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.     

Characterization of (As.Te)1-xSex thin films

1-x Se_x thin films (where x=0.20, 0.23, 0.27, 0.32 and 0.44) have been studied. Increasing the Se content was found to increase the optical energy gap and the activation energy for conduction of the investigated films. The optical energy gap of the As_0.40Te_0.40Se_0.20 films was increased up to 1.21 eV by increasing the film thickness to ∼120 nm, while thermal annealing at 480 K reduced it down to 0.83 eV. The decrease of the optical gap is discussed on the basis of amorphous–crystalline transformations. Received: 07 July 1997/Accepted: 30 July 1997     

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.     

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     

Structural,optical and electrical properties of laser irradiated Pb doped Ga–Se chalcogenide thin films

Using the Transverse Electrical Excitation at Atmospheric Pressure (TEA) nitrogen laser, we had irradiated the amorphous thin films of Ga₁₀Se₈₁Pb₉ chalcogenide glass and the results have been discussed in terms of the structural aspects of Ga₁₀Se₈₁Pb₉ glass. The observed changes are associated with the interaction of the incident photon and the lone-pairs electrons which affects the band gap. The X-ray structural characterization revealed the amorphous nature of as prepared films and polycrystalline nature of the laser irradiated films. The optical band gap of these thin films is measured by using the absorption spectra as a function of photon energy in the wavelength region 400–1200 nm. It is found that the optical band gap decreases while the absorption coefficient increases with increasing the irradiation time. The decrease in the optical band gap has been explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase in exposure time. The dc conductivities and activation energies of these thin films are measured in temperature range 303–403 K. It has been found that the activation energy in Ga₁₀Se₈₁Pb₉ chalcogenide thin films decreases whereas the dc conductivity increases at each temperature by increasing the irradiation time.     

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.     

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.     

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.     

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     

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.     

Composition dependence of the energy gap and thermal diffusivity in bulk As-Se glasses

We have measured the composition dependence of the optical energy gap and thermal diffusivity in bulk As _x Se_1−x (0.10⩽x⩽0.50) glasses using photoacoustic technique. The energy gap shows a threshold minimum value and thermal diffusivity has a threshold maximum value at the stoichiometric composition As₂Se₃ corresponding tox=0.40. The decrease in energy gap is explained on the basis of chemical bonding. It is argued that the threshold percolation of rigidity in the random network is responsible for the peaking of the thermal diffusivity at the stoichiometric composition.     

Laser-induced changes on optical band gap of amorphous and crystallized thin films of Se75S25−xAGx

Optical band gap of amorphous, crystallized, laser induced amorphous and laser induced crystallized films of Se₇₅S_25−xAg_x (x=4, 6 and 8) glassy alloys was studied from absorption spectra. The amorphous and crystallized films were induced by pulse laser for 10 min. After laser irradiation on amorphous and crystalline films, optical band gap was measured. It has been found that the mechanism of the optical absorption follows the rule of indirect transition. The amorphous thin films show an increase in the optical band gap, while the crystallized (thermally annealed) thin films show a decrease in the optical band gap by inducing laser irradiation. Crystallization and amorphization of chalcogenide films were accompanied with the change in the optical band gap. The change in optical energy gap could be determined by identification of the transformed phase. These results are interpreted in terms of concentration of localized states due to shift in Fermi level.     

Investigation of structural and optical properties of 100 MeV F7+ ion irradiated Ga10Se90-xAlx thin films

Present work focuses on the effect of swift heavy ion (SHI) irradiation of 100 MeV F⁷⁺ ions by varying the fluencies in the range of 1 × 10¹² to 1 × 10¹³ ions/cm² on the morphological, structural and optical properties of polycrystalline thin films of Ga₁₀Se_90-xAl_x (x = 0, 5). Thin films of ~300 nm thickness were deposited on cleaned Al₂O₃ substrates by thermal evaporation technique. X-ray diffraction pattern of investigated thin films shows the crystallite growth occurs in hexagonal phase structure for Ga₁₀Se₉₀ and tetragonal phase structure for Ga₁₀Se₈₅Al₅. The further structural analysis carried out by Raman spectroscopy and scanning electron microscopy verifies the defects or disorder of the investigated material increases after SHI irradiation. The optical parameters absorption coefficient (α), extinction coefficient (K), optical band gap (E_g) and Urbach’s energy (E_U) are determined from optical absorption spectra data measured from spectrophotometry in the wavelength range 200–1100 nm. It was found that the values of absorption coefficient and extinction coefficient increase while the value of optical band gap decreases with the increase in ion fluence. This post irradiation change in the optical parameters was interpreted in terms of bond distribution model.     

Effect of Cd and Pb impurities on the optical properties of?fresh?evaporated amorphous (As2Se3)90Ge10 thin films

Transmission spectra (400–1500 nm) of thermally evaporated amorphous [(As₂Se₃)₉₀Ge₁₀]₉₅M₅ thin films have been analyzed to study the effect of impurities (M = Cd and Pb) on their optical properties. The refractive index increases with addition of metal impurities. The dispersion of refractive index has been studied using Wemple–DiDomenico single oscillator model. The optical gap has been estimated using Tauc’s extrapolation and was found to decrease with the addition of metal impurities from 1.46 to 1.36 eV (Cd) and 1.41 eV (Pb) with an uncertainty of ±0.01 eV. The change in optical properties with metal impurities has been explained on the basis of density, polarizability and bond energy of the system.     

Thermal annealing dependence of the optical and electrical properties of amorphous Se79Te15Sb6 thin films

Glassy substrates Se₇₉Te₁₅Sb₆ thin films are thermally evaporated onto chemically cleaned glass. Optical absorption measurements are carried out on as-deposited and thermal annealed Se₇₉Te₁₅Sb₆ films. It is found that the mechanism of the optical absorption follows the rule of non-direct transition. The annealed Se₇₉Te₁₅Sb₆ films show an increase in the optical energy gap with increasing temperature of annealing higher than the glass transition temperature (363 K). The electrical conductivity of the as-deposited and annealed films is found to be of Arrhenius type with temperature in the range 300–360 K. The effect of thermal annealing on the activation energy for conduction is also studied. The results are discussed on the basis of amorphous–crystalline transformations. PACS 61.40; 61.40.D; 64.70.D; 72.80.N; 78.65.M     

Effect of age in vitreous As2Se3 thin films

In this paper are reported the studies of structural changes developed in the photoconductivity response spectrum of amorphous As₂Se₃ thin films with their age. Thin films were prepared by the thermal evaporation of amorphous As₂Se₃. Also reported are the X-ray diffraction studies. An explanation of the phenomenon in terms of structural changes has been attempted.     

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.     

Low-temperature growth of γ phase in thermally deposited In2Se3 thin films

In the present report, we have studied the structural and optical change in the In₂Se₃ thin films prepared by the thermal evaporation method, deposited on a glass substrate and annealed at 250°C. Both the structural and optical studies revealed the formation of γ-In₂Se₃ phase on annealing at such low temperature as 250°C which is not observed before. Raman analysis indicates that the as-prepared film consists of both α and γ-In₂Se₃ phases and the annealed film contains only γ-In₂Se₃ phase. The absorption mechanism in the studied film follows the direct allowed transition. The optical band gap is found to be decreased with annealing due to the increase in the width of localized states near to the band edges. Transmittance is found to be decreased and the absorption is increased with annealing due to the change in the film density which enhances its suitability for solar cell applications.     

Effect of annealing temperature on the optical and electrical properties of amorphous As45.2Te46.6In8.2 thin films

The optical absorption of the As-prepared and annealed As_45.2Te_46.6In_8.2 thin films are studied. Films annealed at temperatures higher than 453 K show a decrease in the optical energy gap (E_o). The value of E_o increases from 1.9 to 2.43 eV with increasing thickness of the As-prepared films from 60 to 140 nm. The effect of thickness on high frequency dielectric constant (?_∞) and carrier concentration (N) is also studied. The crystalline structures of the As_45.2Te_46.6In_8.2 thin films resulting from heat treatment of the As-prepared film at different elevated temperatures is studied by X-ray diffraction. An amorphous-crystalline transformation is observed after annealing at temperatures higher than 453 K. The electrical conductivity at low temperatures is found due to the electrons transport by hopping among the localized states near the Fermi level. With annealing the films at temperatures higher than 473 K (the crystallization onset temperature) for 1 h, the electrical conductivity increases and the activation energy decreases, which can be attributed to the amorphous-crystalline transformations.