镍掺杂对FTO薄膜光电性能的影响及机理分析

硅酸盐通报 ›› 2023, Vol. 42 ›› Issue (9): 3379-3386.

镍掺杂对FTO薄膜光电性能的影响及机理分析

吴宝棋¹, 张琴¹, 刘起英², 史国华², 赵洪力¹

1.燕山大学材料科学与工程学院亚稳材料制备技术与科学国家重点实验室, 秦皇岛 066004;
2.威海中玻新材料技术研发有限公司,威海 264200

收稿日期:2023-05-05 修订日期:2023-06-20 出版日期:2023-09-15 发布日期:2023-09-14
通信作者: 赵洪力,博士,教授。E-mail:zhaohongli@ysu.edu.cn
作者简介:吴宝棋(2000—),男,硕士研究生。主要从事透明氧化物薄膜方面的研究。E-mail:wubaoqi0717@163.com
基金资助:
国家自然科学基金(52172105);泰山产业领军人才工程

Effect of Ni-Doping on Optical and Electrical Properties of FTO Thin Film and Its Mechanism Analysis

WU Baoqi¹, ZHANG Qin¹, LIU Qiying², SHI Guohua², ZHAO Hongli¹

1. State Key Laboratory of Metastable Materials Preparation Technology and Science, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, China;
2. Weihai CNG New Material Technology R&D Co., Ltd., Weihai 264200, China

Received:2023-05-05 Revised:2023-06-20 Online:2023-09-15 Published:2023-09-14

摘要/Abstract

摘要： 本文以单丁基三氯化锡(MBTC)为锡源,氟化铵(NH₄F)为氟源,甲醇为溶剂,六水合氯化镍(NiCl₂·6H₂O)为镍源,采用气溶胶辅助化学气相沉积(AACVD)制备了镍掺杂FTO薄膜。利用分光光度计、四探针电阻仪及霍尔效应测试仪对镍掺杂FTO薄膜的光学性能、电学性能进行表征和分析,并基于第一性原理对掺杂体系的电子结构进行了计算。结果表明,Ni掺杂的FTO薄膜为四方金红石结构,导电性能有所提高。当Ni/Sn为2%(原子数分数)时,品质因数Φ_TC达到3×10^-2 Ω^-1,电阻率ρ为3.79×10^-4 Ω·cm,可见光平均透过率约为80%,载流子浓度n为6.88×10²⁰ cm^-3,迁移率μ为13.31 cm²·V^-1·s^-1。

关键词: 镍掺杂, FTO薄膜, 气溶胶辅助化学气相沉积, 电学性质, 第一性原理

Abstract: Ni-doped FTO thin films were prepared by aerosol-assisted chemical vapor deposition (AACVD) using monobutyltin trichloride (MBTC) as tin source, ammonium fluoride (NH₄F) as fluorine source, methanol as solvent, and nickel chloride hexahydrate (NiCl₂·6H₂O) as nickel source. The optical and electrical properties of FTO thin films were characterized and analyzed by spectrophotometer, four-probe resistor meter and Hall effect tester. The electronic structure of doped system was calculated based on first principles as well. The results indicate that the Ni-doped FTO thin films are tetragonal rutile structure, and the conductivity is improved. When Ni/Sn is 2%(atomic fraction), the quality factor Φ_TC reaches 3×10^-2 Ω^-1, the resistivity ρ is 3.79×10^-4 Ω·cm, the average transmittance of visible light is about 80%, the carrier concentration n is 6.88×10²⁰ cm^-3, and the mobility μ is 13.31 cm²·V^-1·s^-1.

Key words: Ni-doping, FTO thin film, AACVD, electrical property, first principle

中图分类号:

TB43

吴宝棋, 张琴, 刘起英, 史国华, 赵洪力. 镍掺杂对FTO薄膜光电性能的影响及机理分析[J]. 硅酸盐通报, 2023, 42(9): 3379-3386.

WU Baoqi, ZHANG Qin, LIU Qiying, SHI Guohua, ZHAO Hongli. Effect of Ni-Doping on Optical and Electrical Properties of FTO Thin Film and Its Mechanism Analysis[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(9): 3379-3386.

参考文献

[1] 冯梦现, 黄新友, 孙景峰, 等. 二氧化锡透明导电薄膜的研究进展[J]. 中国陶瓷, 2018, 54(1): 1-6.
FENG M X, HUANG X Y, SUN J F, et al. Researching progress of SnO₂ transparent conductive films[J]. China Ceramics, 2018, 54(1): 1-6 (in Chinese).
[2] XIONG L B, GUO Y X, WEN J A, et al. Review on the application of SnO₂ in perovskite solar cells[J]. Advanced Functional Materials, 2018, 28(35): 1802757.
[3] ZHANG Y, XU W X, XU X J, et al. Self-powered dual-color UV: green photodetectors based on SnO₂ millimeter wire and microwires/CsPbBr₃ particle heterojunctions[J]. The Journal of Physical Chemistry Letters, 2019, 10(4): 836-841.
[4] WANG L K, YU J Y, NIU X Y, et al. Effect of F and Nb co-doping on structural, electrical and optical properties of spray deposited tin oxide thin films[J]. Thin Solid Films, 2018, 649: 147-153.
[5] BOUZNIT Y, HENNI A. Characterization of Sb doped SnO₂ films prepared by spray technique and their application to photocurrent generation[J]. Materials Chemistry and Physics, 2019, 233: 242-248.
[6] WANG G, WANG L K, ZHU Y, et al. Insight into electronic structure and optical properties of Nb and F co-doped SnO₂ with hybrid functional theoretical method[J]. Ceramics International, 2020, 46(8): 10341-10347.
[7] SHI G Y, HASHIMOTO T, TRYK D A, et al. Enhanced oxygen reduction electrocatalysis on PtCoSn alloy nanocatalyst mediated by Ta-doped SnO₂ support for polymer electrolyte fuel cells[J]. Electrochimica Acta, 2021, 390: 138894.
[8] JO M H, KOO B R, AHN H J. Fe co-doping effect on fluorine-doped tin oxide transparent conducting films accelerating electrochromic switching performance[J]. Ceramics International, 2020, 46(8): 10578-10584.
[9] BÉLANGER D, DODELET J P, LOMBOS B A, et al. Thickness dependence of transport properties of doped polycrystalline tin oxide films[J]. Journal of the Electrochemical Society, 1985, 132(6): 1398-1405.
[10] MRABET C, BOUKHACHEM A, AMLOUK M, et al. Improvement of the optoelectronic properties of tin oxide transparent conductive thin films through lanthanum doping[J]. Journal of Alloys and Compounds, 2016, 666: 392-405.
[11] HARTMAN P. Crystal growth: an introduction[M]. American: North-Holland Publishing Company, 1973.
[12] SMITH A. Pyrosol deposition of ZnO and SnO₂ based thin films: the interplay between solution chemistry, growth rate and film morphology[J]. Thin Solid Films, 2000, 376(1/2): 47-55.
[13] BURSTEIN E. Anomalous optical absorption limit in InSb[J]. Physical Review, 1954, 93(3): 632-633.
[14] SOUSSI L, GARMIM T, KARZAZI O, et al. Effect of (Co, Fe, Ni) doping on structural, optical and electrical properties of sprayed SnO₂ thin film[J]. Surfaces and Interfaces, 2020, 19: 100467.
[15] HOUAIDJI N, AJILI M, CHOUIAL B, et al. First investigation of structural and optoelectronic properties of F and Ni co-doped SnO₂ sprayed thin films[J]. Optik, 2020, 208: 164026.
[16] VICTOR BABU A, MURUGAN S, BERNICEVICTORIA D C, et al. A novel study on augmented physical parameters of nickel doped stannic oxide film[J]. Materials Research Express, 2020, 7(12): 124001.
[17] AMER M I, MOUSTAFA S H, EL-HAGARY M. Enhanced band structure, optoelectronic and magnetic properties of spray pyrolysis Ni-doped SnO₂ nanostructured films[J]. Materials Chemistry and Physics, 2020, 248: 122892.
[18] HASSANIEN A, HASHEM H, KAMEL G, et al. Performance of transparent conducting fluorine-doped tin oxide films for applications in energy efficient devices[J]. Thin Films Science and Techology, 2016, 5: 55-65.
[19] GAO Q A, JIANG H, LI C J, et al. Tailoring of textured transparent conductive SnO₂∶F thin films[J]. Journal of Alloys and Compounds, 2013, 574: 427-431.
[20] THOMAS R, MATHAVAN T, JOTHIRAJAN M, et al. An effect of lanthanum doping on physical characteristics of FTO thin films coated by nebulizer spray pyrolysis technique[J]. Optical Materials, 2020, 99(C): 109518.