Optical properties change in amorphous (As2S3)0.87Sb0.13 thin films by photo and thermal induced process

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As₂S₃)_0.87Sb_0.13 thin films of 1 μm thickness, were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photo darkening or photo bleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities.     

Effects of annealing temperatures on optical and electrical properties of vacuum evaporated Ga15Se77In8 chalcogenide thin films

The optical constants (absorption coefficient, optical band gap, refractive index, extinction coefficient, real and imaginary parts of dielectric constants) of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses with thickness 4000 Å have been investigated from absorption and reflection spectra as a function of photon energy in the wave length region 400-800 nm. Thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses were thermally annealed for 2 h at three different annealing temperatures 333 K, 348 K and 363 K, which are in between the glass transition and crystallization temperature of Ga₁₅Se₇₇In₈ glasses. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It was found that the optical band gap decreases with increasing annealing temperature. It has been observed that the value of absorption coefficient and extinction coefficient increases while the values of refractive index decrease with increasing annealing temperature. The decrease in optical band gap is explained on the basis of the change in nature of films, from amorphous to crystalline state. The dc conductivity of amorphous and thermally annealed thin films of Ga₁₅Se₇₇In₈ chalcogenide glasses is also reported for the temperature range 298-393 K. It has been observed that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges. The dc conductivity was observed to increase with the corresponding decrease in activation energy on increasing annealing temperature in the present system. These results were analyzed in terms of the Davis-Mott model.     

Effect of thermal annealing on some electrical properties and optical band gap of vacuum evaporated Se65Ga30In5 thin films

Electrical properties and optical band gap of amorphous Se₆₅Ga₃₀In₅ thin films, which were thermally evaporated onto chemically cleaned glass substrates, have been studied before and after thermal annealing at temperatures above the glass transition temperature and below the crystallization temperature. The I-V characteristics, which were recorded in the temperature range (200-300 K), were obtained at different voltages and exhibit an ohmic and non-ohmic behavior at low (0-5 V) and high (5-18 V) voltages, respectively, for annealed and as-prepared films. Analysis of the experimental data in the high voltage range confirms the presence of space charge limited conduction (SCLC) for annealed and as-prepared films. The dependence of DC conductivity on temperature in the low voltage region shows two types of conduction channels: The first is in the range 270-300 K and the other at the lower temperature range (200-270 K). The conduction in the first region is due to thermally activated process, while in the other is due variable range hopping (VRH) of charge carriers in the band tails of the localized states. After annealing, the conductivity has been found to increase but the activation energy decreases. This is attributed to rupturing of Se-In weak bonds and formation of Se-Ga strong bonds. This process changes the concentration of defects in the films which in turn decreases the density of states N(E_F) as predicted by Mott's VRH model. Analysis of the absorption coefficient of annealed and as-prepared films, in the wavelength range 300-700 nm, reveals the presence of parabolic densities of states at the edges of both valence and conduction bands in the studied films. The optical band gap (E_g) was obtained through the use of Tauc's relation and is found to decrease with annealing temperature.     

Effect of composition and deposition parameters on optical properties of Ge25Sb15−xBixS60 thin films

The optical constants of the Ge₂₅Sb_15−xBi_xS₆₀ (0?x?15) chalcogenide films, either as-deposited or after being annealed at various temperatures have been computed in the spectral wavelength range 400-2400 nm from the transmittance and reflectance measurements of normally-incident light. With the increase in bismuth content, the optical energy gap (which is indirect) decreases, while the refractive index increases. The effects of film thickness, substrate type, deposition rate and γ-radiation on optical properties have been studied. The effect of thermal annealing on the growth characteristics and stability of the films has been studied using X-ray diffraction and scanning electron microscopy. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model.     

Compositional effects on the optical properties of Gex Sb40−x Se60 thin films

Ge_x Sb_40−x Se₆₀ (x = 0, 2.42 and 23.41 at.%) thin chalcogenide films were deposited on glass and quartz substrates by the conventional thermal evaporation technique at 300 K. The chemical composition of the bulk material and as-deposited films were determined by energy dispersive analysis X-ray spectrometry (EDAX). X-ray diffraction pattern (XRD) of Ge_x Sb_40−x Se₆₀ (x = 0, 2.42 and 23.41 at.%) thin films indicates that they have amorphous structure. The optical transmission and reflection spectra were measured in the range of 500 to 2500 nm. The optical absorption coefficient spectra were studied for deposited samples. It is observed that the optical absorption edge shift to higher energy range, as the germanium content, x, increases in the film. The type of electronic transition, responsible for the optical properties, is indirect allowed transition. It is found that the optical band gap increases as the Ge content increases.The average coordination number (N_c) in Ge_x Sb_40−x Se₆₀ films increases, but the number of chalcogenide atoms remains constant. The number of Ge - Se bonds and the average bond energy of the system increase with the increase of the average coordination number. The optical band gap, E_g, increases with the increase of the average coordination number, (N_c). Also the energy gap, E₀₄, is discussed in terms of its relation to the chemical composition. The dispersion of the refractive index (n) is discussed in terms of the Single Oscillator Model (SOM) (Wimple - Didomenico model). The single oscillator energy (E₀), the dispersion energy (E_d) and the optical dielectric constant (?_∞) are also estimated.     

Temperature effects on the optoelectronic properties of AgIn5S8 thin films

Polycrystalline AgIn₅S₈ thin films are obtained by the thermal evaporation of AgIn₅S₈ crystals onto ultrasonically cleaned glass substrates under a pressure of ~ 1.3 × 10⁻³ Pa. The temperature dependence of the optical band gap and photoconductivity of these films was studied in the temperature regions of 300-450 K and 40-300 K, respectively. The heat treatment effect at annealing temperatures of 350, 450 and 550 K on the temperature dependent photoconductivity is also investigated. The absorption coefficient, which was studied in the incidence photon energy range of 1.65-2.55 eV, increased with increasing temperature. Consistently, the absorption edge shifts to lower energy values as temperature increases. The fundamental absorption edge which corresponds to a direct allowed transition energy band gap of 1.78 eV exhibited a temperature coefficient of −3.56 × 10⁻⁴ eV/K. The 0 K energy band gap is estimated as 1.89 eV. AgIn₅S₈ films are observed to be photoconductive. The highest and most stable temperature invariant photocurrent was obtained at an annealing temperature of 550 K. The photoconductivity kinetics was attributed to the structural modifications caused by annealing and due to the trapping-recombination centers' exchange.     

Crystal structure and optical absorption investigations on β-In2S3 thin films

The crystal structure of annealed β-In₂S₃ thin films with different thickness was investigated by X-ray diffraction technique. Lattice parameters, crystallite size and microstrain were calculated. It was found that the lattice parameters are independent on film thickness, while annealing temperatures increase them. Crystallite sizes were increased with the increase of the film thickness and improved by annealing temperatures. In all cases, the microstrains were decreased gradually with the increase in both film thickness and annealing temperatures. Optical properties of β-In₂S₃ thin films were performed in the spectral range from 400 to 2500 nm to determine the optical constants (n and k), the high frequency dielectric constant, ε_∞, the lattice dielectric constant, ε_L, and the energy gap. The optical constants were found to be independent on film thickness in the range from 200 to 630 nm. The high frequency dielectric and lattice dielectric constants of the as-deposited film increased by annealing temperatures. The energy gap for the as-deposited In₂S₃ was found to be 2.60 eV and increased to 2.70 and 2.75 eV by annealing at 423 and 473 K for 1 h, respectively.     

Some optical properties of Se-Ge-As amorphous chalcogenide glasses

The effects of composition, film thickness, substrate temperature, and annealing of amorphous thin films of Se₇₅Ge_25−x As _x (5⩽x⩽20) on their optical properties have been investigated. X-ray diffraction revealed the formation of amorphous films. The absorbance and transmission of vacuum-evaporated thin films were used to determine the band gap and refractive index. Optical absorption measurements showed that the fundamental absorption edge is a function of glass composition and the optical absorption is due to indirect transition. The energy gap increases linearly with increasing arsenic content. The optical band gap,E _opt, was found to be almost thickness independent. The shapes of the absorption edge of annealed samples displayed roughly the same characteristic as those of the unannealed films, but were shifted towards shorter wavelengths; as a result,E _opt increased andE _e, the width of the band tails, decreases. The increase inE _opt is believed to be associated with void removal and microstructural re-arrangement during annealing. The influence of substrate temperature on the optical parameters is discussed.     

Metal induced effects on some physical properties of Se0.8Te0.2 amorphous system

Thermally evaporated selenium and tellurium-based thim film glasses were carefully characterized to establish the interdependence between their chemical composition and some physical parameters, such as density and optical energy gap.The effects of different metallic additions and annealing at a temperature below the glass transition temperature T_g on the optical characteristics was explored. The optical energy gap E_opt was found to decrease with the addition of metal, the extent of the diminution dependings on the chemical character of the added metal.     

Electrical and optical properties of (Sb2Se3)2 (Sb2Te3)1 thin films

A study of the synthesized (Sb₂Se₃)₂ (Sb₂Te₃)₁ glassy system has been carried out, X-ray diffraction (XRD) patterns and differential thermal analysis (DTA) of the system studied were used to obtain an insight into the structural information. An investigation of the electrical and optical properties of (Sb₂Se₃)₂ (Sb₂Te₃)₁ thin films prepared by thermal evaporation having different thicknesses (89.2, 214, 223 nm) and annealing temperatures ranging from 300 to 473 K has been carried out. The effect of the thickness and heat treatment on the activation energy E for d.c. conductivity and the density of localized states at the Fermi level N(E_F) were carried out. The electrical conductivity measurements depend on the thickness and annealing temperature, and exhibit two types of conduction mechanisms. Optical absorption measurements have been made on as-deposited and annealed films for the investigated system. The optical transition was found to be indirect. The optical energy gap (E_opt) decreases with increasing thickness and annealing temperatures (below T_g). The corresponding band is approximately twice the conduction activation energy. This effect is interpreted in terms of the density of states model proposed by Mott and Davis. © 2002 Kluwer Academic Publisher     

Nanocomposite thin films of Ga5Sb10Ge25Se60 chalcogenide glass for optical limiting applications

We report a low-cost, scalable method to fabricate optical grade composite thin films for nonlinear optical applications. The transmission and reflection spectra of prepared Ga₅Sb₁₀Ge₂₅Se₆₀/PVA composite films were investigated. Optical band gap of the thin films were calculated using Tauc’s extrapolation method. The band gap of the nanocomposite thin films were found to be tunable depending on the grain size of the films. Nonlinear optical characterization of samples were studied by the Z-scan technique using an Nd:YAG laser (532 nm, 7 ns, 10 Hz). Sequential Z-scan traces were made in four regimes of intensity for films with three different grain sizes. The Z-scan spectra reveal a strong nonlinear absorption depending on the grain size of the films suggesting that the new materials are promising candidates for the development of nonlinear optical devices and are extremely perspective as optical limiters of intense short pulse radiation.     

Phase change and optical band gap behavior of Se0.8S0.2 chalcogenide glass films

Se_0.8S_0.2 chalcogenide glass films have been prepared by thermal vacuum evaporation technique with thickness 583 nm. Annealing process at T ≥ 333 K crystallizes the films and nanostructured films are formed. The crystallite size was increased to 24 nm as the annealing temperature increased to 373 K. Orthorhombic crystalline system was identified for the annealed films. SEM micrographs show that films consist of two parallel surfaces and the thickness was determined by cross section imaging. The optical transmittance is characterized by interference patterns as a result of these two parallel surfaces, besides their average value at longer wavelength decreases as a result of annealing process. The band gap, E_g is red shifted due to crystallization by annealing. As the phase of the films changes from amorphous to crystalline in the annealing temperature range 333–363 K, a non sharp change of the band gap (E_g) is observed. This change was explained by Brus’s model of the energy gap confinement behavior of the nanostructured films. The optical refractive index increases suddenly when the system starts to be crystallized by annealing.     

Electrochemical preparation and characterization of three-dimensional nanostructured Sn2S3 semiconductor films with nanorod network

Three-dimensional (3D) nanostructured Sn₂S₃ semiconductor films have been prepared on ITO-coated glass substrates by potentiostatic electrodeposition at −0.80 V (vs. SCE) from a novel plating bath containing K₄P₂O₃ as a complexing agent and Na₂SO₃ as a stabilizing agent and by subsequent annealing. Results showed that the annealing drove the as-deposited Sn₂S₃ films to grow from a granular structure into a nanorod network structure. The nanorods were around 50-100 nm in diameter and 1000 nm in length. The band gap of the annealed film was 1.65 eV and the conductivity was n type. The carrier mobility achieved up to 20.5 cm² V⁻¹ s⁻¹ due to the direct electrical pathways provided by the nanorod network.     

Characterization of phase transition in silver photo-diffused Ge2Sb2Te5 thin films

Surface activity of thermally evaporated amorphous chalcogenide films of Ge₂Sb₂Te₅ has been investigated. Silver (Ag) is readily deposited on such films from appropriate aqueous ionic solution and Ag diffuses into the films upon irradiation with energetic photons. The composition of Ge₂Sb₂Te₅ thin films and the amount of Ag photo-diffused has been gathered from electron probe micro-analyzer having a wavelength dispersive spectrometer. The composition of the films was found to be very close to the bulk used to deposit films and the amount of Ag photo-diffused was ∼ 0.38 at. %. X-ray diffraction and temperature dependent sheet resistance studies have been used for the structural analysis of the bulk alloy, as-deposited, Ag photo-diffused and annealed films at different temperatures. The films remain amorphous after Ag photo-diffusion into the amorphous Ge₂Sb₂Te₅ films. The reflectivity, reflectivity contrast and extinction coefficient of the crystalline and amorphous photo-diffused thin films are presented. The optical band gaps of the amorphous and crystalline photo-diffused (Ge₂Sb₂Te₅)_100−xAg_x=0.38 phase change thin films have also been calculated from absorption data using UV-VIS spectroscopy.     

Annealing effect on cadmium in situ doping of chemical bath deposited PbS thin films

This paper describes the effect of annealing on PbS and Cd-doped PbS thin films prepared by chemical bath deposition at different bath temperatures (T_b). The X-ray diffraction (XRD), optical absorption, scanning electron microscopy, and energy dispersive X-ray (EDX) analyses have been performed to explore the properties of PbS and PbCdS films. From the XRD measurements, the particle size (D) of as-deposited PbS and PbCdS films is estimated to be 22 (27) and 12 (9) nm, respectively, for a T_b of 75 (85) °C. A reduction in D was noticed upon annealing the films at 200 °C, irrespective of the T_b and the doping. The optical band gap energy (E_g) of as-deposited PbS films grown at different T_b is found to be in the range of 1.22-1.42 eV. Doping of PbS with Cd and annealing have led to increase in E_g up to 2.61 (2.66) eV. Optical studies revealed prominent blue shifts in the E_g of as-deposited and annealed films due to quantum confinement effect. The addition of Cd into PbS was confirmed by EDX analysis.     

Substrate and annealing temperature effects on the optical and electrical properties of Ge20Te80 films

Ge₂₀Te₈₀ films were deposited by thermal evaporation technique onto chemically cleaned glass substrates kept at different substrate temperatures (T_sub=203, 233 and 273 K). The optical data indicated that the width of the localized states tails (E_e) increases while the optical gap (E_o) decreases with increasing the substrate and annealing temperature of the investigated films. From the electrical measurements, the activation energy for conduction and the density of localized states at the Fermi energy, N(E_F), were obtained. The effects of the substrate and annealing temperature on the width of localized states tails and on the density of localized states at the Fermi level have enhanced each other. The changes in the optical and electrical properties are correlated with the amorphous-crystalline transformations.     

Synthesis and properties of GeS2-Ga2S3-PbI2 chalcohalide glasses

The glass-forming region in the GeS₂-Ga₂S₃-PbI₂ system was determined and the basic parameters of thermal and optical properties (glass transition temperature, density, microhardness and transmission window) for these glasses have been measured. Better thermal stability originated from their larger difference between T_x and T_g in the range of 107-161 °C, higher glass transition temperatures between 252 and 398 °C and wide optical transmission window from 0.5 to 12.7 μm make these glasses the promising candidate materials for rare earth doped fiber amplifiers and nonlinear optical devices.     

Optical and electrical properties of Te-substituted Sn-Sb-Se semiconducting thin films

Thin films of Sn₁₀Sb₂₀Se_70-XTe_X (0 ≤ X ≤ 14) composition were deposited using thermal evaporation technique. As-prepared films were amorphous as studied by X-ray diffraction. Surface morphology studies revealed that films have surface roughness ~ 2 nm and av. grain size ~ 30 nm. Optical band gap E_g showed a sharp decrease for initial substitution of Se with Te upto 2 at.%. A broad hump in the optical band gap is observed for further substitution of Se with Te. The trend of optical band gap variation with tellurium content has been qualitatively explained using band model given by Kastner. The dc-conductivity measurements showed thermally activated conduction with single activation energy for the measured temperature regime and followed Meyer-Neldel rule. The dc-activation energy has nearly half the value as that of optical band gap that revealed the intrinsic nature of semiconductor. The annealing below glass transition T_g led to decrease in optical band gap as well as dc-activation energy that might be related to increase of disorder in material with annealing.     

Growth and vacuum post-annealing effect on the properties of the new absorber CuSbS2 thin films

Post-growth treatments in vacuum atmosphere were performed on CuSbS₂ films prepared by the single-source thermal evaporation method on glass substrates. The films were annealed in vacuum atmosphere for 2 h in temperature range 130-200 °C. The effect of this thermal treatment on the structural, optical and electrical properties of the films was studied. X-ray diffraction (XRD) patterns indicated that the films exhibited an amorphous structure for annealing temperature below 200 °C and a polycrystalline structure with CuSbS₂ principal phase. For the films annealed at temperatures below 200 °C one direct optical transition in range 1.8-2 eV was found. For the films annealed at 200 °C, two optical direct transitions emerged at 1.3 and 1.79 eV corresponding to the CuSbS₂ and Sb₂S₃ values respectively. The electrical measurements showed a conversion from low resistivities (3.10^− 2-9.10^− 2) Ω cm for the samples annealed at temperatures below 200 °C to relatively high resistivities (2 Ω cm) for the samples annealed at 200 °C. In all cases the samples exhibited p-Ztype conductivity.     

Study of hydrogenated nanoamorphous silicon(na-Si:H) thin film prepared by RF magnetron sputtering for graded optical band gap (<Emphasis Type="Italic">E</Emphasis><Superscript>opt</Superscript><Subscript>g</Subscript>)

The schematic of the energy band gap figure of the graded optical band gap (E_g^opt) in p-i-n layer in na-Si:H solar cells was given in the paper. The intrinsic hydrogenated nanoamorphous silicon(na-Si:H) thin films with the graded band gap as a function of depth through the films were prepared by varying the processing power, gas pressure, gas composition, and etc., We have carried out a investigation of the relationships between the E_g^opt with the crystallization ratio (Xc) and the E_g^opt with the nanocrystalline grain size (D) in na-Si:H thin films grown by PECVD on glass substrates through XRD, Raman scattering, transmission. The E_g^opt increase with the decreases of the crystallization ratio (Xc) and the nanocrystalline grain size (D). The hydrogen dilution ratio is found to increase basically both the crystallization ratio (Xc) and the nanocrystalline grain size (D). Two relationships in na-Si:H are discussed by the etching effect of atomic hydrogen in the framework of the growth mechanism and the quantum size effect (QSE).