The growth of nanoscale ZnO films by pulsed-spray evaporation chemical vapor deposition and their structural, electric and optical properties

Great interest in nanoscale thin films (sub-100 nm) has been stimulated by the developing demands of functional devices. In this paper, nanoscale zinc oxide (ZnO) thin films were deposited on glass substrates at 300 °C by pulsed-spray evaporation chemical vapor deposition. Scanning electron micrographs indicate uniform surface morphologies composed of nanometer-sized spherical particles. The growth kinetics and growth mode are studied and the relationship between the film thickness and the electric properties with respect to the growth mode is interpreted. X-ray diffraction shows that all ZnO films grown by this process were crystallized in a hexagonal structure and highly oriented with their c-axes perpendicular to the plane of the substrate. Optical measurements show transparencies above 85% in the visible spectral range for all films. The absorbance in the UV spectral range respects well the Beer-Lambert law, enabling an accurate optical thickness measurement, and the absorption coefficient was measured for a selected wavelength. The measured band gap energies exhibit an almost constant value of 3.41 eV for all films with different thicknesses, which attributed to the thickness-independent crystallite size.     

Effect of precursor concentration on structural and optical properties of ZnO microrods by spray pyrolysis

ZnO films have been prepared by spray pyrolysis technique on glass substrate at 500 °C. Zinc Chloride has been used as a precursor. Effect of precursor concentration on structural and optical properties has been investigated. Homogenous films are obtained with precursor concentration rating between 0.1 M and 0.4 M. X-ray diffraction patterns show that ZnO films are polycrystalline with (002) plane as preferential orientation. Field emission scanning electron microscopy images show that ZnO films consist of microrods that their length increases with increasing precursor concentration and tallest microrods obtain by spraying precursor with 0.3 M concentration. The optical transmittance spectrum shows that transmittance increases with decreasing of the concentration and transmittance reaches to a maximum value of about 80% for the visible region ZnO films prepared with 0.1 M. Photoluminescence spectra at room temperature show an ultraviolet emission at 3.21 eV that can be related to band gap and two visible emissions at 2.88 eV and 2.38 eV.     

Effects of the annealing treatment on electrical and optical properties of ZnO transparent conduction films by ultrasonic spraying pyrolysis

Effects of the annealing treatment on properties of ZnO thin films prepared on silica glass substrates by the ultrasonic spraying pyrolysis process were studied. Zinc acetate dihydrate and methanol were used as a starting material and a solvent, respectively. For ZnO thin films untreated with annealing, the preferred grain growth along the (0 0 2) plane was observed. The electrical resistivity and the direct band gap values of these films decreased with increasing the deposit temperature. By applying the annealing treatment in a reducing atmosphere, while the degree of the preferred (0 0 2) orientation of films decreased, the electrical conductivity of films was improved. When compared with the resistivity values of films without the annealing treatment, the values of films annealed in the reducing atmosphere were decreased by about two orders of magnitude. The lowest resistivity value was 1.62×10⁻¹ Ω cm, which was obtained in the film annealed at 500 °C in nitrogen with 5% hydrogen. The optical transmittances of the films were higher than 80% regardless of the application of the annealing treatment in a reducing atmosphere. The direct band gap values of films annealed in a reducing atmosphere were approximately 3.27 eV.     

Growth, structure and optical characterization of high quality ZnO thin films obtained by spray pyrolysis

Zinc oxide thin films were prepared by spray pyrolytic decomposition of zinc acetate onto a glass substrate. Auger spectroscopy showed that the film stoichiometry is close to the ZnO phase with a little excess of oxygen. X-ray diffraction spectra show that the structure belongs to the hexagonal wurtzite crystal type, with a mean crystallite size in the range 20–33 nm. Under optimized deposition conditions films are c-axis oriented, having a full width at half-maximum (FWHM) value of the (002) X-ray diffraction line of 0.23°. Microstructure was analysed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high resolution electron microscopy (HREM). In regard to the crystal growth, a critical temperature was found to be around 600 K. Above this critical temperature the film is c-axis oriented and almost all grains became round shaped. Optical constants, n and k, were determined using only transmittance data and a direct band gap of 3.28 eV was deduced.     

ZnO:In deposition by spray pyrolysis — Influence of the growth conditions on the electrical and optical properties

Indium-doped zinc oxide (ZnO:In) was spray-deposited on glass at a substrate temperature of 370 °C. The spray was generated by means of an ultrasonic nebulizer and using air as carrier gas. To the 0.2 mol/l zinc acetate solution indium acetate has been added as dopant, the [In]/[Zn] ratio was changed between 1 and 5 at.%. The mobility and resistivity have an optimum at an [In]/[Zn] ratio of 3 at.% with values of 2.9 mΩ cm and 12.5 cm²/Vs at a layer thickness of 1.3 μm. The application of a nucleation layer of 100 nm intrinsic ZnO (i-ZnO) on the glass substrate and the subsequent deposition of ZnO:In lead to a layer with significant improvement of the optical properties; the ultraviolet to visible (UV-VIS) light transmittance increased to above 80% in the visible light region. The new layer configuration caused a change in the layer morphology, which is visualised by Scanning Electron Microscope photographs, Energy Dispersive X-ray and X-ray Diffraction measurements. The electrical properties remained unchanged.     

Effect of Li doping on the structural, optical and electrical properties of spray deposited SnO2 thin films

Studies on spray deposited transparent conducting Li doped SnO₂ thin films are scarce. Li (0 to 5 wt.%) doped SnO₂ thin films spray deposited onto glass substrates at 773 K in air from chloride precursors were studied for their structural, optical and temperature dependent electrical behaviors. X-ray diffraction patterns indicated single phase with polycrystalline nature. Systematic variation in surface morphology on Li doping was examined by scanning electron microscopy and atomic force microscopy. Film thickness, optical band gap (direct and indirect), sheet resistance and figure of merit were computed from spectral transmittance and temperature dependent resistivity data. Lithium doping was found to decrease the value of sheet resistance by an order in magnitude. Activation energy was computed from temperature dependent electrical resistivity data measured in the range 300 to 448 K. The 4 wt.% Li doped SnO₂ film was found to have a high value of figure of merit among other films. The results are discussed.     

Morphology and microstructure of textured SnO2 thin films obtained by spray pyrolysis and their effect on electrical and optical properties

Tin dioxide thin films on glass substrate with different Zn doping levels were obtained by spray pyrolysis. Their microstructure, preferred crystallographic orientation, electrical and optical properties were extensively studied. The characterization techniques employed were scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction, electrical conductivity and optical transmission measurements. It was found that the material obtained has a nano-scale texture which characteristic size and orientation strongly depend on the Zn doping level. Doping-induced variations in texture and structure modify both the electrical and optical properties of films (namely, refractive index and transparency). The results obtained are relevant for potential applications of the studied films in gas sensing and photoconductive devices.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Influence of thickness and growth temperature on the optical and electrical properties of ZnO thin films

Zinc oxide transparent conductive thin films were prepared using the pulsed laser deposition technique onto Corning glass substrates and the dependences of their optical and electrical properties on the thickness and the growth temperature were investigated. As shown, the films present 90% average transmittance, their energy gap position depending on the film thickness and the growth temperature. An additional absorption band was also observed near 3.44 eV, the position of its maximum also depending on the growth parameters. Finally, the electrical properties of the films were found to be affected mainly by the growth temperature and less by the thickness.     

Role of precursors on morphology and optical properties of ZnS thin films prepared by chemical spray pyrolysis

This study investigates the effect of different growth parameters on the structural and optical properties of ZnS thin films, prepared using spray pyrolysis. The films were prepared using different Zn:S ratios (between 1:1 and 1:6) and in different growth solutions: (A), zinc chloride and thiourea and (B) dehydrated zinc acetate and thiourea, both in distilled water.By varying the Zn:S ratio in the films, the optical properties (absorption and photoluminescence) show that different species are created during film growth. This was deduced from the wide emission band appearing in the green region of the photoluminescence spectra, and from the change in band gap, which varies between 3.2 and 3.5 eV. Films formed from solution (A) with a Zn:S ratio of 1:3 or 1:4 show the best morphology and transmission. ZnS has a wider band gap than other conventional II-VI semiconductors utilized in various electronic and optical devices and can be expected to provide a useful window layer of solar cells which leads to an improvement in overall efficiency by decreasing absorption loss.     

Effect of alumina doping on structural, electrical, and optical properties of sputtered ZnO thin films

A systematic study of the influence of alumina (Al₂O₃) doping on the optical, electrical, and structural characteristics of sputtered ZnO thin films is reported in this study. The ZnO thin films were prepared on 1737F Corning glass substrates by R.F. magnetron sputtering from a ZnO target mixed with Al₂O₃ of 0-4 wt.%. X-ray diffraction (XRD) analysis demonstrates that the ZnO thin films with Al₂O₃ of 0-4 wt.% have a highly (002) preferred orientation with only one intense diffraction peak with a full width at half maximum (FWHM) less than 0.5°. The electrical properties of the Al₂O₃-doped ZnO thin films appear to be strongly dependent on the Al₂O₃ concentration. The resistivity of the films decreases from 74 Ω·cm to 2.2 × 10^− 3 Ω·cm as the Al₂O₃ content increases from 0 to 4 wt.%. The optical transmittance of the Al₂O₃-doped ZnO thin films is studied as a function of wavelength in the range 200-800 nm. It exhibits high transparency in the visible-NIR wavelength region with some interference fringes and sharp ultraviolet absorption edges. The optical bandgap of the Al₂O₃-doped ZnO thin films show a short-wavelength shift with increasing of Al₂O₃ content.     

Optical,electrical and mechanical properties of Ga-doped ZnO thin films under different sputtering powers

We present the optical, electrical and mechanical properties of Ga-doped zinc oxide (GZO) thin films prepared by radio-frequency (RF) magnetron sputtering at room temperature under different RF powers (80–180 W). The thickness, electron concentration, and electron mobility of the GZO thin film were determined by fitting the visible-to-near-infrared transmittance spectrum of GZO film/glass using the transfer matrix method. The bending force per unit width was measured by a home-made Twyman–Green interferometer with the fast Fourier transform method. The obtained results show that the optical, electrical and mechanical properties of GZO thin film are subject to the RF power. At an RF power of 140 W, the local minimum of bending force per unit width corresponds to the highest electron mobility in GZO thin film. This study demonstrates that the optical, electrical and mechanical properties of GZO thin film can be fully resolved by non-contact optical methods.     

Structural, optical and electrical properties of Al-doped ZnO microrods prepared by spray pyrolysis

Al-doped ZnO thin films were obtained on glass substrates by spray pyrolysis in air atmosphere. The molar ratio of Al in the spray solution was changed in the range of 0-20 at.% in steps of 5 at.%. X-ray diffraction patterns of the films showed that the undoped and Al-doped ZnO films exhibited hexagonal wurtzite crystal structure with a preferred orientation along (002) direction. Surface morphology of the films obtained by scanning electron microscopy revealed that pure ZnO film grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm. However, Al doping resulted in pronounced changes in the morphology of the films such as the reduction in the rod diameter and deterioration in the surface quality of the rods. Nevertheless, the morphology of Al-doped samples still remained rod-like with a hexagonal cross-section. Flower-like structures in the films were observed due to rods slanting to each other when spray solution contained 20 at.% Al. Optical studies indicated that films had a low transmittance and the band gap decreased from 3.15 to 3.10 eV with the increasing Al molar ratio in the spray solution from 0 to 20 at.%.     

Influence of fluorine doping on structural, electrical and optical properties of spray pyrolysis ZnS films

ZnS films were deposited by spray pyrolysis on glass at 500 °C substrate temperature. In order to study the influence of fluorine on the properties of ZnS film, undoped and F-doped films were investigated using X-ray diffraction, scanning electron microscopy and optical transmittance spectroscopy. The absorption coefficient was measured and correlated with the photon energy to estimate the energy gap, which rises from 3.20 to 3.35 eV with increased F content. Carrier concentrations of our samples were determined from Hall effect measurements. It was found that the carrier concentration increases from 7.0 × 10¹² cm^− 3 to 8.0 × 10¹³ cm^− 3 with increasing F content from 0 to 6 wt.% in ZnS films.     

Structural and spectroscopic ellipsometry characterization for electrodeposited ZnO growth at different hydrogen peroxide concentration

This work deals with textural and optical characterization of zinc oxide (ZnO) layers obtained by potentiostatic electroplating at various hydrogen peroxide concentrations (from 0 up to 5 mM). The electrodeposition process was studied by cyclic voltametry and chronoamperometry. The [002] preferred growth orientation of hexagonal phase is obtained for the lowest hydrogen peroxide concentration (1 mM), while additionally X-ray diffraction peaks are observed for hydrogen peroxide concentration ranging from 3 to 5 mM. The optical constants and the thickness of films were determined by spectroscopic ellipsometry measurements. The refractive index of all thin films shows normal dispersion behavior. It was also found that refractive index values decrease with increasing hydrogen peroxide concentration. Further, it was revealed that the changes in the optical properties are correlated to the changes in the surface structure.     

Growth ambient dependent electrical properties of lithium and nitrogen dual-doped ZnO films prepared by radio-frequency magnetron sputtering

Lithium (Li) and nitrogen (N) dual-doped ZnO films with wurtzite structure were prepared by radio-frequency magnetron sputtering ZnO target with Li₃N in growth ambient of pure Ar and the mixture of Ar and O₂, respectively, and then post annealing techniques. The film showed week p-type conductivity as the ambient was pure Ar, but stable p-type conductivity with a hole concentration of 3.46 × 10¹⁷ cm^− 3, Hall mobility of 5.27 cm²/Vs and resistivity of 3.43 Ω cm when the ambient is the mixture of Ar and O₂ with the molar ratio of 60:1. The stable p-type conductivity is due to substitution of Li for Zn (Li_Zn) and formation of complex of interstitial Li (Li_i) and substitutional N at O site, the former forms a Li_Zn acceptor, and the latter depresses compensation of Li_i donor for Li_Zn acceptor. The level of the Li_Zn acceptor is estimated to be 131.6 meV by using temperature-dependent photoluminescence spectrum measurement and Haynes rule. Mechanism about the effect of the ambient on the conductivity is discussed in the present work.     

Structural, electrical and optical characteristics of SnO2:Sb thin films by ultrasonic spray pyrolysis

Antimony-doped tin oxide (SnO₂:Sb) thin films were fabricated by an ultrasonic spray pyrolysis method. The effect of antimony doping on the structural, electrical and optical properties of tin oxide thin films were investigated. Tin(II) chloride dehydrate (SnCl₂·2H₂O) and antimony(III) chloride (SbCl₃) were used as a host and a dopant precursor. X-ray diffraction analysis showed that the non-doped SnO₂ thin film had a preferred (211) orientation, but as the Sb-doping concentration increased, a preferred (200) orientation was observed. Scanning electron microscopy studies indicated that the polyhedron-like grains observed for the non-doped SnO₂ thin films became rounder and decreased in size with the Sb-doping concentration. The lowest resistivity (about 8.4 × 10^− 4 Ω·cm) was obtained for the 3 at.% Sb-doped films. Antimony-doping led to an increase in the carrier concentration and a decrease in Hall mobility. The transmittance level in the near infrared region was lowered with the Sb-doping concentration.     

On the structural, morphological, optical and electrical properties of sol-gel deposited ZnO:In films

Indium-doped zinc oxide thin films deposition was performed by the sol-gel technique using homogeneous and stable solutions of zinc acetate 2-hydrate and indium chloride in ethanol. Films were spin coated onto glass substrates. After drying and after a heat treatment at 450 °C, highly transparent (80%-90%) films were obtained. The effect on the structural, morphological, optical and electrical thin films properties of the dopant concentration was investigated. The temperature dependencies of the electrical conductivity under vacuum and in open atmosphere were analysed and discussed.     

Investigation on structural, electrical and optical properties of tungsten-doped tin oxide thin films

Tungsten-doped tin oxide (SnO₂:W) transparent conductive films were prepared on quartz substrates by pulsed plasma deposition method with a post-annealing. The structure, chemical states, electrical and optical properties of the films have been investigated with tungsten-doping content and annealing temperature. The lowest resistivity of 6.67 × 10^− 4 Ω cm was obtained, with carrier mobility of 65 cm² V^− 1 s^− 1 and carrier concentration of 1.44 × 10²⁰ cm^− 3 in 3 wt.% tungsten-doping films annealed at 800 °C in air. The average optical transmittance achieves 86% in the visible region, and approximately 85% in near-infrared region, with the optical band gap ranging from 4.05 eV to 4.22 eV.     

The effect of rapid thermal annealing on structural and electrical properties of TiB2 thin films

This work reports on the effect of post-deposition rapid thermal annealing on the structural and electrical properties of deposited TiB₂ thin films. The TiB₂ thin films, thicknesses from 9 to 450 nm, were deposited by e-beam evaporation on high resistivity and thermally oxidized silicon wafers. The resistivity of as-deposited films varied from 1820 μΩ cm for the thinnest film to 267 μΩ cm for thicknesses greater than 100 nm. In the thickness range from 100 to 450 nm, the resistivity of TiB₂ films has a constant value of 267 μΩ cm.

A rapid thermal annealing (RTA) technique has been used to reduce the resistivity of deposited films. During vacuum annealing at 7 × 10⁻³ Pa, the film resistivity decreases from 267 μΩ cm at 200 °C to 16 μΩ cm at 1200 °C. Heating cycles during RTA were a sequence of 10 s. According to scanning tunneling microscopy analysis, the decrease in resistivity may be attributed to a grain growth through polycrystalline recrystallization, as well as to an increase in film density.

The grain size and mean surface roughness of annealed films increase with annealing temperature. At the same time, the conductivity of the annealed samples increases linearly with grain size. The obtained results show that RTA technique has a great potential for low resistivity TiB₂ formation.