A study on the wet etching behavior of AZO (ZnO:Al) transparent conducting film

This paper studies the wet etching behavior of AZO (ZnO:Al) transparent conducting film with tetramethylammonium hydroxide (TMAH). The optimum optoelectronic film is prepared first using designated RF power, film thickness and controlled annealing heat treatment parameters. The AZO film is then etched using TMAH etchant and AZ4620 photoresist with controlled etchant concentration and temperature to examine the etching process effect on the AZO film optoelectronic properties. The experimental results show TMAH:H₂O = 2.38:97.62 under 45 °C at the average etch rate of 22 nm/min as the preferred parameters. The activation energy drops as the TMAH concentration rises, while the etch rate increases along with the increase in TMAH concentration and temperature. After lithography, etching and photoresist removal, the conductivity of AZO film dramatically drops from 2.4 × 10⁻³ Ω cm to 3.0 × 10⁻³ Ω cm, while its transmittance decreases from 89% to 83%. This is due to the poor chemical stability of AZO film against AZ4620 photoresist, leading to an increase in surface roughness. In the photoresist postbaking process, carbon atoms diffused within the AZO film produce poor crystallinity. The slight decreases in zinc and aluminum in the thin film causes a carrier concentration change, which affect the AZO film optoelectronic properties.     

Study on the electrical and optical properties of Ag/Al-doped ZnO coatings deposited by electron beam evaporation

A layer of silver was deposited onto the surface of glass substrates, coated with AZO (Al-doped ZnO), to form Ag/AZO film structures, using e-beam evaporation techniques. The electrical and optical properties of AZO, Ag and Ag/AZO film structures were studied. The deposition of Ag layer on the surface of AZO films resulted in lowering the effective electrical resistivity with a slight reduction of their optical transmittance. Ag (11 nm)/AZO (25 nm) film structure, with an accuracy of ±0.5 nm for the thickness shows a sheet resistance as low as 5.6 ± 0.5 Ω/sq and a transmittance of about 66 ± 2%. A coating consisting of AZO (25 nm)/Ag (11 nm)/AZO (25 nm) trilayer structure, exhibits a resistance of 7.7 ± 0.5 Ω/sq and a high transmittance of 85 ± 2%. The coatings have satisfactory properties of low resistance, high transmittance and highest figure of merit for application in optoelectronics devices including flat displays, thin films transistors and solar cells as transparent conductive electrodes.     

Optimization of the optical and electrical properties of electron beam evaporated aluminum-doped zinc oxide films for opto-electronic applications

Aluminum-doped zinc oxide (AZO) thin films have been deposited by electron beam evaporation technique on glass substrates. The structural, electrical and optical properties of AZO films have been investigated as a function of annealing temperature. It was observed that the optical properties such as transmittance, reflectance, optical band gap and refractive index of AZO films were strongly affected by annealing temperature. The transmittance values of 84% in the visible region and 97% in the NIR region were obtained for AZO film annealed at 475 °C. The room temperature electrical resistivity of 4.6×10⁻³ Ω cm has been obtained at the same temperature of annealing. It was found that the calculated refractive index has been affected by the packing density of the thin films, whereas, the high annealing temperature gave rise to improve the homogeneity of the films. The single-oscillator model was used to analyze the optical parameters such as the oscillator and dispersion energies.     

Deposition of quasi-crystal Al-doped ZnO thin films for photovoltaic device applications

Quasi-crystal aluminum-doped zinc oxide (AZO) films were prepared by in situ radio frequency (RF) magnetron sputtering (sputtering without annealing) on glass substrates. The influence of deposition parameters on the optoelectronic and structural properties of the in situ deposited quasi-crystal AZO films was investigated in order to compare resulting samples. X-ray diffraction (XRD) patterns show that the quasi-crystal AZO thin films have excellent crystallization improved with increase of the RF power and substrate temperature, with an extremely preferential c-axis orientation exhibit sharp and narrow XRD pattern similar to that of single-crystal. Field emission scanning electron microscopy (FESEM) images show that quasi-crystal AZO thin films have uniform grains and the grain size increase with the increase of RF power and substrate temperature. Craters of irregular size with the columnar structure are observed in the quasi-crystal AZO thin films at a lower substrate temperature while many spherical shaped grains appeared at a higher substrate temperature. The average optical transmittance of all the quasi-crystal AZO films was over 85% in the 400-800 nm wavelength range. The resistivity of 4.176 × 10⁻⁴ Ω cm with the grain size of 76.4891 nm was obtained in the quasi-crystal AZO thin film deposited at 300 °C, under sputtering power of 140 W.     

Growth characteristics and properties of ZnO:Ga thin films prepared by pulsed DC magnetron sputtering

Transparent conductive ZnO:Ga thin films were deposited on Corning 1737 glass substrate by pulsed direct current (DC) magnetron sputtering. The effects of process parameters, namely pulse frequency and film thickness on the structural and optoelectronic properties of ZnO:Ga thin films are evaluated. It shows that highly c-axis (0 0 2) oriented polycrystalline films with good visible transparency and electrical conductivity were prepared at a pulsed frequency of 10 kHz. Increasing the film thickness also enlarged the grain size and carrier mobility which will subsequently lead to the decrease in resistivity. In summary, ZnO:Ga thin film with the lowest electrical resistivity of 2.01 × 10⁻⁴ Ω cm was obtained at a pulse frequency of 10 kHz with 500 nm in thickness. The surface RMS (root mean square) roughness of the film is 2.9 nm with visible transmittance around 86% and optical band gap of 3.83 eV.     

Low temperature ITO thin film deposition on PES substrate using pulse magnetron sputtering

Experiments were conducted using pulse magnetron sputtering (PMS) to deposit transparent conducting indium tin oxide (ITO) thin film onto flexible polyethersulfone (PES) plastic substrates. The thin film microstructure, optoelectronic and residual stress were analyzed using the modulating PMS power, work pressure, pulse frequency, duty cycle and cycle time process parameters. The residual stress of the thin film was determined by scanning electron microscopy (SEM) combined with the Sony equation. The experimental results show that PMS has a lower process temperature, higher deposition rate and lower resistivity compared with the radio frequency process at the same output power. The duty cycle increase produces the optimum optoelectronic characteristics. When the pressure, power, duty cycle and sputter time are increased, the thin film stress will also increase, causing flexural distortion in the PES plastic substrate. When the deposition thickness reaches 1.5 μm, ITO thin film will appear with a distinct split. Under 5 mtorr work pressure, 60 W power, 33 μs duty time and 2 μs pulse reverse time at duty cycle 95%, thin film with an optimized electrical 3.0 × 10⁻⁴ Ω-cm, RMS surface roughness of 0.85 nm and visible region optical transmittance will be achieved with acquisition of over 85%.     

Surface textured ZnO:Al thin films by pulsed DC magnetron sputtering for thin film solar cells applications

Transparent conducting thin films of ZnO:Al (Al-doped ZnO, AZO) were prepared via pulsed DC magnetron sputtering with good transparency and relatively lower resistivity. The AZO films with 800 nm in thickness were deposited on soda-lime glass substrates keeping at 473 K under 0.4 Pa working pressure, 150 W power, 100 μs duty time, 5 μs pulse reverse time, 10 kHz pulse frequency and 95% duty cycle. The as-deposited AZO thin films has resistivity of 6.39 × 10⁻⁴ Ω cm measured at room temperature with average visible optical transmittance, T_total of 81.9% under which the carrier concentration and mobility were 1.95 × 10²¹ cm⁻³ and 5.02 cm² V⁻¹ s⁻¹, respectively. The films were further etched in different aqueous solutions, 0.5% HCl, 5% oxalic acid, 33% KOH, to conform light scattering properties. The resultant films etched in 0.5% HCl solution for 30 s exhibited high T_total = 78.4% with haze value, H_T = 0.1 and good electrical properties, ρ = 8.5 × 10⁻⁴ Ω cm while those etched in 5% oxalic acid for 150 s had desirable H_T = 0.2 and relatively low electrical resistivity, ρ = 7.9 × 10⁻⁴ Ω cm. However, the visible transmittance, T_total was declined to 72.1%.     

High work function of Al-doped zinc-oxide thin films as transparent conductive anodes in organic light-emitting devices

Deposition of Al-doped ZnO (AZO) films with various film thicknesses on glass substrates was performed to investigate the feasibility of using AZO films as anode electrodes in organic light-emitting devices (OLEDs). The electrical resistivity of the AZO films with a 180-nm thickness was 4.085 × 10⁻² Ω cm, and the average optical transmittance in the visible range was 80.2%. The surface work function for the AZO films, determined from the secondary electron emission coefficients obtained with a focused ion beam, was as high as 4.62 eV. These results indicate that AZO films grown on glass substrates hold promise for potential applications as anode electrodes in high-efficiency OLEDs.     

Electrical and optical properties of Al-doped ZnO thin films by sol-gel process

Al-doped ZnO (AZO) thin films oriented along the (0 0 2) plane have been prepared by the sol-gel process and their electrical and optical properties with post-deposition heating temperature were investigated. The preferred c-axis orientation along the (0 0 2) plane was enhanced with increasing post-deposition heating temperature and the surface of the films showed a uniform and nano-sized microstructure. The electrical resistivity of the films decreased from 73 to 22 Ω cm as the post-deposition heating temperature increased from 500 to 650 °C; however, the film postheated at 700 °C increased greatly to 580 Ω cm. The optical transmittance of the films postheated below 650 °C was over 86%, but it decreased at 700 °C. The electrical and optical properties of the AZO films with post-deposition heating temperature are discussed.     

Deposition of Ni, Ag, and Pt-based Al-doped ZnO double films for the transparent conductive electrodes by RF magnetron sputtering

Ni, Ag, and Pt-based Al-doped ZnO (AZO) films have been deposited as transparent conductivity layers on quartz by RF magnetron sputtering and characterized by X-ray diffraction, Hall measurement, optical transmission spectroscopy, scanning electron microscopy (SEM). The deposition of thicker metal layer in double layers resulted in lowering the effective electrical resistivity with a slight reduction of their optical transmittance. A film consisting of AZO (250 nm)/Ni (2 nm) double structure, exhibits a sheet resistance of 21.0 Ω/sq, a high transmittance of 76.5%, and characterize good adhesion to substrate. These results make the satisfactory for GaN-based light-emitting diodes (LEDs) and solar cells with metal-based AZO double films as current spread layers.     

Optical and electrical characteristics of Al-doped ZnO thin films prepared by aqueous phase deposition

Transparent conducting Al-doped ZnO (AZO) thin films have been deposited by sol-gel route. Starting from an aqueous solution of zinc acetate by adding aluminum chloride as dopant, a c-axis oriented polycrystalline ZnO thin film 100 nm in thickness could be spin-coated on glass substrates via a two-step annealing process under reducing atmosphere. The effects of thermal annealing and dopant concentration on the structural, electrical and optical properties of AZO thin films were investigated. The post-treated AZO films exhibited a homogenous dense microstructure with grain sizes less than 10 nm as characterized by SEM photographs. The annealing atmosphere has prominent impact on the crystallinity of the films which will in turn influence the electrical conductivity. By varying the doping concentrations, the optical and electrical properties could be further adjusted. An optimal doping concentration of Al/Zn = 2.25 at.% was obtained with minimum resistivity of 9.90 × 10⁻³ Ω-cm whereas the carrier concentration and mobility was 1.25 × 10²⁰ cm⁻³ and 5.04 cm² V⁻¹ s⁻¹, respectively. In this case, the optical transmittance in the visible region is over 90%.     

Effect of mesh patterning with UV pulsed-laser on optical and electrical properties of ZnO/Ag-Ti thin films

In this study, the ZnO/Ag-Ti structure for transparence conducting oxide (TCO) is investigated by optimizing the thickness of the Ag-Ti alloy and ZnO layers. The Ag-Ti thin film is deposited by DC magnetron sputtering and its thicknesses is well controlled. The ZnO thin film is prepared by sol-gel method using zinc acetate as cation source, 2-methoxiethanol as solvent and monoethanolamine as solution stabilizer. The ZnO film deposition is performed by spin-coating technique and dried at 150 °C on Corning 1737 glass. Due to the conductivity of ZnO/Ag-Ti is dominated by Ag-Ti, the sheet resistance of ZnO/Ag-Ti decrease dramatically as the thickness of Ag-Ti layer increases. However, the transmittances of ZnO/Ag-Ti become unacceptable for TCO application after the thickness of Ag-Ti layer beyond 6 nm. The as-deposited ZnO/Ag-Ti structure has the optical transmittance of 83% @ 500 nm and the low resistivity of 1.2 × 10⁻⁵ Ω-cm. Furthermore, for improving the optical and electrical properties of ZnO/Ag-Ti, the thermal treatment using laser is adopted. Experimental results indicate that the transmittance of ZnO/Ag-Ti is improved from 83% to 89% @ 500 nm with resistivity of 1.02 × 10⁻⁵ Ω-cm after laser drilling. The optical spectrum, the resistance, and the morphology of the ZnO/Ag-Ti will be reported in the study.     

Dependence of resistivity on structure and composition of AZO films fabricated by ion beam co-sputtering deposition

The correlation between the resistivity and the structure/composition in the aluminum doped zinc oxide (AZO) films fabricated by the ion beam co-sputtering deposition at room temperature was investigated. The various compositions of AZO films were controlled by the sputtered area ratio of Al to Zn target. The structure, Al concentrations and resistivities of the as-deposited films were determined by X-ray diffractometer (XRD), energy dispersive spectrometer (EDS) and four-point probe station, respectively. The lowest resistivity of the deposited film was 5.66 × 10⁻⁴ Ω-cm at the 0.7 wt.% aluminum concentration. The most intense ZnO (0 0 2) diffraction peak, the largest grain size, the longest mean free path, and the highest free carrier concentration in the film result in the lowest resistivity of 5.66 × 10⁻⁴ Ω-cm at room temperature; simultaneously, the thermal stability of the resistivity of the AZO film as a function of the sample temperature was investigated. Below 200 °C the film's resistivity was almost kept at a fixed value and the lowest resistivity of 4.64 × 10⁻⁴ Ω-cm at 247 °C was observed.     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

Effects of post-annealing on structural, optical and electrical properties of Al-doped ZnO thin films

Aluminum-doped zinc oxide (AZO) films were deposited at 400 °C by radio-frequency magnetron sputtering using a compound AZO target. The effects of annealing atmospheres as well as hydrogen annealing temperatures on the structural, optical and electrical properties of the AZO films were investigated. It was found that the electrical resistivity varied depending on the atmospheres while annealing in air, nitrogen and hydrogen at 300 °C, respectively. Comparing with that for the un-annealed films, the resistivity of the films annealed in hydrogen decreased from 9.8 × 10⁻⁴ Ω cm to 3.5 × 10⁻⁴ Ω cm, while that of the films annealed in air and nitrogen increased. The variations in electrical properties are ascribed to both the changes in the concentration of oxygen vacancies and adsorbed oxygen at the grain boundaries. These results were clarified by the comparatively XPS analyzing about the states of oxygen on the surface of the AZO films. There was great increase in electrical resistivity due to the damage of the surfaces, when AZO films were annealed in hydrogen with a temperature higher than 500 °C, but high average optical transmittance of 80-90% in the range of 390-1100 nm were still obtained.     

Influence of substrate temperature and post-treatment on the properties of ZnO:Al thin films prepared by pulsed laser deposition

Highly transparent conductive Al₂O₃ doped zinc oxide (AZO) thin films have been deposited on the glass substrate by pulsed laser deposition technique. The effects of substrate temperature and post-deposition annealing treatment on structural, electrical and optical properties of AZO thin films were investigated. The experimental results show that the electrical resistivity of films deposited at 240 °C is 6.1 × 10⁻⁴ Ω cm, which can be further reduced to as low as 4.7 × 10⁻⁴ Ω cm by post-deposition annealing at 400 °C for 2 h in argon. The average transmission of AZO films in the visible range is 90%. The optical direct band gap of films was dependent on the substrate temperature and the annealing treatment in argon. The optical direct band gap value of AZO films increased with increasing annealing temperature.     

ITO/Au/ITO multilayer thin films for transparent conducting electrode applications

Transparent and conducting ITO/Au/ITO multilayered films were deposited without intentional substrate heating on polycarbonate (PC) substrate using a magnetron sputtering process. The thickness of ITO, Au and ITO metal films in the multilayered structure was constant at 50, 10 and 40 nm, respectively.Although the substrate temperature was kept constant at 70 °C, ITO/Au/ITO films were polycrystalline with an (1 1 0) X-ray diffraction peak, while single ITO films were amorphous. Surface roughness analysis indicated ITO films had a higher average roughness of 1.76 nm, than the ITO/Au/ITO film roughness of 0.51 nm. The optoelectrical properties of the ITO/Au/ITO films were dependent on the Au thin film, which affected the ITO film crystallinity. ITO/Au/ITO films on PC substrates were developed with a resistivity as low as 5.6 × 10⁻⁵ Ω cm and a high optical transmittance of 71.7%.     

Transparent conductive and near-infrared reflective Cu-based Al-doped ZnO multilayer films grown by magnetron sputtering at room temperature

Cu-based Al-doped ZnO multilayer films were deposited on glass substrates by DC magnetron sputtering at room temperature. Three kinds of multilayer structures (AZO/Cu, AZO/Cu/AZO, and Cu/AZO) were designed for comparison, and the effects of the Cu layer thickness on photoelectrical properties of the multilayer films were investigated. The results revealed that the transparent-conductive property and near-infrared reflectance of the films are closely correlated with the Cu layer thickness, and among the three structures, AZO/Cu bi-layer films exhibited preferable photoelectrical properties. The AZO/Cu bi-layer film with a Cu layer thickness of 7 nm displayed the highest figure of merit of 4.82 × 10⁻³ Ω⁻¹, with a low sheet resistance of 21.7 Ω/sq and an acceptable visible transmittance of 80%. The near infrared reflectance above 50% can be simultaneously obtained. The good performance of the coatings indicates that they are promising for coated glasses, thin film solar cells and heat-reflectors.     

Influence of deposition temperature on the crystallinity of Al-doped ZnO thin films at glass substrates prepared by RF magnetron sputtering method

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering method under different substrate temperatures. The microstructural, electrical and optical properties of AZO films were investigated in a wide temperature range from room temperature up to 350 °C by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FESEM), High-Resolution Transmission Electron Microscopy (HRTEM), Hall measurement, and UV–visible meter. The nature of AZO films is polycrystalline thin films with hexagonal wurtzite structure and a preferred orientation along c-axis. The crystallinity and surface morphologies of the films are strongly dependent on the growth temperature, which in turn exerts a great effect on microstructural, electrical and optical properties of the AZO films. The atomic arrangement of AZO film having an wurtzite structure was indeed identified by the HRTEM as well as the Selected Area Electron Diffraction (SAED). The defect density of AZO film was investigated by HRTEM. The film deposited at 100 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.6 × 10⁻⁴ Ω cm. The average transmission of AZO films in the visible range is all over 85%. More importantly, the low-resistance and high-transmittance AZO film was also prepared at a low temperature of 100 °C.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.