Deposition and characterization of pure and Cd doped SnO2 thin films by the nebulizer spray pyrolysis (NSP) technique

Pure and cadmium doped tin oxide thin films were deposited on glass substrates from aqueous solution of cadmium acetate, tin (IV) chloride and sodium hydroxide by the nebulizer spray pyrolysis (NSP) technique. X-ray diffraction reveals that all films have tetragonal crystalline structure with preferential orientation along (200) plane. On application of the Scherrer formula, it is found that the maximum size of grains is 67 nm. Scanning electron microscopy shows that the grains are of rod and spherical in shape. Energy dispersive X-ray analysis reveals the average ratio of the atomic percentage of pure and Cd doped SnO₂ films. The electrical resistivity is found to be 10² Ω cm at higher temperature (170 °C) and 10³ Ω cm at lower temperature (30 °C). Optical band gap energy was determined from transmittance and absorbance data obtained from UV–vis spectra. Optical studies reveal that the band gap energy decreases from 3.90 eV to 3.52 eV due to the addition of Cd as dopant with different concentrations.     

A study on phase transformation of SnOx thin films prepared by reactive magnetron sputtering

In the paper, SnO_x thin films were deposited by reactive magnetron sputtering from a tin target in O₂ containing working gas. The evolution from Sn-containing SnO to tetravalent SnO₂ films was investigated. The films could be classified into three groups according to their optical band gaps, which are E_g<2.5 eV, E_g=3.0–3.3 eV and E_g>3.7 eV. The electric measurements show that high conductivity can be obtained much easier in SnO₂ than in SnO films. A high electron mobility of 15.7 cm² V⁻¹ s⁻¹, a carrier concentration of 1.43×10²⁰ cm⁻³ and a resistivity of 2.8×10⁻³ Ω cm have been achieved in amorphous SnO₂ films. Films with the optical band gap of 3.0–3.3 eV remain amorphous though the substrate temperature is as high as 300 °C, which implies that °btaining high mobility in p-type SnO is more challenging in contrast to n-type SnO₂ films.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

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.     

Substrate temperature effect on structural,optical and electrical properties of vacuum evaporated SnO2 thin films

Tin oxide (SnO₂) thin films were deposited on glass substrates by thermal evaporation at different substrate temperatures. Increasing substrate temperature (T_s) from 250 to 450 °C reduced resistivity of SnO₂ thin films from 18×10⁻⁴ to 4×10⁻⁴▒ Ω ▒cm. Further increase of temperature up to 550 °C had no effect on the resistivity. For films prepared at 450 °C, high transparency (91.5%) over the visible wavelength region of spectrum was obtained. Refractive index and porosity of the layers were also calculated. A direct band gap at different substrate temperatures is in the range of 3.55−3.77 eV. X-ray diffraction (XRD) results suggested that all films were amorphous in structure at lower substrate temperatures, while crystalline SnO₂ films were obtained at higher temperatures. Scanning electron microscopy images showed that the grain size and crystallinity of films depend on the substrate temperature. SnO₂ films prepared at 550 °C have a very smooth surface with an RMS roughness of 0.38 nm.     

Effect of fluorine doping on the structural,optical and electrical properties of spray deposited cadmium stannate thin films

Cadmium stannate (Cd₂SnO₄) thin films were coated on Corning 1737 glass substrates at 540 °C by spray pyrolysis technique, from the aqueous solution of cadmium acetate and tin (II) chloride precursors. Fluorine doped Cd₂SnO₄ (F: Cd₂SnO₄) thin films were prepared by adding ammonium fluoride in the range of 0–5 wt% of the total weight of cadmium acetate and tin (II) chloride in the spray solution. Thickness of the prepared films is about 300 nm. X-ray diffraction analysis of the Cd₂SnO₄ and 3 wt% F: Cd₂SnO₄ films shows the signature for the growth along (222) direction. Scanning electron micrographs showed that fluorine doping effectively modifies the surface morphology of Cd₂SnO₄ films. Average optical transmittance in the visible region (500–850 nm) for Cd₂SnO₄ is ~79% and it is increased to ~83% for 1 wt% doping concentration of the NH₄F in the solution. Fluorescence spectra of F: Cd₂SnO₄ (1 wt% and 3 wt%) exhibit peak at 601 nm. F: Cd₂SnO₄ film (1 wt%) shows mobility of ~42 cm²/V s, carrier concentration of ~9.5×10¹⁹ cm^?3 and resistivity of ~1.5×10^?3 Ω cm.     

Fabrication of Ag nanoparticle/ZnO thin films using dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with photoreduction method and its application

We report a novel method to grow silver nanoparticle/zinc oxide (Ag NP/ZnO) thin films using a dual-plasma-enhanced metal-organic chemical vapor deposition (DPEMOCVD) system incorporated with a photoreduction method. The crystalline quality, optical properties, and electrical characteristics of Ag NP/ZnO thin films depend on the AgNO₃ concentration or Ag content and annealing temperature. Optimal Ag NP/ZnO thin films have been grown with a AgNO₃ concentration of 0.12 M or 2.54 at%- Ag content and 500 °C- rapid thermal annealing (RTA); these films show orientation peaks of hexagonal-wurtzite-structured ZnO (002) and face-center-cubic-crystalline Ag (111), respectively. The transmittance and resistivity for optimal Ag NP/ZnO thin films are 85% and 6.9×10⁻⁴ Ω cm. Some Ag NP/ZnO transparent conducting oxide (TCO) films were applied to InGaN/GaN LEDs as transparent conductive layers. The InGaN/GaN LEDs with optimal Ag NP/ZnO TCO films showed electric and optical performance levels similar to those of devices fabricated with indium tin oxide.     

Effects of Sb,Zn doping on structural,electrical and optical properties of SnO2 thin films

Highly transparent, low resistive pure and Sb, Zn doped nanostructured SnO₂ thin films have been successfully prepared on glass substrates at 400° C by spray pyrolysis method. Structural, electrical and optical properties of pure and Sb, Zn doped SnO₂ thin films are studied in detail. Powder X-ray diffraction confirms the phase purity, increase in crystallinity, size of the grains (90–45 nm), polycrystalline nature and tetragonal rutile structure of thin films. The scanning electron microscopy reveals the continuous change in surface morphology of thin films and size of the grains decrease due to Sb, Zn doping in to SnO₂. The optical transmission spectra of SnO₂ films as a function of wavelength confirm that the optical transmission increases with Sb, Zn doping remarkably. The optical band gap of undoped film is found to be 4.27 eV and decreases with Sb, Zn doping to 4.19 eV, 4.07 eV respectively. The results of electrical measurements indicate that the sheet resistance of the deposited films improves with Sb, Zn doping. The Hall measurements confirm that the films are degenerate n-type semiconductors.     

Structural,morphological, electrical and optical studies of Cr doped SnO2 thin films deposited by the spray pyrolysis technique

Tin oxide (SnO₂) and chromium (Cr) doped tin oxide (Cr:SnO₂) thin films were deposited on the preheated glass substrates at 673 K by spray pyrolysis. Concentration of Cr was varied in the solution by adding chromium (III) chloride hexahydrate from 0 to 3 at%. The effect of Cr doping on the structural, electrical and optical properties of tin oxide films is reported. X-ray diffraction pattern confirms the tetragonal crystal structure for undoped and Cr doped tin oxide films. Scanning electron microscopic photographs show the modification of surface morphology of tin oxide film due to varying concentration of Cr. X-ray photoelectron spectra of Cr:SnO₂ (3 at%) thin film revealed the presence of carbon, tin, oxygen, and chromium. Carrier concentration and mobility of the SnO₂ films decrease with increasing concentration of Cr and 0.5 at% Cr doped tin oxide film acquires a mobility of 70 cm²/V s. Average optical transmittance in the 550–850 nm range varies from 38% to 47% with varying Cr concentration in the solution.     

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.     

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.     

Ultraviolet-assisted annealing for low-temperature solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films

Solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films were prepared at a low temperature of 300 °C using ultraviolet (UV)-assisted annealing instead of conventional high-temperature annealing (> 500 °C). We report the effects of UV irradiation time on the structural, optical, and electrical properties of sol-gel derived GTO thin films and a comparison study of the physical properties of UV-assisted annealed (UVA) and conventional thermally annealed (CTA) GTO thin films. The Ga doping content was fixed at 15 at% in the precursor solution ([Ga]/[Sn]+[Ga] = 15%). After a spin-coating and preheating procedure was performed two times, the dried sol-gel films were heated on a hotplate at 300 °C under UV light irradiation for 1–4 h. Each UVA GTO thin film had a dense microstructure and flat free surface and exhibited an average optical transmittance approaching 85.0%. The level of crystallinity, crystallite size, and hole concentration density of the GTO thin films increased with increasing UV irradiation time. In this study, the UVA 4 h thin film samples exhibited the highest hole concentration (9.87 × 10¹⁷ cm⁻³) and the lowest resistivity (1.8 Ω cm) and had a hole mobility of 5.1 cm²/Vs.     

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.     

Properties of fluorine-doped SnO2 thin films by a green sol–gel method

Fluorine doped tin oxide (FTO) films were fabricated on a glass substrate by a green sol–gel dip-coating process. Non-toxic SnF₂ was used as fluorine source to replace toxic HF or NH₄F. Effect of SnF₂ content, 0–10 mol%, on structure, electrical resistivity, and optical transmittance of the films were investigated using X-ray diffraction, Hall effect measurements, and UV–vis spectra. Structural analysis revealed that the films are polycrystalline with a tetragonal crystal structure. Grain size varies from 43 to 21 nm with increasing fluorine concentration, which in fact critically impacts resultant electrical and optical properties. The 500 °C-annealed FTO film containing 6 mol% SnF₂ shows the lowest electrical resistivity 7.0×10⁻⁴ Ω cm, carrier concentration 1.1×10²¹ cm⁻³, Hall mobility 8.1 cm²V⁻¹ s⁻¹, optical transmittance 90.1% and optical band-gap 3.91 eV. The 6 mol% SnF₂ added film has the highest figure of merit 2.43×10⁻² Ω⁻¹ which is four times higher than that of un-doped FTO films. Because of the promising electrical and optical properties, F-doped thin films prepared by this green process are well-suited for use in all aspects of transparent conducting oxide.     

Effect of Bi doping on structural,morphological, optical and ethanol vapor response properties of SnO2 nanoparticles

The gas sensing behavior of thick films of Bi doped SnO₂ has been investigated towards ethanol vapor. The screen printing technique was used to prepare the thick films. The films were sintered at 650 °C for 2 h. The structural, surface morphological, optical and gas sensing properties of undoped and Bi doped SnO₂ thick films have been studied. X-ray diffraction and Raman spectroscopy confirmed that the films consisted exclusively of tetragonal tin oxide, without any impurity phases. FE-SEM studies revealed the formation of highly porous microstructure with grain size in few tens of nanometers. From the optical studies, the band gap was found to be decreased with bismuth doping (3.96 eV for undoped, 3.83 eV, 3.71 eV and 3.6 eV for 1 mol%, 2 mol% and 3 mol% Bi, respectively). The 3 mol % Bi doped SnO₂ thick films exhibited the highest sensitivity to 100 ppm of ethanol vapor at 300 °C. The effect of microstructure on sensitivity, response time and recovery time of the sensor was studied and discussed.     

Study of structural,electrical and photoconductive properties of F and P co-doped SnO2 transparent semiconducting thin film deposited by spray pyrolysis

Transparent conducting phosphorus–fluorine co-doped tin oxide (SnO₂:(P, F)) thin films have been deposited onto preheated glass substrates using the spray pyrolysis technique by the various dopant quantity of spray solution. The [F/Sn] atomic concentration ratio (x) in the spray solution is kept at value of 0.7 and the [P/Sn] atomic ratio (y) varied at values of 0, 0.001, 0.005, 0.01, 0.02, 0.04, 0.06, and 0.10. The structural, morphological, X-ray diffraction, electrical, optical and photoconductive properties of these films have been studied. It is found that the films are polycrystalline in nature with a tetragonal crystal structure corresponding to SnO₂ phase having orientation along the (110) plane and polyhedrons like grains appear in the FE-SEM image. The average grain size increases with increasing P-dopant concentration. The compositional analysis of FTO:P thin films were studied using EDAX. The Hall effect measurements have shown n-type conductivity in all deposited films. The lowest sheet resistance and highest the carrier concentration about 6.4 Ω/□ and 7.4×10²², respectively, were obtained for the film deposited with y=[P/Sn]=0.01. The films deposited with y=0.04 phosphorus-doped SnO₂:F shows 68% optical transparency. From the photoconductive studies, the P-doped films exhibited sensitivity to incident light especially in y=0.04. The electrical resistivity and carrier concentration vary in rang 6.2×10⁻⁴ to 21.1×10⁻⁴ Ω cm and 7.4×10²² to 1.3×10²² cm⁻³, respectively.     

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.     

Structural,electrical and optical properties of sintered SnO2 pellets

Tin dioxide (SnO₂) powder was prepared by the co-precipitation method using SnCl₂ solution as a precursor. The powder was then pelletized and sintered. Structural characterization of the samples with XRD confirmed that all the pellets were of SnO₂ having polycrystalline nature with the crystallite size of the order of 90 nm. SEM-EDAX was used to confirm the morphology and composition of the samples. The measurements of electrical properties were carried out in the frequency range of 100 Hz to 100 kHz at various fixed temperatures from 40 °C to 160 °C. The a.c. conductivity and the dielectric constant were found to be dependent on both frequency and temperature. The frequency and temperature dependent conduction properties of SnO₂ are found to be in accordance with correlated barrier hoping model. Infrared and visible spectroscopic studies show that a strong vibration band characteristic of the SnO₂ stretching mode was present at around 620 cm^?1 and the samples exhibited optical transmittance in the visible range.     

Influence of N2- and Ar-ambient annealing on the physical properties of SnO2:Co transparent conducting films

Co-doped SnO₂ TCOs were prepared by spray pyrolysis technique and the influence of N₂- and Ar-ambient annealing on their structural, electrical and optical properties was studied. XRD results show that all samples become single phase after post-annealing treatments. In addition, the Co-doped films exhibit a faceting characteristic that is conserved after the post-annealing treatments. Analysis of the XRD patterns shows that the size of crystallite decreases with increasing microstrain and both of them reach extremum at about 20 at% doping level. Electrical measurements demonstrate gradual increase in resistivity with increasing doping level. The annealing causes increase in the electrical resistivity of the cobalt-doped samples. About 40% of this increase should be due to penetration of nitrogen ions within the rutile structure and the remaining 60% may be attributed to the structural and compositional relaxations. The optical spectra show that transparency of the samples in the visible region decreases between 10% and 40% with increasing cobalt content. Although transparency of the samples at lower than 30 at% doping level slightly increases after post-annealing treatments, this increase is compensated for by compositional relaxations in the samples with more cobalt content. The band gap energies are increased by about 1.5% by post annealing treatment.