Preparation of aluminum doped zinc oxide films and the study of their microstructure, electrical and optical properties

Aluminum doped zinc oxide (AZO) polycrystalline thin films were prepared by sol-gel dip-coating process on optical glass substrates. Zinc acetate solutions of 0.5 M in isopropanol stabilized by diethanolamine and doped with a concentrated solution of aluminum nitrate in ethanol were used. The content of aluminum in the sol was varied from 1 to 3 at.%. Crystalline ZnO thin films were obtained following an annealing process at temperatures between 300 °C and 500 °C for 1 h. The coatings have been characterized by X-ray diffraction, UV-Visible spectrophotometry, scanning electron microscopy, and electrical resistance measurement. The ZnO:Al thin films are transparent (∼ 90%) in near ultraviolet and visible regions. With the annealing temperature increasing from 300 °C to 500 °C, the film was oriented more preferentially along the (0 0 2) direction, the grain size of the film increased, the transmittance also became higher and the electrical resistivity decreased. The X-ray diffraction analysis revealed single-phase ZnO hexagonal wurtzite structure. The best conductors were obtained for the AZO films containing 1 at.% of Al, annealed at 500 °C, 780 nm film thickness.     

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.     

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.     

Correlation study between structural, magnetic and transport properties of annealed Co thin films

This paper presents structural, magnetization and transport properties measurements carried out on as-deposited Co (400 Å) thin film as well as samples annealed in the temperature range 100-500 °C in steps of 100 °C for 1 h. The samples used in this work were deposited on float glass substrates using ion beam sputtering technique. The magnetization measurements carried out using MOKE technique, clearly indicates that as-deposited as well as annealed samples up to 500 °C show well saturation magnetization with applied magnetic field. The as-deposited sample shows coercivity value (H_c) of 26 Oe, and it is increased to 94 Oe for 500 °C-annealed sample. A minimum coercivity value of 15 Oe is obtained for 200 °C annealed sample. The XRD measurements of as deposited films show microcrystalline nature of Co film, which becomes crystalline with increase in annealing temperature. The corresponding resistivity measurements show gradual decrease in resistivity. AFM technique was employed to study the surface morphology of as deposited film as well as annealed thin films. Observed magnetization, and resistivity behaviour is mainly attributed to the (i) change in crystal structure (ii) increase in grain size and (iii) stress relaxation due to the annealing treatment.     

Influence of magnetic annealing on high-frequency magnetic properties of FeCoNd films

FeCoNd thin film with thickness of 166 nm has been fabricated on silicon (1 1 1) substrates by magnetron co-sputtering and annealed for one hour under magnetic field at different temperatures (T_a) from 200 °C to 700 °C. The As-deposited and annealed FeCoNd film samples at T_a ≤ 500 °C were amorphous while the ones obtained at T_a ≥ 600 °C were crystallized. We found that the perpendicular anisotropy field gradually decreases as the annealing temperature increases from room temperature to 300 °C. A well induced in-plane uniaxial anisotropy is achieved at the annealing temperature between 400 and 600 °C. The variation of the dynamic magnetic properties of annealed FeCoNd films can be well explained by the Landau-Lifshitz equation with the variation of the anisotropy field re-distribution and the damping constant upon magnetic annealing. The magnetic annealing might be a powerful post treatment method for high frequency application of magnetic thin films.     

Low temperature annealing effects on the structure and optical properties of ZnO films grown by pulsed laser deposition

ZnO thin films were deposited on glass substrates at room temperature (RT) ∼500 °C by pulsed laser deposition (PLD) technique and then were annealed at 150-450 °C in air. The effects of annealing temperature on the microstructure and optical properties of the thin films deposited at each substrate temperature were investigated by XRD, SEM, transmittance spectra, and photoluminescence (PL). The results showed that the c-axis orientation of ZnO thin films was not destroyed by annealing treatments; the grain size increased and stress relaxed for the films deposited at 200-500 °C, and thin films densified for the films deposited at RT with increasing annealing temperature. The transmittance spectra indicated that E_g of thin films showed a decreased trend with annealing temperature. From the PL measurements, there was a general trend, that is UV emission enhanced with lower annealing temperature and disappeared at higher annealing temperature for the films deposited at 200-500 °C; no UV emission was observed for the films deposited at RT regardless of annealing treatment. Improvement of grain size and stoichiometric ratio with annealing temperature can be attributed to the enhancement of UV emission, but the adsorbed oxygen species on the surface and grain boundary of films are thought to contribute the annihilation of UV emission. It seems that annealing at lower temperature in air is an effective method to improve the UV emission for thin films deposited on glass substrate at substrate temperature above RT.     

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.     

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.     

Inkjet-printing of indium tin oxide (ITO) films for transparent conducting electrodes

Indium-tin-oxide (ITO) films have been prepared by inkjet-printing using ITO nanoparticle inks. The electrical and optical properties of the ITO films were investigated in order to understand the effects of annealing temperatures under microwave. The decrease in the sheet resistance and resistivity of the inkjet-printed ITO films was observed as the annealing temperature increases. The film annealed at 400 °C showed the sheet resistance of 517 Ω/sq with the film thickness of ∼580 nm. The optical transmittance of the films remained constant regardless of their annealing temperatures. In order to further reduce the sheet resistance of the films, Ag-grid was printed in between two layers of inkjet-printed ITO. With 3 mm Ag-grid line-to-line pitch, the Ag-grid inserted ITO film has the sheet resistance of 3.4 Ω/sq and the transmittance of 84% after annealing at 200 °C under microwave.     

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.     

Study of annealing-induced changes in CdS thin films using X-ray diffraction and Raman spectroscopy

We have investigated as grown and annealed (300 °C, 400 °C and 500 °C) thin films of CdS grown on GaAs (001) by chemical bath deposition. X-ray diffraction (XRD) shows that the as grown CdS film is polycrystalline and predominantly cubic. A residual compressive stress of the order of 1.45% in the as grown film relaxes on annealing the film at 300 °C. Furthermore, CdS film undergoes a structural phase transition from the metastable cubic phase to the stable hexagonal phase, when, annealed at 500 °C. This is accompanied by significant improvement in crystalline quality of the film. Line shape analysis of the asymmetry of the longitudinal optical phonon shows a disorder-activated mode, which correlates well with the crystalline quality estimated from XRD and photoluminescence measurements. The additional features observed in the Raman spectra ∼ 254 cm^− 1 and 309 cm^− 1 are investigated using temperature dependent Raman spectroscopy and identified as superposition of transverse optical: E₁ (TO) and E₂ phonons at q = 0 and combination mode (two zone-edge E₂ phonons) respectively.     

The effect of substrate temperature on Al-doped ZnO characteristics for organic thin film transistor applications

The influence of substrate temperature on the structural, electrical, and optical properties of aluminum-doped zinc oxide (AZO) films fabricated by radio frequency (RF) magnetron sputtering was investigated. The AZO films were deposited at various substrate temperatures, and the effect of AZO gate electrode conductivity on organic thin film transistor (OTFT) performance was examined. While an increase in the substrate temperature from 100 °C to 300 °C led to an improvement in crystallinity, substrate temperatures over 300 °C caused degradation of the electrical and surface properties. We fabricated OTFTs using AZO films prepared at various substrate temperatures and obtained good device performance. Thus, the performance of an OTFT can be determined by the conductivity of the AZO gate electrode.     

Influence of annealing temperature on the structural, mechanical and wetting property of TiO2 films deposited by RF magnetron sputtering

TiO₂ films have been deposited on silicon substrates by radio frequency magnetron sputtering of a pure Ti target in Ar/O₂ plasma. The TiO₂ films deposited at room temperature were annealed for 1 h at different temperatures ranging from 400 °C to 800 °C. The structural, morphological, mechanical properties and the wetting behavior of the as deposited and annealed films were obtained using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, nanoindentation and water contact angle (CA) measurements. The as deposited films were amorphous, and the Raman results showed that anatase phase crystallization was initiated at annealing temperature close to 400 °C. The film annealed at 400 °C showed higher hardness than the film annealed at 600 °C. In addition, the wettability of film surface was enhanced with an increase in annealing temperature from 400 °C to 800 °C, as revealed by a decrease in water CA from 87° to 50°. Moreover, the water CA of the films obtained before and after UV light irradiation revealed that the annealed films remained more hydrophilic than the as deposited film after irradiation.     

Annealing and oxidation mechanism of evaporated zinc thin films from zinc oxide powder

Zinc oxide (ZnO) thin films were deposited by thermal evaporation of a high quality ZnO powder; the obtained films were then oxidized in the air. We have systematically investigated the influence of annealing temperature ranged from 100 to 400 °C on the films composition and structural and optical properties by using Rutherford Back Scattering (RBS) analysis, X-ray Diffraction (XRD) and UV-Visible transmission respectively. The as grown films exhibit a hexagonal single phase of Zn with no preferential orientation and contain 28% oxygen. With an increase in the annealing temperature the oxygen content is enhanced to the detriment of Zn; samples were totally oxidized at 300 °C and the films are converted to stoichiometric ZnO material. However, in situ XRD pattern analysis shows that the oxidation starts at 250 °C. From the XRD results of annealed Zn samples under an electrical field we inferred that the oxidation mechanism is achieved by the ionization of oxygen atom at the film surface and subsequently followed by the diffusion of the produced ions in the film network.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Sol-gel derived aluminum doped zinc oxide for application as anti-reflection coating in terrestrial silicon solar cells

Sol-gel grown polycrystalline Al doped zinc oxide (AZO) thin films have been deposited on Si wafers, microscopy slide glass and fluorine doped tin oxide coated glass substrates using the spin coating technique. The atomic ratio of Al:Zn in the films is 0.2. From the X-ray diffraction investigations it is found that the preferential growth of (100) reflection peak has taken place in the 450, 550 and 600 °C annealed films. Scanning electron microscopic study has shown that the films contain well-defined grains arranged in a closely packed array. The resistivity of the 500 °C annealed film is measured to be 5 × 10^− 1 Ω cm. The films have exhibited excellent optical transmittance (~ 90%) in the 400-1100 nm wavelength range. Refractive indices (n = 1.9-1.95) of the films on Si wafer are independent of the annealing temperature. Thickness of the films produced at 4000 rpm is in the range of 58-62 nm. The refractive index and thickness of these films are nearly appropriate to cause destructive interference after reflection from front emitters of solar cells. These films have demonstrated a reflectivity value of about 3% at a wavelength of 700 nm. The AZO coated silicon solar cells possess V_oc and I_sc values of 573 mV and 237 mA, respectively.     

Rapid thermal annealed Al-doped ZnO film for a UV detector

A low-resistive Al-doped ZnO (AZO) film was achieved by rapid thermal annealing. A co-sputtering method was used in the initial growth of AZO films and a rapid annealing process was performed on the as-deposited AZO film under N₂ atmosphere for 3 min. An as-deposited AZO film had an optical transmittance of 84.78% at 550 nm and a resistivity of 7.8 × 10^− 3 Ω cm. A rapid annealing process significantly improved the optical transmittance and electrical resistivity of the AZO film to 99.67% and 1 × 10^− 3 Ω cm, respectively. The structural changes of the AZO films were investigated by X-ray diffraction and transmission electron microscopy. The high quality AZO film was used to fabricate a metal-semiconductor-metal (MSM) structure for a UV detector. The MSM device provided a stable current of 25 μA at a bias of 2 V in a dark condition. Under UV illumination, the MSM device was highly responsive to UV light uniformly and repeatedly, and it enhanced the current by 80% at 45 μA. This rapid thermal annealing process may provide a useful method to fabricate quality AZO films for photoelectric applications with a low thermal budget.     

Effects of annealing temperature and thickness on microstructure and properties of sol–gel derived multilayer Al-doped ZnO films

Transparent conductive multilayer Al-doped ZnO (AZO) films were prepared by the spin-on technique with rapid thermal annealing process at low temperature. The effects of annealing temperature and thickness on microstructure, growth behavior, electrical properties and optical properties of AZO films were investigated. It was found that AZO films exhibited stronger preferred c-axis-orientation, the electrical resistivity decreased as it would be expected with the increase of annealing temperature from 400 to 500 °C and the increase of the number of layers in the film from 1 to 6, but the electrical resistivity tended to keep at a certain lowest value of 2.7 × 10⁻⁴ Ω cm when the annealing temperature was above 500 °C and the number of layers did not exceed 6. The average optical transmittance of AZO films was over 90% when number of layers in the film did not exceed 4 and decreased as this number increases, but the annealing temperature had little effect on the average optical transmittance of AZO films.     

Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering

Microstructure and hydrophilicity of nano-titanium dioxide (TiO₂) thin films, deposited by radio frequency magnetron sputtering, annealed at different temperatures, were studied by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle methods. It is found that the crystal phase transforms from amorphous to rutile structure with increase of annealing temperature from room temperature to 800 °C. It is also indicated that the organic contaminants on the surface of the films can be removed and the oxygen vacancies can be reduced by the annealing treatment. Annealed at the temperature below 300 °C, amorphous TiO₂ thin films show rather poor hydrophilicity, and annealed at the temperature range from 400 to 650 °C, the super hydrophilicity anatase of TiO₂ thin films can be observed. However, when the annealing temperature reaches 800 °C, the hydrophilicity of the films declines mainly derived from the appearance of rutile.     

Preparation and characterization of highly (1 1 1)-oriented (Pb,La)(Zr,Ti)O3 thin films by sol-gel processing

Lanthanum modified lead zirconate titanate (Pb_0.91La_0.09)(Zr_0.65Ti_0.35)O₃ (PLZT) ferroelectric thin films were grown on Pt/Ti/SiO₂/Si(1 0 0) and fused quartz substrates using a sol-gel method with rapid thermal annealing processing. The results showed that the highly (1 1 1)-oriented pervoskite PLZT thin film growth on Pt/Ti/SiO₂/Si(1 0 0) substrates. The electrical measurements were conducted on PLZT films in metal-ferroelectric-metal capacitor configuration. The PLZT thin films annealed at 600 °C showed well-saturated hysteresis loops with remanent polarization and coercive electric field values were 10.3 μC/cm² and 36 kV/cm, respectively, at an applied field of 300 kV/cm. At 100 kHz, the dielectric constant and dielectric loss of the film are 682 and 0.021, respectively. The PLZT thin film on fused quartz substrate, annealed at 600 °C, exhibited good optical transmittance, the band gap of optical direct transitions is 3.89 eV.