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 Cu layer thickness on the structural, optical and electrical properties of AZO/Cu/AZO tri-layer films

Highly conducting AZO/Cu/AZO tri-layer films were successfully deposited on glass substrates by RF magnetron sputtering of Al-doped ZnO (AZO) and ion-beam sputtering of Cu at room temperature. The microstructures of the AZO/Cu/AZO multilayer films were studied using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and atomic force microscope (AFM). X-Ray diffraction measurements indicate that the AZO layers in the tri-layer films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. With the increase of Cu thickness, the crystallinity of AZO and Cu layers is simultaneously improved. When the Cu thickness increases from 3 to 13 nm, the resistivity decreases initially and then varies little, and the average transmittance shows a first increase and then decreases. The maximum figure of merit achieved is 1.94 × 10⁻² Ω⁻¹ for a Cu thickness of 8 nm with a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84%.     

Effects of substrate on the structural, electrical and optical properties of Al-doped ZnO films prepared by radio frequency magnetron sputtering

Transparent and conductive Al-doped ZnO (AZO) thin films were deposited on substrates including alkali-free glass, quartz glass, Si, and SiO₂ buffer layer on alkali-free glass by using radio frequency magnetron sputtering. The effects of different substrates on the structural, electrical and optical properties of the AZO films were investigated. It was found that the crystal structures were remarkably influenced by the type of the substrates due to their different thermal expansion coefficients, lattice mismatch and flatness. The AZO film (100 nm in thickness) deposited on the quartz glass exhibited the best crystallinity, followed sequentially by those deposited on the Si, the SiO₂ buffer layer, and the alkali-free glass. The film deposited on the quartz glass showed the lowest resistivity of 5.14 × 10^− 4 Ω cm among all the films, a carrier concentration of 1.97 × 10²¹ cm^− 3 and a Hall mobility of 6.14 cm²/v·s. The average transmittance of this film was above 90% in the visible light spectrum range. Investigation into the thickness-dependence of the AZO films revealed that the crystallinity was improved with increasing thickness and decreasing surface roughness, accompanied with a decrease in the film resistivity.     

Effects of sputtering pressure and Al buffer layer thickness on properties of AZO films grown by rf magnetron sputtering

Transparent and conductive Al-doped (2 wt.%) zinc oxide (AZO) films were deposited on inexpensive soda-lime glass substrates by using rf magnetron sputtering at room temperature. This study analyzed the effects of argon sputtering pressure, which varied in the range from 0.46 to 2.0 Pa, on the morphological, electrical and optical properties of AZO films. The only (0 0 2) diffraction peak of the film were observed at 2θ～34.45°, exhibiting that the AZO films had hexagonal ZnO wurtzite structure, and a preferred orientation with the c-axis perpendicular to the substrate. By applying a very thin aluminum buffer layer with the thickness of 2 nm, findings show that the electrical resistivity was 9.46 × 10⁻⁴ Ω-cm, and the average optical transmittance in the visible part of the spectra was approximately 81%. Furthermore, as for 10 nm thick buffer layer, the electrical resistivity was lower, but the transmittance was decreased.     

Effect of inserting a buffer layer on the characteristics of transparent conducting impurity-doped ZnO thin films prepared by dc magnetron sputtering

In transparent conducting impurity-doped ZnO thin films prepared on glass substrates by a dc magnetron sputtering (dc-MS) deposition, the obtainable lowest resistivity and the spatial resistivity distribution on the substrate surface were improved by a newly developed MS deposition method. The decrease of obtainable lowest resistivity as well as the improvement of spatial resistivity distribution on the substrate surface in Al- or Ga-doped ZnO (AZO or GZO) thin films were successfully achieved by inserting a very thin buffer layer, prepared using the same MS apparatus with the same target, between the thin film and the glass substrate. The deposition of the buffer layer required a more strongly oxidized target surface than possible to attain during a conventional dc-MS deposition. The optimal thickness of the buffer layer was found to be about 10 nm for both GZO and AZO thin films. The resistivity decrease is mainly attributed to an increase of Hall mobility rather than carrier concentration, resulting from an improvement of crystallinity coming from insertion of the buffer layer. Resistivities of 3 × 10^− 4 and 4 × 10^− 4Ω cm were obtained in 100 nm-thick-GZO and AZO thin films, respectively, incorporating a 10 nm-thick-buffer layer prepared at a substrate temperature around 200 °C.     

Highly transparent conductive and near-infrared reflective ZnO:Al thin films

Al-doped ZnO (AZO) thin films have been prepared on glass substrates by pulsed laser deposition. The structural, optical, and electrical properties were strongly dependent on the growth temperatures. The lowest resistivity of 4.5 × 10⁻⁴ Ωcm was obtained at an optimized temperature of 350 °C. The AZO films deposited at 350 °C also had the high optical transmittance above 87% in the visible range and the low transmittance (<15% at 1500 nm) and high reflectance (∼50% at 2000 nm) in the near-IR region. The good IR-reflective properties of ZnO:Al films show that they are promising for near-IR reflecting mirrors and heat reflectors.     

Structural, optical and electrical properties of AZO/Cu/AZO tri-layer films prepared by radio frequency magnetron sputtering and ion-beam sputtering

Highly conducting tri-layer films consisting of a Cu layer sandwiched between Al-doped ZnO (AZO) layers (AZO/Cu/AZO) were prepared on glass substrates at room temperature by radio frequency (RF) magnetron sputtering of AZO and ion-beam sputtering of Cu. The tri-layer films have superior photoelectric properties compared with the bi-layer films (Cu/AZO, AZO/Cu) and single AZO films. The effect of AZO thickness on the properties of the tri-layer films was discussed. The X-ray diffraction spectra show that all films are polycrystalline consisting of a Cu layer with the cubic structure and two AZO layers with the ZnO hexagonal structure having a preferred orientation of (0 0 2) along the c-axis, and the crystallite size and the surface roughness increase simultaneously with the increase of AZO thickness. When the AZO thickness increases from 20 to 100 nm, the average transmittance increases initially and then decreases. When the fixed Cu thickness is 8 nm and the optimum AZO thickness of 40 nm was found, a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84% in the wavelength range of visible spectrum of tri-layer films have been obtained. The merit figure (F_TC) for revaluing transparent electrodes can reach to 1.94 × 10⁻² Ω⁻¹.     

Highly conductive alumina-added ZnO ceramic target prepared by reduction sintering and its effects on the properties of deposited thin films by direct current magnetron sputtering

To obtain a suitable sputtering target for depositing transparent conducting Al-doped ZnO (AZO) films by using direct current (DC) magnetron sputtering, this study investigates the possibility of using atmosphere controlled sintering of Al₂O₃ mixed ZnO powders to prepare highly conductive ceramic AZO targets. Experimental results show that a gas mixture of Ar and CO could produce a sintered target with resistivity in the range of 2.23 × 10^− 4 Ω cm. The fairly low resistivity was mainly achieved by the formation of both aluminum substitution (Al_Zn) and oxygen vacancy (V_O), thus greatly increasing the carrier concentration. Compared to usual air sintered target, the thin film deposited by the Ar + CO sintered target exhibited lower film resistivity and more uniform spatial distribution of resistivity. A film resistivity as low as 6.8 × 10^− 4 Ω cm was obtained under the sputtering conditions of this study.     

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.     

Al-doped ZnO (AZO) films deposited by reactive sputtering with unipolar-pulsing and plasma-emission control systems

Al-doped ZnO (AZO) films were deposited on fused silica glass substrates unheated or heated at 200 °C by reactive dc sputtering using a Zn-Al alloy target with mid-frequency pulsing (50 kHz) and the plasma control unit with a feedback system of the optical emission intensity of the atomic O* line at 777 nm to control oxygen gas flow. The stable and reproducible depositions were successfully carried out in the transition region. The deposition rates attained in this study were about 10-20 times higher than the one by conventional sputtering using oxide targets. The AZO films with the lowest resistivity of 3.8 × 10^− 4 Ω cm was deposited on the substrate heated at 200 °C with a sputter power of 4 kW, where the deposition rate was 385 nm/min.     

Indium tin oxide films deposited by thermionic-enhanced DC magnetron sputtering on unheated polyethylene terephthalate polymer substrate

Indium tin oxide thin films were deposited onto polyethylene terephthalate substrates via thermionic enhanced DC magnetron sputtering at low substrate temperatures. The structural, optical and electrical properties of these films are methodically investigated. The results show that compared with traditional sputtering, the films deposited with thermionic emission exhibit higher crystallinity, and their optical and electrical properties are also improved. Indium tin oxide films deposited by utilizing thermionic emission exhibit an average visible transmittance of 80% and an electrical resistivity of 4.5 × 10⁻⁴ Ω cm, while films made without thermionic emission present an average visible transmittance of 74% and an electrical resistivity of 1.7 × 10⁻³ Ω cm.     

Substrate temperature dependence of the properties of Ga-doped ZnO films deposited by DC reactive magnetron sputtering

Ga-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The influence of substrate temperature on the structural, electrical, and optical properties of ZnO:Ga films was investigated. The X-ray diffraction (XRD) studies show that higher temperature helps to promote Ga substitution more easily. The film deposited at 350 °C has the optimal crystal quality. The morphology of the films is strongly related to the substrate temperature. The film deposited is dense and flat with a columnar structure in the cross-section morphology. The transmittance of the ZnO:Ga thin films is over 90%. The lowest resistivity of the ZnO:Ga film is 4.48×10⁻⁴ Ω cm, for a film which was deposited at the substrate temperature of 300 °C.     

Improvements of spatial resistivity distribution in transparent conducting Al-doped ZnO thin films deposited by DC magnetron sputtering

The relationship between two techniques developed for improving the resistivity distribution on the substrate surface in transparent conducting Al-doped ZnO (AZO) thin films prepared at a temperature of 200 °C by dc magnetron sputtering depositions (dc-MSD) using various sintered AZO targets has been investigated. One improvement method superimposes an rf component onto the dc-MSD (rf + dc-MSD). The other improvement method uses conventional dc-MSD with a low resistivity AZO target prepared under optimized conditions. An improvement of resistivity distribution resulted from a decrease in the resistivity of targets used in the preparation of AZO thin films by dc-MSD either with or without superimposing rf power. However, the resistivity distribution of AZO thin films resulting from depositions using rf-superimposed dc-MSD with lower-resistivity targets was not significantly improved over that of AZO thin films prepared by conventional dc-MSD using targets with the same low resistivities. The use of rf superimposition only resulted in improved resistivity distribution in thin films when the AZO targets had a resistivity higher than around 1 × 10^− 3 Ω cm. It should be noted that sintered AZO targets optimized for the preparation of AZO thin films with lower resistivity as well as more uniform resistivity distribution on the substrate surface tended to exhibit a lower resistivity.     

室温下射频磁控溅射制备ZnO:Al透明导电薄膜及其性能研究

采用射频磁控溅射技术,在室温下,以ZnO:Al2O3(2%Al2O3(质量比))为靶材,在石英玻璃基底上,采用不同工艺条件制备了ZnO:Al(AZO)薄膜。使用扫描电子显微镜观察了薄膜的表面形貌,X射线衍射分析了薄膜的结构,四探针测量仪得到薄膜的表面电阻,轮廓仪测量了薄膜厚度,并计算了电阻率,最后采用分光光度计测量了薄膜的透过率;研究了溅射功率、溅射气压与薄膜厚度对薄膜电阻率及透过率的影响。结果表明:所制备的AZO薄膜具有(002)择优取向,并且发现薄膜厚度对薄膜的光电性能有明显影响,溅射气压和溅射功率对薄膜电学性能有较大影响,但是对薄膜透过率影响不大。当功率为1kW、溅射气压0.052Pa、AZO薄膜厚度为250nm时,其电阻率为8.38×10-4Ω·cm,波长在550nm处透过率为89%,接近基底的本底透过率92%。当薄膜厚度为1125 nm时薄膜的电阻率降至最低(6.16×10-4Ω·cm)。     

Electrical mechanism analysis of Al2O3 doped zinc oxide thin films deposited by rotating cylindrical DC magnetron sputtering

Cost efficient and large area deposition of superior quality Al₂O₃ doped zinc oxide (AZO) films is instrumental in many of its applications, including solar cell fabrication due to its numerous advantages over indium tin oxide (ITO) films. In this study, AZO films were prepared by a highly efficient rotating cylindrical direct current (DC) magnetron sputtering system using an AZO target, which has a target material utilization above 80%, on glass substrates in argon (Ar) ambient. A detailed analysis on the electrical, optical, and structural characteristics of AZO thin films was performed for the solar cell, as well as display applications. The properties of films were found to critically depend on deposition parameters, such as sputtering power, substrate temperature, working pressure, and film thickness. A low resistivity of ~ 5.5 × 10^− 4 Ω cm was obtained for films deposited at 2 kW, keeping the pressure, substrate temperature and thickness constant at 3 mTorr, 230 °C and ~ 1000 nm respectively. This was due to an increase in carrier mobility and large grain size. Mobility is found to be controlled by ionized impurity scattering within the grains, since the mean free path of carriers is much smaller than the grain size of the films. The AZO films showed a high transparency of ~ 90% in the long wavelength region. Our results offer a cost-efficient AZO film deposition method that can fabricate films with significant low resistivity and high transmittance that can be applied in thin-film solar cells, as well as thin film transistor (TFT) and non-volatile memory (NVM).     

Structural and optoelectronic properties of Al-doped zinc oxide films deposited on flexible substrates by radio frequency magnetron sputtering

Al-doped zinc oxide (AZO) thin films were deposited onto flexible polyethylene terephthalate substrates, using the radio frequency (RF) magnetron sputtering process, with an AZO ceramic target (The Al₂O₃ content was about 2 wt.%). The effects of the argon sputtering pressure (in the range from 0.66 to 2.0 Pa), thickness of the Al buffer layer (thickness of 2, 5, and 10 nm) and annealing in a vacuum (6.6 × 10^− 4 Pa), for 30 min at 120 °C, on the morphology and optoelectronic performances of AZO films were investigated. The resistivity was 9.22 × 10^− 3 Ω cm, carrier concentration was 4.64 × 10²¹ cm^− 3, Hall mobility was 2.68 cm²/V s and visible range transmittance was about 80%, at an argon sputtering pressure of 2.0 Pa and an RF power of 100 W. Using an Al buffer decreases the resistivity and optical transmittance of the AZO films. The crystalline and microstructure characteristics of the AZO films are improved by annealing.     

The properties of Al doped ZnO thin films deposited on various substrate materials by RF magnetron sputtering

Transparent conductive Al-doped ZnO (AZO) thin films were deposited on various substrates including glass, polyimide film (PI) and stainless steel, using radio frequency magnetron sputtering method. The structural, electrical and optical properties of AZO thin films grown on various substrates were systematically investigated. We observe that substrate materials play important roles in film crystallization and resistivity but little on optical transmittance. X-ray diffractometer study shows that all obtained AZO thin films have wurtzite phase with highly c-axis preferred orientation, and films on glass present the strongest (002) diffraction peaks. The presence of compression stress plays critical role in determining the crystalline structure of AZO films, which tends to stretch the lattice constant c and enlarge the (002) diffraction angle. Although the films on the glass present the finest electrical properties and the resistivity reaches 12.52 × 10-4 Ωm, AFM study manifests that films on flexible substrates, especially stainless steel, bestrew similar inverted pyramid structure which are suitable for window material and electrode of solar cells. The average optical transmittance of AZO thin films deposited on glass and PI are both around 85% in the visible light range (400–800 nm).     

Effect of target properties on transparent conducting impurity-doped ZnO thin films deposited by DC magnetron sputtering

For the purpose of using transparent conducting impurity-doped ZnO thin films in liquid crystal display (LCD) applications, the relationship between the properties of dc magnetron sputtering (dc-MS) deposited thin films and the properties of the oxide targets used to produce them is investigated. Both Al-doped and Ga-doped ZnO (AZO and GZO) thin films were deposited on glass substrates using a dc-MS apparatus with various high-density sintered AZO or GZO disk targets (diameter of about 150 mm); the target and substrate were both fixed during the depositions. Using targets with a lower resistivity results in attaining more highly stable dc-MS depositions with higher deposition rates and lower arcing. In addition, dc-MS depositions using targets with a lower resistivity produced improvements in resistivity distribution on the substrate surface. It was found that the oxygen content in deposited thin films decreased as the oxygen content of the target used in the deposition was decreased. As a result, the dc-MS deposition of transparent conducting impurity-doped ZnO thin films suitable for LCD applications requires the preparation of significantly reduced AZO and GZO targets with low oxygen content.     

Physical properties of hydrogenated Al-doped ZnO thin layer treated by atmospheric plasma with oxygen gas

Hydrogenated Al-doped ZnO (H:AZO) thin films were deposited on glass substrates at room temperature by radio-frequency magnetron sputtering at various hydrogen flow rates. The addition of hydrogen improved the resistivity of the H:AZO films significantly. A thin insulating layer was produced on H:AZO films by atmospheric pressure plasma with Ar/O₂ reactive gas. The resistivity degenerated and the optical band gap of the oxygen plasma-treated H:AZO films decreased from 3.7 eV to 3.4 eV. This was attributed to a decrease in the hydrogen concentration at the film surface according to elemental depth analysis.     

Optimization of sputtering parameters for deposition of Al-doped ZnO films by rf magnetron sputtering in Ar + H2 ambient at room temperature

The effects of sputtering pressure and power on structural and optical-electrical properties of Al-doped ZnO films were systemically investigated at substrate temperature of room temperature and H₂/(Ar + H₂) flow ratio of 5%. The results show that carrier concentration and mobility of the films show nonmonotone change due to the evolution of microstructure and lattice defect of the films caused by introduction of H₂ with increasing sputtering pressure and power. The transmittance of the films is also found to be related to the introduction of H₂ in addition to usually considered surface roughness and crystallinity. Finally, optimized sputtering pressure and power are 0.8 Pa and 100 W, respectively, and obtained minimum resistivity and highest transmittance are 1.43 × 10^− 3 Ω·cm and 90.5%, respectively. In addition, it is found that E_g of the films is mainly controlled by the carrier concentration, but crystallite size and stress should also be considered for the films deposited at different powers.