Effect of different dopant elements (Al,Mg and Ni) on microstructural,optical and electrochemical properties of ZnO thin films deposited by spray pyrolysis (SP)

In the present work we studied the influence of the dopant elements and concentration on the microstructural and electrochemical properties of ZnO thin films deposited by spray pyrolysis. Transparent conductive thin films of zinc oxide (ZnO) were prepared by the spray pyrolysis process using an aqueous solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] on soda glass substrate heated at 400 ± 5 °C. AlCl₃, MgCl₂ and NiCl₂ were used as dopant. The effect of doping percentage (2–4%) has been investigated. Afterwards the samples were thermally annealed in an ambient air during one hour at 500 °C. X-ray diffraction showed that films have a wurtzite structure with a preferential orientation along the (0 0 2) direction for doped ZnO. The lattice parameters a and c are estimated to be 3.24 and 5.20 ?, respectively. Transmission allowed to estimate the band gaps of ZnO layers. The electrochemical studies revealed that the corrosion resistance of the films depended on the concentration of dopants.     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

Structural,electrical and optical studies on spray-deposited aluminium-doped ZnO thin films

Thin films of zinc oxide (ZnO) were deposited on cleaned glass substrates by chemical spray pyrolysis technique using Zn(CH₃COO)₂ as precursor solution. Also, aluminium-doped thin films of ZnO were prepared by using AlCl₃ as doping solution for aluminium. The dopant concentration [Al/Zn atomic percentage (at%)] was varied from 0 to 1.5 at% in thin films of ZnO prepared in different depositions. Structural characterization of the deposited films was performed with X-ray diffraction (XRD) studies. It confirmed that all the films were of zinc oxide having polycrystalline nature and possessing typical hexagonal wurtzite structure with crystallite size varying between 100.7 and 268.6 nm. The films exhibited changes in relative intensities and crystallite size with changes in the doping concentration of Al. The electrical studies established that 1 at% of Al-doping was the optimum for enhancing electrical conduction in ZnO thin films and beyond that the distortion caused in the lattice lowered the conductivity. The films also exhibited distinct changes in their optical properties at different doping concentrations, including a blue shift and slight widening of bandgap with increasing Al dopant concentration.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

Growth of ultra-thin TiO2 films by spray pyrolysis on different substrates

In the present study TiO₂ films were deposited by spray pyrolysis method onto ITO covered glass and Si (1 0 0) substrates. The spray solution containing titanium(IV) isopropoxide, acetylacetone and ethanol was sprayed at a substrate temperature of 450 °C employing 1-125 spray pulses (1 s spray and 30 s pause). According to AFM, continuous coverage of ITO and Si substrates with TiO₂ layer is formed by 5-10 and below 5 spray pulses, respectively. XPS studies revealed that TiO₂ film growth on Si substrate using up to 4 spray pulses follows 2D or layer-by-layer-growth. Above 4 spray pulses, 3D or island growth becomes dominant irrespective of the substrate. Only 50 spray pulses result in TiO₂ layer with the thickness more than XPS measurement escape depth as any signal from the substrate could not be detected. TiO₂ grain size remains 30 nm on ITO and increases from 10-20 nm to 50-100 nm on Si substrate with the number of spray pulses from 1 to 125.     

Preparation and characterization of iron oxide thin films by spray pyrolysis using methanolic and ethanolic solutions

Iron oxide thin films have been obtained by spray pyrolysis using 100% methanolic and ethanolic solutions of iron tri-chloride. The films were deposited onto ITO-coated glass substrates. The preparative conditions have been optimized to obtain compact, pin-hole-free and smooth thin films which are adherent to the substrate. The structural, morphological and compositional characterizations have been carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The films deposited using ethanolic solution results into pure hematite; α-Fe₂O₃ thin films, however, films deposited using methanolic solution consists of hematite and maghemite-c phases of iron oxide. The films are nanocrystalline with particle size of 30-40 nm. The optical absorbance of the film was of the order of 10⁵ cm⁻¹. The optical band gap of films was found to be 2.26 and 2.20 eV for the films deposited using methanolic and ethanolic solutions, respectively.     

Properties of highly oriented spray-deposited fluorine-doped tin oxide thin films on glass substrates of different thickness

Transparent conducting thin films of fluorine-doped tin oxide (FTO) have been deposited onto the preheated glass substrates of different thickness by spray pyrolysis process using SnCl₄·5H₂O and NH₄F precursors. Substrate thickness is varied from 1 to 6 mm. The films are grown using mixed solvent with propane-2-ol as organic solvent and distilled water at optimized substrate temperature of 475 °C. Films of thickness up to 1525 nm are grown by a fine spray of the source solution using compressed air as a carrier gas. The films have been characterized by the techniques such as X-ray diffraction, optical absorption, van der Pauw technique, and Hall effect. The as-deposited films are preferentially oriented along the (2 0 0) plane and are of polycrystalline SnO₂ with a tetragonal crystal structure having the texture coefficient of 6.19 for the films deposited on 4 mm thick substrate. The lattice parameter values remain unchanged with the substrate thickness. The grain size varies between 38 and 48 nm. The films exhibit moderate optical transmission up to 70% at 550 nm. The figure of merit (φ) varies from 1.36×10⁻⁴ to 1.93×10⁻³ Ω⁻¹. The films are heavily doped, therefore degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (R_s) of 7.5 Ω is obtained for a typical sample deposited on 4 mm thick substrate. The resistivity (ρ) and carrier concentration (n_D) vary over 8.38×10⁻⁴ to 2.95×10⁻³ Ω cm and 4.03×10²⁰ to 2.69×10²¹ cm⁻³, respectively.     

Studies on the structural and electrical properties of spray deposited SnO2:Sb thin films as a function of substrate temperature

Thin films of antimony doped tin oxide (SnO₂:Sb) were prepared by spray pyrolysis technique using SnCl₂ as precursor with the various antimony doping levels ranging from 1 to 4 wt%. The XRD analysis showed that the undoped SnO₂ films grow in (211) preferred orientation whereas the Sb doped films grow in (200) plane. Scanning electron microscopy studies indicated that the surface of the films prepared with lower doping level (1 wt%) consists of larger grains whereas those prepared with higher doping levels (>1 wt%) consist of smaller grains. The sheet resistance has been found to be reduced considerably (2.17 Ω/□) for Sb doped films. To the best of our knowledge this is the lowest sheet resistance obtained for Sb doped SnO₂ thin films.     

Influence of substrate temperature and Cobalt concentration on structural and optical properties of ZnO thin films prepared by Ultrasonic spray technique

Pure and Cobalt doped zinc oxide were deposited on glass substrate by Ultrasonic spray method. Zinc acetate dehydrate, Cobalt chloride, 4-methoxyethanol and monoethanolamine were used as a starting materials, dopant source, solvent and stabilizer, respectively. The ZnO samples and ZnO:Co with Cobalt concentration of 2 wt.% were deposited at 300, 350 and 400 °C. The effects of substrate temperature and presence of Co as doping element on the structural, electrical and optical properties were examined. Both pure and Co doped ZnO samples are (0 0 2) preferentially oriented. The X-ray diffraction results indicate that the samples have polycrystalline nature and hexagonal wurtzite structure with the maximum average crystallite size of ZnO and ZnO:Co were 33.28 and 55.46 nm. An increase in the substrate temperature and presence doping the crystallinity of the thin films increased. The optical transmittance spectra showed transmittance higher than 80% within the visible wavelength region. The band gap energy of the thin films increased after doping from 3.25 to 3.36 eV at 350 °C.     

Metal-semiconductor transition in undoped ZnO films deposited by spray pyrolysis

ZnO films were deposited on glass substrate by using spray pyrolysis method. Films were deposited at different solution molarities 0.02 and 0.1 M. The films are highly transparent in the visible range of the electromagnetic spectrum with a transmission reaching up values to 90%. Band gaps were calculated as 3.24 and 3.28 eV with the help of transmission spectrums. When the solution molarity of the sprayed solution is increased from 0.02 to 0.1 M, carrier concentrations of the films increase from 1.6×10¹⁹ cm⁻³ to 5.1×10¹⁹ cm⁻³. Temperature-dependent conductivity measurements of these conducting and transparent films also showed, for the first time, a metal-semiconductor transition (MST). The deposited ZnO films show metallic conductivity above ∼420 K and semiconducting behavior at temperatures below it.     

Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

Preparation and properties of spray-deposited ZnIn2Se4 nanocrystalline thin films

Zinc indium selenide (ZnIn₂Se₄) thin films have been deposited onto amorphous and fluorine doped tin oxide (FTO)-coated glass substrates using a spray pyrolysis technique. Aqueous solution containing precursors of Zn, In, and Se has been used to obtain good quality deposits at different substrate temperatures. The preparative parameters such as substrate temperature and concentration of precursors solution have been optimized by photoelectrochemical technique and are found to be 325 °C and 0.025 M, respectively. The X-ray diffraction patterns show that the films are nanocrystalline with rhombohedral crystal structure having lattice parameter a=4.05 Å. The scanning electron microscopy (SEM) studies reveal the compact morphology with large number of single crystals on the surface. From optical absorption data the indirect band gap energy of ZnIn₂Se₄ thin film is found to be 1.41 eV.     

Highly oriented (1 0 0) ZnO thin films by spray pyrolysis

Undoped ZnO thin films have been deposited onto glass substrates by spray pyrolysis. The structural, electrical and optical properties were studied on thin films, prepared from precursor solutions with varying the ethanol concentrations. X-ray diffraction studies have shown polycrystalline nature of the films with a hexagonal wurtzite-type structure. The preferential orientation plane (1 0 0) of the ZnO thin film is found to be sensitive to ethanol concentration. The texture coefficient (TC) and grain size value have been calculated. Also ethanol concentration was found to have significant effect on sheet resistivity of the films.     

Diagnostic study of the roughness surface effect of zirconium on the third-order nonlinear-optical properties of thin films based on zinc oxide nanomaterials

Zinc oxide (ZnO) and zirconium doped zinc oxide (ZnO:Zr) thin films were deposited by reactive chemical pulverization spray pyrolysis technique on heated glass substrates at 500 °C using zinc and zirconium chlorides as precursors. Effects of zirconium doping agent and surface roughness on the nonlinear optical properties were investigated in detail using atomic force microscopy (AFM) and third harmonic generation (THG) technique. The best value of nonlinear optical susceptibility χ⁽³⁾ was obtained from the doped films with less roughness. A strong third order nonlinear optical susceptibility χ⁽³⁾ = 20.12 × 10⁻¹² (esu) of the studied films was found for the 3% doped sample.     

Investigation on the effect of Zr doping in ZnO thin films by spray pyrolysis

Zirconium doped zinc oxide thin films with enhanced optical transparency were prepared on Corning 1737 glass substrates at the substrate temperature of 400 °C by spray pyrolysis method for various doping concentrations of zirconium (IV) chloride in the spray solution. The X-ray diffraction studies reveal that the films exhibit hexagonal crystal structure with polycrystalline grains oriented along (0 0 2) direction. The crystalline quality of the films is found to be deteriorating with the increase of doping concentration and acquires amorphous state for higher concentration of 8 at.% in precursor solution. The average transmittance for 5 at.% (solution) zirconium doped ZnO film is significantly increased to ∼92% in the visible region of 500-800 nm. The room temperature photoluminescence (PL) spectra of films show a band edge between 3.41 and 3.2 eV and strong blue emission at 2.8 eV irrespective of doping concentration and however intensity increases consistently with doping levels. The vacuum annealing at 400 °C reduced the resistivity of the films significantly due to the coalescence of grains and the lowest resistivity of 2 × 10⁻³ Ω cm is observed for 3 at.% (solution) Zr doped ZnO films which envisages that it is a good candidate for stable TCO material.     

The crystalline structure,conductivity and optical properties of Co-doped ZnO thin films

Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)⁻¹. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.     

Photoluminescence and photoelectrochemical properties of nanocrystalline ZnO thin films synthesized by spray pyrolysis technique

A simple and inexpensive spray pyrolysis technique (SPT) was employed for the synthesis of nanocrystalline zinc oxide (ZnO) thin films onto soda lime glass and tin doped indium oxide (ITO) coated glass substrates at different substrate temperatures ranging from 300 °C to 500 °C. The synthesized films were polycrystalline, with a (0 0 2) preferential growth along c-axis. SEM micrographs revealed the uniform distribution of spherical grains of about 80-90 nm size. The films were transparent with average visible transmittance of 85% having band gap energy 3.25 eV. All the samples exhibit room temperature photoluminescence (PL). A strong ultraviolet (UV) emission at 398 nm with weak green emission centered at 520 nm confirmed the less defect density in the samples. Moreover, the samples are photoelectrochemically active and exhibit the highest photocurrent of 60 μA, a photovoltage of 280 mV and 0.23 fill factor (FF) for the Zn₄₅₀ films in 0.5 M Na₂SO₄ electrolyte, when illuminated under UV light.     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.