导电薄膜材料的研究进展

doi:10.11949/0438-1157.20230366

摘要/Abstract

摘要：

导电薄膜材料由于导电性好、透射率高、可弯曲折叠等优点，在光电转换、电热转换、电磁转换等领域应用广泛。薄膜材料的导电填料主要包括金属及其化合物、碳基材料和导电聚合物。单种导电材料往往难以适应导电性和稳定性的双重需求，两种或两种以上的导电材料以掺杂或组装的方式制备复合导电薄膜表现出更好的导电性和环境稳定性，表面改性是改善导电材料与衬底结合强度的有力方法。以导电性能为重点综述了各类导电薄膜材料的特性及优缺点，提出改善导电薄膜材料导电性和稳定性的建议，为导电薄膜材料的研究提供参考。

关键词: 膜, 电子材料, 复合材料, 稳定性

Abstract:

Due to the advantages of high conductivity, high transmittance and bendability, conductive film materials are widely used in photoelectric conversion, electrothermal conversion, electromagnetic conversion and other fields. Currently, conductive fillers for thin film materials mainly include metals and their compounds, carbon-based materials and conductive polymers. In general, it is difficult for a single conductive material to adapt to the dual needs of conductivity and stability. Composite conductive films prepared by doping or assembling two or more conductive materials show better conductivity and environmental stability. Surface modification is a powerful way to improve the bonding strength of conductive materials to substrates. This paper summarizes the characteristics, advantages and disadvantages of various conductive thin film materials focusing on the conductive properties, and puts forward suggestions for improving the conductivity and stability of conductive thin film materials, providing reference for the research of conductive thin film materials.

Key words: film, electronic materials, composites, stability

中图分类号:

TB 333

蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.

Bin CAI, Xiaolin ZHANG, Qian LUO, Jiangtao DANG, Liyuan ZUO, Xinmei LIU. Research progress of conductive thin film materials[J]. CIESC Journal, 2023, 74(6): 2308-2321.

图/表 8

图1 银片油墨(a)和银片/离子复合油墨(b)低温烧结机理示意图[15]

Fig.1 Schematic diagrams of low-temperature sintering mechanism of Ag flake ink (a) and Ag flake/ion composite ink (b)[15]

图2 玻璃包覆的亚微米铜粉薄膜的制备[25]

Fig.2 Preparation of thin film of submicron copper powder coated with glass[25]

图3 柔性CZA导电膜制作工艺[33]

Fig.3 Flexible CZA conductive film fabrication process[33]

图4 复合TCF的制备工艺示意图[46]

Fig.4 Schematic illustration of the fabrication process of composite TCF[46]

图5 (a) PEDOT∶PSS/ANFs复合薄膜的导电性[56]；(b) 导电聚合物薄膜的方块电阻与EG和Trion X-100含量的关系[54]；(c) 涂有2个循环AgNW的PDA@PC薄膜的透射率和电导率[18]；(d) 不同表面活性剂和喷涂法制备的TCF的透射率和方块电阻[42]

Fig.5 (a) Electrical properties of PEDOT∶PSS/ANFs composite films[56]; (b) Sheet resistance of conductive polymer films as a function of the content of EG and Triton X-100[54]; (c) Transmittance and conductivity of PDA@PC films coated with 2 cycles of AgNWs[18]; (d) Sheet resistance as a function of optical transmittance for the TCFs (SWCNT-H) prepared with different surfactants and spray coating method[42]

图6 在PET衬底上沉积Cu/石墨烯/AZO多层膜的原理图[68]

Fig.6 The schematic illustration of Cu/Graphene/AZO multilayer film deposited on the PET substrate[68]

图7 (a) 弯曲处理后的方块电阻[33]；(b) AZO膜和Cu/石墨烯/AZO膜方块电阻与应变的关系[68]；(c) 重复弯曲时AZO膜和Cu/石墨烯/AZO膜的电阻变化[68]；(d) PM300薄膜和PM300F薄膜的相对电阻变化与老化时间的关系[61]；(e) 有无MGFs涂层的原始AgNW、AgNW-ZnO和ZnO-AgNW膜在85℃下热退火120 h后的方块电阻变化[70]；(f)暴露在室温环境条件下120 d样品方块电阻的变化[70]

Fig.7 (a) The sheet resistance as a function of bending treatment[33]; (b) The sheet resistance of AZO and the Cu/Graphene/AZO multilayer versus strain[68]; (c) The resistance increase of AZO and the Cu/Graphene/AZO multilayer versus bending cycles[68]; (d) Relative resistance variation of PM300 film and PM300F film versus aging time[61]; (e) Sheet resistance changes of pristine AgNW, AgNW-ZnO and ZnO-AgNW with and without MGFs coating after thermal annealing at 85℃ for 120 h[70]; (f) Sheet resistance changes of the samples exposed to ambient condition at room temperature for 120 d[70]

表1 不同导电材料的导电性及优缺点

Table 1 Conductivity， advantages and disadvantages of different conductive materials

种类	表面电阻/(Ω/sq)	优点	缺点
金属及其化合物
氧化铟锡	10¹	导电性好、透射率高	毒性、资源稀缺、脆性大
纳米银	10^-2~10¹	导电性、透射率、柔韧性好	与基体结合弱、成本高
纳米铜	10⁰~10¹	导电性、柔韧性好，成本较低	室外暴露、氧化腐蚀下易被损坏
氧化锌	10²	易于掺杂其他元素提高光电性能、成本较低	弯曲、折叠容易损坏导电网络
碳基材料
碳纳米管	10²	导电性好、密度低、性能稳定	不易分散均匀
石墨烯	10²~10³	导电性好、密度低、性能稳定	存在表面缺陷、不易分散均匀
碳纤维	>10³	成本低、柔韧性好、性能稳定	不易分散均匀、导电性和透射率较低
导电聚合物	10⁰~10¹	导电性好、密度低、柔韧性好	成本较高、较易被氧化
MXene纳米片	10¹	高导电性、亲水性	力学性能较差
金属/碳基复合材料	10⁰~10¹	导电性好、力学性能好、稳定性好	成本较高，容易团聚

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