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}     

Optical limiting in fullerenes, colloidal metal solutions, and semiconductors in the field of pico-and nanosecond pulses of an Nd:YAG laser

Optical limiting of pico-and nanosecond pulsed radiation of a Nd:YAG laser (λ=1064 and 532 nm) is studied in solutions of fullerenes (C₆₀ and C₇₀), semiconductor crystals and films (GaAs, As₂S₃, As₂₀S₈₀, 2As₂S₃/As₂Se₃, and 3As₂S₃/As₂Se₃), and colloidal solutions of metals (Au, Ag, Pt, and Cu). The effect of the particle aggregation in silver solutions on the optical limiting is considered. Optical limiting mechanisms, specifically, reverse saturable absorption, two-photon absorption, and self-action effects, are discussed. Nonlinear absorption coefficients of the studied materials are measured.     

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.     

Kinetics of photo‐darkening and self‐bleaching in amorphous As2S3 and As2Se3 thin films

The kinetics of photo‐darkening of amorphous As₂S₃ and a‐As₂Se₃ thin films follows a single exponential, but the magnitude and the rate of the process is higher in case of As₂S₃. The kinetics of self‐bleaching (dark relaxation) in advance photo‐darkened state follows a stretched exponential (SRE) with different stretching parameter for a‐As₂S₃ and a‐As₂Se₃. Within the J. C. Phillips approach we suppose that photo‐darkening in amorphous As₂S₃ films is, to some extent, accompanied by changes in short‐range order interactions, while photo‐darkening of amorphous As₂Se₃ is accompanied rather by changes in Coulomb interactions. The self‐bleaching process reduced the magnitude of photo‐darkening up to 45% and 60% for amorphous As₂S₃ and As₂Se₃ films, respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Photoinduced phenomena in mAs2S3·nAs2Se3 amorphous films and their application in micro-optics technology

Photoinduced phenomena, such as photodarkening, photorefraction, and photodissolution, were studied in different compositions of three-component mAs₂S₃·nAs₂Se₃ amorphous films. The main emphasis was on the effect of photoinduced change of dissolution rate since this effect is the basis of many applications of amorphous chalcogenide films. The results of the investigation were compared with photoinduced effects in binary As₂S₃ and As₂Se₃ films. Advanced micro-optical devices: micro-lens and micro-mirror arrays, diffractive gratings, and photonic bandgap crystals, based on three-component amorphous films which possessed optimal photodissolution characteristics were developed. The primary parameters of the micro-optical devices developed are discussed.     

Optical properties of chalcogenide glasses in the terahertz spectral region

Optical properties of chalcogenide glasses of three different compositions (As₂S₃, As₂S₃ × As₂Se₃, and As₂Se₃) are studied via terahertz pulsed spectroscopy. Absorption coefficients and refractive indices are measured in a frequency range of 0.2–1.6 THz. The results show that the phonon modes of the studied materials vary with the composition of the glasses.     

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.     

Photoinduced phenomena in amorphous As<Subscript>4</Subscript>S<Subscript>3</Subscript>Se<Subscript>3</Subscript>–Sn films

We investigate the kinetics of photodarkening and recording of holographic diffraction gratings in amorphous As₄S₃Se₃ thin-film structures doped with tin (Sn) in concentrations of 0–10 at %. It is established that an increase in the Sn concentration leads to a decrease in the photodarkening rate and degree. The photodarkening kinetics is approximated by a stretched exponential function. It is found that an increase in the Sn concentration leads to a decrease in the transmission (photodarkening) variation in the investigated As₄S₃Se₃–Sn films. It is determined that, in the recording of holographic diffraction gratings at a Sn concentration of 3–8 at %, the As₄S₃Se₃–Sn films exhibit the maximum sensitivity and diffraction efficiency of the recorded gratings. It is shown that the dependence of diffraction efficiency on the As₄S₃Se₃ film thickness has the maximum at a film thickness of 4 µm.     

Infrared properties of AsχTe1−χ glasses

Infrared reflection and transmission measurements in As_χTe_1?χ glasses (45?×?55) show well-defined Gaussian vibrational absorption peaks. Comparisons with spectra observed in crystalline and glassy As₂S₃ and As₂Se₃ indicate that the local order in As_χTe_1?χ glasses is not like that found in crystalline As₂Te₃, but rather it consists primarily of AsTe₃ pyramids which are probably linked together in a fashion similar to that found in As₂S₃ and As₂Se₃.     

Hydrogenated chalcogenide glasses As2−xSe3+x and As2−xS3+x prepared by plasma decomposition

Amorphous semiconductors As_2?xSe_3+x and As_2?xS_3+x have been prepared by glow discharge decomposition of a gas mixture of AsH₃  H₂Se and AsH₃  H₂S respectively. The films contain about 3–8 at. percent hydrogen according to infrared transmission measurements. Both S-H and Se-H vibrational modes were observed. Results of the D.C. electrical conductivity, X-ray structural analyses and optical absorption are presented. The films composition was found to be close to $\text{As:Se = As:S}\text{=}\text{2}\text{3}$.     

Thickness distribution of thin amorphous chalcogenide films prepared by pulsed laser deposition

Amorphous chalcogenide thin films were prepared from As₂Se₃, As₃Se₂ and InSe bulk glasses by pulsed laser deposition using a KrF excimer laser. Thickness profiles of the films were determined using variable angle spectroscopic ellipsometry. The influence of the laser beam scanning process during the deposition on the thickness distribution of the prepared thin films was evaluated and the corresponding equations suggested. The results were compared with experimental data.     

ESR in X-irradiated As2O3 glass

X-irradiation of glassy As₂O₃ at 77K or 300K produces an unusually large density (～5×10¹⁸ cm^-3) of paramagnetic centers which are stable at 300K. The average spin-Hamiltonian parameters (g = 1.998, g_⊥ = 1.984, A₆ = 243G, A_⊥ = 114G) indicate that these centers are analogous to those previously observed in As₂Se₃ and As₂S₃ glasses and that they consist of unpaired electrons localized on a non-bonding 4p orbital of an As atom. Unlike the results obtained for As₂Se₃ and As₂S₃, the concommitant holes in As₂O₃ are trapped on Fe²⁺ impurity sites which become Fe³⁺ and not on non-bonding oxygen p orbitals. The radiation induced ESR is also accompanied by a stable optical absorption tail which lies within the band gap and increases exponentially with energy. This absorption can be partially bleached with the application of sub-band-gap light.     

Photoelectron spectra of As4S3, P4S3, P4Se3 and As4O6

The He(I) UV photoelectron spectra of As₄S₃, P₄S₃, P₄Se₃ and As₄O₆ are reported in this paper. The spectra of As₄S₃ and the isostructural molecules P₄S₃ and P₄Se₃ comprise seven broad but clearly defined peaks, whilst the spectrum of As₄O₆ consists of six peaks and two shoulders. By comparing the spectra with one another and with the photoelectron spectra of other arsenic and phosphorus compounds, the character and symmetry species of the highest-energy occupied molecular orbitals of the molecules have been assigned.     

Multiphonon absorption in As2S3As2Se3 glasses

Multiphonon absorption in As₂S₃ and As₂Se₃ glasses is well explained by a molecular model in terms of combination bands of high frequency vibrational modes of pyramidal AsY₃ and bent AsYAs groups (Y = SorSe). Multiphonon absorption coefficients in mixed As₂S₃As₂Se₃ glasses are nearly additive in terms of the pure components, suggesting a high degree of non-random mixing.     

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     

A.C. conductivity of bulk glassy chalcogenides

The a.c. conductivity of amorphous Se, Se₉₀Ge₁₀, Se₇₅Ge₂₅, As₂Se₃, As₂S₃, and As₄₅Te₄₀Ge₁₅ has been measured at room temperature in the 20 MHz–35 GHz range. The results display a contact effect we explicit. For the six materials, the conductivity is roughly proportional to ω^s with $\text{s}{}^{\mathrm{\approx }}\text{1}$ up to the microwave region (no saturation is observed). The experimental results are analysed with regard to the electronic and the atomic contributions but a better estimate of some parameters is necessary to confirm any model.     

Influence of Ge addition on the optical properties of As40Se50Ge10 thin film probed by spectroscopy techniques

The thin films of As₄₀Se₆₀ and As₄₀Se₅₀Ge₁₀ were prepared on glass substrates by thermal evaporation method with thickness 1000 nm. The prepared films were amorphous in nature which was confirmed through X-ray diffraction. The chemical composition and the surface picture were obtained from energy dispersive X-ray analysis and Scanning Electron Microscopy analysis. The transmission data of the two films were collected in the wavelength range 400–1000 nm. The transmission percentage is found to be decreased whereas the absorption coefficient is increased with the Ge addition. The addition of Ge into As₄₀Se₆₀ is found to increase the refractive index and the extinction coefficient of As₄₀Se₅₀Ge₁₀ thin film. The decrease in optical band gap is explained on the basis of increase in density of states and disorderness due to Ge addition. The optical absorption in the film is due to allowed indirect transition, and the homopolar bond density is increased with Ge addition. The Raman shift observed in the two films clearly supports the optical changes due to Ge addition.     

Study of As-Sb-Se chalcogenide glasses by NQR and EPR spectroscopy methods

In this paper experimental results obtained by both ⁷⁵As NQR and EPR spectroscopy are presented for the three-component system As-Sb-Se. The ⁷⁵As NQR spectra of glasses of structures (As₂Se₃)_0.78 (Sb₂Se₃)_0.22, (As₂Se₃)_0.75 (Sb₂Se₃)_0.25, (As₂Se₃)_0.5 (Sb₂Se₃)_0.5 have broad lines with two Sb-NQR lines (corresponding to the Sb₂Se₃ units) and two ⁷⁵As-NQR lines (corresponding to the As₂Se₃ units). Differences in the EPR spectra of the different glasses arise because of the different amounts of arsenic and antimony in their structure.     

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.