Ag基透明导电复合膜的制备及性能研究

发布时间：2018-01-25 23:34

本文关键词： 透明导电膜磁控溅射 ITO/Ag/ITO FTO/AgFTO AZO/Ag/AZO　出处：《山东建筑大学》2015年硕士论文　论文类型：学位论文

【摘要】：传统透明导电材料掺锡氧化铟(ITO)具有方阻低、可见光范围内透过性好等优点,被广泛用作各种显示器和太阳能电池的透明电极。然而,稀缺资源In不但价格昂贵,而且有毒,减少或避免对In的消耗必然成为透明导电膜的发展趋势。因此,可作为ITO替代品的掺氟氧化锡(FTO)和掺铝氧化锌(AZO)受到了人们越来越多的关注。但是,ITO、FTO和AZO等透明导电氧化物(TCO)的导电性能受制于半导体的导电机制,导电率难以实现进一步提高,故TCO已经越来越不能满足先进光电装置对其导电性能提出的更高要求。因此,深入探究比单层TCO厚度更薄、导电更好的三明治结构复合膜ITO/Ag/ITO(IAI)以及新型复合膜FTO/Ag/FTO(FAF)、AZO/Ag/AZO(ZAZ)的制备和性能具有特别重要的意义。本文利用直流磁控溅射法,在室温下玻璃基底上制备了ITO膜、Ag膜、ITO/Ag膜、Ag/ITO膜、ITO/Ag/ITO复合膜、FTO膜、FTO/Ag/FTO复合膜、AZO膜、AZO/Ag膜和AZO/Ag/AZO复合膜。采用扫描电子显微镜、原子力显微镜、表面轮廓仪、可见光分光光度计和四探针测量仪对薄膜的表面形貌、膜层厚度、光电学性能等进行表征。通过分析ITO和Ag膜的表面形貌、沉积规律和光电学性能可知：玻璃基底上沉积ITO膜后表面粗糙度增大,随着ITO沉积时间的延长,ITO膜沉积速率逐渐增大,透过率逐渐降低,方阻逐渐减小；随着Ag沉积时间的延长,Ag膜由岛状结构转变为连续薄膜,沉积速率逐渐减小,透过率逐渐降低,方阻逐渐减小。通过对ITO/Ag/ITO复合膜的结构特点和光电学性能分析可知：ITO/Ag/ITO复合膜的导电性能取决于Ag层,但明显受到外层ITO膜的影响；IAI复合膜中ITO(34nm)/Ag(11nm)/ITO(34nm)的光电学性能最佳,最大可见光透过率为85.97%,方阻为5.46Ω/sq,哈克性能指数为0.0404Ω-1。通过对FTO膜的组织结构、沉积规律、光电学性能分析可知,随着FTO沉积时间的延长,FTO的结构由均质状转变为大胞状,沉积速率变化较小,透过率先降低后提高,方阻始终超出四探针测量量程。通过研究FTO/Ag/FTO复合膜的光电学性能可知：FAF复合膜中FTO(50nm)/Ag(11nm)/FTO(50nm)的光电学性能最好,最大可见光透过率为83.31%,方阻为7.19Ω/sq,哈克性能指数为0.0224Ω-1。通过对比分析IAI和FAF复合膜的性能可知：FAF膜的哈克性能指数低,光电学性能明显不如IAI；IAI膜和FAF膜均在Ag膜厚度为11nm时获得最佳光电学性能。通过对AZO膜的组织结构、沉积规律和光电学性能分析可知：随着AZO沉积时间延长,AZO膜始终保持小胞状生长,沉积速率基本不变,透过率逐渐降低,方阻逐渐减小。通过对比ITO、FTO、AZO的特性可知：在沉积速率上,FTO最大,ITO次之,AZO最小；在光学性能上,AZO膜透过性最佳,ITO膜次之,FTO膜最差；在电学性能上,ITO膜导电性最佳,AZO膜次之,FTO膜最差。通过镀制不同Ag层厚度的AZO(25nm)/Ag膜并分析其表面形貌可知：底层AZO上Ag膜的生长过程为岛状结构→岛结构联合→网状结构→连续薄膜,且AZO(25nm)/Ag中Ag膜的临界厚度与Glass/Ag中基本一致。通过研究AZO/Ag/AZO光电学性能可知,AZO(27nm)/Ag(9nm)/AZO(27nm)的光电学性能最佳,最大可见光透过率为86.28%,方阻为4.29Ω/sq,哈克性能指数为0.0533Ω-1。通过对比分析IAI、FAF、ZAZ三种复合膜的性能可知,ZAZ的光电学性能明显优于IAI和FAF,且获得最优性能时中间层Ag膜厚度仅为9nm,底层AZO膜的低表面粗糙度和外层AZO膜的低沉积速率促使Ag膜在更薄厚度下连续。
[Abstract]:The traditional transparent conductive indium tin oxide (ITO) with low resistance, the range of visible light transmittance and good transparent electrode is widely used for various displays and solar cells. However, the scarcity of resources of In are not only expensive and toxic, reduce or avoid the consumption of In will become the development trend of transparent conductive film. Therefore, ITO can be used as substitute of fluorine doped tin oxide (FTO) and Al Zinc Oxide (AZO) have attracted more and more attention. However, ITO, FTO and AZO transparent conductive oxide (TCO) conductive performance in semi conductor by the conductive mechanism, the conductivity is difficult to achieve further improve. Therefore, TCO has been increasingly unable to meet the higher requirements of the advanced photoelectric device presented on the conductive properties. Therefore, in-depth study of the thickness of the thinner than single-layer TCO sandwich structure composite conductive film, better ITO/Ag/ITO (IAI), a novel composite membrane FTO/ Ag/FTO (FAF), AZO/Ag/AZO (ZAZ) preparation and performance is of great significance. This paper uses the DC magnetron sputtering at room temperature on glass substrate were prepared by ITO membrane, Ag membrane, ITO/Ag membrane, Ag/ITO membrane, ITO/Ag/ITO composite membrane, FTO membrane, FTO/Ag/FTO composite film, AZO film, AZO/Ag film and the AZO/Ag/AZO composite film by scanning electron microscopy, atomic force microscopy, surface profiler, visible light spectrophotometer and four probe measuring instrument of surface morphology, film thickness, optical properties were characterized. The surface morphology analysis of ITO and Ag films, deposition and photoelectric properties shows that: glass the substrate surface roughness of ITO film deposited after the degree increases, with increasing ITO deposition time, deposition rate of ITO film increases, the transmittance decreased, resistance decreased gradually; along with the prolonging of deposition time of Ag, the Ag film changes from the island structure for continuous film, sink The deposition rate decreases and the transmittance decreased, resistance decreased gradually. The structure characteristics of ITO/Ag/ITO composite films and photoelectric properties analysis showed that the ITO/Ag/ITO composite membrane conductivity depends on the Ag layer, but significantly affected by outer membrane ITO; IAI composite membrane ITO (34nm) /Ag (11nm (/ITO) 34nm) photoelectricproperties best, the maximum transmittance of visible light is 85.97%, the square resistance is 5.46 ohms /sq, Huck performance index is 0.0404 ohm -1. through the organizational structure of FTO film deposition, analysis performance of photoelectricity, with FTO deposition time of FTO, the structure changed from homogeneous to large the cellular deposition rate, small changes, through the first decreased and then increased, the square resistance always exceed four probe measurement range. The performance of FTO/Ag/FTO composite membrane by photoelectric research: FAF composite membrane FTO (50nm) /Ag (11nm) /FTO (50nm) of the optical performance of the best, the most High visible light transmittance is 83.31%, the square resistance is 7.19 ohms /sq performance index for the performance of the hack 0.0224 ohm -1. through the comparative analysis of IAI and FAF composite film: FAF film Huck performance index is low, photoelectric properties than IAI; IAI and FAF films in the thickness of Ag is 11nm the best photoelectric properties. The structure of AZO film, deposition and photoelectric properties analysis shows that with the deposition time of AZO prolonged, AZO film has always maintained vesiculate growth, the deposition rate is basically unchanged, the transmittance decreased, resistance decreased gradually. Compared with the ITO, FTO, AZO: the biggest characteristic that in FTO the deposition rate, ITO, AZO, minimum; optical performance, AZO membrane permeability, ITO membrane, FTO membrane is the worst; in the electrical properties of ITO films, the best, AZO membrane, FTO membrane is the worst. By depositing different thickness of Ag layer (AZO 25nm) /Ag film And analyze the surface morphology of the growth process of Ag film on the bottom of AZO island structure, network structure, and island structure combined with continuous thin film, and AZO (25nm) Glass/Ag Ag and the critical thickness of /Ag film in the same school. The performance through the research of AZO/Ag/AZO photoelectric, AZO (27nm) /Ag (9nm) /AZO (27nm) photoelectricproperties best, the maximum transmittance of visible light is 86.28%, the square resistance is 4.29 ohms /sq, Huck performance index is 0.0533 ohm -1. through the comparative analysis of IAI, FAF, the ZAZ performance of three kinds of membranes, ZAZ photoelectric properties are superior to those of IAI and FAF, and obtain the optimal performance the middle layer Ag film thickness is only 9nm, low deposition rate and roughness of the outer AZO film AZO film on the surface of low to a continuous Ag film in thinner thickness.

【学位授予单位】：山东建筑大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.2

【参考文献】