Influence of thermal annealing on optical and structural properties change in Bi-doped Ge30Se70 thin films

The effect of annealing on the structural and optical properties of thermally evaporated Ge₃₀Se₇₀ and Ge₃₀Se₆₀Bi₁₀ thin films is reported in this paper. The prepared films were thermally annealed at 250°C to optimize the optical properties which can be used for the optical device fabrication. X-ray diffraction study revealed no structural transformation whereas the surface morphology changed as observed from scanning electron microscopy. The optical properties of the deposited and annealed films have been investigated by using a UV–VIS–NIR spectrophotometer in the wavelength range of 400–1100?nm. The optical band gap of the Ge₃₀Se₇₀ annealed film is found to be increased while the energy gap of the Bi-doped annealed Ge₃₀Se₆₀Bi₁₀ thin film decreased which is explained by the chemical disorderness, defect states and density of localized states in the mobility gap. The Tauc parameter and Urbach energy which measure the degree of disorder changed with the annealing process. The transmittivity increases and the absorption power decreases in the Ge₃₀Se₇₀ annealed film, whereas the reverse effect is noticed for the annealed Ge₃₀Se₆₀Bi₁₀ thin film. The irreversible nature of this change can be useful for optical recording purposes.     

Structural and optical properties of Ge20SbxSe80-x films

20 Sb_xSe_80-x (where 10≤x≤40 at.%) thin films. The optical absorption results indicate that the absorption mechanism is due to non-direct transition. The optical gap of the as-deposited films was found to decrease monotonically with increasing antimony content, a result which was interpreted on the basis of the chemical-bond approach proposed by Bicerno and Ovshinsky. Annealing of the Ge₂₀Sb₄₀Se₄₀ films at temperatures higher than 450 K was found to decrease the optical gap and increase the refractive index of the investigated film. Increasing the amount of crystalline GeSe₂ and Sb₂Se₃ phases while increasing the annealing temperature could be responsible for the continuous decrease of the optical gap of the Ge₂₀Sb₄₀Se₄₀ film. Received: 4 November 1997/Accepted: 16 December 1997     

Study of the dynamics and mechanisms of deformation of thin chalcogenide As(Ge)<Subscript>2</Subscript>Se<Subscript>3</Subscript> films by nanoindentation

The mechanical properties of As₂Se₃ and Ge₂Se₃ thin films have been studied by the method of quasi-static nonoindentation. The mechanisms of formation and recovery of the indentations in the studied materials have been analyzed under conditions of their local loading. It has been revealed that the deformation mechanism of the chalcogenide films changes in going from As₂Se₃ to Ge₂Se₃. It has been found that, during deformation of the As₂Se₃ film under the indenter, the accumulation of plastic deformation prevails, and, for the Ge₂Se₃ film, the substantial mechanism is the relaxation of its deformation.     

Reversible photo-induced volume changes in evaporated As2S3 and As4Se5Ge1 films

Reversible photo-induced volume changes have been observed accompanying reversible optical absorption edge shift produced by successive cycles of band gap illumination and annealing for well-annealed evaporated As₂S₃ and As₄Se₅Ge₁ films. The As₂S₃ film shows an increase in its volume by illumination, while As₄Se₅Ge₁ film shows a decrease. Qualitative discussion has been given in connection with pressure-induced optical constant change.     

Characterization of new quaternary chalcogenide As–Ge–Se–Sb thin films

This paper reports the effect of replacement of selenium by antimony on the optical gap and some other physical parameters of new quaternary chalcogenide As₁₄Ge₁₄Se_{72? x} Sb _x (where x = 3, 6, 9, 12 and 15 at%) thin films. Thin films with thickness 200–220 nm of As₁₄Ge₁₄Se_{72? x} Sb _x were prepared by thermal evaporation of the bulk samples. Increasing antimony content was found to affect the average heat of atomization, the average coordination number, number of constraints and cohesive energy of the As₁₄Ge₁₄Se_{72 ?x} Sb _x alloys. Optical absorption measurements showed that the fundamental absorption edge is a function of composition. Optical absorption is due to allowed, non-direct transition and the energy gap decreases with the increasing antimony content. The chemical bond approach has been applied successfully to interpret the decrease in the optical gap with increasing antimony content.     

Experimental study and configurational-coordinate model for photo-induced effects in amorphous As2Se3 films

The optical absorption of As₂Se₃ thin films is studied in the UV–VIS spectral range and the value of the optical energy gap is determined. The effect of photo-irradiation on the optical absorption and transmission of thin film samples is also investigated. The optical energy gap was found to decrease with photo-irradiation time. The results of photo-irradiation are discussed in correlation with the structural aspects of As₂Se₃. A model is proposed to account for the structural changes, resulting from photo-irradiation, causing the decrease of the energy gap. The effect of γ-radiation on the optical absorption of As₂Se₃ thin films was studied also and no detectable effect on the value of the optical energy gap was observed.     

Femtosecond optical Kerr effect study of Ge10As40S30Se20 film

The results of the femtosecond optical heterodyne detection of optical Kerr effect at 805 nm with the 80 fs ultrafast pulses in amorphous Ge₁₀As₄₀S₃₀Se₂₀ film is reported in this paper. The film shows an optical non-linear response of 200 fs under ultrafast 80 fs-pulse excitation, and the values of real and imaginary parts of non-linear susceptibility χ⁽³⁾ were 9.0×10⁻¹² and −4.0×10⁻¹² esu, respectively. The large third-order non-linearity and ultrafast response are attributed to the ultrafast distortion of the electron orbits surrounding the average positions of the nucleus of Ge, As, S and Se atoms. This Ge₁₀As₄₀S₃₀Se₂₀ chalcogenide glass would be expected as a promising material for optical switching technique.     

Optical properties of Ge-As-Te thin films

Different compositions of Ge_xAs₁₀Te_90−x (x=5, 10, 15, 20, and 25 at%) chalcogenide glasses were prepared by the usual melt quench technique. Amorphous Ge_xAs₁₀Te_90−x thin films were deposited onto cleaned glass substrates using the thermal evaporation method. Transmission spectra, T(λ), of the films at normal incidence were measured in the wavelength range 400-2500 nm. A straightforward analysis proposed by Swanepoel based on the use of the maxima and minima of the interference fringes has been used to drive the film thickness, d, the complex index of refraction, n, and the extinction coefficient, k. It was found that, the addition of Ge content at the expense of Te atoms shifts the optical band gap to the short wavelength side (blue shift of the optical band gap) while the refractive index are found to decreases. The obtained results of the refractive index were discussed in terms of the electronic polarizability and the single-oscillator Wemple and DiDomenico model (WDD). The optical absorption is due to the allowed non-direct optical transitions. The observed increase in the optical band gap with the increase in Ge content was discussed in terms of the width of the tail states in the gap and the covalent bond approach.     

Reversible and athermal photo-vitrification of As50Se50 thin films deposited onto silicon wafer and glass substrates

Photo-vitrification of As₅₀Se₅₀ thin films deposited onto silicon wafer and glass substrates has been studied using X-ray diffraction, far-infrared, and differential infrared spectroscopies. The optical study of this photo-amorphization effect has been carried out by two different methods enabling the determination of the average thickness and refractive index of a wedge-shaped thin film. The refractive-index behaviour of the as-evaporated, crystallized, and photo-vitrified As₅₀Se₅₀ films is analyzed within the single-oscillator approach. The optical-absorption edge is described using the non-direct transition model, and the optical energy gap is calculated. In the course of the vitrification of an As₅₀Se₅₀ thin film deposited on a silicon substrate the photo-oxidation of the film has been additionally detected and arsenic trioxide micro-crystals were formed on the surface of the film. Such oxidation has not been observed with As₅₀Se₅₀ films deposited on glass substrates, which demonstrates that the photo-vitrification phenomenon depends also on the type of substrate. Finally, it is concluded from the optical study that a reversible photo-darkening effect accompanies the photo-induced vitrification phenomenon. Received: 3 August 1998 / Accepted: 13 January 1999 / Published online: 7 April 1999     

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.     

The optical,structural and thermal optimizations of Ge-As-Se-S-Te glasses

The optical, structural and thermal optimizations of Ge₃₃As₁₂Se₅₅ glass were the aim of this study. In this regards, Ge₃₃As₁₂Se₄₅M₁₀ (M = Se, Te, S and S_0.5Te_0.5) glasses were synthesized by conventional melt quenching technique in quartz ampule. The prepared samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The fundamental absorption edge for prepared samples was also analyzed in terms of the theory proposed by Davis and Mott. The addition of S and Te elements to melting batch has deleterious effects on optical properties of Ge₃₃As₁₂Se₅₅ glass. Mg and Al can act as gettering elements for reduction of the intensity of oxide absorption bands from FTIR spectra (without any effects on optical properties of Ge₃₃As₁₂Se₅₅ glass). The precipitation of GeSe phase, during crystallization process, has negligible effects on optical properties of Ge₃₃As₁₂Se₅₅ glass.     

Optical constants for Ge30− x Se70Ag x (0 ≤ x ≤ 30 at%) thin films based only on their reflectance spectra

In this paper, different homogenous compositions of Ge_{30? x} Se₇₀Ag _x (0?≤?x?≤?30 at%) thin films were prepared by thermal evaporation. Reflection spectra, R(λ), for the films were measured in the wavelength range 400–2500?nm. A straightforward analysis proposed by Minkov [J. Phys. D: Appl. Phys. 22 (1989) p.1157], based on the maxima and minima of the reflection spectra, allows us to derive the real and imaginary parts of the complex index of refraction and the film thickness of the studied films. Increasing Ag content at the expense of Ge atoms is found to affect the refractive index and the extinction coefficient of the films. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple–DiDomenico model. Optical absorption measurements were used to obtain the fundamental absorption edge as a function of composition. With increasing Ag content, the refractive index increases while the optical band gap decreases. The compositional dependence of the optical band gap for the Ge_{30? x} Se₇₀Ag _x (0?≤?x?≤?30) thin films is discussed in terms of the chemical bond approach.     

Characterisation of thin films obtained by laser ablation of Ge28Se60Sb12 glasses

Films of nominal composition Ge₂₈Se₆₀Sb₁₂ were deposited on microscope slides by pulsed laser deposition (PLD), using either bulk or powdered glassy targets and a Nd:YAG laser (λ=266 nm). The films with thickness comprised between 400 and 800 nm showed a smooth and dense morphology. They were homogeneous in composition all over the samples with a composition somewhat deficient in selenium compared to the nominal one: Ge_28.1±0.3Se_56.1±0.1Sb_15.8±0.2 and Ge_29.0±0.3Se_55.5±0.1Sb_15.5±0.2 for films obtained from powdered glassy targets and bulk targets, respectively. The optical characteristics of the films were extracted from the transmission spectra recorded between 250 and 2500 nm. In particular, the refractive index at 1.5 μm was found to be 2.75±0.03, close to that of the bulk glass, as expected for dense films. The decrease in the optical band gap and the increase in the Urbach absorption edge with the film thickness were attributed to an increase in disorder.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

Photoinduced absorption edge shift of As20Se60Tl20 films

As₂₀Se₆₀Tl₂₀ bulk material was prepared firstly then thermal evaporation method was used to prepare As₂₀Se₆₀Tl₂₀ films. Illumination effect at room temperature for the mentioned films has been studied within the homogeneous glass-forming region. The prepared film samples were amorphous, this is depicted by X-ray chart. Optical properties have been studied using spectrophotometric measurements. The absorption edge was shifted to shorter wavelengths due to light exposure or photobleaching effect. It was found that the extinction coefficient and the optical band gap have opposite character after illumination.     

Electrical and optical properties of amorphous Te40As38Ge10Si12 thin films

Electrical, optical and structural, properties, of Te₄₀As₃₈Ge₁₀Si₁₀ thin films were studied. X-ray diffraction patterns indicate that these films are in an amorphous state. The dark electrical resistivity of Te₄₀As₃₈Ge₁₀Si₁₂ films was measured at room temperature and at elevated temperature. The thermal activation energy E was determined. The optical constants (refractive index n and absorption index k) of such films were determined in the spectral range of 0.5–2.0 m. The absorption coefficient () of this system was also determined using the known equation =4k/. The refractive index n has anomalous behaviour near the absorption edge. Analysis of the absorption spectrum reveals indirect optical transitions. The corresponding forbidden-band width was determined. Its value is approximately twice the thermal activation energy.     

Optical band gap and refractive index dispersion parameters of As x Se70Te30−x (0≤x≤30 at.%) amorphous films

Amorphous As _x Se₇₀Te_30?x thin films with (0≤x≤30 at.%) were deposited onto glass substrates by using thermal evaporation method. The transmission spectra T(λ) of the films at normal incidence were measured in the wavelength range 400–2500 nm. A straightforward analysis proposed by Swanepoel based on the use of the maxima and minima of the interference fringes has been used to drive the film thickness, d, the complex index of refraction, n, and the extinction coefficient, k. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model (WDD). Increasing As content is found to affect the refractive index and the extinction coefficient of the As _x Se₇₀Te_30?x films. With increasing As content the optical band gap increases while the refractive index decreases. The optical absorption is due to allowed indirect transition. The chemical bond approach has been applied successfully to interpret the increase of the optical gap with increasing As content.     

Ge2Sb2Te5薄膜光学性能和短波长静态记录特性的研究

利用直流磁控溅射制备了单层Ge₂Sb₂Te₅薄膜,研究了薄膜在400～800 nm区域的反射、透过光谱,计算了它的吸收系数,发现薄膜在400～800 nm波长范围内具有较强的吸收.随着薄膜厚度的增加,相应的禁带宽度Eg也随之增加.对Ge2Sb2Te5薄膜光存储记录特性的研究发现,在514.5 nm波长激光辐照样品时,薄膜具有良好的写入对比度,擦除前后的反射率对比度在6%~18%范围内.对实验结果进行了分析.     

硫系非晶半导体薄膜中的超快光 Kerr效应

利用飞秒激光超外差光Kerr(OHD-OKE)技术研究了As₂S₃, As₂Se₃, GeS₂, GeSe₂, Ge₂₀As₂₅S₅₅, Ge₂₀As₂₅Se₅₅, Ge₁₀As₄₀S_{20关键词： 全光开关 硫系非晶半导体薄膜 飞秒激光超外差光Kerr(OHD-OKE) 三阶非线性}     

Effect of nonlinear refraction and two-photon absorption on the optical limiting in amorphous chalcogenide films

This paper reports on the results of investigations into the nonlinear optical characteristics of chalcogenide films (As₂S₃, As₂₀S₈₀, 2As₂S₃/As₂Se₃, 3As₂S₃/As₂Se₃). The nonlinear refractive indices and two-photon absorption coefficients for these films are measured using the Z-scan technique at wavelengths of a picosecond Nd: YAG laser (λ=1064 and 532 nm). The optical limiting due to Kerr-type nonlinearities is analyzed.