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%.     

掺杂透明导电半导体薄膜的光电性能研究

掺杂氧化锌透明导电膜(AZO)是一种重要的光电子信息材料，其制备方法有真空蒸镀法、磁控溅射法，化学气相沉积和脉冲激光沉积法等。该文采用溶胶 凝胶（sol gel)工艺在普通玻璃基片上成功地制备出Al3+掺杂型ZnO透明导电薄膜。将这种薄膜在空气和真空中以不同的温度进行了退火处理，并对薄膜进行了XRD分析和光电性能研究。结果表明，所制备的薄膜为钎锌矿型结构，在c轴方向择优生长，真空退火有利于薄膜结晶状况的改善，并使薄膜的载流子浓度大幅度地增加而电阻率下降，并且真空退火对薄膜的透射率影响不大。     

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.     

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.     

The transparence comparison of Ga- and Al-doped ZnO thin films

The Ga-doped ZnO (GZO) and Al-doped ZnO (AZO) thin films were grown on quartz glass substrates by pulsed laser deposition under different oxygen partial pressures (PO₂). The transparent performances of films versus properties of structure and conductivity were discussed. With the increase of PO₂, the transmittance of both GZO films and AZO films increased to maximum and then decreased which were in according with the change of crystallization quality. The transmittance of GZO films was higher than that of AZO films, which were not dominated by the impurity ions induced by doping. AFM images and surface roughness mean square coefficients showed that the surfaces of GZO films were smoother than that of AZO films, which were due to the dopant Ga acting as the surfactant and smoothed the GZO films surface.     

Improvement in electrical and photovoltaic properties of a-Si/c-Si heterojunction with slanted nano-columnar amorphous silicon thin films for photovoltaic applications

The flat a-Si and slanted nanocolumnar (S-nC) a-Si thin films were prepared on c-Si and corning glass substrates by e-beam physical vapor deposition (EB-PVD) technique. The structural properties of all the grown thin films were determined by X-Ray Diffraction (XRD) analysis and Raman spectroscopy. Surface and cross-sectional morphology of a-Si/c-Si and S-nC a-Si/c-Si heterojunctions were investigated by Field Emission Scanning Electron Microscopy (FE-SEM). Sculptured thin films demonstrate potential for significant nanoscale applications in the area of thin film technology. The electrical and photovoltaic properties of these heterojunctions have been investigated by means of dc current–voltage (I–V) measurements at room temperature in dark and light conditions. The S-nC STFs' performance has been found to be improvable on changing the morphology of the thin film. We have found that, the porous morphology of this structure improves the photosensitivity features in photovoltaic devices and solar cell technology. We gained a high open voltage value, such as 900 mV in S-nC a-Si/c-Si thin film, without any doping process.     

Surface roughness characterization of Al-doped zinc oxide thin films using rapid optical measurement

Transparent conductive oxide thin films have been widely investigated in photoelectric devices such as flat panel display (FPD) and solar cells. Al-doped zinc oxide (AZO) thin films have been widely employed in FPD. Measuring the surface roughness of AZO thin films is important before the manufacturing of photoelectric device using AZO thin films because surface roughness of AZO thin films will significantly affect the performance of photoelectric device. Traditional methods to measure surface roughness of AZO thin films are scanning electron microscopy and atomic force microscopy. The disadvantages of these approaches include long lead time and slow measurement speed. To solve this problem, an optical inspection system for rapid measurement of the surface roughness of AZO thin films is developed in this study. It is found that the incident angle of 60° is a good candidate to measure the surface roughness of AZO thin films. Based on the trend equation y=−3.6483x+2.1409, the surface roughness of AZO thin films (y) can be directly deduced from the peak power density (x) using the optical inspection system developed. The maximum measurement-error rate of the optical inspection system developed is less than 8.7%.The saving in inspection time of the surface roughness of AZO thin films is up to 83%.     

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

Transparent conducting oxide (TCO) thin films such as SnO2, In2O3, and Cd2SnO4, have been used extensively as sensor devices, surface acoustic wave devices, coating to heat glass windows and transparent electrodes for solid state display devices, solar cells[1,2] because of their high optical transparency in the visible range, infrared reflec-tance and low d.c. resistivity. Although SnO2 film was developed early, nowadays Sn-doped In2O3 (ITO) films are the predominant TCO thin film in …     

Effects of substrate temperature on the efficiency of hydrogen incorporation on the properties of Al-doped ZnO films

Al-doped ZnO (AZO) transparent conducting films were successfully prepared on glass substrates by RF magnetron sputtering at different substrate temperatures in Ar and H₂ + Ar sputtering ambient. The effects of substrate temperature on the effectiveness of hydrogen incorporation in Al-doped ZnO films were investigated. The microstructural, electrical and optical properties of AZO films were systematically analyzed by surface profiler, X-ray diffractometry, scanning electron microscope, four-point probe measurement and UV/vis spectrophotometer. The XRD patterns and SEM pictures indicate that the crystallinity of AZO thin films was markedly improved with hydrogen incorporation at low substrate temperature, while the improvement of crystallinity was not an obvious change at high substrate temperature. The results also indicate that hydrogen incorporation has the stronger effectiveness on the transparent conductive properties of AZO films with the substrate temperature decreasing. The resistivity of the films decreases, especially for lower substrate temperatures, due to the incorporation of hydrogen atoms. These results suggest that substrate temperature should be controlled to the lower level to effectively reduce resistivity without detriment to transmittance of AZO thin films when hydrogen is incorporated.     

Growth and characterization of pulsed laser deposited ZnO thin films

One of the most important and promising materials from metal oxides is ZnO with specific properties for near UV emission and absorption optical devices. The properties of ZnO thin films strongly depend on the deposition method. Among them, pulsed laser deposition (PLD) plays an important role for preparing various kinds of ZnO films, e.g. doped, undoped, monocrystalline, and polycrystalline. Different approaches — ablation of sintered ZnO pellets or pure metallic Zn as target material are described. This contribution is comparing properties of ZnO thin films deposited from pure Zn target in oxygen atmosphere and those deposited from sintered ZnO target. There is a close connection between final thin film properties and PLD conditions. The surface properties of differently grown ZnO thin films are measured by secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, different approaches — ablation of sintered ZnO pellet or pure metallic Zn as target materials are described. The main results characterize typical properties of ZnO films versus technological parameters are presented. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Optical constants of Na-doped ZnO thin films by sol-gel method

The structural and optical properties of pure and Na-doped ZnO thin films have been investigated by X-ray diffraction (XRD), atom force microscopy and UV-Vis spectrophotometer. The crystal structure of all the thin films is the hexagonal wurtzite. The average grain size and surface roughness increases with the increase of the Na/Zn ratio. The optical band gap of the thin films decreases from 3.26 to 3.12 eV by increasing the Na/Zn ratio from 0.0 to 0.10. Transmittance spectra were used to determine the optical constants of the thin films, and the effect of Na/Zn ratio on the optical constants was investigated. With the increase of Na/Zn ratio, the refractive index decreases and the extinction coefficient increases in the 380-700 nm spectral range.     

气相沉积法制备聚酰亚胺薄膜的热环化研究

采用两种单体同时蒸发沉积聚合方法制备得到聚酰亚胺（PI）薄膜。对不同温度下和不同恒温时间的聚酰胺酸（PAA）薄膜进行了红外分析,将300 ℃恒温3 h以上的薄膜脱膜,用白光干涉仪测量了PI薄膜热环化前后表面质量。采用热重分析仪在不同升温速率条件下对薄膜进行了分析。结果表明,在热环化过程中,随着温度增加亚胺化程度逐渐增加。在300 ℃时随着恒温时间增加亚胺化程度逐渐增加,恒温3 h以上薄膜亚胺化较为完全,可以获得完整且不易破损的自支撑薄膜。在热环化过程中,升温速率较低时薄膜的亚胺化程度在低温区转化率提高,过量单体蒸发更完全,故一般选择较小的升温速率,约10 ℃/min甚至更低。采用上述热环化工艺得到了亚胺化程度较高且不易破损的PI薄膜,其表面均方根粗糙度为9.8 nm。     

Excimer laser deposition of thin amorphous carbon films

A new carbon film deposition technique, based upon excimer laser vaporization of graphite in a flowing gas system has been developed. The low temperature vapor (LTV) technique alleviates high temperatures occurring in most other deposition methods. In this technique the UV laser ablation occurs in an inert flowing gas atmosphere. Atoms and molecules evaporated from graphite are cooled by gas entrainment before condensing on a substrate. The resulting films of amorphous carbon or hydrogenated amorphous carbon are free from strain. Measurement of the optical band gap of these films shows that E_g can be controlled by the hydrogen content of the carrier gas.     

气相沉积法制备聚酰亚胺薄膜的热环化研究

采用两种单体同时蒸发沉积聚合方法制备得到聚酰亚胺（PI）薄膜。对不同温度下和不同恒温时间的聚酰胺酸（PAA）薄膜进行了红外分析,将300 ℃恒温3 h以上的薄膜脱膜,用白光干涉仪测量了PI薄膜热环化前后表面质量。采用热重分析仪在不同升温速率条件下对薄膜进行了分析。结果表明,在热环化过程中,随着温度增加亚胺化程度逐渐增加。在300 ℃时随着恒温时间增加亚胺化程度逐渐增加,恒温3 h以上薄膜亚胺化较为完全,可以获得完整且不易破损的自支撑薄膜。在热环化过程中,升温速率较低时薄膜的亚胺化程度在低温区转化率提高,过量单体蒸发更完全,故一般选择较小的升温速率,约10 ℃/min甚至更低。采用上述热环化工艺得到了亚胺化程度较高且不易破损的PI薄膜,其表面均方根粗糙度为9.8 nm。     

Structural and physical properties of ZnO:Al films grown on glass by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on glass substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and grow with a c-axis orientation in the film growth direction. The films grow mainly with columnar grains perpendicular to the substrate and some granular grains also exist in the films. The film deposited at 673 K and 0.4 Pa has the largest grains whereas that prepared at 300 K and 0.4 Pa consists of the smallest grains and is porous. The films exhibit an n-type semiconducting behavior at room temperature. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity (3.40 × 10⁻³ Ω cm), the highest free electron concentration (4.63 × 10²⁰ cm⁻³) and a moderate Hall mobility (4.0 cm² V⁻¹ s⁻¹). The film deposited at 300 K and 0.4 Pa has the highest resistivity and the lowest free electron concentration and Hall mobility. A temperature dependence of the resistivity reveals that the carrier transport mechanism is Mott’s variable range hopping in the temperature region below 100 K and thermally activated band conduction above 215 K. The activation energy for the film deposited at 300 K and 0.4 Pa is 41 meV and that for the other films is about 35 meV. All the films have an average optical transmittance of over 85% in the visible wavelength range. The absorption edge of the film deposited at 300 K and 0.4 Pa shifts to the longer wavelength (redshift) relative to the films prepared under the other conditions.     

Electroluminescence of double-doped diamond thin films

A new electroluminescence device is fabricated by microwave plasma chemical vapour deposition system and electron beam vapour deposition system. It is comprised of highly doped silicon/diamond/boron/nitrogen-doped diamond/indium tin oxide thin films. Effects of process parameters on morphologies and structures of the thin films are detected and analysed by scanning electron microscopy, Raman spectrometer and x-ray photoelectron spectrometer. A direct-current (DC) power supply is used to drive the electroluminescence device. The blue light emission with a luminance of 1.2 cd·m 2 is observed from this double-doped diamond thin film electroluminescence device at an applied voltage of 105 V.     

Magnetoelectrical properties of W doped ZnO thin films

ZnO thin films were deposited on the Si(100) substrate by rf sputtering using a 99.999% pure commercially bought and a home made target under 100 W power. The home made ZnO target, including 1–2% tungsten, was synthesized via solid state reaction. Thin films were deposited under a flow of 70% argon and 30% O₂ gas mixture followed by post-deposition annealing under 1 Torr oxygen atmosphere. Both deposition and post-deposition annealing were done at 420±1 °C. The structural analyses show that the films were in the [0002] preferred direction and that W atoms are bound to the oxygen atoms by replacing the Zn host atoms. Although no specific change was observed in the magnetic properties as a result of W doping, significant changes in the electrical properties were observed, as determined by the longitudinal and transversal magneto-electrical measurements. It was found that the W impurities induce better insulating properties due to lower carrier concentration and higher resistivity values. On the other hand, the enhanced positive magnetoresistivity and the existence of polarized spin currents, which were not specific for pure ZnO thin films, were observed in W doped ZnO films below 10 K.     

热处理参数对溶胶-凝胶法制备氧化锌薄膜特性的影响

采用溶胶-凝胶旋涂法在Si(111)衬底上生长了ZnO薄膜，并用荧光光谱、原子力显微镜和XRD对ZnO薄膜样品进行了分析.结果表明，溶胶-凝胶旋涂法制备的ZnO薄膜为纤锌矿结构，其c轴取向程度与热处理温度有很大的关系.当热处理温度小于550℃时，氧化锌薄膜在室温下均有较强的紫外带边发射峰，而可见波段的发射很弱；当热处理温度高于550℃时，可见波段发射明显增强.对经过不同时间热处理的ZnO薄膜样品分析表明，氧化锌薄膜的荧光特性及表面形貌与热处理时间也有很大关系，时间过短可见波段的发射较强，但时间过长会导致晶 关键词： ZnO薄膜 光致发光     

Influence of glucose on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method on glass substrates followed by calcinations at 500 °C for an hour. The effect of glucose on the structure and optical properties of the films was studied. The structural characteristics of the samples were analyzed by X-ray diffractometer (XRD) and atomic force microscope (AFM). The optical properties were studied by a UV-visible spectrophotometer. The results show that some of the prepared ZnO thin films have a high preferential oriented c-axis orientation with compact hexagonal wurtzite structure due to a proper amount of glucose introducing. After introducing the glucose additive in ZnO colloids, the intensity of (002) peak, the transmittance, and the optical band gap of the ZnO thin films increases because of the enhanced ZnO crystallization. On the contrary, the absorbance, the film thickness, and the surface root-mean-square (RMS) roughness of the ZnO thin films decreases. The glucose additive could not only improve the surface RMS roughness and microstructure of ZnO thin films, but also enhance the transmittance and the energy band gap more easily.     

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.