Zhang Zeyao, Yan Wenqing, Chen Yuguang, Chen Shaochuang, Jia Guodong, Sheng Jian, Zhu Sheng, Xu Zihan, Zhang Xinrui, Li Yan
Peking University Shenzhen Institute, Shenzhen 518057, China.
PKU-HKUST ShenZhen-HongKong Institution, Shenzhen 518057, China.
ACS Nano. 2022 Jan 25;16(1):1063-1071. doi: 10.1021/acsnano.1c08812. Epub 2021 Dec 20.
Possessing excellent electronic and mechanical properties and great stability, single-walled carbon nanotubes (SWCNTs) are exceptionally attractive in fabricating flexible transparent conductive films. Doping is a key step to further enhance the conductivity of the SWCNT films and the reliable doping is highly needed. We developed a feasible strategy that uses solid acids such as phosphotungstic acid (PTA) to dope the SWCNT films stably relying on the nonvolatility of the dopants. The sheet resistance of the films was reduced to around a half of the original value meanwhile with no obvious change in transmittance. The doping effect maintained during a 700 days' observation. The excellent flexibility of the PTA-doped films was demonstrated by a bending test of 1000 cycles, during which the sheet resistance and transmittance was basically unaffected. The blue shifts of G band in the Raman spectra and the increase of work function measured by the Kelvin probe force microscopy both reveal the p-type doping of the films by PTA. The strong acidity of PTA plays a key role in the doping effect by increasing the redox potential of the ambient O and thus the Fermi level of the SWCNTs is brought down. The great feasibility and robustness of our doping strategy are desirable in the practical application of SWCNT-based flexible transparent conductive films. This strategy can be extended to the p-type doping of various CNT-based assemblies (such as sponges and forests) as well as other material families, expanding the application spectrum of polyacids.
单壁碳纳米管(SWCNT)具有优异的电子和机械性能以及良好的稳定性,在制备柔性透明导电薄膜方面极具吸引力。掺杂是进一步提高SWCNT薄膜导电性的关键步骤,且迫切需要可靠的掺杂方法。我们开发了一种可行的策略,即使用磷钨酸(PTA)等固体酸,依靠掺杂剂的非挥发性来稳定地掺杂SWCNT薄膜。薄膜的方块电阻降低至约为原始值的一半,同时透光率没有明显变化。在700天的观察期内,掺杂效果得以保持。通过1000次循环的弯曲测试证明了PTA掺杂薄膜具有出色的柔韧性,在此期间方块电阻和透光率基本不受影响。拉曼光谱中G带的蓝移以及开尔文探针力显微镜测量的功函数增加均表明薄膜被PTA进行了p型掺杂。PTA的强酸性通过提高周围O的氧化还原电位在掺杂效果中起关键作用,从而降低了SWCNT的费米能级。我们的掺杂策略具有极大的可行性和稳健性,在基于SWCNT的柔性透明导电薄膜的实际应用中具有优势。该策略可扩展到各种基于CNT的组件(如海绵和森林)以及其他材料家族的p型掺杂,拓宽了多元酸的应用范围。