulfur compositions. The luminescence peak for the random alloy as a function of temperature shows anomalous behavior, while that for the ordered alloy exhibits normal behavior. From the temperature dependence of luminescence intensity for the random alloy, the quenching process can be understood with additional thermal activation energy besides exciton dissociation energy. Through the analysis of the temperature variation of the luminescence line width, the exciton-optical phonon coupling constant is found to be reduced in the random alloy. The results of this study demonstrate that exciton is localized by the potential fluctuation in the random alloy and that the potential fluctuation is significantly constrained in the ordered alloy.     

Determinations of the transient thermal lensing effect in metal cluster Polymer {WS4Cu4I2(bpe)3}n solution by the use of the Z-scan

The nonlinear optical (NLO) properties of a novel cluster Polymer {WS₄Cu₄I₂(bpe)₃}_n solution are studied by using Z-scan technique with laser pulses of 4.5 ns pulse-width at a wavelength of 532 nm. The results show that the cluster solution possesses strong nonlinear absorption and refraction. Nonlinear refraction of the cluster is composed of third-order nonlinear refraction and transient thermal effect. The thermal effect is mainly due to the strong nonlinear absorption. Numerical simulations obtained by solving simultaneously photo-acoustic and electromagnetic wave equations, agrees basically with experimental results.     

High pressure optical study of KTbP2Se6

We have observed a pressure induced phase transition in KTbP₂Se₆ at about 9.2 GPa which was accompanied by a discontinuous jump of the absorption edge of about 0.5 eV into the red. We have proposed that the high pressure phase is due to charge transfer from the selenium to the phosphorous accompanied by the formation of a Se-Se bond. In order to exclude a model which involves a 4f-5d charge transfer in Tb, leading to the intervalence charge transfer from Tb³⁺P⁴⁺-Tb⁴⁺P³⁺,we have measured the pressure dependence of the luminescence of the crystal field split levels of the Tb-ion. A comparison of the pressure dependence of the luminescence spectra of KTb(MoO₄)₂ and KTbP₂Se₆ shows that such a charge transfer does not occur in KTbP₂Se₆.     

Red electroluminescent process excited by hot holes in SrGa2S4:Ce, Mn thin film

This paper reports the first observation of red electroluminescence (EL) in SrGa₂S₄:Ce, Mn thin film. The EL spectrum consists of single broad emission band having a peak wavelength of 665 nm. The dominant EL decay time was 31 μs. The relationship between the applied voltage and the EL waveform was measured in single insulating thin film electroluminescent (TFEL) devices. An asymmetric EL waveform was observed in SrGa₂S₄:Ce, Mn TFEL devices under a rectangular applied voltage. The polarity of the EL waveform in these devices was different from the waveform in manganese-activated zinc sulfide ZnS:Mn devices. This indicates that hot holes excite the Mn²⁺ ions to cause the red EL.     

Controlled synthesis and relationship between luminescent properties and shape/crystal structure of Zn2SiO4:MN phosphor

Mn-doped Zn₂SiO₄ phosphors with different morphology and crystal structure, which show different luminescence and photoluminescence intensity, were synthesized via a low-temperature hydrothermal route without further calcining treatment. As-synthesized zinc silicate nanostructures show green or yellow luminescence depending on their different crystal structure obtained under different preparation conditions. The yellow peak occurring at 575 nm comes from the β-phase zinc silicate, while the green peak centering at 525 nm results from the usual α-phase zinc silicate. From photoluminescence spectra, it is found that Zn₂SiO₄ nanorods have higher photoluminescence intensity than Zn₂SiO₄ nanoparticles. It can be ascribed to reduced surface-damaged region and high crystallinity of nanorods.     

Low-temperature thermal conductivity of GexAs40−xS60 glasses

Thermal conductivity, k, of Ge_xAs_40−xS₆₀ glasses has been measured between 4.5 and 300 K. A variation of k with the composition is found and dependences of its parameters on the mean coordination numbers are established. Analyses have been made within but also independently of the soft-potential model. Some correlations and scaling laws are proposed.     

Femtosecond Z-scan measurement of third-order optical nonlinearities in anatase TiO2 thin films

Anatase phase TiO₂ films have been grown on fused silica substrate by pulsed laser deposition technique at substrate temperature of 750 °C under the oxygen pressure of 5 Pa. From the transmission spectra, the optical band gap and linear refractive index of the TiO₂ films were determined. The third-order optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. The real and imaginary parts of third-order nonlinear susceptibility χ⁽³⁾ were determined to be −7.1 × 10⁻¹¹esu and −4.42 × 10⁻¹²esu, respectively. The figure of merit, T, defined by T=βλ/n₂, was calculated to be 0.8, which meets the requirement of all-optical switching devices. The results show that the anatase TiO₂ films have great potential applications for nonlinear optical devices.     

Formation of Ge35In8S57 amorphous films for optical applications

Thin films of In-doped Ge-S in the form of Ge₃₅In₈S₅₇ with different film thickness were deposited using an evaporation method. The X-ray diffraction studies demonstrate that the as-prepared films are amorphous in nature for these films. Some optical constants were calculated at a thickness of 150, 300, 450 and 900?nm and annealing temperature of 373, 413, 437 and 513?K. Our optical observations show that the mechanism of the optical transition obeys the indirect transition. It was found that the energy gap, E_g, decreases from 2.44 to 2.20?eV with expanding the thickness of the film from 150 to 900?nm. On the other hand, it was found that E_g increases with annealing temperature from 373 to 513?K. The increment in the band gap can be attributed to the gradual annealing out of the unsaturated bonds delivering a decreasing the density of localized states in the band structure. Using the single oscillator model, the dispersion of the refractive index is described. The dispersion constants of these films were calculated with different both thickness and annealing temperatures. Additionally, both of nonlinear susceptibility, χ⁽³⁾ and nonlinear refractive index, n₂ were calculated.     

Structural, thermal and optical studies of mechanical alloyed Ga40Se60 mixture

A mixture of elemental Ga and Se with the nominal composition Ga₄₀Se₆₀ was submitted to the Mechanical alloying technique and their structural, thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV-VIS‐NIR absorbance spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga₂Se₃ phase nucleation, which is in the nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to amorphous-crystalline phase transition and structural relaxation of Ga₂Se₃ phase. Based on this a small amount of the as-milled sample was annealed at 723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase. The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Effect of sintering aid (CdCl2) on the optical and structural properties of CdZnS screen-printed film

Sulphides of zinc and cadmium have been utilized effectively in various opto-electronic devices. In the present work cadmium zinc sulphide (Cd_0.4Zn_0.6S) thin film has been deposited on ultra clean glass substrate by a simple inexpensive screen-printing method using cadmium sulphide, zinc sulphide, anhydrous cadmium chloride and ethylene glycol. Cadmium chloride has been used as sintering aid and ethylene glycol as a binder. Effect of sintering aid on the optical and structural properties of prepared cadmium zinc sulphide film has been investigated. The optical band gap (E_g) of the film has been studied by using reflection spectra in wavelength range 325–600 nm. It is found that reflection spectra suffer a drastic fall at two places, which is indicative of two band gaps of film viz. 2.38 eV and 2.9 eV corresponding to CdS and Cd_0.6Zn_0.4S, respectively. This is suggestive of the fact that cadmium zinc sulphide is a wide band gap semiconducting material. X-ray diffraction also confirms the formation of Cd_0.6Zn_0.4S composition.     

Crystallization kinetics in new Sb14As29Se52Te5 amorphous glass

Differential scanning calorimetry (DSC) under non-isothermal conditions is used to study the crystallization kinetics of Sb₁₄As₂₉Se₅₂Te₅ chalcogenide glass. In addition, two approaches are used to analyze the dependence of glass transition temperature (T_g) on the heating rate (α). One is empirical linear relationship between (T_g) and ln(α). The second approach is the use of straight line vs. 1/T_g for the evaluation of the activation energy for glass transition. The phases at which the alloy crystallizes after the thermal treatment have been identified by using X-ray diffraction. The diffractogram of the transformed material shows the presence of some crystallites of As, Te, AsSb, As₂Se₃, Sb₂Se₃ and AsSe_.5Te_.5 in the residual amorphous matrix.     

Optical phonon modes and structure of ZnGa2Se4 and ZnGa2S4

We present the infrared and Raman study of the optical phonon modes of the defective compounds ZnGa₂Se₄ and ZnGa₂S₄. Most of the compounds have been found to crystallize in the thiogallate structure (defect chalcopyrite) with space group where all cations and vacancies are ordered. For some Zinc compounds a partially disordered cationic sublattice with various degrees of cation and vacancy statistical distribution, which lead to the higher symmetry (defect stannite), has been reported. For ZnGa₂Se₄ we have found three modes of A symmetry, showing Raman activity only. In addition, we have observed each five modes of B and E symmetry, showing infrared as well as Raman activity. The number of modes and their symmetry assignment, based on polarized measurements, clearly indicate space group for the investigated crystals of ZnGa₂Se₄.Regarding ZnGa₂S₄ we have found three modes exclusively showing Raman activity (2A⊕1B₁), and only eight modes showing infrared as well as Raman activity (3B₂⊕5E). The assignment of the modes has been derived by analyzing the spectral positions of the vibrational modes in comparison to a number of compounds. From the number and symmetry assignment of the optical phonon modes we confirm that ZnGa₂S₄ most likely crystallizes in space group .     

Heat capacity and thermal expansion of CdCr2Se4 and CdCr2S4

The thermodynamic properties of the spinel ferromagnetic compounds CdCr₂Se₄ and CdCr₂S₄ have been investigated by making heat capacity and thermal expansion measurements on single crystals. For both compounds, the ferromagnetic transition is marked by λ-type thermal anomalies, and the results provide a pressure dependence of the transition temperatures that is in agreement with direct measurements. Below the transition, CdCr₂S₄ shows an anomalous heat-capacity contribution and negative thermal expansion, which are in contrast to the conventional behavior found in CdCr₂Se₄.