Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.     

Comparative study on structural and optical properties of CdS films fabricated by three different low-cost techniques

Highly crystalline and transparent cadmium sulphide films were fabricated at relatively low temperature by employing an inexpensive, simplified spray technique using perfume atomizer (generally used for cosmetics). The structural, surface morphological and optical properties of the films were studied and compared with that prepared by conventional spray pyrolysis using air as carrier gas and chemical bath deposition. The films deposited by the simplified spray have preferred orientation along (1 0 1) plane. The lattice parameters were calculated as a = 4.138 Å and c = 6.718 Å which are well agreed with that obtained from the other two techniques and also with the standard data. The optical transmittance in the visible range and the optical band gap were found as 85% and 2.43 eV, respectively. The structural and optical properties of the films fabricated by the simplified spray are found to be desirable for opto-electronic applications.     

A correlation for crystallite size of undoped ZnO thin film with the band gap energy – precursor molarity – substrate temperature

Transparent conducting undoped zinc oxide thin films were deposited on glass substrate by ultrasonic spray and spray pyrolysis techniques. The thin films were deposited at different substrate temperatures ranging between 300 and 450 °C with various precursor molarities. The correlation between the structural and optical properties suggests that the crystallites sizes of the films are predominantly influenced by the band gap energy of the thin films. The data of the correlation is suspected of involving some experimental measurement errors and therefore discarded in the development of the present correlation. The coefficient of correction is equal to 0.01, indicating high quality representation of data based on Eq. (1). The correlation also indicates that the crystallites sizes of the films are predominantly influenced by the band gap energy and the precursor molarity of the thin films. The model proposed of undoped ZnO thin film with substrate temperature was investigated.     

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.     

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.     

Flame spray deposition of nanocrystalline dense Ce0.8Gd0.2O2 − δ thin films: Deposition mechanism and microstructural characterization

Nanocrystalline dense sub-micron thin films of Ce_0.8Gd_0.2O_2 − δ have been successfully deposited by flame spray deposition. The deposition mechanism has been identified as droplet deposition. The deposition temperature of the substrate was as low as 200 °C and the deposition rate ∼ 30 nm/min. Under these conditions the droplets have a very limited residence time in the hot zone of the flame and are deposited as liquid, forming smooth films free of particles. They exhibited a dense and crack-free microstructure. Grain growth, lattice constant, crystallographic density and surface roughness have been investigated as a function of annealing temperature. The good quality of the films, in association with the high deposition rates at low deposition temperatures shows the preeminence of the flame spray method for depositing thin films for micro-solid oxide fuel cells.     

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.     

Nanoporous nickel oxide thin films and its improved electrochromic performance: Effect of thickness

Electrochromic properties of chemically bath deposited nanoporous NiO thin films were investigated as a function of film thickness using Ni sulphate precursor, aqueous ammonia and potassium persulphate as complexing and oxidizing agents respectively. The films were characterized for their structural, morphological, optical and electrochromic properties using X-ray diffraction, scanning electron microscopy, FT-IR spectroscopy, cyclic voltammetry, chronoamperometry and optical transmittance studies. X-ray diffraction patterns show that the films are polycrystalline, consisting of NiO cubic phase. Infrared spectroscopy results show the presence of free hydroxyl ion and water in NiO thin films. SEM micrographs revealed nanoporous nature composed of interconnected nanoporous network, forming well defined 3D nano envelopes. The optical band gap energy was found to be decreased from 3.22 to 2.80 eV with increasing film thickness. The electrochromic properties of all the films were investigated in aqueous (KOH) and non aqueous (LiClO₄-PC) electrolyte by means of cyclic voltammetry (CV), chronocoulometry (CC) and optical studies. The transmittance modulations or optical density differences during the coloring/bleaching process were found to be increased with the film thickness. This increment in optical differences led to an increase in coloration efficiency (CE) to about 95 cm²/C, which is two times more than that observed in KOH and response time of 2.9 s for bleaching (reduction) and 3.5 s for coloration (oxidation) observed for the film deposited at 60 min with excellent electrochemical stability up to 3000 c/b cycles in LiClO₄-PC electrolyte.     

A study of structural, compositional and optical properties of spray-deposited non-stoichiometric (Zn,Fe)S thin films

Non-stoichiometric ternary chalcogenides (Zn,Fe)S were prepared in the film form by pyrolytic spray deposition technique, using air/nitrogen as the carrier gas. The precursor solution comprised of ZnCl₂, FeCl₂ and thiourea. The depositions were carried out under optimum conditions of experimental parameters viz. carrier gas (air/nitrogen) flow rate, concentration of precursor constituents, nozzle substrate distance and temperature of quartz substrate. The deposited thin films were later sintered in argon at 1073 K for 120 min.The structural, compositional and optical properties of the sintered thin films were studied. X-ray diffraction studies of the thin films indicated the presence of (Zn,Fe)S solid solution with prominent cubic sphalerite phase while surface morphology as determined by scanning electron microscopy (SEM) revealed a granular structure.The chemical composition of the resulting thin films as analyzed by energy dispersive X-ray analysis (EDAX) reflected the composition of the precursor solutions from which the depositions were carried out with Fe at% values ranging from 0.4 up to 33.SEM micrographs of thin films reveal that the grain sizes of the thin films prepared using air as carrier gas and N₂ as carrier gas are in the vicinity of 300 and 150 nm, respectively.The diffuse transmittance measurements for thin films, as a function of wavelength reveal the dependence of direct optical band gap on Fe content and type of phase.     

Electrostatic spray deposited zinc oxide films for gas sensor applications

In this work, thin films of zinc oxide (ZnO) for gas-sensor applications were deposited on platinum coated alumina substrate, using electrostatic spray deposition (ESD) technique. As precursor solution zinc acetate in ethanol was used. Scanning electron microscopy (SEM) evaluation showed a porous and homogeneous film morphology and the energy dispersive X-ray analysis (EDX) confirmed the composition of the films with no presence of other impurities. The microstructure studied with X-ray diffraction (XRD) and Raman spectroscopy indicated that the ZnO oxide films are crystallized in a hexagonal wurtzite phase. The films showed good sensitivity to 1 ppm nitrogen dioxide (NO₂) at 300 °C while a much lower sensitivity to 12 ppm hydrogen sulphide (H₂S).     

Effect of deposition temperature on orientation and electrical properties of (K0.5Na0.5)NbO3 thin films by pulsed laser deposition

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) thin films have been prepared on Pt/TiO₂/SiO₂/Si substrates by pulsed laser deposition process. The structures, crystal orientations and electrical properties of thin films have been investigated as a function of deposition temperature from 680 °C to 760 °C. It is found that the deposition temperature plays an important role in the structures, crystal orientations and electrical properties of thin films. The crystallization of thin films improves with increasing deposition temperature. The thin film deposited at 760 °C exhibits strong (0 0 1) preferential orientation, large dielectric constant of 930 and the remnant polarization of 8.54 μC/cm².     

Deposition of BN interphase coatings from B-trichloroborazine and its effects on the mechanical properties of SiC/SiC composites

Boron nitride thin films were deposited on silicon carbide fibers by chemical vapor deposition at atmospheric pressure from the single source precursor B-trichloroborazine (Cl₃B₃N₃H₃, TCB). The film growth and structure, as a function of deposition temperature, hydrogen gas flow rate, and deposition time, were discussed. The deposition rate reaches a maximum at 1000 °C, then decreases with the increasing of temperature, and the apparent activation energy of the reaction is 127 kJ/mol. Above 1000 °C, gas-phase nucleation determines the deposition process. The deposited BN films were characterized by Raman spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of BN interphase on the mechanical properties of the unidirectional SiC fiber-reinforced SiC matrix (SiC/SiC) composites was also investigated. The results show that the flexural strength of SiC/SiC composites with and without coating is 276 MPa and 70 MPa, respectively, which indicates that BN interphase coating deposited from B-trichloroborazine precursor can effectively adjust the fiber/matrix interface, thus causing a dramatic increase in the mechanical properties of the composites.     

Effects of post-thermal treatments on morphological and optical properties of NiO/Ni(OH)2 thin films synthesized by solution growth

Room temperature deposition of PVP capped nanostructured NiO/Ni(OH)₂ thin film, the morphological and optical characterizations by solution growth technique are reported. The nanostructured thin films which were deposited on optical glass substrates were annealed at different temperatures and then subjected to structural, morphological and optical characterizations. X-ray diffraction measurements of the films revealed that higher temperatures during the thermal treatment enhanced the crystallinity of the thin films. The SEM surface micrographs show non-interconnected uniformly deposited fibre-like structures with approximate lengths between 400 and 1200 nm. The optical band gap energy roughly decreased from about 2.7 eV to about 2.2 eV with thermal treatment. The absorbance of the thin films annealed at 300 and 400 °C was as high as 90% in the visible region of the electromagnetic spectrum. These materials could be useful in solar thermal conversion processes.     

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.     

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 oxygen pressure on structure and properties of Bi1.5Zn1.0Nb1.5O7 pyrochlore thin films prepared by pulsed laser deposition

The Bi₂O₃-ZnO-Nb₂O₅ (BZN) cubic pyrochlore thin films were prepared on Pt/TiO₂/SiO₂/Si(1 0 0) substrates by using pulsed laser deposition process. The oxygen pressure was varied in the range of 5-50 Pa to investigate its effect on the structure and dielectric properties of BZN thin films. It is found that oxygen pressure during deposition plays an important role on structure and other properties of BZN films. The BZN films deposited at temperature of 650 °C and at O₂ pressure of 5 Pa have an amorphous BZN and Nb₂O₅ phases but exhibits a cubic pyrochlore structure with a preferential (2 2 2) orientation when the oxygen pressure increases to 10 Pa. Dielectric constant and loss tangent of the films deposited at 10 Pa are 185 and 0.0008 at 10 kHz, respectively. The dielectric tunability is about 10% at a dc bias field of 0.9 MV/cm.     

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.     

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.     

Effect of solution molarity on the characteristics of vanadium pentoxide thin film

Vanadium pentoxide (V₂O₅) thin films have been prepared by spray pyrolysis technique. The influence of solution molarity on the characteristics of the V₂O₅ has been investigated. X-ray diffraction analysis (XRD) showed that, the films deposited at ≥0.1 M were orthorhombic structure with a preferential orientation along 〈0 0 1〉 direction. Moreover, the crystallinity was improved by increasing solution molarity. The microstructure parameters have been evaluated by using a single order Voigt profile method. The optical band gaps, determined by using Tauc plot, have been found to be 2.50 ± 0.02 and 2.33 ± 0.02 eV for the direct and indirect allowed transition, respectively. Also the complex optical constants for the wavelength range 300-2500 nm are reported. At room temperature, the dark conductivity as a function of solution molarity showed the range of 5.74 × 10⁻² ± 0.03 to 3.36 × 10⁻¹ ± 0.02 Ω⁻¹ cm⁻¹. While at high temperature, the behaviour of electrical conductivity dominated by grain boundaries. The values of activation energy and potential barrier height were 0.156 ± 0.011 and 0.263 ± 0.012 eV, respectively.     

Growth mechanism and optoelectronic properties of nanocrystalline In2O3 films prepared by chemical spray pyrolysis of metal-organic precursor

Thin films of indium oxide, In₂O₃, were deposited by chemical spray pyrolysis technique, using aqueous alcoholic solutions of indium acetylacetonate (In-acac) precursor, on glass substrates kept at temperatures between 300 and 500 °C. The structural, optical, and electrical properties have been investigated as a function of deposition temperature, precursor concentration, carrier gas pressure, and substrate-to-nozzle distance. X-ray diffraction studies showed that the formation of nanocrystalline In₂O₃ films is preferentially oriented along (2 2 2) plane. The surface morphological modifications with substrate temperature were observed using scanning electron and atomic force microscopic studies. Optical transmittance behavior of the films in the visible and IR region was strongly affected by the deposition parameters. The optical band gap values observed are between 3.53 and 3.68 eV. The long wavelength limit of refractive index is 1.83. The Hall mobility is found to vary from 23 to 37 cm²/V s and carrier density is found nearly constant at about 10²⁰ cm⁻³.