Effect of solvent volume on the physical properties of undoped and fluorine doped tin oxide films deposited using a low-cost spray technique

Undoped and fluorine doped tin oxide films were deposited from starting solutions having different values of solvent volume (10-50 ml) by employing a low cost and simplified spray technique using perfume atomizer. X-ray diffraction studies showed that there was a change in the preferential orientation from (2 1 1) plane to (1 1 0) plane as the volume of the solvent was increased. The sheet resistance (R_sh) of undoped SnO₂ film was found to be minimum (13.58 KΩ/□) when the solvent volume was lesser (10 ml) and there was a sharp increase in R_sh for higher values of solvent volume. Interestingly, it was observed that while the R_sh increases sharply with the increase in solvent volume for undoped SnO₂ films, it decreases gradually in the case of fluorine doped SnO₂ films. The quantitative analysis of EDAX confirmed that the electrical resistivity of the sprayed tin oxide film was mainly governed by the number of oxygen vacancies and the interstitial incorporation of Sn atoms which in turn was governed by the impinging flux on the hot substrate. The films were found to have good optical characteristics suitable for opto-electronic devices.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

Preparation and characterization of transparent NiO thin films deposited by spray pyrolysis technique

Nickel oxide thin films were successfully fabricated with various deposition time (t_d = 5, 10, and 15 min) on glass substrates using spray pyrolysis technique. The deposited films undergo thermal treatment at 350 °C for various annealing time (t_a = 0, 15, 30 and 60 min). In this study, the effect of t_d and t_a on film thickness was observed and their influence on structural, morphological and optical properties were investigated. The films deposited with t_d = 5 min showed amorphous structure while the films grown at higher deposition time became partially crystallized with preferred growth along (1 1 1) direction. Heat treatment carried out in air allowed us to tune the polycrystalline structure and the diffraction intensity at preferred peak increases with the increase in t_a which is a consequence of better crystallinity. This was reflected in the AFM micrographs of the films which suggested that the thermal annealing (or increasing t_a) facilitates the process of grain-growth, and improves the crystalline microstructure. The optical transmission of the films was found to vary with t_d and t_a and thus film thickness. The thinner films show higher transparency in the UV–vis spectral region. The optical band gap was blue-shifted from 3.35 eV to 3.51 eV depending on t_a. The effect of t_a on the various optical constants of the NiO films has also been discussed.     

Preparation of ZnO-doped Al films by spray pyrolysis technique

Al-doped zinc oxide (AZO) thin films have been prepared by spray pyrolysis (SP) technique of zinc acetate and aluminium nitrate, and the effect of thickness on structural and optical properties has been investigated. The structural and optical characteristics of the AZO films were examined by X-ray diffraction (XRD) and double-beam spectrophotometry. These films, deposited on glass substrates at an optimal substrate temperature (T_S = 450 °C), have a polycrystalline texture with a hexagonal structure. Transmission measurements showed that for visible wavelengths, the AZO films have an average transmission of over 90%. The optical parameters have been calculated. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for the sprayed films is also reported. Optical band gap of AZO is 3.30 and 3.55 eV, respectively, depending on the film thicknesses.     

Physical properties of Pb doped ZnS thin films prepared by ultrasonic spray technique

In the present work, high quality Pb doped ZnS thin films were deposited on glass substrates at 450°C using spray ultrasonic technique. The dependence of the structural, morphological and optical properties of the films on the lead (Pb) doping amount was investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis–NIR spectrophotometry, and four-point method. The improvement of the obtained Pb:ZnS thin films properties were discussed as a function of Pb concentration (0.5 to 2 at.%). The average crystallite size of Pb:ZnS was found in the range of 25–37 nm. The scanning electron microscopy (SEM) reveals that the films are continuous, homogeneous and dense. The UV–vis–NIR spectroscopy characterizations demonstrated that all the films exhibit good transmittance (60–70%) in the visible region and their optical band gap energy ($E_{\mathrm{g}}$) changes from 3.92 to 3.6 eV. The films electrical resistivity showed an apparent dependence on Pb content.     

Electrical and optical properties of Ga doped zinc oxide thin films deposited at room temperature by continuous composition spread

Ga doped ZnO (GZO) thin films were deposited on glass substrates at room temperature by continuous composition spread (CCS) method. CCS is thin films growth method of various Ga_xZn_1−xO(GZO) thin film compositions on a substrate, and evaluating critical properties as a function position, which is directly related to material composition. Various compositions of Ga doped ZnO deposited at room temperature were explored to find excellent electrical and optical properties. Optimized GZO thin films with a low resistivity of 1.46 × 10⁻³ Ω cm and an average transmittance above 90% in the 550 nm wavelength region were able to be formed at an Ar pressure of 2.66 Pa and a room temperature. Also, optimized composition of the GZO thin film which had the lowest resistivity and high transmittance was found at 0.8 wt.% Ga₂O₃ doped in ZnO.     

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant (‘a’ and ‘c’), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10⁶ Ω-cm at higher temperature and 10⁵ Ω-cm at lower temperature.     

Sensing of LPG with nanostructured zinc oxide thin films grown by spray pyrolysis technique

Nanostructured zinc oxide thin films were prepared by spray pyrolysis technique using Zn(NO₃)₂·6H₂O as the precursor solution. The resulting films were investigated by X-ray diffraction and scanning electron microscopy to know crystal structure, size of crystallites and surface morphology. The films have been found to be polycrystalline zinc oxide, possessing hexagonal wurtzite crystal structure and nanocrystallite with grain size of approximately 30-35 nm. The LPG sensing performance of the films has been investigated at various concentrations of LPG in air at operating temperatures varying from 225 to 400 °C. At 325 °C the maximum responses of 46.3% and 48.9% have been observed, respectively, for concentrations of 0.8 and 1 vol% of LPG in air (1 vol% of LPG in air corresponds to 50% LEL of LPG in air). The recovery time has been found to be less than the response time for all concentrations of LPG. A possible reaction mechanism of LPG sensing has been proposed.     

Influence of target substrate distance on the properties of transparent conductive Si doped ZnO thin films

Si doped zinc oxide (SZO, Si3%) thin films are grown at room temperature on glass substrates under argon atmosphere, using direct current magnetron sputtering. The influence of the target substrate distances on structure, morphology, optical and electrical properties of SZO thin films is investigated. Experimental results show that the target substrate distances have a significance impact on the growth rate, crystal quality and electrical properties of the films, and have little impact on the optical properties of the films. SZO thin film samples grown on glasses are polycrystalline with a hexagonal wurtzite structure and have a preferred orientation along the c-axis perpendicular to the substrate. When the target substrate distance decreases from 76 to 60 mm, the degree of crystallization of the films increased, the grain size increases, and the resistivity of films decreases. However, when the distance continuously decreases from 60 to 44 mm, the degree of crystallization of the films decreased, the grain size decreases, and the resistivity of the films increases. SZO(3%) thin films deposited at a target substrate distance of 60 mm show the lowest resistivity of 5.53 × 10⁻⁴ Ω cm, a high average transmission of 94.47% in the visible range, and maximum band gap of 3.45 eV under 5 Pa of argon at sputtering power of 75 W for sputtering time of 20 min.     

Laser energy density, structure and properties of pulsed-laser deposited zinc oxide films

Zinc oxide thin films were deposited on soda lime glass substrates by pulsed laser deposition in an oxygen-reactive atmosphere at 20 Pa and a constant substrate temperature at 300 °C. A pulsed KrF excimer laser, operated at 248 nm with pulse duration 10 ns, was used to ablate the ceramic zinc oxide target. The structure, the optical and electrical properties of the as-deposited films were studied in dependence of the laser energy density in the 1.2-2.8 J/cm² range, with the aid of X-ray Diffraction, Atomic Force Microscope, Transmission Spectroscopy techniques, and the Van der Pauw method, respectively. The results indicated that the structural and optical properties of the zinc oxide films were improved by increasing the laser energy density of the ablating laser. The surface roughness of the zinc oxide film increased with the decrease of laser energy density and both the optical bang gap and the electrical resistivity of the film were significantly affected by the laser energy density.     

Some physical properties of In doped copper oxide films produced by ultrasonic spray pyrolysis

In this work, we have reported the effect of In doping on structural, optical and surface properties of copper oxide films obtained by a low-cost ultrasonic spray pyrolysis technique. Thicknesses, refractive indices and extinction coefficients of the films have been determined by Spectroscopic ellipsometry technique using Cauchy-Urbach model for fitting. A very good agreement was found between experimental and theoretical parameters with low MSE values. Transmission and reflectance spectra have been taken by UV Spectrophotometer, and band gap values have been determined by optical method. Structural properties of the films were investigated with X-ray diffraction patterns. In doping caused the films to growth through some certain directions. Atomic force microscope images have been taken to see the effect of In doping on surface topography and roughness of copper oxide films. Surface properties of undoped films have been improved by In doping. Lowest roughness values have been obtained for In doping at 1%. As a result, we have concluded that properties of copper oxide films which are commonly used in solar cells may have improved by In doping (especially In doped at 1%).     

Quenching of photoconductivity in Fe doped CdS thin films prepared by spray pyrolysis technique

Fe doped CdS films are prepared using spray pyrolysis technique. All the samples are found to be of single phase and crystallized in hexagonal lattice. The X-ray diffraction peaks position of Cd_1−xFe_xS shifts to higher angle with increasing Fe concentration indicating decrease in cell volume. The temperature dependence of resistivity follows Arrhenius behavior having lower activation energy with increasing Fe concentration in dark while there is a little variation in light. Pure CdS films are having large photoconductivity. Upon Fe incorporation, this photoconductivity gradually decreases and for concentration more than 20%, it is almost vanished. Note worthy observation is the changes seen in morphology with AFM, viz. nanorod features seen in CdS is changed to continuous nanorod like structures depicting signatures of Ostwald ripening.     

Cathodoluminescent and nonlinear optical properties of undoped and erbium doped nanostructured ZnO films deposited by spray pyrolysis

We have deposited zinc oxide (ZnO) and erbium doped zinc oxide (ZnO:Er) thin films on heated glass substrates using spray pyrolysis technique. The effect of erbium dopant on structural, morphological, luminescent and nonlinear optical properties was studied. The deposited films have been analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), ex situ compositional analysis (ESCA), profilometry, cathodoluminescence (CL) and third harmonic generation (THG) measurements. All films were polycrystalline, having a preferential growth orientation along the ZnO (0 0 2) plane, with a corresponding average crystallite size of less than 41 nm. Addition of erbium can effectively control the film surface morphology and its cathodoluminescent properties. The films containing low erbium concentration show a uniform surface covered with hexagonal shaped grains and a strong UV light emission intensity as well as TH response. In contrast, when the erbium doping ratio exceeds 3%, a porous surface with columnar textural growth becomes more pronounced, and a substantial reduction of the cathodoluminescent and TH response. A strong TH signal was obtained for the film with good crystalline quality at the concentration of 2%. Third order nonlinear optical susceptibility (χ^〈3〉) values of the studied materials were in the remarkable range of 10⁻¹² esu.     

Effect of indium incorporation on properties of SnS thin films prepared by spray pyrolysis

Tin sulphide (SnS) thin films were deposited on glass substrate at different substrate temperature (T_s = 325 °C, 350 °C and 375 °C) by pyrolytic decomposition using stannous chloride and thiourea as precursor solutions. Also, indium-doped SnS thin films were prepared by using InCl₃ as dopant source. The dopant concentration [In/Sn] was varied from 2 at% to 6 at%. The XRD analysis revealed that the films were polycrystalline in nature having orthorhombic crystal structure with a preferred grain orientation along (1 1 1) plane. Due to In doping, the orientation of the grains in the (1 1 1) plane was found to be deteriorated. Atomic force microscopy (AFM) measurements revealed that the surface roughness of the films decreased due to indium doping. The optical properties were investigated by measuring the transmittance characteristics which were used to find the optical band gap energy, refractive index and extinction coefficient. The energy band gap value was decreased from 1.60 to 1.43 eV with increasing In concentration. The photoluminescence (PL) measurements of thin films showed strong emission band centered at 760 nm. Using Hall Effect measurements electrical resistivity, carrier concentration and Hall mobility have been determined.     

Influence of Y doping concentration on the properties of nanostructured MxZn1−xO (M=Y) thin film deposited by nebulizer spray pyrolysis technique

Yttrium doped Zinc Oxide (Y_xZn_1−xO) thin films deposited at a substrate temperature 400 °C. The effect of substrate temperature on the structural, surface morphology, compositional, optical and electrical properties of Y_xZn_1−xO thin films was studied. X-ray diffraction studies show that all films are polycrystalline in nature with hexagonal crystal structure having highly textured (002) plane parallel to the surface of the substrate. The structural parameters, such as lattice constants (a and c), crystallite size (D), dislocation density (δ), microstrain (σ) and texture coefficient were calculated for different yttrium doping concentrations (x). High resolution scanning electron microscopy measurements reveal that the surface morphology of the films change from platelet like grains to hexagonal structure with grain size increase due to the yttrium doping. Energy dispersive spectroscopy confirms the presence of Y, Zn and O elements in the films prepared. Optical studies showed that all samples have a strong optical transmittance higher than 70% in the visible range. A slight shift of the absorption edge towards the large wavelengths was observed as the Y doping concentration increased. This result shows that the band gap is slightly decreased from 3.10 to 2.05 eV with increase of the yttrium doping concentrations (up to 7.5%) and then slightly increased. Room temperature PL measurements were done and the band-to-band emission energies of films were determined and reported. The complex impedance of the 10%Y doped ZnO film shows two distinguished semicircles and the diameter of the arcs got decreased in diameter as the temperature increases from 70 to 175 °C.     

Highly conducting and crystalline doubly doped tin oxide films fabricated using a low-cost and simplified spray technique

Doubly doped (simultaneous doping of antimony and fluorine) tin oxide films (SnO₂:Sb:F) have been fabricated by employing an inexpensive and simplified spray technique using perfume atomizer from aqueous solution of SnCl₂ precursor. The structural studies revealed that the films are highly crystalline in nature with preferential orientation along the (2 0 0) plane. It is found that the size of the crystallites of the doubly doped tin oxide films is larger (69 nm) than that (27 nm) of their undoped counterparts. The dislocation density of the doubly doped film is lesser (2.08×10¹⁴ lines/m²) when compared with that of the undoped film (13.2×10¹⁴ lines/m²), indicating the higher degree of crystallinity of the doubly doped films. The SEM images depict that the films are homogeneous and uniform. The optical transmittance in the visible range and the optical band gap of the doubly doped films are 71% and 3.56 eV respectively. The sheet resistance (4.13 Ω/□) attained for the doubly doped film in this study is lower than the values reported for spray deposited fluorine or antimony doped tin oxide films prepared from aqueous solution of SnCl₂ precursor (without using methanol or ethanol).     

Effect of fluorine doping on highly transparent conductive spray deposited nanocrystalline tin oxide thin films

The undoped and fluorine doped thin films are synthesized by using cost-effective spray pyrolysis technique. The dependence of optical, structural and electrical properties of SnO₂ films, on the concentration of fluorine is reported. Optical absorption, X-ray diffraction, scanning electron microscope (SEM) and Hall effect studies have been performed on SnO₂:F (FTO) films coated on glass substrates. The film thickness varies from 800 to 1572 nm. X-ray diffraction pattern reveals the presence of cassiterite structure with (2 0 0) preferential orientation for FTO films. The crystallite size varies from 35 to 66 nm. SEM and AFM study reveals the surface of FTO to be made of nanocrystalline particles. The electrical study reveals that the films are degenerate and exhibit n-type electrical conductivity. The 20 wt% F doped film has a minimum resistivity of 3.8 × 10⁻⁴ Ω cm, carrier density of 24.9 × 10²⁰ cm⁻³ and mobility of 6.59 cm² V⁻¹ s⁻¹. The sprayed FTO film having minimum resistance of 3.42 Ω/cm², highest figure of merit of 6.18 × 10⁻² Ω⁻¹ at 550 nm and 96% IR reflectivity suggest, these films are useful as conducting layers in electrochromic and photovoltaic devices and also as the passive counter electrode.     

Structural and electrical properties of fluorine doped tin oxide films prepared by spray-pyrolysis technique

Fluorine doped SnO₂ films have been successfully prepared at optimized substrate temperature of 723 K by spray pyrolysis technique. The XRD analysis confirmed that films deposited with F/Sn ratio of 0.05 showed a partial amorphous nature whereas films deposited with F/Sn = 0.10 exhibited tetragonal structure (2 0 0) as the preferred orientation and polycrystalline structure. The lattice constants were found to be a = 0.4750 and c = 0.3197 nm. The theoretically constructed XRD pattern for SnO₂ was used to compare with experimental pattern, the difference between them is discussed. By using SEM analysis, the surface morphology of the films was observed as an effect of the variation of F/Sn ratio. At low temperature, the mobility due to lattice, polar, impurity, grain boundary and neutral scattering was estimated for SnO₂ and the possible scattering mechanisms were assigned to SnO₂:F films using experimentally obtained electrical data. The Mott parameters were determined by applying variable range hopping (VRH) conduction mechanism for SnO₂:F films (F/Sn = 0.05) where band conduction mechanism shifted to VRH conduction at below about 250 K.     

超声喷雾热解法制备SnS薄膜的物性研究

用超声喷雾热解法制备SnS多晶薄膜,对比了三种不同前驱液配比浓度对SnS薄膜性能的影响。XRD测试表明,当前驱液为硫脲(0.5 mol·L-1)+四氯化锡(0.5 mol·L-1)+去离子水时,SnO2的衍射峰强度比较大;当前驱液为硫脲(0.6 mol·L-1)+四氯化锡(0.5 mol·L-1)+去离子水时,SnS的衍射峰占主要地位,其中也含有一定量的SnO2;当前驱液为硫脲(0.7 mol·L-1)+四氯化锡(0.5 mol·L-1)+去离子水时,退火后的薄膜为单一的SnS薄膜,具有斜方晶系结构。SEM观测发现,薄膜均匀、致密,前驱液中硫脲浓度较大时,颗粒也较大。透过谱测试表明,浓度对薄膜透过率影响较小。结合器件的暗I-V和C-V测试,用三种前驱液配比浓度所制备的器件的结特性差异不大;当前驱液中硫脲浓度较大时,载流子浓度相对较大。