柔性衬底氢掺杂ZnO:Al(AZO)薄膜的类金属导电性质及其应用研究

The study of metallike conductive properties in AZO thin films is a forward project in the areas of electronic information materials, physics and devices. However, there are some problems in the films prepared by magnetron sputtering method at low temperature, i.e. high and unstable resistivity etc. And also there are few reports about the films on flexible substrates. In this project, hydrogen will be doped into AZO films prepared on flexible substrates by magnetron sputtering method in order to improve their conductive properties and thermostability. By the characterization and analyses of structure, thermostability, electrical properties for the samples, the information can be obtained on microstructure, surface morphology, electronic states and dopants distribution in the samples. And it will be also discussed that the existing states of H-related defects in the films under different growing conditions and technical process, the influencing mechanism of H-related defects on the electrical properties, and how to improve long-term stability of the electrical properties in the films. On the basis of theoretical guidance, also by the adjustment of preparing conditions, the annealing treatment, and the surface treatment of substrates, the techniques will be further optimized, the controllable preparation of HAZO films can be realized on flexible substrates at low temperature, thin films with metallike conductive properties can be obtained and their conductive thermostability can be also effectively improved. Finally, the preparation conditions and techniques adapted to industrial production can be achieved, which will lay the theoretical and experimental foundation for the application of HAZO thin films to the area of flexible devices.

AZO薄膜类金属导电性质的研究是当前电子信息材料、物理与器件领域的前沿课题。但磁控溅射法在低温下制备的薄膜存在电阻偏高和稳定性较差等问题，且关于柔性衬底薄膜的研究相对较少。本项目拟利用磁控溅射技术，在柔性衬底上采用H掺杂的方法来改善AZO导电薄膜的导电性能及其热稳定性。通过对薄膜结构和热稳定性等的表征及对样品电学性能的测试分析，获得样品的微观结构、表面形貌、电子态、杂质分布等方面的信息，探讨不同生长条件和工艺技术下H相关缺陷在薄膜中的存在状态、H缺陷对薄膜电学性质的影响机理、及如何提高薄膜电学性能的长期稳定性。在理论指导的基础上，再通过改变生长条件、退火处理、衬底表面处理等手段，进一步优化工艺，实现低温下柔性衬底上HAZO薄膜的可控生长，获得具有类金属导电性质的薄膜，改善薄膜的热稳定性。最终获得适合生产条件下HAZO薄膜的制备工艺和技术，为实现其在柔性器件方面的应用奠定理论和实验基础。

柔性衬底上制备的ZnO基类金属透明导电薄膜在柔性显示、柔性太阳能电池等领域有广泛的应用前景。但由于柔性衬底质地柔软、不耐高温，造成柔性衬底上薄膜结晶质量差且容易开裂，严重影响其导电性能和热稳定性。本项目重点针对这一问题开展研究，利用磁控溅射室温下在柔性衬底上通过氢掺杂的方法来改善薄膜的导电性能及其热稳定性。.1、在石英等硬质衬底和PMMA、PET等柔性衬底上沉积ZnO基透明导电薄膜（ZnO、ZnO:Al、ZnO:Ga），研究制备条件和处理工艺对薄膜光电性能的影响，通过对样品微观结构、成分、电子态、杂质分布等方面的测试表征，分析了H相关缺陷在薄膜中的存在状态和作用机理。H的主要作用是钝化薄膜中吸附氧、Oi、VZn等本征受主缺陷，造成吸附氧的脱附、形成复合体(如VZn-Hn)和Oi逸出等，导致薄膜导电性能大为改善。.2、在机理分析的指导下，重点优化柔性衬底上薄膜的工艺参数，包括溅射功率、多次成膜工艺、高阻缓冲层、氢气流量比等，实现了低温下柔性衬底上薄膜的可控生长，有效提高了薄膜的导电性能。其中HAZO/AZO/PET薄膜电阻率为6.93×10-4 Ω·cm，可见光平均透过率T>85%。.3、开展了柔性衬底表面HAZO薄膜应用性能研究，重点测试了HAZO/AZO/PET薄膜的附着性能和热稳定性。样品的附着力为11.02 mN，非常接近商用ITO/PET薄膜（11.20 mN）；样品在不超过105℃环境中热稳定性达到△ρ<20%，也与商用ITO/PET相近。.4、针对薄膜近红外区域透过率较低的情况，以“降低载流子浓度，增大迁移率”为思路，选用1 wt.% Al2O3的靶材制备HAZO薄膜，在保持10-4 Ω·cm电阻率的条件下，薄膜在近红外区域的透过率得以提高。.5、AZO薄膜的导电性能好，SZO薄膜的热稳定性好，ZnO:Al-Sc透明导电薄膜实现了两种掺杂元素的优势互补，电阻率能达到10-4Ω·cm量级，优于SZO薄膜；热稳定性小于20%，优于AZO薄膜。分析认为薄膜的电学性能热稳定性与O相关缺陷态的类型和含量密切关联。.6、发表SCI论文25篇，EI论文4篇，中文核心论文2篇；授权中国发明专利3项，申请7项；项目主持人作为导师培养毕业研究生9人。