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.     

Improved thermal stability of ZnO transparent conducting films with a ZnO overlayer

A study of the thermal stability of transparent conducting ZnO thin film in air is reported. By depositing a thin ZnO overlayer (~ 10 nm) on aluminum and gallium-codoped ZnO thin film (AGZO), the thermal stability of the AGZO thin film could be significantly improved. Electrical and structural characterizations of the AGZO thin films with and without the overlayer were performed and the mechanism of the enhanced thermal stability by the overlayer was proposed.     

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.     

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.     

Heat generation properties of Ga doped ZnO thin films prepared by rf-magnetron sputtering for transparent heaters

Ga doped ZnO (GZO) thin films were prepared by rf-magnetron sputtering on glass substrate for window heater applications. Electrical and optical properties of these films were analyzed in order to investigate on substrate temperature and rf power dependencies. High quality GZO films with a resistivity of 1.30 × 10^− 4 Ω cm and a transparency above 90% in the visible range were able to be formed. GZO films have been patterned on glass substrate as a line heater. This GZO line heater showed the rapid heat radiation property from room temperature to 90 °C for 22 s at the applied voltage of 42 V. These results could provide a possibility to use GZO as effective transparent heaters.     

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.     

多孔ZnO薄膜结构与光学性能研究

采用sol-gel提拉法,以聚乙二醇(PEG2000)为模板剂,醋酸锌为前驱体,乙醇为溶剂,二乙醇胺为络合剂,在玻璃基片上生长了多孔ZnO薄膜,利用SEM和紫外分光光度计分析了多孔ZnO薄膜的表面形貌和光学性质。研究了涂膜层数,模板剂加入量对多孔ZnO薄膜结构和透射率的影响。实验结果表明:随着涂膜层数的增加,薄膜的透射率有减小的趋势;当镀膜层数一定时,加入PEG2000后,有利于ZnO多孔结构的形成,在一定范围内,孔尺寸随PEG加入量的增加而增大,薄膜的紫外-可见光透射率随PEG加入量的增加而减小。     

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.     

Growth of ZnO layers for transparent and flexible electronics

We have deposited and characterised ZnO on flexible and transparent plastic polymer. We employed a specially designed vapour phase growth system with elemental sources for zinc and oxygen and deposited thin ZnO films at temperatures below 400 °C. Basic photoluminescence characterisation confirms ZnO. Ohmic contacts were fabricated on these layers and the layers exhibit significantly high electron concentration with carrier mobility μ of up to 10.78 cm² V⁻¹ s⁻¹. Furthermore, we show how these layers can be processed with conventional device processing techniques.     

Filtered vacuum arc deposition of transparent conducting Al-doped ZnO films

Transparent conducting ZnO:Al and ZnO films of 380-800 nm thickness were deposited on glass substrates by filtered vacuum arc deposition (FVAD), using a cylindrical Zn cathode doped with 5-6 at.% Al or a pure Zn cathode in oxygen background gas with pressure P = 0.4-0.93 Pa. The crystalline structure, composition and electrical and optical properties of the films were studied as functions of P. The films were stored under ambient air conditions and the variation of their resistance as function of storage time was monitored over a period of several months.The Al concentration in the film was found to be 0.006-0.008 at.%, i.e., a few orders of magnitude lower than that in the cathode material. However, this low Al content influenced the film resistivity, ρ, and its stability. The resistivity of as-deposited ZnO:Al films, ρ = (6-8) × 10^− 3 Ω cm, was independent of P and lower by a factor of 2 in comparison to that of the ZnO films deposited by the same FVAD system. The ρ of ZnO films 60 days after deposition increased by a factor of ∼ 7 with respect to as-deposited films. The ZnO:Al films deposited with P = 0.47-0.6 Pa were more stable, their ρ first slowly increased during the storage time (1.1-1.4 times with respect to as-deposited films), and then stabilized after 30-45 days.     

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.     

Low-temperature fabrication of superconducting FeSe thin films by pulsed laser deposition

Superconducting FeSe thin films were prepared at a substrate temperature of 320 °C by pulsed laser deposition. X-ray diffraction and transmission electron microscopic analyses showed that highly c-axis-orientated and high-quality films were obtained on various substrate materials, including single-crystal MgO, LaAlO₃, SrTiO₃ and (100)-Si, and amorphous-SiO_x, at such low temperature. From transport measurements all the films showed low-temperature structural phase transition at ∼ 60-90 K and superconducting transition at onset temperature varies from ∼ 7 K to < 2 K, depending on the substrate used. The transport property of FeSe film on Si was found most different from all the others, in spite of their similarity in structural analysis. Chemical analysis demonstrated that Fe and Se homogeneously distributed in the film and the stoichiometry of FeSe and the bonding states of Fe and Se are as well uniform along the film growth direction.     

ZnO thin films prepared by atomic layer deposition and rf sputtering as an active layer for thin film transistor

Recently, the application of ZnO thin films as an active channel layer of transparent thin film transistor (TFT) has become of great interest. In this study, we deposited ZnO thin films by atomic layer deposition (ALD) from diethyl Zn (DEZ) as a metal precursor and water as a reactant at growth temperatures between 100 and 250 °C. At typical growth conditions, pure ZnO thin films were obtained without any detectable carbon contamination. For comparison of key film properties including microstructure and chemical and electrical properties, ZnO films were also prepared by rf sputtering at room temperature. The microstructure analyses by X-ray diffraction have shown that both of the ALD and sputtered ZnO thin films have (002) preferred orientation. At low growth temperature T_s ≤ 125 °C, ALD ZnO films have high resistivity (> 10 Ω cm) with small mobility (< 3 cm²/V s), while the ones prepared at higher temperature have lower resistivity (< 0.02 Ω cm) with higher mobility (> 15 cm²/V s). Meanwhile, sputtered ZnO films have much higher resistivity than ALD ZnO at most of the growth conditions studied. Based upon the experimental results, the electrical properties of ZnO thin films depending on the growth conditions for application as an active channel layer of TFT were discussed focusing on the comparisons between ALD and sputtering.     

Low-temperature growth of ZnO nanostructures by oxygen plasma oxidation of ZnCl2

The thermodynamically forbidden reaction between ZnCl₂ and O₂ was able to take place by using oxygen plasma, yielding cone-shaped ZnO nanostructure. In situ optical emission spectroscopy was used to identify the excited species during the plasma enhanced reaction. The determination of excited temperature suggested that the addition of O₂ had great contribution to the enhanced dissociation of ZnCl₂. The successful synthesis of ZnO indicates that the chlorides may replace the organometallics as a new precursor in thin film preparation industry.     

Growth of MgO thin films with subsequent fabrication of ZnO rods: Structural and photoluminescence properties

We have grown magnesium oxide (MgO) films by the simple evaporation of MgB₂ powders. The subsequent deposition of ZnO by using an atomic layer deposition (ALD) technique generated the ZnO rods on MgO films, realizing the first production of rod-like structures using ALD. We have employed X-ray diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy to characterize the samples. PL of MgO films exhibited two emission bands peaked in the blue and blue-green region, respectively. The deposition of ZnO rods changed the shape of the PL spectrum.     

Thermally stable transparent conducting and highly infrared reflective Ga-doped ZnO thin films by metal organic chemical vapor deposition

Highly transparent conductive Ga-doped ZnO (GZO) thin films have been prepared on glass substrates by metal organic chemical vapor deposition. The effect of Ga doping on the structural, electrical and optical properties of GZO films has been systematically investigated. Under the optimum Ga doping concentration (∼4.9 at.%), c-axis textured GZO film with the lowest resistivity of 3.6 × 10⁻⁴ Ω cm and high visible transmittance of 90% has been achieved. The film also exhibits low transmittance (<1% at 2500 nm) and high reflectance (>70% at 2500 nm) to the infrared radiation. Furthermore, our developed GZO thin film can well retain the highly transparent conductive performance in oxidation ambient at elevated temperature (up to 500 °C).     

Improvement in moisture durability of ZnO transparent conductive films with Ga heavy doping process

Moisture durability of ZnO transparent conductive films was achieved with Ga heavy doping by off-axis type rf magnetron sputtering. The resistivity of 10.9 at.% Ga-doped ZnO was 1.3 × 10⁻³ Ωcm and changed less than 5% of resistivity over a 9400-h reliability test at a temperature of 85 °C and humidity of 85%. The crystal structural analysis of the heavily Ga-doped ZnO films indicated that the c-axis was oriented in various directions as well as the perpendicular direction to the substrate surface. The heavily doped Ga disorders the crystal growth of ZnO films and forms a different crystal structure from conventional ZnO.     

Ultrathin Al-doped transparent conducting zinc oxide films fabricated by pulsed laser deposition

Al-doped transparent conducting zinc oxide (AZO) films, approximately 20-110 nm-thick, were deposited on glass substrates at substrate temperatures between 200 and 300 °C by pulsed laser deposition (PLD) using an ArF excimer laser (λ = 193 nm). When fabricated at a substrate temperature of 260 °C, a 40-nm-thick AZO film showed a low resistivity of 2.61 × 10^− 4 Ω·cm, carrier concentration of 8.64 × 10²⁰ cm^− 3, and Hall mobility of 27.7 cm²/V·s. Furthermore, for an ultrathin 20-nm-thick film, a resistivity of 3.91 × 10^− 4 Ω·cm, carrier concentration of 7.14 × 10²⁰ cm^− 3, and Hall mobility of 22.4 cm²/V·s were obtained. X-ray diffraction (XRD) spectra, obtained by the θ-2θ method, of the AZO films grown at a substrate temperature of 260 °C showed that the diffraction peak of the ZnO (0002) plane increased as the film thickness increased from 20 to 110 nm. The full-width-at-half-maximum (FWHM) values were 0.5500°, 0.3845°, and 0.2979° for film thicknesses of 20, 40, and 110 nm, respectively. For these films, the values of the average transmittance in visible light wavelengths (400-700 nm) were 95.1%, 94.2%, and 96.6%, respectively. Field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM) observations showed that even the 20-nm-thick films did not show island structures. In addition, exfoliated areas or vacant and void spaces were not observed for any of the films.     

Structural, electrical and bending properties of transparent conductive Ga-doped ZnO films on polymer substrates

We investigated the characteristics of highly transparent conductive Ga-doped ZnO (GZO) polycrystalline films of 100 nm thickness deposited on glass and polymer substrates. GZO films were deposited by ion plating with dc-arc discharge. We developed multiple-deposition method to obtain various deposition process temperatures lower than 100 °C. Cross-sectional SEM images show that all the GZO films have columnar structure. Analysis of data obtained by XRD measurements shows that all the GZO films with wurtzite structure exhibit highly (002) orientation perpendicular to the substrate. The resistivity of the GZO films deposited on polyester and glass substrates were 5.0 × 10^-4 Ω · cm. The mechanical bending properties of the GZO films were investigated by comparing the sheet resistance determined before and after a bending test with various bending diameters. For the bending diameter of more than 30 mm, all the GZO films exhibited excellent bending properties with no change in sheet resistance. For the bending diameter of less than 20 mm, we found the sheet resistance affected by the bending. We demonstrated that our multiple-deposition method to achieve different controllable polyester substrate temperatures is highly suitable for improving the bending properties of GZO films.