Abstract Poly(3,4-ethylenedioxythiophene/permethylated β-cyclodextrin) polypseudorotaxane (PEDOT⋅TMβCD) (P1) was synthesized by the chemical oxidation of 3,4-ethylenedioxythiophene (EDOT) as an inclusion complex with 2,3,6-tri-O-methyl β-cyclodextrin (TMβCD) (EDOT·TMβCD) with a five-fold excess of iron (III) chloride oxidant over the stoichiometric amount in water. The obtained P1 was converted to its P2 polyrotaxane by the end capping of the PEDOT backbones with bulky triphenylmethane to avoid the dethreading of TMβCD. The chemical structures of P1 and P2 were proved by FT-IR and 1H NMR spectroscopy. The coverage ratios of the P1 and P2 chains were found to be 43.7 ± 5.2% and 27.1 ± 2.8%, respectively. Rotaxane formation results in improvements of the solubility in common organic solvents, as well better film forming ability combined with a high transparency. The UV–Vis absorption of P2 in C6H5Cl/CHCl3 (1/1 v/v) exhibits a hypsochromic shift of 4 nm compared with P1. Atomic force microscopy, AFM, indicated that the P1 film is more uniformly distributed over the substrate area compared to that of the P2, although both surfaces have the roughness parameter values close to 2.90 nm. The newly synthesized compounds were then applied as dopant/additive-free hole transport materials in perovskite solar cells. P1 exhibited a photovoltaic performance of 5.54% under 1 sun illumination, whereas P2 showed a lower efficiency (3.8%) attributed to its lower photocurrent density. These performances are comparable to those obtained for control devices using as hole transporter spiro-OMeTAD (6.27% as dopant/additive-free hole transport material, 14.41% in LiTFSI and tert-butylpyrridine doped system).

中文翻译：

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聚（3,4-亚乙基二氧噻吩/全甲基化β-环糊精）聚假轮烷和聚轮烷：钙钛矿太阳能电池中空穴传输材料的合成、表征和应用

摘要 聚（3,4-亚乙基二氧噻吩/全甲基化 β-环糊精）聚假轮烷（PEDOT⋅TMβCD）（P1）是通过 3,4-亚乙基二氧噻吩（EDOT）与 2,3,6-三-O-甲基 β-环糊精 (TMβCD) (EDOT·TMβCD) 与水中的化学计量量相比，氯化铁 (III) 氧化剂过量五倍。通过用庞大的三苯甲烷封端 PEDOT 主链，将获得的 P1 转化为其 P2 聚轮烷，以避免 TMβCD 脱螺纹。P1和P2的化学结构由FT-IR和1H NMR光谱证实。发现 P1 和 P2 链的覆盖率分别为 43.7 ± 5.2% 和 27.1 ± 2.8%。轮烷的形成提高了在普通有机溶剂中的溶解度，以及更好的成膜能力和高透明度。与 P1 相比，P2 在 C6H5Cl/CHCl3 (1/1 v/v) 中的 UV-Vis 吸收表现出 4 nm 的低色移。原子力显微镜 (AFM) 表明，与 P2 相比，P1 薄膜更均匀地分布在基板区域上，尽管两个表面的粗糙度参数值都接近 2.90 nm。然后将新合成的化合物用作钙钛矿太阳能电池中的掺杂剂/无添加剂空穴传输材料。P1 在 1 次阳光照射下表现出 5.54% 的光伏性能，而 P2 由于其较低的光电流密度而表现出较低的效率（3.8%）。这些性能与使用作为空穴传输器 spiro-OMeTAD 的控制器件获得的性能相当（6.27% 作为掺杂剂/无添加剂的空穴传输材料，14。