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.     

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.     

Annealing effects on physical properties of doped CdTe thin films for photovoltaic applications

Polycrystalline Cadmium Telluride (CdTe) thin films were prepared on glass substrates by thermal evaporation at the chamber ambient temperature and then annealed for an hour in vacuum ~1×10⁻⁵ mbar at 400 °C. These annealed thin films were doped with copper (Cu) via ion exchange by immersing these films in Cu (NO₃)₂ solution (1 g/1000 ml) for 20 min. Further these films were again annealed at different temperatures for better diffusion of dopant species. The physical properties of an as doped sample and samples annealed at different temperatures after doping were determined by using energy dispersive x-ray analysis (EDX), x-ray diffraction (XRD), Raman spectroscopy, transmission spectra analysis, photoconductivity response and hot probe for conductivity type. The optical band gap of these thermally evaporated Cu doped CdTe thin films was determined from the transmission spectra and was found to be in the range 1.42–1.75 eV. The direct energy band gap was found annealing temperatures dependent. The absorption coefficient was >10⁴ cm⁻¹ for incident photons having energy greater than the band gap energy. Optical density was observed also dependent on postdoping annealing temperature. All samples were found having p-type conductivity. These films are strong potential candidates for photovoltaic applications like solar cells.     

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.     

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.     

Effect of annealing on structural,optical and electrical properties of pulse electrodeposited tin sulfide films

Polycrystalline tin sulfide (SnS) thin films were grown on conducting glass substrates by pulse electrodeposition. The effect of annealing on the physical properties such as structure, morphology, optical, and opto-electronic properties were evaluated to understand the effect of post-deposition treatment for SnS films. Annealing at temperatures higher than 250 °°C resulted in the formation of SnS₂ as a second phase, however, no significant grain growth or morphological changes were observed for films after annealing at 350 °C. A small change in band gap of 0.1 eV observed for films annealed at 350 °C was interpreted as due to the formation of SnS₂ rather than due to morphological changes. This interpretation was supported by X-ray diffractometry, scanning electron microscopy, and Raman spectral data. The electric conduction in the films is controlled by three shallow trap levels with activation energies 0.1, 0.05, and 0.03 eV. The trap with energy 0.03 eV disappeared after annealing at higher temperature, however, the other two traps were unaffected by annealing.     

Effect of post deposition heat treatment on microstructure parameters,optical constants and composition of thermally evaporated CdTe thin films

Thin film microstructure and its properties can be effectively altered with post deposition heat treatments. In this respect, CdTe thin films were deposited on glass substrates at a substrate temperature of 200 °C using thermal evaporation technique, followed by air annealing at different temperatures from 200 to 500 °C. Structural analysis reveals that CdTe thin films have a cubic zincblend structure with two oxide phases related to CdTe₂O₅ and CdTeO₃ at annealing temperature of 400 and 500 °C respectively. Regardless of the annealing temperature, the plane (111) was found to be the preferred orientation for all films. The crystallite size was observed to increase with annealing temperature. All films were found to display higher lattice parameters than the standard, and hence found to carry a compressive stress. Optical measurements suggest high uniformity of films both before and after post deposition heat treatment. Films annealed at 400 °C displayed superior optical properties due to its high refractive index, optical conductivity, relative density and low disorder. Furthermore, according to the compositional measurements, CdTe thin films were found to exhibit Te rich and Cd rich nature at regions near the substrate and center of the film respectively, for all annealing temperatures. However, composition of the regions near the substrate was found to become more Te rich with increasing annealing temperature. The study suggests that changing the annealing temperature as a post deposition treatment affects structural and optical properties of CdTe thin film as well as its composition. According to the observations, films annealed at 400 °C can be concluded to be the best films for photovoltaic applications due to its superior optical and structural properties.     

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).     

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.     

Enhancement in optical characteristics of c-axis-oriented radio frequency–sputtered ZnO thin films through growth ambient and annealing temperature optimization

High-quality radio frequency–sputtered ZnO were grown on Si substrates at 400 °C at various partial gas pressures (Ar/Ar+O2). Subsequently, to remove as-grown defects, high temperature annealing from 700 to 900 °C on as-grown samples in constant oxygen flow for 10 s was performed. X-ray diffraction study confirmed the formation of highly crystalline films with a dominant peak at (002). The sample grown in 50% Ar and 50% O₂ ambient exhibited the lowest linewidth (2θ=~0.2728°) and highest stoichiometry. Grain size of the as grown samples decreased with increase in the partial pressure of oxygen till a certain ratio (1:1), and photoluminescence (PL) improved with increase in annealing temperature. Low-temperature (18 K) PL measurements showed a near-band-edge emission peak at 3.37 eV, and the highest peak intensity (more than six orders compared to others with narrow linewidth of ~0.01272 eV) was exhibited by the sample annealed at 900 °C and was six orders higher than that of the as-grown sample. All as-grown samples exhibited dominant visible-range peaks due to emission from defect states.     

Effect of annealing temperature on optical and electrical properties of lead sulfide thin films

Lead sulfide (PbS) thin films with 150 nm thickness were prepared onto ultra-clean quartz substrate by the RF-sputtering deposition method. Deposited thin films of PbS were annealed at different temperatures 100 °C, 150 °C, 200 °C, 250 °C and 300 °C. X-ray diffraction pattern of thin films revealed that thin films crystallized at 150 °C. Crystalline thin films had cubic phase and rock salt structure. The average crystallite size of crystalline thin films was 22 nm, 28 nm and 29 nm for 150 °C, 200 °C and 250 °C respectively. From 150 °C to 250 °C increase in annealing temperature leads to increase in crystallite arrangement. FESEM images of thin films revealed that crystallite arrangement improved by increasing annealing temperature up to 250 °C. Increase in DC electrical conductivity by increasing temperature confirmed the semiconductor nature of crystalline thin films. Increase in dark current by increasing annealing temperature showed the effect of crystallite arrangement on carrier transport. Photosensitivity decreased by increasing annealing temperature for crystalline thin films that it was explained at the base of thermal quenching of photoconductivity and adsorption of oxygen at the surface of thin films that leads to the formation of PbO at higher temperatures.     

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.     

Effects of thermal annealing on the morphology of the AlxGa(1−x)N films

Effects of thermal annealing on the morphology of the Al_xGa_(1−x)N films with two different high Al-contents (x=0.43 and 0.52) have been investigated by atomic force microscopy (AFM). The annealing treatments were performed in a nitrogen (N₂) gas ambient as short-time (4 min) and long-time (30 min). Firstly, the films were annealed as short-time in the range of 800–950 °C in steps of 50–100 °C. The surface root-mean-square (rms) roughness of the films reduced with increasing temperature at short-time annealing (up to 900 °C), while their surface morphologies were not changed. At the same time, the degradation appeared on the surface of the film with lower Al-content after 950 °C. Secondly, the Al_0.43Ga_0.57N film was annealed as long-time in the range of 1000–1200 °C in steps of 50 °C. The surface morphology and rms roughness of the film with increasing temperature up to 1150 °C did not significantly change. Above those temperatures, the surface morphology changed from step-flow to grain-like and the rms roughness significantly increased.     

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.     

Impact of vacuum and nitrogen annealing on HVE SnS photoabsorber films

Researchers worldwide focus on new earth abundant and cheap absorber materials for use in thin film solar cells that allow wider use of photovoltaics in energy production. SnS is one of such promising absorber materials that comprises earth abundant elements (Sn, S). We describe here the effect of annealing of high vacuum evaporated (HVE) SnS thin films in vacuum and nitrogen atmosphere with relatively high pressures of nitrogen. SnS thin films with a thickness of 500 nm were deposited onto the surface of glass by HVE at a substrate temperature of 300 °C. The as-deposited SnS thin films were annealed at 500 °C and 550 °C for 1 h in vacuum as well as in nitrogen with respect to ambient (N₂) pressure that varied in the range of 500–2000 mbar. We analyze crystalline quality, crystal structure, elemental and phase compositions, and electrical properties of SnS films before and after the annealing process and their changes. Our results show that the use of pressurized inert ambient, such as nitrogen, improves the crystalline quality as well as the electrical properties of SnS thin films. The enhanced growth of crystals and modification of microstructural properties of SnS thin films as a function of annealing conditions (type of ambient, annealing temperature and ambient pressure) are discussed in detail.     

Structural,optical, and photocatalytic properties of the spray deposited nanoporous CdS thin films; influence of copper doping,annealing, and deposition parameters

Nanoporous thin films of Cd_1−xCu_xS (0≤x≤0.06) were grown on a heated glass substrate employing a home-made spray pyrolysis technique. The influences of [Cu]/[Cd] and the annealing in the range 300–500 °C on the structural and morphological properties of the films were investigated by X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), field emission scanning electron microscope (FE-SEM) and atomic force microscopy (AFM). The influences of Cu doping ratio, solution flow rate, and the deposition time on the optical properties and photocatalytic activity of these films are also reported. The films are of polycrystalline nature and hexagonal structure. Increasing the Cu doping ratio and annealing temperature improve the (1 0 1) preferential orientation. The crystallite size is ranged from 23.82 to 32.11 nm. XRD and FTIR reveal the formation of CdO in the 6% Cu-doped CdS film annealed at 400 °C and in all films annealed at 500 °C. The pure CdS film is of a porous structure and the close-packing and porosity of the films increase with increasing Cu%. Also, the pore diameter can be controlled from 50 to 15 nm with the increase of Cu content. The films showed transmittance below 70%. The optical band gap of the films is decreased from 2.43 to 1.82 eV with increasing Cu% and flow rate/deposition time. Additionally, the refractive indices and dispersion parameters of the films are also affected by the deposition conditions. Cu doping enhanced the films' photostability as well as the photocatalytic removal of methylene blue (MB).     

Effect of high-temperature annealing on lanthanum aluminate thin films grown by ALD on Si(1 0 0)

Amorphous lanthanum aluminate thin films were deposited by atomic layer deposition on Si(1 0 0) using La(ⁱPrCp)₃, Al(CH₃)₃ and O₃ species. The effects of post-deposition rapid thermal annealing on the physical and electrical properties of the films were investigated. High-temperature annealing at 900 °C in N₂ atmosphere leads to the formation of amorphous La-aluminosilicate due to Si diffusion from the substrate. The annealed oxide exhibits a uniform composition through the film thickness, a large band gap of 7.0 ± 0.1 eV, and relatively high dielectric constant (κ) of 18 ± 1.     

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.     

Effects of RTA temperatures on conductivity and micro-structures of boron-doped silicon nanocrystals in Si-rich oxide thin films

In this work, the B-doped Si rich oxide (SRO) thin films were deposited and then annealed using rapid thermal annealing (RTA) to form SiO₂-matrix silicon nanocrystals (Si NCs). The effects of the RTA temperatures on the structural properties, conduction mechanisms and electrical properties of B-doped SRO thin films (BSF) were investigated systematically using Hall measurements, Fourier transform infrared spectroscopy and Raman spectroscopy. Results showed that the crystalline fraction of annealed BSF increased from 41.3% to 62.8%, the conductivity was increased from 4.48×10⁻³ S/cm to 0.16 s/cm, the carrier concentration was increased from 8.74×10¹⁷ cm⁻³ to 4.9×10¹⁸ cm⁻³ and the carrier mobility was increased from 0.032 cm² V⁻¹ s⁻¹ to 0.2 cm² V⁻¹ s⁻¹ when the RTA temperatures increased from 1050 °C to 1150 °C. In addition, the fluctuation induced tunneling (FIT) theory was applicable to the conduction mechanisms of SiO₂-matrix boron-doped Si-NC thin films.     

Thermal annealing effect on zinc nitride thin films deposited by reactive rf-magnetron sputtering process

Zinc nitride films were deposited by reactive radio-frequency magnetron sputtering using a zinc target in a nitrogen and argon plasma. The deposited films were annealed in either air or O₂ at 300 °C to investigate the annealing effect on the microstructure, optical properties, and electronic characteristics of zinc nitride films. It was found that the annealing process decreased the crystallinity of zinc nitride films. It was also found that the optical band gap decreased from 1.33 eV to 1.14 eV after annealing. The analysis of film composition suggested that the concentration of oxygen increased slightly after annealing. Although the conduction type of both as-deposited and annealed films were n-type, the annealed films exhibited a higher resistivity, lower carrier concentration and lower mobility than the as-deposited films. Also, it was found that the as-deposited films did not exhibit any photoconducting behavior whereas the annealed films exhibited a pronounced photoconducting behavior.