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.     

Fluorine-doped ZnO transparent conducting thin films prepared by radio frequency magnetron sputtering

Fluorine-doped ZnO transparent conducting thin films were prepared by radio frequency magnetron sputtering at 150 °C on glass substrate. Thermal annealing in vacuum was used to improve the optical and electrical properties of the films. X-ray patterns indicated that (002) preferential growth was observed. The grain size of F-doped ZnO thin films calculated from the full-width at half-maximum of the (002) diffraction lines is in the range of 18-24 nm. The average transmittance in visible region is over 90% for all specimens. The specimen annealed at 400 °C has the lowest resistivity of 1.86 × 10^− 3 Ω cm, the highest mobility of 8.9 cm² V^− 1 s^− 1, the highest carrier concentration of 3.78 × 10²⁰ cm^− 3, and the highest energy band gap of 3.40 eV. The resistivity of F-doped ZnO thin films increases gradually to 4.58 × 10^− 3 Ω cm after annealed at 400 °C for 4 h. The variation of the resistivity is slight.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

The influence of annealing temperature on the structural, electrical and optical properties of ion beam sputtered CuInSe2 thin films

CuInSe₂ (CIS) thin films were prepared by ion beam sputtering deposition of copper layer, indium layer and selenium layer on BK7 glass substrates followed by annealing at different temperatures for 1 h in the same vacuum chamber. The influence of annealing temperature (100-400 °C) on the structural, optical and electrical properties of CIS thin films was investigated. X-ray diffraction (XRD) analysis revealed that CIS thin films exhibit chalcopyrite phase and preferential (112) orientation when the annealing temperature is over 300 °C. Both XRD and Raman show that the crystalline quality of CIS thin film and the grain size increase with increasing annealing temperature. The reduction of the stoichiometry deviation during the deposition of CIS thin films is achieved and the elemental composition of Cu, In and Se in the sample annealed at 400 °C is very near to the stoichiometric ratio of 1:1:2. This sample also has an optical energy band gap of about 1.05 eV, a high absorption coefficient of 10⁵ cm⁻¹ and a resistivity of about 0.01 Ω cm.     

Preparation and characterization of indium zinc oxide thin films by electron beam evaporation technique

In this work, the preparation of In₂O₃-ZnO thin films by electron beam evaporation technique on glass substrates is reported. Optical and electrical properties of these films were investigated. The effect of dopant amount and annealing temperature on the optical and electrical properties of In₂O₃-ZnO thin films was also studied. Different amount of ZnO was used as dopant and the films were annealed at different temperature. The results showed that the most crystalline, transparent and uniform films with lowest resistivity were obtained using 25 wt% of ZnO annealed at 500 °C.     

Structure, luminescence and electrical properties of ZnO thin films annealed in H2 and H2O ambient: A comparative study

Undoped ZnO films were grown on a c-plane sapphire by plasma-assisted molecular-beam epitaxy technique, and subsequently annealed at 200-500 °C with steps of 100 °C in water vapour and hydrogen ambient, respectively. It is found that the c-axis lattice constant of the ZnO films annealed in hydrogen or water vapour at 200 °C increases sharply, thereafter decreases slowly with increasing annealing temperature ranging from 300 °C to 500 °C. The stress in the as-grown ZnO films was more easily relaxed in water vapour than in hydrogen ambient. Interestingly, the controversial luminescence band at 3.310 eV, which is often observed in photoluminescence (PL) spectra of the ZnO films doped by p-type dopants, was observed in the PL spectra of the annealed undoped ZnO films and the PL intensity increases with increasing annealing temperature, indicating that the 3.310 eV band is not related to p-type doping of ZnO films. The electron concentration of the ZnO films increases sharply with increasing annealing temperature when annealed in hydrogen ambient but decreases slowly when annealed in water vapour. The mechanisms of the effects of annealing ambient on the properties of the ZnO films are discussed.     

Effects of heat treatment on properties of ITO films prepared by rf magnetron sputtering

Indium tin oxide (ITO) films were deposited on glass substrates by rf magnetron sputtering using a ceramic target (In₂O₃-SnO₂, 90-10 wt%) without extra heating. The post annealing was done in air and in vacuum, respectively. The effects of annealing on the structure, surface morphology, optical and electrical properties of the ITO films were studied. The results show that the increase of the annealing temperature improves the crystallinity of the films, increases the surface roughness, and improves the optical and electrical properties. The transmittance of the films in visible region is increased over 90% after the annealing process in air or in vacuum. The resistivity of the films deposited is about 8.125×10⁻⁴ Ω cm and falls down to 2.34×10⁻⁴ Ω cm as the annealing temperature is increased to 500°C in vacuum. Compared with the results of the ITO films annealed in air, the properties of the films annealed in vacuum is better.     

Effect of deposition parameters and annealing temperature on the structure and properties of Al-doped ZnO thin films

Transparent conductive films of Al-doped ZnO (AZO) were deposited onto inexpensive soda-lime glass substrates by radio frequency (rf) magnetron sputtering using a ZnO target with an Al content of 3 wt%. The Taguchi method with a L₉ orthogonal array, signal-to-noise (S/N) ratio and analysis of variance (ANOVA) were employed to examine the performance characteristics of the coating operations. This study investigated the effect of the deposition parameters (rf power, sputtering pressure, thickness of AZO films, and substrate temperature) on the electrical, structural, morphological and optical properties of AZO films. The grey-based Taguchi method showed the electrical resistivity of AZO films to be about 9.15 × 10⁻³ Ω cm, and the visible range transmittance to be about 89.31%. Additionally, the films were annealed in a vacuum ambient (5.0 × 10⁻⁶ Torr) at temperatures of 400, 450, 500 and 600 °C, for a period of 30 min. It is apparent that the intensity of the X-ray peaks increases with annealing treatment, leading to improved crystallinity of the films. By applying annealing at 500 °C in a vacuum ambient for 30 min, the AZO films show the lowest electrical resistivity of 2.31 × 10⁻³ Ω cm, with about 90% optical transmittance in the visible region and a surface roughness of Ra = 12.25 nm.     

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.     

Effect of post-annealing on the optoelectronic properties of ZnO:Ga films prepared by pulsed direct current magnetron sputtering

In this study, highly conductive films of ZnO:Ga (GZO) were deposited by pulsed direct current magnetron sputtering to explore the effect of post-annealing on the structural, electrical and optical properties of the films. XRD patterns showed that after annealing, the intensity of c-axis preferentially oriented GZO (002) peak was apparently improved. GZO film annealing at 300 °C for 0.5 h exhibits lowest resistivity of 1.36 × 10^− 4 Ω cm. In addition, the film shows good optical transmittance of 88% with optical band gap, 3.82 eV. Carrier concentration and optical band gap both decreases with the annealing temperature. Besides, the near-infrared transmittance at 1400 nm is below 5%, while the reflectivity at 2400 nm is as high as 70%.     

Annealing effect on properties of transparent and conducting ZnO thin films

This work presents the effect of postdeposition annealing on the structural, electrical and optical properties of undoped ZnO (zinc oxide) thin films, prepared by radio-frequency sputtering method. Two samples, 0.17 and 0.32 µm-thick, were annealed in vacuum from room temperature to 350 °C while another 0.32 µm-thick sample was annealed in air at 300 °C for 1 h. X-ray diffraction analysis revealed that all the films had a c-axis orientation of the wurtzite structure normal to the substrate. Electrical measurements showed that the resistivity of samples annealed in vacuum decreased gradually with the increase of annealing temperature. For the 0.32 µm-thick sample, the gradual decrease of the resistivity was essentially due to a gradual increase in the mobility. On the other hand, the resistivity of the sample annealed in air increased strongly. The average transmission within the visible wavelength region for all films was higher than 80%. The band gap of samples annealed in vacuum increased whereas the band gap of the one annealed in air decreased. The main changes observed in all samples of this study were explained in terms of the effect of oxygen chemisorption and microstructural properties.     

Activation of phosphorous doping in high quality ZnO thin film grown on Yttria-stabilized zirconia (1 1 1) by thermal treatment

Phosphorous doped (P-doped) ZnO thin films are grown on c-sapphire and Yttria-stabilized zirconia (YSZ) (111) substrates by pulsed laser deposition. Post growth annealing is carried out to activate phosphorous to act as acceptor. The rocking curve of annealed P-doped ZnO films grown on YSZ (111) has full width at half maximum of 0.08°, more than two times narrower than that of the as-grown one. Neutral acceptor bound exciton (A⁰X) is observed from low temperature photoluminescence with estimated activation energy of 11.3 meV. Low carrier concentration of as-grown P-doped ZnO films indicated phosphorous doping creates acceptor states and/or reduced the oxygen vacancies. The carrier concentration of annealed samples is reduced by five order magnitudes from 3.21 × 10¹⁸ cm^− 3 to 1.21-8.19 × 10¹³ cm^− 3. At annealing temperature of 850 °C, the sample has the lowest carrier concentration and highest resistivity. This is an indication that the phosphorous in P-doped ZnO has been activated.     

The effect of annealing on Al-doped ZnO films deposited by RF magnetron sputtering method for transparent electrodes

In this study, transparent conducting Al-doped zinc oxide (AZO) films with a thickness of 150 nm were prepared on Corning glass substrates by the RF magnetron sputtering with using a ZnO:Al (Al₂O₃: 2 wt.%) target at room temperature. This study investigated the effects of the post-annealing temperature and the annealing ambient on the structural, electrical and optical properties of the AZO films. The films were annealed at temperatures ranging from 300 to 500 °C in steps of 100 °C by using rapid thermal annealing equipment in oxygen. The thicknesses of the films were observed by field emission scanning electron microscopy (FE-SEM); their grain size was calculated from the X-ray diffraction (XRD) spectra using the Scherrer equation. XRD measurements showed the AZO films to be crystallized with strong (002) orientation as substrate temperature increases over 300 °C. Their electrical properties were investigated by using the Hall measurement and their transmittance was measured by UV-vis spectrometry. The AZO film annealed at the 500 °C in oxygen showed an electrical resistivity of 2.24 × 10^− 3 Ω cm and a very high transmittance of 93.5% which were decreased about one order and increased about 9.4%, respectively, compared with as-deposited AZO film.     

Annealing effect of ZnO/Au/ZnO transparent conductive films

Au intermediate ZnO (ZAZ) thin films were prepared by radio frequency and direct current magnetron sputtering on glass substrates and then vacuum annealed. The thickness of each layer of the ZAZ films was set at 50 nm, 3 nm, and 47 nm, respectively. The structural, electrical, and optical properties of ZAZ films were investigated with respect to the variation of annealing temperature.As-deposited AZO films showed X-ray diffraction peaks corresponding to ZnO (002) and Au (111) planes and those peak intensities increased with post-deposition vacuum annealing. The optical and electrical properties of the films were strongly influenced by post-deposition annealing. Although the optical transmittance of the films deteriorated with an Au interlayer, as-deposited ZAZ films showed a low resistivity of 2.0 × 10⁻⁴ Ω cm, and the films annealed at 300 °C had a lower resistivity of 9.8 × 10⁻⁵ Ω cm. The work function of the films increased with annealing temperature, and the films annealed at 300 °C had a higher work function of 4.1 eV than the films annealed at 150 °C. The experimental results indicate that vacuum-annealed ZAZ films are attractive candidates for use as transparent electrodes in large area electronic applications such as solar cells and large area displays.     

Effect of annealing on the electrical, optical and structural properties of cadmium stannate thin films prepared by spray pyrolysis technique

Polycrystalline thin films of cadmium stannate (Cd₂SnO₄) were deposited by spray pyrolysis method on the Corning substrates at substrate temperature of 525 °C. Further, the films were annealed at 600 °C in vacuum for 30 min. These films were characterized for their structural, electrical and optical properties. The experimental results showed that the post-deposition annealing in vacuum has a significant influence on the properties of the films. The average grain size of the film was increased from 27.3 to 35.0 nm on heat treatment. The average optical transmittance in the visible region (500-850 nm) is decreased from 81.4% to 73.4% after annealing in vacuum. The minimum resistivity achieved in the present study for the vacuum annealed films is the lowest among the reported values for the Cd₂SnO₄ thin films prepared by spray pyrolysis method.     

The properties of radio frequency sputtered transparent and conducting ZnO:F films on polyethylene naphthalate substrate

We report on the properties of ZnO:F films deposited by RF sputtering on polyethylene naphthalate (PEN) substrates and compared them with films deposited on glass. Detailed and systematic investigations of various properties of films were deposited on PEN substrates were carried out as functions of thickness and annealing ambient. The films were deposited at room temperature and annealed at 150 °C in either Ar or 7% H₂/Ar ambients. These films exhibited carrier concentrations between 2 × 10¹⁸/cm³ and 9.5 × 10¹⁹/cm³, mobility between 3 and 11 cm²/V-s, and resistivity between 10^− 1 and 10^− 2 Ω-cm. Hall mobility variation with concentration has been explained assuming ionized impurity and lattice scattering to be the dominant mechanisms. The transmission of the films varied from 68 to 80% with increasing thickness and the absorption edge was limited by the absorption of the PEN substrate. The mechanical flexibility of the films was measured in terms of its critical radius of bending which was determined from the onset of a sharp increase in electrical resistance. The critical radius varied between 6.5 and 17 mm for film thicknesses varying from 20 to 200 nm. The thickness dependence of critical strain and critical radius can be explained by Griffith defect theory.     

Effect of annealing temperature on structural, electrical and optical properties of B-N codoped ZnO thin films

The B-N codoped p-type ZnO thin films have been prepared by radio frequency magnetron sputtering using a mixture of nitrogen and oxygen as sputtering gas. The effect of annealing temperature on the structural, electrical and optical properties of B-N codoped films was investigated by using X-ray diffraction, Hall-effect, photoluminescence and optical transmission measurements. Results indicated that the electrical properties of the films were extremely sensitive to the annealing temperature and the conduction type could be changed dramatically from n-type to p-type, and finally changed to weak p-type in a range from 600 °C to 800 °C. The B-N codoped p-type ZnO film with good structural, electrical and optical properties can be obtained at an intermediate annealing temperature region (e.g., 650 °C). The codoped p-type ZnO had the lowest resistivity of 2.3 Ω cm, Hall mobility of 11 cm²/Vs and carrier concentration of 1.2 × 10¹⁷ cm^− 3.     

Room temperature deposition of Al-doped ZnO films on quartz substrates by radio-frequency magnetron sputtering and effects of thermal annealing

High-quality Al-doped zinc oxide (AZO) thin films have been deposited on quartz substrates by radio-frequency magnetron sputtering at room temperature for thin film solar cell applications as transparent conductive oxide (TCO) electrode layers. Effects of post-deposition annealing treatment in pure nitrogen and nitrogen/hydrogen atmosphere have been investigated. Annealing treatments were carried out from 300 °C to 600 °C for compatibility with typical optoelectronic device fabrication processes. A series of characterization techniques, including X-ray diffraction, scanning electron microscopy, Hall, optical transmission, and X-ray photoelectron spectroscopy has been employed to study these AZO materials. It was found that there were significant changes in crystallinity of the films, resistivity increased from 4.60 × 10^− 4 to 4.66 × 10^− 3 Ω cm and carrier concentration decreased from 8.68 × 10²⁰ to 2.77 × 10²⁰ cm^− 3 when annealing in 400 °C pure nitrogen. Whereas there were no significant changes in electrical and optical properties of the AZO films when annealing in 300-500 °C nitrogen/hydrogen atmosphere, the electrical stability of the AZO films during the hydrogen treatment is attributed to both desorption of adsorbed oxygen from the grain boundaries and production of additional oxygen vacancies that act as donor centers in the films by removal of oxygen from the ZnO matrix. These results demonstrated that the AZO films are stably suited for TCO electrodes in display devices and solar cells.     

Effect of annealing temperature on the properties of IZO films and IZO based transparent TFTs

This work shows the effect of the annealing temperature and atmosphere on the properties of r.f. magnetron sputtered indium-zinc oxide (IZO) thin-films of two types: one a conductive film (as-deposited, room temperature) that exhibits a resistivity of 3.5 × 10^− 4 Ω cm; the other, a semiconductor film with a resistivity ∼ 10² Ω cm. The annealing temperatures were changed between 125 and 500 °C. Crystallization of the more conductive films was already noticeable at temperatures around 400 °C. Three different annealing atmospheres were used — vacuum, air and oxygen. For the conductive films, only the oxygen atmosphere was critical, leading to an increase of the electrical resistivity of more than one order of magnitude, for temperatures of 250 °C and above. Concerning the semiconductor films, both temperature and atmosphere had a strong effect on the film's properties, and the resistivity of the annealed films was always considerably smaller than the as-deposited films. Finally, some results of the application of these films to transparent TFTs are shown.     

Effect of annealing temperature on ZnO:Al/p-Si heterojunctions

Al-doped, zinc oxide (ZnO:Al) films with a 1.2 at.% Al concentration were deposited on p-type silicon wafers using a sol-gel dip coating technique to produce a ZnO:Al/p-Si heterojunction. Following deposition and subsequent drying processes, the films were annealed in vacuum at five different temperatures between 550 and 900 °C for 1 h. The resistivity of the films decreased with increasing annealing temperature, and an annealing temperature of 700 °C provided controlled current flow through the ZnO:Al/p-Si heterojunction up to 20 V. The ZnO:Al film deposited on a p-type silicon wafer with 1.2 at.% Al concentration was concluded to have the potential for use in electronic devices as a diode after annealing at 700 °C.