Effect of thermal annealing on physical properties of vacuum evaporated In2S3 buffer layer for eco-friendly photovoltaic applications

The present communication reports the effect of thermal annealing on the physical properties of In₂S₃ thin films for eco-friendly buffer layer photovoltaic applications. The thin films of thickness 150 nm were deposited on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing in air atmosphere within a low temperature range 150–450 °C. These as-deposited and annealed films were subjected to the X-ray diffraction (XRD), UV–vis spectrophotometer, current–voltage tests and scanning electron microscopy (SEM) for structural, optical, electrical and surface morphological analysis respectively. The compositional analysis of as-deposited film is also carried out using energy dispersive spectroscopy (EDS). The XRD patterns reveal that the as-deposited and annealed films (≤300 °C) have amorphous nature while films annealed at 450 °C show tetragonal phase of β-In₂S₃ with preferred orientation (109) and polycrystalline in nature. The crystallographic parameters like lattice constant, inter-planner spacing, grain size, internal strain, dislocation density and number of crystallites per unit area are calculated for thermally annealed (450 °C) thin films. The optical band gap was found in the range 2.84–3.04 eV and observed to increase with annealing temperature. The current–voltage characteristics show that the as-deposited and annealed films exhibit linear ohmic behavior. The SEM studies show that the as-deposited and annealed films are uniform, homogeneous and free from crystal defects and voids. The grains in the thin films are similar in size and densely packed and observed to increase with thermal annealing. The experimental results reveal that the thermal annealing play significant role in the structural, optical, electrical and morphological properties of deposited In₂S₃ thin films and may be used as cadmium-free eco-friendly buffer layer for thin films solar cells applications.     

Structural and optoelectronic properties of nanostructured TiO2 thin films with annealing

About 480 nm thick titanium oxide (TiO₂) thin films have been deposited by electron beam evaporation followed by annealing in air at 300–600 °C with a step of 100 °C for a period of 2 h. Optical, electrical and structural properties are studied as a function of annealing temperature. All the films are crystalline (having tetragonal anatase structure) with small amount of amorphous phase. Crystallinity of the films improves with annealing at elevated temperatures. XRD and FESEM results suggest that the films are composed of nanoparticles of 25–35 nm. Raman analysis and optical measurements suggest quantum confinement effects since Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk TiO₂ Optical band gap energy of the as-deposited TiO₂ film is 3.24 eV, which decreases to about 3.09 eV after annealing at 600 °C. Refractive index of the as-deposited TiO₂ film is 2.26, which increases to about 2.32 after annealing at 600 °C. However the films annealed at 500 °C present peculiar behavior as their band gap increases to the highest value of 3.27 eV whereas refractive index, RMS roughness and dc-resistance illustrate a drop as compared to all other films. Illumination to sunlight decreases the dc-resistance of the as-deposited and annealed films as compared to dark measurements possibly due to charge carrier enhancement by photon absorption.     

Effect of thermal annealing on structural and optical properties of titanyl phthalocyanine thin films

Thin films of titanyl phthalocyanine (TiOPc) have been deposited on both fused quartz and glass substrates by the thermal evaporation technique. The structural and optical properties of the as-deposited and annealed films have been reported. The structural features of the as-deposited and annealed films have been studied by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and Fourier-transform infrared (FT-IR) technique. The optical constants (refractive index, n, and absorption index, k) of the films have been presented for the first time in the wavelength range 200–2500 nm by using spectrophotometric measurements at nearly normal incidence. The band gaps of the as-deposited film at 1.48 eV and 2.5 eV corresponding to Q-band and B or Soret band were red-shifted to 1.15 eV and 2.19 eV, respectively, when the film annealed at 433 K.     

Properties of CuAlO2 thin films deposited by polyacrylamide gel route

CuAlO₂ films were deposited on clean glass substrates by the acrylamide sol–gel dip coating technique. The coated films were dried in air oven for 30 min followed by heat treatment in air at different temperatures in the range of 350–500 °C. The films annealed at low temperatures exhibited weak x-ray diffraction (XRD) peaks. As the post anneal temperature increased beyond 375 °C, the XRD pattern exhibited the diffraction peaks of rhombohedral CuAlO₂. Surface morphology of the films indicated that the films annealed at low temperatures exhibit small grains. As the annealing temperature increases larger grains are observed. The root mean square (rms) value of the surface roughness increases with annealing temperature. The films exhibited optical transmission above 75%. The films post annealed at low temperature exhibited lower transmission. Optical band gap in the range of 3.43–3.75 eV was obtained for the films annealed at different temperature. Hall measurements indicated p-type conductivity. Resistivity of the films decreased from 25.0 to 2.0 Ω cm as the anneal temperature increased. Mobility and carrier density increased with annealing temperature.     

Optical and electrical properties of nickel oxide thin films synthesized by sol–gel spin coating

Nickel oxide thin films were prepared by the sol–gel technique combined with spin coating onto glass substrates. The as-deposited films were pre-heated at 275 °C for 15 min and then annealed in air at different temperatures. The effects of the annealing temperature on the structural and optical properties of the films are studied. The results show that 600 °C is the optimum annealing temperature for preparation of NiO films with p-type conductivity and high optical transparency. Then, by using these optimized deposition parameters, NiO thin films of various thicknesses were deposited at the same experimental conditions and annealed under different atmospheres. Surface morphology of the films was investigated by atomic force microscopy. The surface morphology of the films varies with the annealing atmosphere. Optical transmission was studied by UV–vis spectrophotometer. The transmittance of films decreased as the thickness of films increased. The electrical resistivity, obtained by four-point probe measurements, was improved when NiO layers were annealed in N₂ atmosphere at 600 °C.     

The correlation of γ-irradiation,particle size and their effects on physical properties of AgInSe2 nanostructure thin films

In this work the effect of γ-irradiation on the optical and electrical properties of near stoichiometric AgInSe₂ nanostructure thin films have been characterized. The XRD pattern of ingot AgInSe₂ powder prepared by solid state reaction showed tetragonal polycrystalline single-phase structure. The thin films of thickness 75 nm were prepared by inert gas condensation (IGC) technique at using constant Ar flow and substrate temperature of 300 K.Thin films were exposed to annealing process at 473 K for 2 h in vacuum of 10⁻² Torr. The amorphous and tetragonal nanocrystalline structures were detected for as-deposited and annealed films respectively by grazing incident in-plane X-ray diffraction (GIIXD) technique. The structure and average particle size of annealed irradiated films by different γ-doses from 0 to 4 Mrad were determined using high resolution transmission electron microscope (HRTEM). Optical transmission, reflection and absorption spectra were studied for both annealed unirradiated and irradiated films. Two optical transitions for each annealed unirradiated and film exposed to γ-irradiation doses from 0 to 4 Mrad were observed. The evaluated E_g1 due to 1^st transition have decreased from 1.52 to 1.44 eV and E_g2 due to 2^nd transition have decreased from 2.83 to 2.30 eV as the particle size increased from 7.3 to 9.5 nm by raising the irradiation dose up to 1 Mrad. The behavior of d.c. electrical conductivity with temperature that measured under vacuum was examined for all films under investigation. The evaluated activation energies due to irradiation doses are ranging from 0.58 to 0.68 eV.     

Effect of annealing temperature on structural,electrical and optical properties of spray pyrolytic nanocrystalline CdO thin films

Nanocrystalline CdO thin films were prepared onto a glass substrate at substrate temperature of 300 °C by a spray pyrolysis technique. Grown films were annealed at 250, 350, 450 and 550 °C for 2.5 h and studied by the X-ray diffraction, Hall voltage measurement, UV-spectroscopy, and scanning electron microscope. The X-ray diffraction study confirms the cubic structure of as-deposited and annealed films. The grain size increases whereas the dislocation density decreases with increasing annealing temperature. The Hall measurement confirms that CdO is an n-type semiconductor. The carrier density and mobility increase with increasing annealing temperature up to 450 °C. The temperature dependent dc resistivity of as-deposited film shows metallic behavior from room temperature to 370 K after which it is semiconducting in nature. The metallic behavior completely washed out by annealing the samples at different temperatures. Optical transmittance and band gap energy of the films are found to decrease with increasing annealing temperature and the highest transmittance is found in near infrared region. The refractive index and optical conductivity of the CdO thin films enhanced by annealing. Scanning electron microscopy confirms formation of nano-structured CdO thin films with clear grain boundary.     

Antimony sulfide (Sb2S3) thin films by pulse electrodeposition: Effect of thermal treatment on structural,optical and electrical properties

Antimony sulfide films have been deposited by pulse electrodeposition on Fluorine doped SnO₂ coated glass substrates from aqueous solutions containing SbCl₃ and Na₂S₂O₃. The crystalline structure of the films was characterized by X-ray diffraction, Raman spectroscopy and TEM analysis. The deposited films were amorphous and upon annealing in nitrogen/sulfur atmosphere at 250 °C for 30 min, the films started to become crystalline with X-ray diffraction pattern matching that of stibnite, Sb₂S₃, (JCPDS 6-0474). AFM images revealed that Sb₂S₃ films have uniformly distributed grains on the surface and the grain agglomeration occurs with annealing. The optical band gap calculated from the transmittance and the reflectance studies were 2.2 and 1.65 eV for as deposited and 300 °C annealed films, respectively. The annealed films were photosensitive and exhibited photo-to-dark current ratio of two orders of magnitude at 1 kW/m² tungsten halogen radiation.     

Investigation of structural and optoelectronic properties of annealed nickel phthalocyanine thin films

Thin films of nickel phthalocyanine (NiPc) were prepared by thermal evaporation and the effects of annealing temperature on the structural and optical properties of the samples were studied using different analytical methods. Structural analysis showed that the grain size and crystallinity of NiPc films improved as annealing temperature increased from 25 to 150 °C. Also, maximum grain size (71.3 nm) was obtained at 150 °C annealing temperature. In addition, NiPc films annealed at 150 °C had a very smooth surface with an RMS roughness of 0.41 nm. Optical analysis indicated that band gap energy of films at different annealing temperatures varied in the range of 3.22–3.28 eV. Schottky diode solar cells with a structure of ITO/PEDOT:PSS/NiPc/Al were fabricated. Measurement of the dark current density–voltage (J–V) characteristics of diodes showed that the current density of films annealed at 150 °C for a given bias was greater than that of other films. Furthermore, the films revealed the highest rectification ratio (23.1) and lowest barrier height (0.84 eV) demonstrating, respectively, 23% and 11% increase compared with those of the deposited NiPc films. Meanwhile, photoconversion behavior of films annealed at 150 °C under illumination showed the highest short circuit current density (0.070 mA/cm²) and open circuit voltage of (0.55 V).     

Annealing effect on structural and optical properties of Se87.5Te10Sn2.5 thin films

Thin films of Se_87.5Te₁₀Sn_2.5 were prepared by vacuum thermal evaporation technique. Various optical constants were calculated for the studied composition. The mechanism of the optical absorption follows the rule of direct transition. It was found that the optical energy gap (E_g) decreases from 2.26 to 1.79 eV with increasing the annealing temperature from 340 to 450 K. This result can be interpreted by the Davis and Mott model. On the other hand, the maximum value of the refractive index (n) is shifted towards the long wavelength by increasing the annealing temperature. In addition, the high frequency dielectric constant (ε_L) increased from 31.26 to 48.11 whereas the ratio of the free carriers concentration to its effective of mass N/m^⁎ decreased from 4.3 to 2.09 (×10⁵⁷ (m⁻³ Kg⁻¹)). The influence of annealed temperature on the structure was studied by using the X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD studies show that the as-deposited films are amorphous in nature, but the crystallinity improved with increasing the annealing temperature. Furthermore the particle size and crystallinity increased whereas the dislocation and strains decreased with increasing the annealing temperature. SEM examination showed that the annealing temperature induced changes in the morphology of the as-deposited film.     

Behavior of chemically deposited PbS thin films subjected to two different routes of post deposition annealing

Lead sulfide (PbS) thin films were prepared on soda lime glass substrates at room temperature by Chemical Bath Deposition (CBD) technique. This paper reports a comparative study of characteristic properties of as-prepared PbS thin films after thermal treatment through two different routes. Studies were carried out for as-prepared as well as rapidly and gradually annealed samples at 100, 200 and 300 °C. The characterizations of the films were carried out using X-ray diffraction, scanning electron microscopy and optical measurement techniques. The structural studies confirmed the polycrystalline nature and the cubic structure of the films. As-deposited films partly transformed to Pb₂O₃ when gradually annealed to 300 °C. The presence of nano crystallites was revealed by structural and optical absorption measurements. The values of average crystallite size were found to be in the range 18–20 nm. The variation in the microstructure, thickness, grain size, micro strain and optical band gap on two types of annealing were compared and analyzed. Data showed that post deposition parameters and thermal treatment strongly influence the optical properties of PbS films. Optical band gap of the film gets modified remarkably on annealing. Direct band gap energy values for rapidly and gradually annealed samples varied in the range of 1.68–2.01 eV and 1.68–2.12 eV respectively. Thus we were succeeded in tailoring direct band gap energies by post deposition annealing method.     

Influence of working pressure on the structural,optical and electrical properties of sputter deposited AZO thin films

Highly oriented crystalline aluminum doped zinc oxide (AZO) films were sputter deposited on glass substrates and a systematic investigation on the as deposited and etched films was reported for its further application in silicon thin film solar cell. Influence of the deposition pressure (from 2 to 8 mTorr) and post-annealing temperature (at 400 °C for 5 min) on the structural, optical and electrical properties of the as-deposited and etched samples were analyzed. The optimum condition for its reproducibility and large area deposition is determined and found that the depositions made at 8 mTorr at 200 W having the distance from source to substrate of 9 cm. All the AZO films exhibited a c-axis preferred orientation perpendicular to the substrate and their crystallinity was improved after annealing. From the XRD pattern the grain size, stress and strain of the films were evaluated and there is no drastic variation. Optical transmittance, resistivity, Hall mobility and carrier concentration for the as deposited and etched-annealed films were found to improve from 79 to 82%; 2.97 to 3.14×10⁻⁴ Ω cm; 25 to 38 cm²/V s; 8.39 to 5.96×10²⁰/cm³ respectively. Based on the triangle diagram between figure of merit and Hall mobility, we obtained a balance of point between the electrical and optical properties to select the deposition condition of film for device application.     

Influence of annealing temperature on nanostructured thin films of tungsten trioxide

Tungsten trioxide thin films of ~300 nm thickness have been deposited on indium tin oxide coated glass and silicon substrates by thermal evaporation technique. Influence of annealing temperature on the structural, vibrational, morphological, optical and gas sensing properties of these films has been extensively studied to search out the possible applications in opto-electronic and gas sensing devices. From the studies of optical transmittance spectra it is observed that optical band gap decreases from 3.24 to 2.72 eV with increase in annealing temperature. It is also observed that because of annealing the photoluminescence yield of the films increases. All films, especially the annealed films have shown reasonably good gas sensing behavior in acetylene environment. The film annealed at 500 °C shows better optical as well as gas sensing behaviors and hence can have good device applications.     

Effects of annealing temperature on the photoluminescence of RF sputtered Barium titanate thin films

BaTiO₃ thin films were deposited onto quartz substrates by an RF magnetron sputtering method. The films deposited at room temperature and annealed at 773–1173 K were characterized using X-ray diffraction (XRD)Scanning electron microscopy (SEM), UV–vis spectroscopy and Photoluminescence spectroscopy (PL). X-ray diffraction studies revealed that the film is amorphous in nature at 773 K and that the crystallinity increases with increase in annealing temperature. The average crystallite size of the films increased from 13–18 nm and the optical band gap decreased in the range of 4.33–3.43 eV, with increase in annealing temperature. The films exhibited good adherence to the substrates and the SEM images showed smooth surface morphology. Energy dispersive X-ray (EDX) analysis confirmed the presence of barium, titanium and oxygen in the film. The red-shifts of excitonic UV emission peaks were observed in all samples which can be attributed to the stress produced due to lattice distortions. The visible PL emission intensity showed appreciable enhancement with post-deposition annealing.     

Effect of rapid thermal annealing on properties of thermally evaporated nanostructured CdTe thin film treated with CdCl2

The effects of rapid thermal annealing on properties of crystalline nanostructured CdTe films treated with CdCl₂ and prepared by vacuum evaporation are described. X-ray diffraction confirmed the crystalline nature of post-treated films with high preferential orientation around 23.7°, corresponding to a (1 1 1) diffracted plane of cubic phase. Optical band gap of CdTe films increased from 1.4 eV to 1.48 eV after annealing at 500 °C for 90 s. Atomic force microscopy of annealed films revealed an increase in root mean square roughness and grain size with increased annealing time. Electrical measurements of as-grown and annealed films are consistent with p-type; film resistivity has decreased significantly with increased annealing time.     

Variation of the structural,optical and electrical properties of CBD CdO with processing temperature

Nanostructures of CdO thin films are prepared by chemical bath deposition (CBD) technique. The synthesized film is annealed in static air by using the hotplate at 373, 473, 573 and 673 K for 10 min. The effect of annealing temperature on structural, morphological, optical and electrical properties of CdO thin films has been investigated. The prepared thin films are characterised by X-ray diffraction (XRD), atomic force microscope (AFM), optical reflection microscope (ORM), UV–Visible Spectrophotometer and electrical resistivity. XRD shows the emergence of the cubic phase of CdO film in a preferred orientation (111) plane at 573 K. The AFM and ORM show that CdO films have smooth homogeneous surface in the formula with the emergence of nanoclusters gathering as nanoparticles with the average of grain size about 100 nm at 573 K. The optical properties prove that deposited films have high transparency within the visible range of the spectrum that reaches to more than 85% with a wide band gap that extends from 2.42 eV to 2.7 eV. The electrical properties of the CdO films show that resistivity decreases with increased annealing temperatures. In addition, it is proved that more than one activation energy appears and they change according to the temperature of annealing and this comes as a result of the polycrystalline structure. This study indicates that the properties of CdO thin films could be improved with annealing temperature and these films can be used in many technological applications.     

Flash evaporated cadmium sulfide films

Cadmium sulfide (CdS) thin films were deposited by the flash evaporation technique onto glass substrates kept at temperatures in the range 30–300 °C. The source material was CdS powder synthesized in the laboratory. The films exhibited hexagonal structure with dislocation density and the stress decreased as the substrate temperature increased. An optical band gap of 2.39 eV was obtained for the films deposited at 300 °C. Raman spectra exhibited peaks corresponding to Longitudinal Optical phonons of CdS with the full width at half maximum decreasing with increase of substrate temperature. Room temperature resistivity values are lower than earlier reports on chemically deposited CdS films.     

Influence of annealing temperature on the phase composition and optical properties of CuInS2 films

We studied the growth of CuInS₂ thin films by single-source evaporation of CuInS₂ powder in a high-vacuum system with a base pressure of 10^?3 Pa. After evaporation, the films were annealed in a sulfur atmosphere at temperatures from 200 to 500 °C for 1 h. XRD curves and Raman spectra of the films demonstrated that chalcopyrite CuInS₂ was the major crystalline phase. The morphology of Cu_xS exhibited a star-like structure, which we report for the first time. The phase composition and optical properties of our polycrystalline thin films were effectively modified by annealing in S. For films annealed at 200 and 350 °C, a secondary CuIn₁₁S₁₇ phase appeared, which may be related to solid-state reaction in the S atmosphere. This secondary CuIn₁₁S₁₇ phase has not been widely reported in previous studies. After annealing at 500 °C, only a chalcopyrite phase was detected, with bandgap energy of 1.46 eV, which is nearly identical to the optimal bandgap energy (1.5 eV) of single-crystal CuInS₂. This indicates that the composition of the CuInS₂ film annealed at 500 °C was nearly stoichiometric. The bandgap of the samples first increased and then decreased with increasing annealing temperature, which may be attributed to an increase in grain size, the secondary CuIn₁₁S₁₇ phase, and deviation from stoichiometry.     

Composition,structure and electrical properties of DC reactive magnetron sputtered Al2O3 thin films

Thin films of alumina (Al₂O₃) were deposited over Si 〈1 0 0〉 substrates at room temperature at an oxygen gas pressure of 0.03 Pa and sputtering power of 60 W using DC reactive magnetron sputtering. The composition of the as-deposited film was analyzed by X-ray photoelectron spectroscopy and the O/Al atomic ratio was found to be 1.72. The films were then annealed in vacuum to 350, 550 and 750 °C and X-ray diffraction results revealed that both as-deposited and post deposition annealed films were amorphous. The surface morphology and topography of the films was studied using scanning electron microscopy and atomic force microscopy, respectively. A progressive decrease in the root mean square (RMS) roughness of the films from 1.53 nm to 0.7 nm was observed with increase in the annealing temperature. Al–Al₂O₃–Al thin film capacitors were then fabricated on p-type Si 〈1 0 0〉 substrate to study the effect of temperature and frequency on the dielectric property of the films and the results are discussed.     

Influence of thermal annealing on electrical and optical properties of indium tin oxide thin films

Transparent conducting indium tin oxide (ITO) thin films with the thickness of 300 nm were deposited on quartz substrates via electron beam evaporation, and five of them post-annealed in air atmosphere for 10 min at five selected temperature points from 200 °C to 600 °C, respectively. An UV–vis spectrophotometer and Hall measurement system were adopted to characterize the ITO thin films. Influence of thermal annealing in air atmosphere on electrical and optical properties was investigated in detail. The sheet resistance reached the minimum of 6.67 Ω/sq after annealed at 300 °C. It increased dramatically at even higher annealing temperature. The mean transmittance over the range from 400 nm to 800 nm reached the maximum of 89.03% after annealed at 400 °C, and the figure of merit reached the maximum of 17.79 (Unit: 10⁻³ Ω⁻¹) under the same annealing condition. With the annealing temperature increased from 400 °C to 600 °C, the variations of transmittance were negligible, but the figure of merit decreased significantly due to the deterioration of electrical conductivity. With increasing the annealing temperature, the absorption edge shifted towards longer wavelength. It could be explained on the basis of Burstein–Moss shift. The values of optical band gap varied in the range of 3.866–4.392 eV.