多元氧化物结构复合式透明导电薄膜的研究

In order to broaden the application of transparent conductive film, and to make the use of sunlight efficiently, research take great effort to achieve the high transmittance in near infrared spectrum of high conductive films; also to make the p-n node active devices become transparent, research on the realization of high conductivity of P doped transparent conductive thin films. During this process the applicant is putting forward to prepare Zn-Sn-O thin films by the method of CVD, using Zn, Sn metal organic source for reaction precursor. In order to achieve controllable optical band gap of the film,and improve infrared transmittance selectivitly. Research on conditions for preparation of doped n type and p type conductive film. Creatively put forward the design of the structural combined type of thin film, with the combination of structure and electrical characteristics of different barrier layer of structural combined type of transparent conducting thin film,the optical properties, electrical properties and low radiation performance of the thin film will be studied, to make films get low infrared emissivity ( < 0.15 ) and low resistivity ( < 10-4 Ωocm) on the basis of high transmittance of visible light ( > 85% ),and have better thermal stability， in order to adapt to different areas of the the requirements of TCO film. The growth mechanism of Zn-Sn-O thin films of this project will be clear under CVD conditions.The infrared transmittance and the mechanism of doping elements effect on the electrical properties of thin film will be studied. With the combination of structure and electrical characteristics of different barrier layer of structural combined type of transparent conducting thin film,the optical properties, electrical properties and low radiation performance of the thin film will be studied, to make films get low infrared emissivity ( < 0.15 ) and low resistivity ( < 10-4 Ωocm) on the basis of high transmittance of visible light ( > 85% ),and have better thermal stability， in order to adapt to different areas of the the requirements of TCO film. the preparation conditions and the conductive mechanism of doped film will be concerned, the high conductive film with p doped type will be realized at last. From the analysis and practice, the influence of conductive layer and transition layer effect on the optical and electrical properties of structural composite thin film will be studied.

为拓宽透明导电薄膜的应用范围，实现太阳光的高效利用，研究重点突破高导电薄膜在近红外的高透过率；为使p-n结有源器件的透明化，研究实现透明导电薄膜的高导电率p型掺杂。在此过程中，申请者提出采用CVD方法以Zn、Sn的金属有机源为反应先驱体制备Zn-Sn-O薄膜，实现薄膜光学禁带宽度可控，红外透过率选择性增加；探讨n型和p 型导电薄膜的掺杂制备条件和影响机理；同时创新性提出结构复合式薄膜的设计思想，结合不同过渡层的结构与电学特点研究结构复合式薄膜的光学性能、电学性能和低辐射性能，使薄膜在高可见光透射率（＞85%）基础上，拥有红外低辐射率（＜0.15）和低电阻率（＜10-4Ωocm），同时具有较高热稳定性，以满足后续加工要求。本项目将重点关注透明导电薄膜的红外透过率规律，研究掺杂元素对薄膜光学、电学性能的影响机理及导电机理，探究结构复合式薄膜中导电层及过渡层对薄膜光学及电学性能造成的影响。

为了实现太阳光的高效利用和玻璃的节能保温，研究制备高导电性低辐射镀膜玻璃。为所制备的镀膜玻璃具有可见光高透过及中红外线高反射的性能，实验采用化学气相沉积法以Zn、Sn的金属有机源为反应前驱体，在玻璃衬底上制备Zn-Sn-O（简称ZTO）透明导电氧化物薄膜，利用SEM、XRD、紫外-可见分光光度计和四探针测试仪等分析方法，研究ZTO薄膜的生长机制，通过不同Sn/Zn比，调控薄膜光学禁带宽度，研究其对薄膜光学性能和低辐射性能的影响机理。实验结果表明：当锡锌比从1:1减少到1:2.6时，ZTO薄膜以SnO2四方金红石结构为主晶型，逐渐被ZnO纤锌矿结构取代，并伴随出现Zn2SnO4尖晶石结构。当Sn/Zn比为1:1.6时，薄膜成膜性质较好，膜厚度较均匀，约为713.24 nm，薄膜的方块电阻最小，半球辐射率最低，为0.167。通过不同的Sn/Zn比，调控薄膜的光学禁带宽度在3.22~3.30 eV范围内变化，实现在376~384 nm波段内太阳光的可控吸收与反射。实验研究结果表明：采用化学气相沉积的方法成功制取了具有节能效果的低辐射镀膜玻璃。实验还研究制备了两种不同复合方式的ZTO薄膜对结晶性质影响，依据二维错配度理论和双层型薄膜的XRD数据，经计算得出双层型薄膜的优先成核发生在ZnO晶体的（100）面与SnO2晶体的（110）面之间。