Effect of thermal annealing treatment on structural, electrical and optical properties of transparent sol-gel ZnO thin films

Effect of thermal annealing in different ambients on the structural, electrical and optical properties of the sol-gel derived ZnO thin films are studied. XRD results show that the annealed ZnO films with wurtzite structure are randomly oriented. Crystallite size, carrier concentration, resistivity and mobility are found to be dependent on the annealing temperature. The change in carrier concentration is discussed with respect to the removal of adsorbed oxygen from the grain boundaries. The highest carrier concentration and lowest resistivity are 8 × 10¹⁸ cm⁻³ and 2.25 × 10⁻¹ Ω cm, respectively, for the film annealed at 500 °C in vacuum. The annealed films are highly transparent with average transmission exceeding 80% in the wavelength region of 400-800 nm. In all three ambients, the optical band gap value does not change much below 500 °C temperature while above this temperature band gap value decreases for nitrogen and air and increases for vacuum.     

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.     

Influence of annealing temperature on the properties of ZnO:Zr films deposited by direct current magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were deposited on quartz substrates by direct current (DC) magnetron sputtering at room temperature. The influence of post-annealing temperature on the structural, morphological, electrical and optical properties of ZnO:Zr films were investigated. When annealing temperature increases from room temperature to 573 K, the resistivity decreases obviously due to an improvement of the crystallinity. However, with further increase in annealing temperature, the crystallinity deteriorates leading to an increase in resistivity. The films annealed at the optimum annealing temperature of 573 K in vacuum have the lowest resistivity of 9.8 × 10⁻⁴ Ω cm and a high transmittance of above 92% in the visible range.     

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.     

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.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

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.     

Thermal stability of carrier centers in various types of transparent conductive ZnO and Ga-doped ZnO films

We investigated the thermal stability of the transparent conductive properties of undoped ZnO and Ga-doped ZnO (GZO) films when they were annealed in a high vacuum with stepwise increasing temperature. The ZnO samples included V_O-rich and Zn-rich ZnO films; the primary donors were respectively oxygen vacancies (V_O) or Zn atoms highly unsaturated with oxygen atoms. V_O-rich ZnO was the most unstable against annealing; resistivity initially within the 10⁻³ Ω cm range diverged higher than 10 Ω cm when a critical temperature was exceeded. The critical temperature between 350 and 450 °C depended on the film thickness, which indicated that V_O's were diminished through recombination with migrating interstitial oxygen atoms. In contrast, Zn-rich ZnO films remained highly conductive up to 550 °C. They became more and more transparent and their crystallinity improved at higher annealing temperatures, which was the consequence of metallic-like Zn atoms being removed through desorption from the surface or being accommodated into the crystalline lattice. Comparatively, GZO films were more robust against annealing with their resistivities remaining unchanged up to 350 °C.     

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.     

Effect of post annealing on structural and optical properties of ZnO thin films deposited by vacuum coating technique

We report the effect of annealing temperature on structural, electrical and optical properties of polycrystalline zinc oxide thin films grown on p-type silicon (100) and glass substrates by vacuum coating technique. The XRD and AFM measurements confirmed that the thin films grown by this technique have good crystalline hexagonal wurtzite structures and homogenous surfaces. The study also reveals that the rms value of thin film roughness increases from 6 to 16 nm, the optical band gap increases from 3.05 to 3.26 eV and resistivity from 0.3 to 5 Ωcm when the post-deposition annealing temperature is changed from 400 to 600 °C. It is observed that ZnO thin film annealed at 600 °C after deposition provide a smooth and flat texture suited for optoelectronic applications.     

Rapid thermal-plasma annealing of ZnO:Al films for silicon thin-film solar cells

Rapid thermal annealing of sputter-deposited ZnO and Al-doped ZnO (AZO) films with and without an amorphous silicon (a-Si) capping layer was investigated using a radio-frequency (rf) argon thermal plasma jet at atmospheric pressure. The resistivity of bare ZnO films on glass decreased drastically from 10⁶ to 10³ Ω·cm at maximum surface temperatures T_max above 650 °C, whereas the resistivity increased from 10^− 4 to 10^− 3-10^− 2 Ω·cm for bare AZO films. On the other hand, the resistivity of AZO films with a 30-nm-thick a-Si capping layer remained below 10^− 4 Ω·cm, even after TPJ annealing at a T_max of 825 °C. X-ray diffraction and X-ray photoemission electron studies revealed that the film crystallization of both AZO and a-Si layers was promoted without the formation of an intermixing layer. Additionally, the crystallization of phosphorous- and boron-doped a-Si layers at the sample surface was promoted, compared to that of intrinsic a-Si under identical plasma annealing conditions. The role of the a-Si capping layer on sputter-deposited AZO and ZnO films during TPJ annealing is demonstrated. The effects of the mixing of phosphorous and boron impurities in a-Si:H during TPJ annealing of flat and textured AZOs are also discussed.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Effect of open air annealing on spin coated aluminum doped ZnO nanostructure

Aluminum doped ZnO thin film nanostructures were prepared by spin coating deposition on glass and silicon substrates. Electrical, optical and structural properties of these films were analyzed in order to investigate their dependence on post annealing temperature and number of coating cycles. Ultraviolet–Visible spectrophotometry and X-Ray diffraction (XRD) analysis confirmed that the films are optically transparent and polycrystalline in nature. Scanning electron microscopy (SEM) reveals worm like homogeneous morphology. Chemical analysis was carried out by Fourier transform infrared spectroscopy (FTIR). Atomic force microscopy (AFM) showed mountain and valley like nanostructure. Optimized films with a low resistivity of 2.11 × 10⁻¹ Ω cm were obtained at open air annealing temperature of 375 °C.     

Low-resistance and highly transparent Ag/IZO ohmic contact to p-type GaN

The electrical, structural, and optical characteristics of Ag/ZnO-doped In₂O₃ (IZO) ohmic contacts to p-type GaN:Mg (2.5 × 10¹⁷ cm^− 3) were investigated. The Ag and IZO (10 nm/50 nm) layers were prepared by thermal evaporation and linear facing target sputtering, respectively. Although the as-deposited and 400 °C annealed samples showed rectifying behavior, the 500 and 600 °C annealed samples showed linear I-V characteristics indicative of the formation of an ohmic contact. The annealing of the contact at 600 °C for 3 min in a vacuum (~ 10^− 3 Torr) resulted in the lowest specific contact resistivity of 1.8 × 10^− 4 Ω·cm² and high transparency of 78% at a wavelength of 470 nm. Using Auger electron spectroscopy, depth profiling and synchrotron X-ray scattering analysis, we suggested a possible mechanism to explain the annealing dependence of the electrical properties of the Ag/IZO contacts.     

Effect of annealing on the characteristics of Au/Cr bilayer films grown on glass

Au layers with thickness of about 110 nm were sputter-deposited on unheated glass substrates coated with a Cr layer about 20 nm thick. The chamber was evacuated to a pressure of 2 Pa and then sputtering was carried out at Ar pressure of 4 Pa. The Au/Cr bilayer films were annealed in a vacuum of 5×10⁻⁴ Pa at 170°C, 180°C, 200°C and 250°C for from 5 to 120 min, respectively. Atomic force microscopy was used to observe the structural characteristic of the bilayer films. Auger electron spectroscopy was used to analyze the composition inside the Au layers. The sheet resistance of the films was measured using the four-point probe technique. The grain size of the bilayer film gradually increases with an increase in annealing temperature while its average surface roughness ranging from 4.5 to 6.8 nm does not show any systematic change with annealing temperature and time. No impurities such as carbon, nitrogen and oxygen are detected inside all of the Au layers. When the annealing temperature reaches 200°C and the annealing time exceeds 30 min, chromium atoms markedly diffuse into the Au layer. Furthermore, for the bilayer films annealed at 250°C, chromium atoms have markedly diffused into the Au layer even for annealing time of 5 min. Regardless of the increase in grain size of the Au layer, the diffusion of chromium atoms into the Au layer causes an increase in the resistivity of the bilayer film.     

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.     

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.     

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.     

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.     

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.