Transport characteristics of thermally degraded ZnO films doped with Al

The thermal degradation characteristics of Al doped ZnO (AZO) films, which were prepared by radio frequency magnetron sputtering at room temperature and subsequently annealed in air, were examined by making comparisons with those of the as-deposited and the vacuum-annealed AZO films. AZO films annealed in air at temperature higher than 300 °C exhibited severely degraded conductivity due to the decrease of carrier concentration and Hall mobility, which could be interpreted as grain boundary scattering from the thermally activated mobility behavior. Experimental observations, that vacuum-annealing of the as-deposited AZO film led to substantial reduction in carrier concentration and that subsequent vacuum-annealing of the air-annealed AZO film could not restore the carrier concentration unlike the restoration of Hall mobility up to 80%, led to a perception that substantial amount of free carriers in the as-deposited AZO film were generated from oxygen vacancies. It was proposed that ratios of the barrier height to the Fermi level, which were determined by taking into account the non-parabolic nature of the conduction band, could be used as a measure for the influence of grain boundary scattering on the overall electron transport mechanism in AZO films.     

Effects of substrate temperature and Zn addition on the properties of Al-doped ZnO films prepared by magnetron sputtering

Al-doped ZnO (AZO) films prepared at different substrate temperature and AZO films with intentional Zn addition (ZAZO) during deposition at elevated substrate temperature were fabricated by radio frequency magnetron sputtering on glass substrate, and the resulting structural, electrical, optical properties together with the etching characteristics and annealing behavior were comparatively examined. AZO films deposited at 150 °C showed the optimum electrical properties and the largest grain size. XPS analysis revealed that AZO films deposited at elevated temperature of 450 °C contained large amount of Al content due to Zn deficiency, and that intentional Zn addition during deposition could compensate the deficiency of Zn to some extent. It was shown that the electrical, optical and structural properties of ZAZO films were almost comparable to those of AZO film deposited at 150 °C, and that ZAZO films had much smaller etching rate together with better stability in severe annealing conditions than AZO films due possibly to formation of dense structure.     

Properties of ITO–AZO bilayer thin films prepared by magnetron sputtering for applications in thin-film silicon solar cells

In this paper we study the electro-optical behavior and the application of indium–tin oxide (ITO) and aluminum-doped zinc oxide (AZO) bilayer thin films for silicon solar cells. ITO–AZO bilayer thin films were deposited on glass substrates using radio-frequency magnetron sputtering. The experimental results show that a decrease in the electrical resistivity of the ITO–AZO bilayer thin films has been achieved without significant degradation of optical properties. In the best case the resistivity of the bilayer films reached a minimum of 5.075×10^?4 Ω?cm when the thickness of the AZO buffer layer was 12 nm. The ITO–AZO bilayer films were applied as the front electrodes of amorphous silicon solar cells and the short-circuit current density of the solar cells was considerably increased.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.     

粉末靶制备的AZO/Ag/AZO透明导电薄膜的光电性能

室温下,采用射频磁控溅射AZO粉末靶和Ag靶在玻璃基底上制备Ag层厚度分别为12 nm和15 nm两组对称结构掺铝氧化锌/银/掺铝氧化锌(AZO/Ag/AZO)透明导电薄膜,研究了Ag层和AZO层厚度对薄膜光电性能的影响。结果表明:3层薄膜的可见光区平均透光率达到了80%,550 nm处的最高透过率达到了88%,方块电阻小于5 Ω/□。Ag层厚度是影响AZO/Ag/AZO薄膜光电性能的主要因素,AZO层的厚度对薄膜光学性能影响较大。     

Spectroscopic Ellipsometry Study on Surface Roughness and Optical Property of AZO Films Prepared by Direct-Current Magnetron Reactive Sputtering Method

All as-deposited AZO films by direct current magnetron reactive sputtering （DC-MS） exhibit ZnO characteristic （002） and （103） diffraction peaks. Especially, AZO films prepared at 200℃ show a strongest （002） c-axis pref- erential orientation due to the minimum stress along the （002） orientation. The results show that larger stress easily induces a rougher surface. The film real and imaginary parts of dielectric constants show a sharp changes near the optical absorption edge due to the interband direct transition. The film blue and red shifts of the optical absorption edge can be explained in terms of the change of Free-electron concentration in as-deposited AZO films.     

功率密度对中频磁控溅射制备 AZO薄膜性能的影向

利用中频磁控溅射法在普通玻璃衬底上沉积掺铝氧化锌(ZnO ∶ Al,简称AZO)薄膜,通过调整溅射功率密度参数得到沉积速率与功率密度之间的关系,制备了不同厚度的AZO薄膜.利用台阶仪、XRD、XPS、紫外可见分光光度计和Hall测试系统等方法研究了功率密度与厚度对AZO薄膜结构、组分、光学和电学性能的影响.实验结果表明...     

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.     

The effect of SiO2 buffer layer on the electrical and structural properties of Al-doped ZnO films deposited on soda lime glasses

In this paper, the influence of SiO₂ buffer layer on electrical and structural properties of AZO films on soda lime glasses has been investigated. The results showed that the Hall mobility and carrier concentration of AZO films deposited on soda lime glasses at high temperature could be enhanced by introducing SiO₂ layers. The optical absorption edges of AZO films with SiO₂ buffer layer are blue shifted compared with that of buffer layer free due to the increase of carrier concentration. SiO₂ layers prepared at 400 °C more effectively suppress the diffusion of Na atoms into AZO films compared with that prepared at room temperature. On the other hand, the in-plane stress dependence of optical band gap is linear for AZO films deposited on quartz glass substrates, but is deviated from linearity in the case of soda lime glass substrates.     

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 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 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.     

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.     

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.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

生长条件对脉冲激光沉积制备ZnO：Al薄膜光电性能的影响

本文研究了脉冲激光沉积(PLD)生长过程中, 铝掺量、氧压及衬底温度等实验参数对ZnO:Al(AZO)薄膜生长的影响, 并利用扫描电子显微镜、原子力显微镜、X射线衍射、霍尔效应、光透射光谱等实验手段对其透明导电性能进行了探讨. 变温霍尔效应和光透射测量表明, 当靶材中铝掺量大于0.5 wt%时, 所制备AZO薄膜中铝施主在80 K时已完全电离, 因Bernstein-Moss (BM) 效应其带隙变大, 均为重掺杂简并半导体. 进一步系统研究了氧压和衬底温度对AZO薄膜透明导电性能的影响, 实验发现当氧压为1 Pa, 衬底温度为200 ℃时, AZO 导电性能最好, 其霍尔迁移率为28.8 cm²/V·s, 薄膜电阻率最小可达2.7×10^-4 Ω·cm, 且在可见光范围内光透过率超过了85%. 氧压和温度的增加, 都会导致薄膜电阻率变大. 关键词： 脉冲激光沉积法 ZnO：Al薄膜 透光性 导电性     

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.     

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.     

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.     

Damp heat and thermal cycling-induced degradation mechanism of AZO and CIGS films in Cu(In,Ga)Se2 photovoltaic modules

This paper characterizes and compares the degradation mechanisms of Cu(In,Ga)Se₂ (CIGS)-based thin film photovoltaic (PV) modules during exposure to damp heat (85 °C/85% RH) for 1000 h and thermal cycling (−40 °C/85 °C) for 1000 cycles. After damp heat (DH) exposure, the efficiency of the PV modules was reduced from the initial value of ∼12.5 ± 0.1% to 10.5 ± 0.2% due to increase of the resistivity in the AZO and CIGS layers. The optical band gap was also decreased from the initial value of 3.60 eV–3.54 eV after 1000-h DH exposure. This behavior was associated with oxygen adsorption and the generation of hydroxides in the AZO layer. The efficiency of the PV modules after subjection to thermal cycling (TC) was decreased to 11.4 ± 0.2% due to increase of the resistivity of the AZO and CIGS layers. The increase in the resistivity was interpreted as being due to oxygen adsorption, as well as the formation of micro-cracks in the AZO films.