Synthesis of high-quality AZO polycrystalline films via target bias radio frequency magnetron sputtering

The deposition rate, transmittance and resistivity of aluminium-doped zinc oxide (AZO) films deposited via radio frequency (r.f.) sputtering change with target thickness. An effective method to control and maintain AZO film properties was developed. The strategy only involved the regulation of target bias voltage of r.f. magnetron sputtering system. The target bias voltage considerably influenced AZO film resistivity. The resistivity of the as-deposited AZO film was 9.82×10⁻⁴ Ω cm with power density of 2.19 W/cm² at target self-bias of −72 V. However, it decreased to 5.98×10⁻⁴ Ω cm when the target bias voltage was increased to −112 V by applying d.c. voltage. Both growth rate and optical band gap of AZO film increased with the absolute value of target bias voltage – growth rate increased from 10.54 nm/min to 25.14 nm/min, and band gap increased from 3.57eV to 3.71 eV when target bias voltage increased from −72 V to −112 V at r.f. power density of 2.19 W/cm². The morphology of AZO films was slightly affected by the target bias voltage. Regulating target bias voltage is an effective method to obtain high-quality AZO thin films deposited via r.f. magnetron sputtering. It is also a good choice to maintain the quality of AZO film in uptime manufacturing deposition.     

Preparation and optical properties of W-doped VO2/AZO bilayer composite film

In order to improve its visible light transmittance, W-doped VO₂ thin film was prepared with direct current (DC) reactive magnetron sputtering on the surface of Al-doped ZnO (AZO) thin film deposited on quartz glass substrate in advance with radio frequency (RF) magnetron sputtering. The effects of sputtering power for AZO film were investigated on the crystal structures, surface morphologies and optical properties of AZO thin film and W-doped VO₂/AZO bilayer composite film. The results show that the crystallinity of both AZO monolayer film and the bilayer film first increases and then decreases with the increase of sputtering power. As the sputtering power increases, the film thickness increases. The integral visible luminous transmittance (T_lum) of the W-doped VO₂/AZO bilayer film decreases continuously, and the solar modulation efficiency (ΔT_sol) increases first and then decreases. When the sputtering power is 150 W, T_lum and ΔT_sol of W-doped VO₂/AZO bilayer film are 30.14% and 11.95%, 2.77% and 1.71% higher than those of W-doped VO₂ monolayer film, respectively.     

Influence of ZnO buffer layer on AZO film properties by radio frequency magnetron sputtering

Transparent conductive films of Al-doped zinc oxide (AZO) were deposited on glass substrates under various ZnO buffer layer deposition conditions (radio frequency (r.f.) power, sputtering pressure, thickness, and annealing) using r.f. magnetron sputtering at room temperature. This work investigates the influence of ZnO buffer layer on structural, electrical, and optical properties of AZO films. The use of grey-based Taguchi method to determine the ZnO buffer layer deposition processing parameters by considering multiple performance characteristics has been reported. Findings show that the ZnO buffer layer improves the optoelectronic performances of AZO films. The AZO films deposited on the 150-nm thick ZnO buffer layer exhibit a very smooth surface with excellent optical properties. Highly c-axis-orientated AZO/ZnO/glass films were grown. Under the optimized ZnO buffer layer deposition conditions, the AZO films show lowest electrical resistivity of 6.75 × 10⁻⁴ Ω cm, about 85% optical transmittance in the visible region, and the best surface roughness of R_a = 0.933 nm.     

Deposition and characterization of AZO thin films on flexible glass substrates using DC magnetron sputtering technique

Al-doped zinc oxide (AZO) thin films were deposited onto flexible ultra-thin glass substrates by using a direct current (DC) magnetron sputtering process. The effects of sputtering power, working pressure and substrate temperature on the morphology and optoelectronic performances of AZO films were investigated. The optimal sputtering power, working pressure and substrate temperature for AZO film were determined to be 100 W, 0.9 Pa and 150 ℃, respectively. Further increasing or decreasing the sputtering power, working pressure and substrate temperature degrades the quality of AZO films. XRD patterns show all as-sputtered AZO thin films are preferred to grow along <0002> direction. Moreover, the largest grain size, which depicts the best microstructure of AZO films, matches with the smallest stress value. It can be seen from SEM images that the surface is smooth and dense. The smallest value of the resistivity is 1.784×10⁻³ Ω cm and the average transmittance of all AZO films in the visible range is about 80%. The X-ray photoelectron spectroscopy spectra show that the amount of Al element in the AZO film is very small.     

Enhancing optical and electrical properties of Al-doped ZnO coated polyethylene terephthalate substrates by laser annealing using overlap rate controlling strategy

Aluminum-doped zinc oxide (AZO) layers were deposited on polyethylene terephthalate (PET) flexible substrates and optimized by laser annealing using a 532 nm nanosecond pulsed laser. Effects of overlap rates, i.e. laser spot overlap rate (SO_R) and laser scan line overlap rate (LO_R), on AZO/PET films were investigated by X-ray diffractometer (XRD), scanning electron microscope (SEM), UV–visible transmittance spectra and digital four-point probe instrument, respectively. Laser annealing could greatly enhance grain crystallinity, increase crystallite size and avoid damage to the PET flexible substrates, thus effectively enhance transmittance and conductivity of the films. The results showed that the AZO/PET film annealed by using 85% SO_R and 60% LO_R presented the highest average visible transmittance of 76.2% and the lowest resistivity of 1.95×10⁻³ Ω cm, which respectively improved by approximately 23% and 75% compared to those of the as-deposited AZO/PET film. This work may be of great importance from the viewpoint of performance optimization of transparent conductive oxide (TCO) flexible films.     

Room temperature preparation of high performance AZO films by MF sputtering

Aluminum-doped zinc oxide (AZO) thin films have been deposited by MF magnetron sputtering from a ceramic oxide target without heating the substrates. This study has investigated effects of sputtering power on the structural, electrical and optical properties of the AZO films. The films delivered a hexagonal wurtzite structure with (002) preferential orientation and uniform surface morphology with 27–33 nm grain size. The results indicate that residual stress and grain size of the AZO films are dependent on sputtering power. The minimum resistivity of 7.56×10^?4 Ω cm combined with high transmittance of 83% were obtained at deposited power of 1600 W. The films delivered the advantages of a high deposition rate at low substrate temperature and should be suitable for the fabrication of low-cost transparent conductive oxide layer.     

Study of Cu-based Al-doped ZnO multilayer thin films with different annealing conditions

AZO/Cu/AZO multilayer thin films produced under different annealing conditions are studied in this paper, to examine the effects of atmosphere and annealing temperature on their optical and electrical properties. The multilayer thin films are prepared by simultaneous RF magnetron sputtering (for AZO) and DC magnetron sputtering (for Cu). The thin films were annealed in a vacuum or an atmosphere of oxygen at temperatures ranging from 100 to 400 °C in steps of 100 °C for 3 min. High-quality multilayer films (at Cu layer thickness of 15 nm) with resistivity of 1.99×10⁻⁵ Ω-cm and maximum optical transmittance of 76.23% were obtained at 400 °C annealing temperature in a vacuum. These results show the films to be good candidates for use as high quality electrodes in various displays applications.     

AZO导电薄膜的研究进展及应用

综述了透明导电薄膜的性能、种类、制备工艺、研究及应用状况,重点讨论了掺铝氧化锌(AZO)薄膜的结构、导电机理、光电性能和当前的研究焦点,指出了需要进一步从材料选择、制备工艺的研究、多层膜光学设计等方面提高透明导电薄膜的综合性能,以满足尖端技术的需要.     

High-performance indium-free flexible transparent ATO/Au/ATO tri-layer films by magnetron sputtering

Due to the scarcity of indium (In) in the earth and its potential harm to individuals, the development of In-free transparent conductive film is considered crucial. In this work, In-free SnO₂:Sb/Au/SnO₂:Sb (ATO/Au/ATO, SAS) tri-layer films with high transparency and conductivity were successfully prepared on polycarbonate (PC) substrates by RF and DC magnetron sputtering at room temperature. The influence of the Au layer thickness on microstructure, electrical and optical performances was systematically studied after fixing the ATO thickness to 50 nm. It was indicated by X-ray diffraction patterns that ATO is amorphous and Au is oriented along (111). The trend of increasing and then decreasing light transmission with Au layer thickness was observed in both experimental and simulation results. The improved figure of merit (FoM, 1.89 × 10^?2 Ω^?1) was achieved in SAS tri-layer film, the resistivity and average transmittance of which was lowered to 7.50 × 10^?5 Ω cm and 81.4%, respectively, when Au layer thickness is 11 nm. Moreover, the mechanism of the variation of optical and electrical properties at different Au layer thickness was proposed. Particularly, the SAS tri-layer films also exhibit superior flexibility, durability and adhesion. These results demonstrate SAS tri-layer films are promising alternative to ITO in flexible electronics applications.     

Solution processed,vertically aligned,AZO nanocolumn array for chemiresistive sensor application with UV-enhanced sensitivity

In this work, a wide and highly sensitive chemiresistive sensor has been developed based on the AZO nanocolumn array film. This is meant for the room detection of H₂O₂ under UV illumination. A cost-effective one step multi-layers growth process was adopted for the synthesis of the AZO nanocolumn array. The experimental studies were done by scanning electron microscopy (SEM), transmission and electron microscopy (TEM).Then X-ray diffraction confirmed that the AZO column array was closely packed, connected, vertically aligned, and polycrystalline, with a high surface area. This structure ensures better electrical conduction over random and separated nanostructures. The hall-effect measurement indicates that the AZO film was n-type, with high conductivity (3.60 × 10³ Ωcm), high carrier density (11.3 × 10²⁰cm⁻³) and with acceptable mobility (0.95 cm²/Vs). The x-ray photoemission spectroscopy suggests that the AZO film consists of a large amount of adsorbed oxygen-related species at the sheath layer of the thin-film, which is vital for sensors. By the UV light activation, sensors based on the AZO nanocolumn array exhibited enhanced H₂O₂ detection properties at room temperature. At a concentration from 15 μM to 30 mM, H₂O₂ sensitivity evaluated by relative response was remarkably increased from 15% to 36%. The operation under ambient conditions and wide range sensing shows that this chemiresistive AZO sensor is adequate for biomedical and environmental applications.     

Sputtered AZO Thin Films for TCO and Back Reflector Applications in Improving the Efficiency of Thin Film a-Si:H Solar Cells

We report the properties of Al doped ZnO (AZO) thin films on glass substrates and its effect on the efficiency of amorphous silicon (a-Si:H) solar cells as the back reflector. Oriented AZO thin films were grown using DC magnetron sputtering by varying Ar gas flow rates. The influence of Ar flow rate on the structural, electrical and optical properties of AZO thin films suitable for transparent conducting oxide (TCO) and back reflector applications was investigated. The (a-Si:H) solar cells, with and without AZO back reflector, were fabricated on FTO coated glass substrates using the PECVD technique. The solar cells were tested using a Sun simulator under AM 1.5 condition. Enhancement in current density from 12.46 to 14.24 mA/cm² with the AZO back reflector was observed, thereby increasing the efficiency of the solar cell from 6.38 to 7.82 %, respectively.     

Fabrication and thermo stability of the SnO2/Ag/SnO2 tri-layer transparent conductor deposited by magnetic sputtering

Using the magnetic sputtering technique, the SnO₂/Ag/SnO₂ tri-layer transparent films were fabricated on float glasses successfully. Compared with the commercial FTO (F-doped SnO₂) film, the SnO₂/Ag/SnO₂ tri-layer films have higher visible-light transmittance and better conductivity. The total thickness of the SnO₂/Ag/SnO₂ films is one third of the commercial FTO film leading to the high visible-light transmittance. The high carrier concentration of the SnO₂/Ag/SnO₂ films contributes to the tri-layer films’ low resistivity. In addition, to further improve the performance of the SnO₂/Ag/SnO₂ tri-layer films, samples were annealed under different temperatures. The results illustrate that the lowest sheet resistance (5.92 Ω/sq) and the highest visible-light transmittance (87.0%) were obtained after annealing at 200 °C. Furthermore, the thermal stability of the films could be enhanced by a multi-step annealing process due to the recrystallization effect.     

Facile synthesis of metal organic decomposition Al-doped ZnO ink for inkjet printing and fabrication of highly transparent conductive film

In this paper, a MOD (Metal organic decomposition) Al doped ZnO (AZO) ink was directly used for inkjet printing transparent and conductive AZO films. The ink was synthesized by using zinc acetate dihydrate and aluminum nitrate nonahydrate as precursor, 1,2-diaminopropane as a complexing agent, ethyl alcohol as solution, ethyl cellulose as addition agent. The thermal decomposition behavior of the MOD ink was investigated. The various MOD AZO inks were inkjet printed and heated at different temperatures for different times. The films were studied by X-ray diffraction, scanning electron microscopy, resistivity measurements and ultraviolet–visible spectroscopy. The results demonstrated that 0.2 M AZO (2 at%) film heated at 250 °C for 120 min showed highly preferential growth along the c-axis, uniform microstructure with a resistivity of 0.03 Ω cm and high transmittance more than 90% in the visible range of the spectrum with an optical band gap at 3.326 eV.     

Optical and electrical properties of Al doped ZnO thin film with preferred orientation in situ grown at room temperature

To optimize the process and obtain highly conducting and transparent Aluminum-doped zinc oxide (AZO) thin films, AZO films were deposited on glass substrates at room temperature by Radio-frequency (RF) magnetron sputtering with various Argon flow rates. The influences of Argon flow rate on structure, morphology, optical, electrical and photoluminescence properties of AZO films were investigated by varying the Argon flow rate from 36 to 68 sccm. The best quality AZO film with resistivity 1.39 × 10⁻³ Ω cm, sheet resistance 8.2 Ω/sq and 84.2% average visible transmittance was prepared at 44 sccm for 30 min. Also, the self-heating effect of target was investigated by preparing AZO films for 10 min and 20 min at 44 sccm, 180 W and 1.0 Pa. The influence of increasing structural quality actually affected by Argon flow rate was more prominent on carrier concentration than mobility. The schematic illustration of microstructural evolution was proposed. The average growth rate of around 60 nm/min demonstrated the self-heating effect of target was weak and could be ignored.     

The Sintering Trajectory and Electrical Properties of Niobium‐Doped Titania Sputtering Targets

Nb‐doped TiO₂ (TNO) films, which are highly conductive and transparent, can be used as transparent conductive oxide (TCO) films. A predominant manufacturing method for TCO film is magnetron sputtering, and the material of the sputtering target affects the performance of the film. The objective of this study was to investigate the sintering densification, microstructure, and electrical properties of TNO and TiO₂ sputtering targets. The results showed that the segregation of Nb at the grain boundary in TNO helps to facilitate densification and inhibit grain growth. After 1200°C sintering, the sintered density of TNO target achieves almost 100% of the theoretical density. Moreover, the Nb₂O₅ additive greatly improves the electrical properties, decreasing the resistivity of TiO₂ from >10⁸ Ωcm to 4.6 × 10¹ Ωcm. Correlations between TNO sputtering target investigated in this study and TNO sputtered film reported in the literature are also preliminarily established. The resistivity of TNO film with an anatase structure is obviously lower than that of TNO target with a rutile structure.     

Damp-heat durability comparison of Al-doped ZnO transparent electrodes deposited at low temperatures on glass and PI-tape/PC substrates

Durability performances are compared for Al-doped ZnO (AZO) transparent electrodes deposited on hard slide-glass and flexible polyimide-tape attached to polycarbonate (PI-tape/PC) substrates. To identify the appropriate sputtering configuration, the AZO thin films are first deposited on the glass substrates via reactive RF-magnetron sputtering under 90 sccm of argon gas and 3 sccm of oxygen gas at room temperature (RT) with 83 to 90 W of RF power for 30 min. When deposited, only the sputtering configuration with 85 W of RF power could produce the AZO films with acceptable optoelectrical properties for transparent electrodes: 80% average visual transparency and 10 Ω/□ at the thickness of 1.1 μm. The temperature at the surface of the substrates rises from RT to 88 °C due to the sputtering with 85W of RF power for 30 min, and this configuration is successfully conducted for AZO film depositions on both the glass and PI-tape/PC substrates. After exposure to a damp-heat (DH) test at 85 °C and 85% relative humidity (RH) for 25 days, the conductivity of the AZO films on the PI-tape/PC substrates is significantly degraded: many cracks are visible on the films, significantly decreasing the Hall mobility. Conversely, the films deposited on the glass substrates exhibit durable high conductivity, no cracks, and excellent stability of the Hall mobility. Despite this significant difference in Hall mobility evolution, the films on both substrates show similar patterns of a slight decrease in carrier concentrations, suggesting that chemical characteristics, extensively reported as the key for the DH degradation of AZO films, are less involved in this durability study featuring AZO films prepared via a low oxygen-to-argon gas ratio of reactive sputtering at low temperatures.     

Transparent and high infrared reflection film having sandwich structure of SiO2/Al:ZnO/SiO2

New transparent and high infrared reflection films having the sandwich structure of SiO₂/Al:ZnO(AZO)/SiO₂ were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO₂ (110 nm)/AZO (860 nm)/SiO₂ (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO₂ film can diminish the interference coloring and increase transparency; the inner SiO₂ film improves the adhesion of the coating to the glass substrate and prevents Ca²⁺ and Na⁺ in the glass substrate from entering the AZO film.     

不同衬底上ZnO:Al透明导电薄膜的性能

室温下,采用射频磁控溅射法在玻璃和聚对苯二甲酸乙二醇酯（polyethylene terephthalate,PET）上沉积了掺铝的氧化锌（ZnO：Al,AZO）透明导电薄膜。通过X射线衍射仪分析不同衬底上AZO薄膜的结构,采用四探针测试仪及紫外可见光分光光度计测试薄膜的光电性能。结果表明：沉积在两种衬底上的AZO薄膜都具有六方纤锌矿结构,最佳取向均为[002]方向;玻璃衬底和PET衬底上制备的AZO薄膜的方阻分别为19/sq和45/sq,薄膜透光率均高于90%。实验表明,柔性衬底透明导电氧化物薄膜可以代替硬质衬底透明导电薄膜使电子器件向小型化、轻便化方向发展。     

Fabrication of highly efficient TiO2/Ag/TiO2 multilayer transparent conducting electrode with N ion implantation for optoelectronic applications

Fabrication of highly conductive and transparent TiO₂/Ag/TiO₂ (referred hereafter as TAT) multilayer films with nitrogen implantation is reported. In the present work, TAT films were fabricated with a total thickness of 100 nm by sputtering on glass substrates at room temperature. The as-deposited films were implanted with 40 keV N ions for different fluences (1×10¹⁴, 5×10¹⁴, 1×10¹⁵, 5×10¹⁵ and 1×10¹⁶ ions/cm²). The objective of this study was to investigate the effect of N⁺ implantation on the optical and electrical properties of TAT multilayer films. X-ray diffraction of TAT films shows an amorphous TiO₂ film with a crystalline peak assigned to Ag (111) diffraction plane. The surface morphology studied by atomic force microscopy (AFM) and field emission scanning electron microscope (FESEM) revealed smooth and uniform top layer of the sandwich structure. The surface roughness of pristine film was 1.7 nm which increases to 2.34 nm on implantation for 1×10¹⁴ ions/cm² fluence. Beyond this fluence, the roughness decreases. The oxide/metal/oxide structure exhibits an average transmittance ~80% for pristine and ~70% for the implanted film at fluence of 1×10¹⁶ ions/cm² in the visible region. The electrical resistivity of the pristine sample was obtained as 2.04×10⁻⁴ Ω cm which is minimized to 9.62×10⁻⁵ Ω cm at highest fluence. Sheet resistance of TAT films decreased from 20.4 to 9.62 Ω/□ with an increase in fluence. Electrical and optical parameters such as carrier concentration, carrier mobility, absorption coefficient, band gap, refractive index and extinction coefficient have been calculated for the pristine and implanted films to assess the performance of films. The TAT multilayer film with fluence of 1×10¹⁶ ions/cm² showed maximum Haacke figure of merit (FOM) of 5.7×10⁻³ Ω⁻¹. X-ray photoelectron spectroscopy (XPS) analysis of N 1s and Ti 2p spectra revealed that substitutional implantation of nitrogen into the TiO₂ lattice added new electronic states just above the valence band which is responsible for the narrowing of band gap resulting in the enhancement in electrical conductivity. This study reports that fabrication of multilayer transparent conducting electrode with nitrogen implantation that exhibits superior electrical and optical properties and hence can be an alternative to indium tin oxide (ITO) for futuristic TCE applications in optoelectronic devices.     

Low-temperature growth of highly conductive and transparent aluminum-doped ZnO film by ultrasonic-mist deposition

Aluminum-doped ZnO (AZO) thin films are grown by ultrasonic-mist deposition method for the transparent conducting oxides (TCO) applications at low temperatures. The AZO films can be grown at a temperature as low as 200 °C with zinc acetylacetonate and aluminum acetylacetonate sources. The lowest resistivity of grown AZO films is 1.0×10⁻³ Ω·cm and the lowest sheet resistance of 1 μm thick films is 10 Ω/□, which is close to that of commercial indium tin oxide (ITO) or Asahi U-type SnO₂: F glass. The highest carrier concentration and mobility are 5.6×10²⁰ cm⁻³ and 15 cm²/V·sec, respectively. Optical transmittance of the AZO films is found over 75% for all growth conditions. We believe that the properties of grown AZO films in this study are the best among all reported previously elsewhere by solution processes.