Four ZnPc‐dimers with 2,5‐thienyl (ZnPc−th−ZnPc 1), 2,7‐fluorenyl (ZnPc−flu−ZnPc 2), 3,6‐bisthienylldiketopyrrolopyrrole (ZnPc−DPP−ZnPc 3) and 1,4‐phenyl (ZnPc−p−ZnPc 4) bridges have been studied as dopant‐free hole transporting materials (HTMs) in perovskite solar cells (PSCs). The synthesis and characterization of ZnPc−th−ZnPc 1 and ZnPc−flu−ZnPc 2 dimers are reported for the first time. Steady state and time resolved photoluminescence demonstrate the good hole‐extraction capability of these materials. The best efficiencies obtained for dimers 1, 2, 3 and 4 are 15.5 %, 15.6 %, 16.8 % and 15.7 %, respectively, without the addition of dopants. Besides, these derivatives demonstrated better stability both in dark storage conditions with a relative humidity <20 % for 500 h and at 50 °C with a relative humidity >60 % for 160 h when compared to doped spiro−OMeTAD. The push‐pull nature of dimer ZnPc−DPP−ZnPc 3 has led to the highest efficiency among the ZnPc derivatives under study demonstrating that donor‐acceptor‐donor systems can be good alternatives to commonly used materials due their energy levels, low cost and the final morphology of the hole transporting layer.

中文翻译：

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酞菁锌共轭二聚体是钙钛矿太阳能电池中高效无掺杂空穴传输材料。

四个ZnPc二聚体，分别带有2,5-噻吩基（ZnPc-th-ZnPc 1），2,7-芴基（ZnPc-flu-ZnPc 2），3,6-双噻吩基二酮吡咯并吡咯（ZnPc-DPP-ZnPc 3）和1,4在钙钛矿型太阳能电池（PSC）中，对苯基（ZnPc-p-ZnPc 4）桥作为无掺杂空穴传输材料（HTM）进行了研究。ZnPc-th-ZnPc 1和ZnPc-flu-ZnPc 2二聚体的合成和表征是首次报道。稳态和时间分辨的光致发光表明这些材料具有良好的空穴提取能力。为二聚物得到的最佳效率1，2，3和4在不添加掺杂剂的情况下，分别为15.5％，15.6％，16.8％和15.7％。此外，与掺杂的螺-OMeTAD相比，这些衍生物在相对湿度<20％的黑暗条件下500小时和在50°C相对湿度> 60％的条件下160小时都表现出更好的稳定性。在研究的ZnPc衍生物中，二聚体ZnPc-DPP-ZnPc 3的推挽特性使其效率最高，这表明供体-受体-供体系统可以替代常用材料，因为它们的能级，低成本和低能耗。空穴传输层的最终形态。