The thermoelectric conversion capabilities and stabilities of carbon nanotubes (CNTs) in n-type organic semiconductors are important properties that urgently need improvement for large-scale and low-grade thermal energy applications. Importantly, conventional methods for preparing n-type CNT sheets are disadvantageous because they are incompatible with printing, which is an inherent advantage of organic materials for large-scale applications. Herein, we report the systematic preparation of CNT sheets containing dopant polymers using a drop-casting method that enhances thermoelectric performance and is adaptable to printing. The CNTs exhibit a large, negative Seebeck (S) value that depends on the level of the highest occupied molecular orbital of the dopant polymer, with the optimal poly(N-vinyl-2-pyrrolidone)-poly(vinyl alcohol) graft copolymer (PVP–PVA) providing a large negative S value and a power factor of 289 μW m⁻¹ K⁻². The inclusion of 1,2-diphenylhydrazine as a secondary dopant significantly improved the ZT value of the PVP–PVA/CNT from 5.26 × 10⁻³ for the undoped system to 1.34 × 10⁻². Correspondingly, the power factor was ~20% more atmospherically stable after 31 d at room temperature compared to the undoped system. This excellent performance provides new avenues for the development of drop-cast fabricated n-type CNT films without the need for n-doping processes.

碳纳米管 (CNT) 在 n 型有机半导体中的热电转换能力和稳定性是重要的性质，在大规模和低品位热能应用中急需改进。重要的是，制备 n 型 CNT 片的常规方法是不利的，因为它们与印刷不兼容，这是有机材料用于大规模应用的固有优势。在此，我们报告了使用滴注法系统制备含有掺杂聚合物的 CNT 片材，该方法可提高热电性能并适用于印刷。碳纳米管表现出较大的负塞贝克 ( S ) 值，这取决于掺杂聚合物的最高占据分子轨道的水平，最佳聚 ( N-vinyl-2-pyrrolidone)-聚乙烯醇接枝共聚物 (PVP-PVA) 提供大的负S值和 289 μW m ^-1  K ^-2的功率因数。包含1,2-二苯肼作为二次掺杂剂显着提高了PVP-PVA/CNT的ZT值，从未掺杂系统的5.26 × 10 ^-3到1.34 × 10 ^-2。相应地，与未掺杂的系统相比，在室温下 31 天后，功率因数在大气中的稳定性高约 20%。这种优异的性能为开发滴铸制造的 n 型 CNT 薄膜提供了新的途径，而无需 n 掺杂工艺。