High quality transparent conductive ZnO/Ag/ZnO multilayer films deposited at room temperature

We have fabricated, by simultaneous DC and RF magnetron sputtering, multilayer transparent electrodes having much lower electrical resistance than the widely used transparent conductive oxide electrodes. The multilayer structure consists of three layers (ZnO/Ag/ZnO). Ag films with different film thickness were used as metallic layers. Optimum thicknesses of Ag and ZnO films were determined for high optical transmittance and good electrical conductivity. Several analytical tools such as spectrophotometer, atomic force microscopy, scanning electron microscopy and four-point probe were used to explore the possible changes in electrical and optical properties. A high quality transparent electrode, having resistance as low as 3 Ω/sq and high optical transmittance of 90% was obtained at room temperature and could be reproduced by controlling the preparation process parameters. The electrical and optical properties of ZnO/Ag/ZnO multilayers were determined mainly by the Ag film properties. The performance of the multilayers as transparent conducting materials was also compared using a figure of merit.     

Design of ZnO/Ag/ZnO multilayer transparent conductive films

We have studied the properties of ZnO/Ag/ZnO multilayers prepared on glass substrates by simultaneous RF magnetron sputtering of ZnO and dc magnetron sputtering of Ag. The electrical and optical performance of Ag and ZnO single layer films was also investigated. Different optimization procedures were used for good transparent conductive film. Several analytical tools such as spectrophotometer, scanning electron microscope (SEM), four-point probes were used to explore the causes of the changes in electrical and optical properties. Low sheet resistance of 3 Ω/sq. and transmittance over 90% at 580 nm was achieved. The results of optimization condition of both oxide layers and metallic Ag layers were illustrated.     

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.     

Nb-doped TiO2 thin films for photovoltaic applications

Polycrystalline titania and Nb:TiO₂ thin films were deposited by RF magnetron sputtering. The influence of post-deposition annealing in vacuum and hydrogen atmosphere on the structure, morphology, oxidation states and optical properties was studied by X-ray diffraction, atomic force microscopy, XPS and UV–VIS spectroscopy. The heat treatment of titanium dioxide thin films in vacuum and H₂ atmosphere induces structural and morphological changes. The band gap narrowing was observed for the transparent as-deposited Nb:TiO₂ films, while annealing at 420 °C in H₂ atmosphere resulted in an enhancement of the electrical conductivity. Further on, TiO₂/p-CdTe photovoltaic devices with efficiency of 1.8% were fabricated and their characteristic ‘enhancement’ is discussed.     

The stability of zinc oxide transparent electrodes fabricated by R.F. magnetron sputtering

The stability of the electrical, optical and mechanical properties of sputtered zinc oxide (ZnO) thin films with resistivities from 10^?2 to 10^?4 ωcm were investigated. No significant changes in these properties are observed for ZnO films exposed to air at room temperature for 10 months. A change in the electrical resistance of the ZnO films with temperature up to 400 °C is observed in various ambients such as vacuum, inert gases and air. After heat treatment in these ambients at 400 °C, the resistivity of the films increased by one to ten orders of magnitude. The increased resistivity can be returned to the resistivity of the virgin state, within one order of magnitude, by heat treatment in a hydrogen ambient at temperatures near 400 °C. For practical use of ZnO films at high temperatures, the increase in the resistivity might become a disadvantage for ZnO transparent electrodes fabricated by r.f. magnetron sputtering.     

Influence of annealing temperature on the properties of ZnO:Zr films deposited by direct current magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were deposited on quartz substrates by direct current (DC) magnetron sputtering at room temperature. The influence of post-annealing temperature on the structural, morphological, electrical and optical properties of ZnO:Zr films were investigated. When annealing temperature increases from room temperature to 573 K, the resistivity decreases obviously due to an improvement of the crystallinity. However, with further increase in annealing temperature, the crystallinity deteriorates leading to an increase in resistivity. The films annealed at the optimum annealing temperature of 573 K in vacuum have the lowest resistivity of 9.8 × 10⁻⁴ Ω cm and a high transmittance of above 92% in the visible range.     

Effect of ZnO buffer layer on AZO film properties and photovoltaic applications

Aluminum-doped ZnO (AZO) transparent conducting films were deposited on glass substrates with and without intrinsic ZnO (i-ZnO) buffer layers by a home made and low cost radio-frequency (RF) magnetron sputtering system at room temperature in pure argon ambient and under a low vacuum level. The films were examined and characterized for electrical, optical, and structural properties for the application of CIGS solar cells. The influence of sputter power, deposition pressure, film thickness and residual pressure on electrical and optical properties of layered films of AZO, i-ZnO and AZO/i-ZnO was investigated. The optimization of coating process parameters (RF power, sputtering pressure, thickness) was carried out. The effects of i-ZnO buffer layer on AZO films were investigated. By inserting thin i-ZnO layers with a thickness not greater than 125 nm under the AZO layers, both the carrier concentration and Hall mobility were increased. The resistivity of these layered films was lower than that of single layered AZO films. The related mechanisms and plasma physics were discussed. Copper indium gallium selenide (CIGS) thin film solar cells were fabricated by incorporating bi-layer ZnO films on CdS/CIGS/Mo/glass substrates. Efficiencies of the order of 7–8% were achieved for the manufactured CIGS solar cells (4–5 cm² in size) without antireflective films. The results demonstrated that RF sputtered layered AZO/i-ZnO films are suitable for application in low cost CIGS solar cells as transparent conductive electrodes.     

Optimization of ZnO:Al/Ag/ZnO:Al structures for ultra-thin high-performance transparent conductive electrodes

Al-doped ZnO (AZO)/Ag/AZO multilayer coatings (50-70 nm thick) were grown at room temperature on glass substrates with different silver layer thickness, from 3 to 19 nm, by using radio frequency magnetron sputtering. Thermal stability of the compositional, optical and electrical properties of the AZO/Ag/AZO structures were investigated up to 400 °C and as a function of Ag film thickness. An AZO film as thin as 20 nm is an excellent barrier to Ag diffusion. The inclusion of 9.5 nm thin silver layer within the transparent conductive oxide (TCO) material leads to a maximum enhancement of the electro-optical characteristics. The excellent measured properties of low resistance, high transmittance in the visible spectral range and thermal stability allow these ultra-thin AZO/Ag/AZO structures to compete with the 1 μm thick TCO layer currently used in thin film solar cells.     

不同退火工艺对AZO膜性能的影响

掺铝氧化锌(AZO)薄膜由于其独特的光学和电学性能而倍受人们的青睐。本文采用射频磁控溅射技术,制备了综合性能优良的AZO薄膜,通过不同退火工艺处理,研究了其对AZO薄膜的组织结构、电学性能及光学性能的影响。氮气环境下的退火使得AZO膜出现了更为明显的蓝移现象,氢气环境下的退火提高了薄膜的导电性。     

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.     

Optical, electrical and structural characteristics of Al:ZnO thin films with various thicknesses deposited by DC sputtering at room temperature and annealed in air or vacuum

Transparent and conductive Al-doped ZnO (AZO) films have been grown with various thicknesses between 0.3 and 1.1 μm by magnetron sputtering at room temperature onto soda lime glass substrates. After deposition, the samples have been annealed at temperatures ranging from 150 to 450 °C in air or vacuum. The optical, electrical, and structural characteristics of the AZO coatings have been analyzed as a function of the film thickness and the annealing parameters by spectrophotometry, Hall effect measurements, and X-ray diffraction. As-grown layers are found polycrystalline, with hexagonal structure that shows some elongation of the unit cells along the c-axis, having visible transmittance ∼85-90% and resistivity ∼1.6-2.0 mΩ cm, both parameters slightly decreasing when the film thickness increases. Heating in air or vacuum produces further elongation of the crystalline lattice together with some increase of the visible transmittance and a decrease of the electrical resistance that depends on the heating temperature and atmosphere. The best characteristics have been obtained after treatment in vacuum at 350 °C, where the highest carrier concentrations are achieved, giving visible transmittance ∼90-95% and resistivity ∼0.8-0.9 mΩ cm for the AZO layers with various thicknesses. Some relationships between the analyzed properties have been established, showing the dependence of the lattice distortion, the band gap energy and the mobility on the carrier concentration.     

Properties of Nb-doped ZnO transparent conductive thin films deposited by rf magnetron sputtering using a high quality ceramic target

Nb-doped ZnO films with (002) orientation have been grown on glass substrates by rf magnetron sputtering followed by vacuum annealing at 400°C for 3 h. The microstructures and surface figures of the Nbdoped ZnO films were investigated with X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. And its optical and electrical properties were measured at room temperature using a four-point probe technique and 756-type spectrophotometer, respectively. X-ray diffraction (XRD) revealed that the films are highly textured along the c axis and perpendicular to the surface of the substrate. After annealing at 400°C for 180 min under vacuum, transmittance of about 90% in visible region for Nb doped ZnO films was confirmed by the optical transmission spectra, and the low resistivity of 5·47 × 10⁻³ Ω·cm was obtained.     

ZnO/Cu/ZnO multilayer films: Structure optimization and investigation on photoelectric properties

A series of ZnO/Cu/ZnO multilayer films has been fabricated from zinc and copper metallic targets by simultaneous RF and DC magnetron sputtering. Numerical simulation of the optical properties of the multilayer films has been carried out in order to guide the experimental work. The influences of the ZnO and Cu layer thicknesses, and of O₂/Ar ratio on the photoelectric and structural properties of the films were investigated. The optical and electrical properties of the multilayers were studied by optical spectrometry and four point probe measurements, respectively. The structural properties were investigated using X-ray diffraction. The performance of the multilayers as transparent conducting coatings was compared using a figure of merit. In experiments, the thickness of the ZnO layers was varied between 4 and 70 nm and those of Cu were between 8 and 37 nm. The O₂/Ar ratios range from 1:5 to 2:1. Low sheet resistance and high transmittance were obtained when the film was prepared using an O₂/Ar ratio of 1:4 and a thickness of ZnO (60 nm)/Cu (15 nm)/ZnO (60 nm).     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

ZnO:Sn/Ag/ZnO:Sn复合薄膜电极的防氧化性能研究

随着分辨率的提高,传统金属电极在电阻率和抗氧化性能方面已经不适合作为需要高温热处理的场致发射显示器件中的薄膜电极。本文采用5.77%(原子比)Sn掺杂的ZnO:Sn作为Ag层的保护层,利用磁控溅射法制备ZnO:Sn/Ag/ZnO:Sn复合薄膜及其电极,并采用X射线衍射、光学显微镜、扫描电子显微镜和电性能测试系统研究复合薄膜及其电极在经过不同温度退火后的晶体结构、表面形貌和电学性能的变化。ZnO:Sn膜层致密,25 nm厚的ZnO:Sn足以保护Ag层在530℃的高温中不被明显氧化,电极电阻率低达2.0×10-8Ω.m左右。     

Dependence of the electrical and optical properties of sputter-deposited ZnO:Ga films on the annealing temperature,time, and atmosphere

Effects of annealing process parameters such as annealing temperature, time, and atmosphere on the electrical resistivity and transmittance properties of Ga-doped ZnO (ZnO:Ga) thin films deposited on glass by rf magnetron sputtering were investigated. The electrical resistivity of a ZnO:Ga thin film is effectively decreased with increasing annealing temperature and time in a reducing atmosphere such as N₂ + 5%H₂. This is attributed to passivation of grain boundaries and zinc ions by hydrogen atoms resulting in increases in carrier concentration and mobility. Also the resistivity of 4.9 × 10⁻⁴Ω cm was obtained by annealing at 200°C for 15 h in the same atmosphere, which is not bad for a transparent conductor for solar cell applications. However, annealing at a temperature higher than 400°C is less effective. The lowest resistivity of 2.3 × 10⁻⁴Ω cm was obtained by annealing at 400°C for 1 h in an N₂ + 5%H₂ atmosphere. The optical transmittance of the ZnO:Ga film is improved by annealing regardless of the annealing atmosphere. Annealing in N₂ + 5%H₂ atmosphere widens the optical band gap, while annealing in an O₂ atmosphere makes the band gap narrower, which can be explained as a blue shift phenomenon.     

Transparent conducting zinc oxide thin film prepared by off-axis rf magnetron sputtering

Highly conducting and transparent ZnO : Al thin films were grown by off-axis rf magnetron sputtering on amorphous silica substrates without any post-deposition annealing. The electrical and optical properties of the films deposited at various substrate temperatures and target to substrate distances were investigated in detail. Optimized ZnO : Al films have conductivity of 2200 S cm^-1 and average transmission in the visible range is higher than 85%. The conductivity and mobility show very little temperature dependence.     

Transparent conductive film having sandwich structure of gallium-indium-oxide/silver/gallium-indium-oxide

New transparent conductive films having the sandwich structure of gallium-indium-oxide/silver/gallium-indium-oxide (GIO/Ag/GIO) were prepared by conventional magnetron sputtering method at ambient substrate temperature. The electrical and optical properties of the films were compared with those of conventional indium-tin-oxide (ITO) films and ITO/Ag/ITO sandwich films. The GIO/Ag/GIO (40 nm/8 nm/40 nm) sandwich films, in which the GIO film was deposited using a GIO ceramic target with In content [In/(Ga + In)] of 10 at.%, exhibited a low sheet resistance of 11.3 Ω/sq and a large average transmittance of over 92.9% in the visible region (400-800 nm). This GIO/Ag/GIO films also exhibited a novel characteristic of transparency in the ultraviolet region; they showed high transmittance of 82.2% at the wavelength of 330 nm and 40.8% at the wavelength of 280 nm, which was not shown in the ITO films and the ITO/Ag/ITO sandwich films. The GIO/Ag/GIO sandwich films are useful as transparent electrode for emitting devices of ultraviolet radiation because of both their high conductivity and high transparency in the ultraviolet region.     

The effect of annealing on structural, electrical and optical properties of nanostructured ZnS/Ag/ZnS films

In this paper a ZnS/Ag/ZnS (ZAZ) nano-multilayer structure is designed theoretically and optimum thicknesses of ZnS and Ag layers are calculated at 35 and 17 nm, respectively. Several conductive transparent ZAZ nano-multilayer films are deposited on a glass substrate at room temperature by thermal evaporation method. Changes in the electrical, structural, and optical properties of samples are investigated with respect to annealing in air at different temperatures. High-quality nano-multilayer films with the sheet resistance of 8 Ω/sq and the optical transmittance of 83% at 200 °C annealing temperature are obtained. The figure of merit is applied on the ZAZ films and their performance as transparent conductive electrodes are determined.     

Formation of F-doped ZnO transparent conductive films by sputtering of ZnF2

Fluorine-doped ZnO transparent conductive thin films were successfully deposited on glass substrate by radio frequency magnetron sputtering of ZnF₂. The effects of rapid thermal annealing in vacuum on the optical and electrical properties of fluorine-doped ZnO thin films have been investigated. X-ray diffraction spectra indicate that no fluorine compounds, such as ZnF₂, except ZnO were observed. The specimen annealed at 500 °C has the lowest resistivity of 6.65 × 10^? 4 Ω cm, the highest carrier concentration of 1.95 × 10²¹ cm^? 3, and the highest energy band gap of 3.46 eV. The average transmittance in the visible region of the F-doped ZnO thin films as-deposited and annealed is over 90%.