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.     

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.     

Corrosion behavior of Al, Sc-co-doped ZnO thin films in 3.5% NaCl solution

The corrosion behavior of Al, Sc-co-doped zinc oxide films (with Sc-dopant varying in 0, 0.01, 0.13, 0.24 and 1.07 wt.% Sc) in 3.5% NaCl solution has been investigated. It was compared to that of the commercial indium tin oxide (ITO) thin film. The films were prepared by sputtering on the ZnO (4 N) target with RF and on the targets of Al (4 N), Al-0.4 wt.% Sc, Al-0.8 wt.% Sc, Al-1.7 wt.% Sc alloy and pure Sc with DC. The electrochemical studies revealed that the corrosion resistance of the films increases in the order AZO < Sc-doped AZO < ITO < annealed AZO (at 300 °C for 1 h). The AZO doped with higher Sc-content is more resistant to corrosion. Examining the surface morphology through atomic force microscope (AFM) and scanning electron microscope (SEM), the film, which is more susceptible to corrosion depicted a rougher surface. The electrical resistivity of the films maintained almost unchanged in 120-h test. However, the optical transmittance varied with the concentration of Sc-dopant in the films. The higher Sc-dopant in the film the more stable it is to maintain higher transmittance. Higher corrosion resistance for the Sc-doped AZO in comparison with the monotonic AZO is attributed to a release of lattice strain by the Sc (III)-dopant which its size is similar to Zn (II). The most corrosion-resistant specimen (i.e., Sc-doped AZO annealed at 300 °C for 1 h) is considered to have the complete release of the lattice strain.     

Preparation of Al-doped ZnO thin films as transparent conductive substrate in dye-sensitized solar cell

We have prepared aluminum-doped Zinc oxide (AZO) thin films on glass substrates by rf magnetron sputtering technique using ZnO ceramic target in pure argon gas with different aluminum concentrations. The bandgap of the ZnO films slightly widens with increase in Al content and the lowest sheet resistance of AZO films with Al concentration of 4.3 at.% was obtained. The effects of post-annealing treatment on structural, electrical and optical properties of the AZO thin films were investigated. Using AZO thin film with 4.3 at.% Al as the transparent substrate, a titanium dioxide based dye-sensitized solar cell was constructed and a solar to electrical energy conversion efficiency of 2.9% was achieved under AM 1.5 solar simulated sunlight.     

Microstructure and properties of Al-doped ZnO thin films by nonreactive DC magnetron sputtering at room temperature following rapid thermal annealing

A series of Al-doped ZnO (AZO) thin films deposited by nonreactive DC magnetron sputtering at room temperature following rapid thermal annealing was studied to examine the influence of these Al doping concentration, sputtering power and annealing temperature on their microstructure, electrical and optical transport properties. AZO thin films with Al dopant of 3 wt% were oriented more preferentially along the (002) direction, bigger grain size and lower electrical resistivity The resistivity of AZO films decreases with the increase of Al content from 1 to 3 wt%, sputtering power from 60 to 100 W and the annealing temperature from 50 to 250 °C. Sputtering power and annealing had some effect on the average transmittance of AZO thin films. For AZO thin films with Al doping level of 3 wt%, the lowest electrical resistivity of 5.3 × 10⁻⁴ Ω cm and the highest optical transmittance of 88.7% could gain when the sputtering power was 100 W and the annealing temperature was 200 °C or above.     

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.     

Enhanced conductivity of aluminum doped ZnO films by hydrogen plasma treatment

Aluminum doped zinc oxide (AZO) thin films prepared by radio-frequency (RF) magnetron sputtering at various RF power were treated by hydrogen plasma to enhance the characteristics for transparent electrode applications. The hydrogen plasma treatment was carried out at 300 °C in a plasma enhanced chemical vapor deposition system. X-ray diffraction analysis shows that all AZO films have a (002) preferred orientation and film crystallinity seems no significant change after plasma treatment. The plasma treatment not only significantly decreases film resistivity but enhances electrical stability as aging in air ambient. The improved electrical properties are due to desorption of weakly bonded oxygen species, formation of Zn-H type species and passivation of deep-level defects during plasma treatment.     

Low temperature synthesis of sol–gel derived Al-doped ZnO thin films with rapid thermal annealing process

A series of sol–gel derived Al-doped ZnO (AZO) thin films with rapid thermal annealing process at low temperature were studied to examine the influence of annealing temperature and the Al doping concentration on their microstructure, electrical and optical transport properties. Crystalline AZO thin films were obtained following an annealing process at temperatures between 400 and 600 °C for 10 min in argon gas ambient. AZO thin films with Al doping of 1 at% were oriented more preferentially along the (002) direction, and have larger grain size and lower electrical resistivity, while the highest average optical transmittances of 92% were observed in AZO films with Al doping of 2 at%. With the annealing temperature increasing from 400 to 600 °C, the grain size of AZO films increased, the optical transmittance became higher, and the electrical resistivity decreased to a lowest value of 1.2 × 10⁻⁴ Ω cm resulting from the increase of the carrier concentration and the mobility.     

Effect of the [Al/Zn] ratio in the starting solution and deposition temperature on the physical properties of sprayed ZnO:Al thin films

Aluminum-doped zinc oxide thin films (ZnO:Al) were deposited on sodocalcic glass substrates by the chemical spray technique, using zinc acetate and aluminum pentanedionate as precursors. The effect of the [Al/Zn] ratio in the starting solution, as well as the substrate temperature, on the physical characteristic of ZnO:Al thin films was analyzed. We have found that the addition of Al to the starting solution decreases the electrical resistivity of the films until a minimum value, located between 2 and 3 at.%; a further increase in the [Al/Zn] ratio leads to an increase in the resistivity. A similar resistivity tendency with the substrate temperature was encountered, namely, as the substrate temperature is increased, a minimum value of around 475 °C in almost all the cases, was obtained. At higher deposition temperatures the film resistivity suffers an increase. After a vacuum-thermal treatment, performed at 400 °C for 1 h, the films showed a resistivity decrease about one order of magnitude, reaching a minimum value, for the films deposited at 475 °C, of 4.3 × 10^− 3 Ω cm.The film morphology is strongly affected by the [Al/Zn] ratio in the starting solution. X-ray analysis shows a (002) preferential growth in all the films. As the substrate temperature increases it is observed a slight increase in the transmittance as well as a shift in the band gap of the ZnO:Al thin films.     

In situ X-ray photoelectron spectroscopy studies of interactions of evaporated metals with electroactive polyaniline films

Transparent conductive aluminum-doped zinc oxide (AZO) films were prepared by an ultrasonic spray pyrolysis method. A vertical type hot wall furnace was used as a reactor in the deposition system Zinc acetate dissolved in methanol was selected as a precursor. The substrate temperature was varied from 180 °C to 240 °C. Aluminum (Al) was doped into ZnO films by incorporating anhydrous aluminum chloride AlCl₃ in the zinc acetate CH₃CO₂)₂Zn solution. The proportion of the Al in the starting solution was varied from 0 wt % to 3.0 wt %. The crystallographic properties and surface morphologies of the films were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The resistivity of the films was measured by the Van der Pauw method, and the mobility and carrier concentration were obtained through Hall effect measurements. Transmittance was measured in the visible region. The effects of substrate temperature and aluminum content in the starting solution on the structural and electrical properties of the AZO films are discussed.     

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.     

Microstructural and optical properties of Ga-doped ZnO semiconductor thin films prepared by sol-gel process

Transparent thin films of Ga-doped ZnO (GZO), with Ga dopant levels that varied from 0 to 7 at.%, were deposited onto alkali-free glass substrates by a sol-gel process. Each spin-coated film was preheated at 300 °C for 10 min, and then annealed at 500 °C for 1 h under air ambiance. The effects of Ga dopant concentrations on crystallinity levels, microstructures, optical properties, and electrical resistivities of these ZnO thin films were systematically investigated. Photoluminescence spectra of GZO thin films were examined at room temperature. XRD results revealed that the undoped ZnO thin films exhibited a preferred orientation along the (002) plane and that the ZnO thin films doped with Ga showed degraded crystallinity. Experimental results also showed that Ga doping of ZnO thin films could markedly decrease surface roughness, improve transparency in the visible range, and produce finer microstructures than those of undoped ZnO thin films. The most promising films for transparent thin film transistor (TTFT) application produced in this study, were the 3 and 5 at.% Ga-doped ZnO thin films, both of which exhibited an average transmittance of 90.6% and an RMS roughness value of about 2.0 nm.     

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.     

Influence of annealing treatments for ZnO-doped Zr0.8Sn0.2TiO4 thin films by RF magnetron sputtering

Zirconium tin titanium oxide doped 1 wt.% ZnO thin films on n-type Si substrate were deposited by rf magnetron sputtering at a fixed rf power of 300 W, a substrate temperature of 450 °C, a deposition pressure of 5 mTorr and an Ar/O₂ ratio of 100/0 with various annealing temperatures and annealing times. Electrical properties and microstructures of 1 wt.% ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films prepared by rf magnetron sputtering on n-type Si(100) substrates at different annealing temperatures (500 °C-700 °C) and annealing times (2 h-6 h) have been investigated. The structural and morphological characteristics analyzed by X-ray diffraction (XRD) and atomic force microscope (AFM) were sensitive to the treatment conditions such as annealing temperature and annealing time. At an annealing temperature of 600 °C and an annealing time of 6 h, the ZnO-doped (Zr_0.8Sn_0.2)TiO₄ thin films possess a dielectric constant of 46 (at f = 10 MHz), a dissipation factor of 0.059 (at f = 10 MHz), and a low leakage current density of 3.8 × 10^− 9 A/cm² at an electrical field of 1 kV/cm.     

衬底温度和氧分压对ZnO：Al薄膜性能的影响研究术

以掺杂质量数为2％的Al2O3：ZnO为靶材,用激光脉冲沉积法,通过改变氧压和衬底温度调整薄膜的性能,制备得到相对优质的ZnO：Al薄膜,采用x射线衍射、紫外-可见分光光度计和霍尔效应测试仪等表征其物相、光学和电学性能,最终得到电阻率为1．27×10^-3Ω／cm^-3、平均光透过率超过80％的透明导电薄膜。     

Effect of annealing temperature on growth of Ce-ZnO nanocomposite thin films: X-ray photoelectron spectroscopy study

Ce-doped ZnO nanocomposite thin films with Ce/Zn ratio fixed at optimum value (10 at.%) have been prepared via sol-gel method at different annealing temperatures varied from 180 to 500 °C. The synthesized samples were characterized employing atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) techniques. According to AFM analysis, the average grain size increased from about 70 nm to 150 nm by increasing the annealing temperature from 300 to 500 °C. Moreover, based on the XPS data analysis, it was found that three major metal ions namely Ce³⁺, Ce⁴⁺, and Zn²⁺ coexist on the surface of the nanocomposite films. XPS data analysis also revealed that Ce³⁺ ion is oxidized to Ce⁴⁺ ion with increasing annealing temperature. Due to oxidation, the ratio of [Ce^3±]/[Ce total] changed from 68.8 to 38.1% by increasing the annealing temperature from 180 to 500 °C. In addition, the Ce/Zn ratio increased from 0.21 to 0.42 when increasing the annealing temperature from 180 to 500 °C indicating migration of Ce ions toward the surface at higher temperatures. Finally, the XRD measurements determined that the ZnO thin films have a hexagonal wurtzite structure and CeO₂ crystallites are formed at 500 °C in the Ce-doped ZnO nanocomposite thin films.     

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.     

Growth and characterization of non-polar ZnO thin films by pulsed laser deposition

Non-polar ZnO thin films were fabricated on r-plane sapphire substrates by pulsed laser deposition at various temperatures from 100 to 500 °C. The effects of the substrate temperature on structural, morphological and optical properties of the films were investigated. Based on the X-ray diffraction analysis, the ZnO thin films grown at 300, 400 and 500 °C exhibited the non-polar (a-plane) orientation and those deposited below 300 °C exhibited polar (c-plane) orientation. In the optical properties of non-polar ZnO films, there were two photoluminescence peaks detected. The peaks (near-band edge emission, blue emission) are due to electron transitions from band-to-band and shallow donor level to valence band, respectively.     

ZnO∶Al薄膜制备及光电性能研究

利用溶胶-凝胶法在玻璃基板上制备了Al/Zn原子掺杂比例为0～0.25的掺铝氧化锌(ZnO∶Al或AZO)薄膜,随后分别将其在空气,氧气和氮气3种不同气氛中退火处理,研究了薄膜的光学、电学与结构方面的性质.X射线衍射分析表明AZO薄膜是具有c轴择优取向的六方纤锌矿结构多晶体;通过紫外-可见光分光计测定表明该薄膜在可见光范围内具有>80%的高透过率,随着铝掺杂比例的增大光学能隙增大且吸收边向短波方向移动.     

Al掺杂ZnO薄膜的制备及其电学性能研究

采用溶胶-凝胶法在玻璃基底上制备掺杂铝的氧化锌薄膜.研究了不同的铝掺杂浓度、薄膜厚度以及退火温度对电阻率的影响,结果表明掺杂铝摩尔分数为2%、退火温度在550℃时电阻率最低,电阻率随着薄膜厚度的增加而减小.通过XRD和SEM对薄膜的组织结构和形貌进行了表征,结果表明样品表面相对平整、致密,AZO薄膜保持着ZnO六角纤锌矿结构,说明了Al原子对Zn原子的有效替位.