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.     

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.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

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.     

Low resistivity transparent conducting CdO thin films deposited by DC reactive magnetron sputtering at room temperature

Transparent conducting cadmium oxide (CdO) films were deposited on PET (polyethylene terephthalate) substrate by DC reactive magnetron sputtering at room temperature. All the films deposited at room temperature were polycrystalline in rock-salt structure. Dependences of the physical properties of the CdO films on the oxygen partial pressure were systematically studied. The films deposited at low oxygen flow rate were (200) oriented, while the films deposited at an oxygen flow rate greater than 20 sccm were (111) oriented. The average grain size of the CdO films decreased as the oxygen flow rate increases as determined by XRD and SEM. The Hall effect measurement showed that CdO films have high concentration, low resistivity, and high mobility. Both the mobility and the concentration of the carrier decreased with the increase of the oxygen flow rate. A minimum sheet resistance of 36.1 Ω/□, or a lowest resistivity of 5.44 × 10^− 4 Ω cm (6.21 × 10²⁰/cm³, μ = 19.2 cm²/Vs) was obtained for films deposited at an oxygen flow rate of 10 sccm.     

Anode material properties of Ga-doped ZnO thin films by pulsed DC magnetron sputtering method for organic light emitting diodes

This study examined the anode material properties of Ga-doped zinc oxide (GZO) thin films deposited by pulsed DC magnetron sputtering along with the device performance of organic light emitting diodes (OLEDs) using GZO as the anode. The structure and electrical properties of the deposited films were examined as a function of the substrate temperature. The electrical properties of the GZO film deposited at 200 °C showed the best properties, such as a low resistivity, high mobility and high work function of 5.3 × 10^− 4Ω cm, 9.9 cm²/Vs and 4.37 eV, respectively. The OLED characteristics with the GZO film deposited under the optimum conditions showed good brightness > 10,000 cd/m². These results suggest that GZO films can be used as the anode in OLEDs, and a lower deposition temperature of 200 °C is suitable for flexible devices.     

Structural characterization of ZnO thin films deposited by dc magnetron sputtering

In this work we present recent results on ZnO thin films grown by dc magnetron sputtering technique at room temperature (RT), focusing on structural and surface characterization using conventional cross-section transmission electron microscopy (XTEM) and high resolution cross section transmission electron microscopy (HRXTEM) in an attempt to understand the thickness influence on film, mechanical and optical properties as well as photoreduction/oxidation conductivity changes. Films were found to be polycrystalline with a columnar mode of growth. For films with thickness over 100 nm, XTEM and HRTEM analysis evidenced the presence of a small grains transition layer near interface with the substrate, feature which plays an important role in ZnO thin films for gas sensing application. The control of such structural parameters is proved to be critical for the improvement of their gas sensing performance.     

Comparative study on early stages of film growth for transparent conductive oxide films deposited by dc magnetron sputtering

Early stages of film growth were investigated on three different kinds of representative transparent conductive oxide films including tin doped indium oxide (ITO), indium zinc oxide (IZO) and gallium doped zinc oxide (GZO) films deposited on unheated alkali free glass substrates by dc magnetron sputtering. The variations in sheet resistance, film coverage and average surface roughness showed clearly that ITO and GZO films possessed Volmer-Weber growth mode. In contrast, the evolution of islands is not clearly observed for IZO film. The nucleation density of IZO film is considered to be much higher than that of ITO and GZO films.     

A study of amorphous and crystalline phases in In2O3-10 wt.% ZnO thin films deposited by DC magnetron sputtering

We report on the processing, phase stability, and electronic transport properties of indium oxide (In₂O₃) doped with 10 wt.% zinc oxide (ZnO) deposited to a thickness of 100 nm using DC magnetron sputter deposition at room temperature and 350 °C. We compare the optimum oxygen content in the sputter gas for pure In₂O₃ and doped with (i) 10 wt.% ZnO and (ii) 9.8 wt.% SnO₂. Amorphous IZO films were annealed at 200 °C in air and N₂/H₂ and resistivity, Hall mobility, and carrier density along with molar volume change were monitored simultaneously as a function of time at temperature. We report that annealing the amorphous oxide in air at 200 °C does not lead to crystallization but does result in a 0.5% decrease in the amorphous phase molar volume and an associated drop in carrier density. Annealing in forming gas leads to an increase in carrier density and a small decrease in molar volume. We also report that when annealed in air at 500 °C, the amorphous IZO phase may crystallize either in the cubic bixbyite or in a recently observed rhombohedral phase.     

Effect of deposition geometry on structural, electrical and optical properties of ZnO:Al films by magnetron sputtering

Al-doped ZnO films were prepared by the dc magnetron sputtering technique on Suprasil-1 substrates at a temperature of 470 K. Plasma-emission monitoring was used to stabilize oxygen flow to the deposition chamber. The effect of substrate position during deposition on the structural, electrical and optical properties of the films was investigated. It was found that preparation of low-resistance films with high optical transmission over the visible region is possible under condition of low plasma effects on the growing film.     

磁控溅射ITO薄膜的退火处理

采用直流磁控溅射方法在室温下玻璃基板上制备ITO(Indium tin oxide)薄膜,并在真空中不同温度(100℃~400℃)下退火处理.研究了退火对薄膜表面形貌、电光特性的影响.XRD测试发现薄膜在200℃退火后结晶,优选晶向为(222).随退火温度升高,方块电阻迅速下降,表面更加平整,薄膜在可见光范围平均透过率提高到85%.     

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.     

利用脉冲直流磁控溅射制备ZnO:Al薄膜的研究

利用中频脉冲直流磁控溅射法制备了平面ZnO:Al(AZO)透明导电薄膜,研究了沉积压力、衬底温度和溅射功率对AZO薄膜光电性能、薄膜稳定性的影响.结果表明:在较低沉积压力、衬底温度及溅射功率下,可获得具有低电阻率、高透过率、高稳定性的AZO薄膜.     

Low-temperature deposited Titanium-doped zinc oxide thin films on the flexible PET substrate by DC magnetron sputtering

Transparent conducting Titanium-doped zinc oxide thin films (TZO) with high transparency and relatively low resistivity were firstly deposited on water-cooled polyethylene terephthalate (PET) substrates at room temperature by DC magnetron sputtering. The microstructure, optical and electrical properties of the deposited films were investigated and discussed. The XRD patterns show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity decreases when the sputtering power increases from 45 W to 60 W. However, as the puttering power continue increases from 60 W to 90 W, the electrical resistivity increases rapidly. When the puttering power is 60 W, the films deposited on PET substrate have the lowest resistivity of 4.72 × 10⁻⁴ Ω cm and a relatively high transmittance of above 92% in the visible range.     

Optical characterization of transparent nickel oxide films deposited by DC current reactive sputtering

In this paper, we characterize high transparency p-type semiconducting NiO thin films deposited by Direct Current Reactive Magnetron Sputtering from a pure Ni target in a mixture of oxygen and argon gases on Corning glass/SnO₂:F substrates at different oxygen contents ranging from 0% at 30%. The influence of the O₂/Ar ratio and thickness on transmittance has been examined using ultraviolet-visible spectroscopy. The results show that whatever the oxygen proportion into the discharge, the nickel oxide films exhibit a polycrystalline structure. At low oxygen content, the preferential orientation is (111), for stoichiometric films the XRD diagram is powder-like whereas the preferential orientation is (200) for higher oxygen content. For low and high oxygen content, the transmittance is low. Thanks to plasma method and its ability to tune the oxygen content in the discharge and therefore the film composition, we have been able to explore carefully the intermediate zone and obtain transparent films. The optical absorption coefficient α has been calculated from the transmittance and the variation of (αhν)² versus the photon energy (hν) for nickel oxide is presented. The optical band gap energy has been evaluated and varies from 3.2 to 3.8 eV.     

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.     

直流磁控溅射铝纳米颗粒膜的微结构及电学特性

采用直流磁控溅射法,以高纯铝(99.99%)为靶材,高纯氩气(99.999%)为起辉气体,在经机械抛光的单晶Si衬底上制备铝纳米颗粒薄膜。利用X射线衍射仪(XRD)、光学薄膜测厚仪、扫描电子显微镜(SEM)和四探针测试仪分别测试了铝纳米颗粒薄膜的晶相结构、薄膜厚度、表面形貌及电阻率。XRD衍射图谱表明此薄膜为面心立方的多晶结构,择优取向为Al(111)晶面。随溅射功率由30 W增至300 W,铝纳米颗粒薄膜的沉积速率由3.03 nm/min增加至20.03 nm/min;而随溅射压强由1 Pa增加至3 Pa,沉积速率由2.95 nm/min降低到1.66 nm/min。在溅射功率为150 W,溅射压强为1.0 Pa条件下制备的样品具有良好的晶粒分布。随溅射功率从80 W增大到160 W,样品电阻率由4.0×10-7Ω·m逐渐减小到1.9×10-7Ω·m;而随溅射压强从1 Pa增至3 Pa,样品电阻率由1.9×10-7Ω·m增加到7.1×10-7Ω·m。     

磁控溅射低温制备ZnO:Al透明导电薄膜的正交设计

采用锌铝(2%(质量分数))合金靶,保持真空腔在50℃低温下,结合正交试验表,运用直流反应磁控溅射法制得ZnO∶Al(ZAO)薄膜.通过分光光度计、半导体霍尔效应测试等手段对薄膜各项性能进行了表征.通过正交分析法对所得样品相关特征指标进行分析,在少量的9组实验下,得到溅射功率、时间、靶基距和氧流量百分比4个独立工艺参数对薄膜特性影响的同时,得出直流反应磁控溅射法制备ZAO薄膜的最优组合工艺为:溅射时间20min,靶基距6cm,溅射功率80W,氧流量百分比7%;对应样品的Фic值达4.1050×10-2/Ω,电阻率为3.9×10-4Ω·cm,载流子浓度达1.09×1021/cm3.     

Structures and properties of the Al-doped ZnO thin films prepared by radio frequency magnetron sputtering

Al-doped ZnO thin films were deposited by radio frequency magnetron sputtering using a ZnO target with 2 wt.% Al₂O₃. The structures and properties of the films were characterized by the thin film X-ray diffraction, high resolution transmission electron microscopy, Hall system and ultraviolet/visible/near-infrared spectrophotometer. The Al-doped ZnO film with high crystalline quality and good properties was obtained at the sputtering power of 100 W, working pressure of 0.3 Pa and substrate temperature of 250 °C. The results of further structure analysis show that the interplanar spacings d are enlarged in other directions besides the direction perpendicular to the substrate. Apart from the film stress, the doping concentration and the doping site of Al play an important role in the variation of lattice parameters. When the doping concentration of Al is more than 1.5 wt.%, part of Al atoms are incorporated in the interstitial site, which leads to the increase of lattice parameters. This viewpoint is also proved by the first principle calculations.     

Cu2O thin films deposited by reactive direct current magnetron sputtering

The Cu₂O thin films were prepared on quartz substrate by reactive direct current magnetron sputtering. The influences of oxygen partial pressure and gas flow rate on the structures and properties of deposited films were investigated. Varying oxygen partial pressure leads to the synthesis of Cu₂O, Cu₄O₃ and CuO with different microstructures. At a constant oxygen partial pressure of 6.6 × 10^− 2 Pa, the single Cu₂O films can be obtained when the gas flow rate is below 80 sccm. The as-deposited Cu₂O thin films have a very high absorption in the visible region resulting in the visible-light induced photocatalytic activity.