Developing dopant-free hole-transporting materials (HTMs) for high-performance perovskite solar cells (PVSCs) has been a very active research topic in recent years since HTMs play a critical role in optimizing interfacial charge carrier kinetics and in turn determining device performance. Here, a novel dendritic engineering strategy is first utilized to design HTMs with a D-A type molecular framework, and diphenylamine and/or carbazole is selected as the building block for constructing dendrons. All HTMs show good thermal stability and excellent film morphology, and the key optoelectronic properties could be fine-tuned by varying the dendron structure. Among them, MPA-Cz-BTI and MCz-Cz-BTI exhibit an improved interfacial contact with the perovskite active layer, and non-radiative recombination loss and charge transport loss can be effectively suppressed. Consequently, high power conversion efficiencies (PCEs) of 20.8% and 21.35% are achieved for MPA-Cz-BTI and MCz-Cz-BTI based devices, respectively, accompanied by excellent long-term storage stability. More encouragingly, ultrahigh fill factors of 85.2% and 83.5% are recorded for both devices, which are among the highest values reported to date. This work demonstrates the great potential of dendritic materials as a new type of dopant-free HTMs for high-performance PVSCs with excellent FF.

近年来，开发用于高性能钙钛矿太阳能电池（PVSC）的无掺杂空穴传输材料（HTM）一直是非常活跃的研究课题，因为HTM在优化界面电荷载流子动力学并进而确定器件性能方面起着至关重要的作用。在这里，首先使用一种新颖的树状工程策略来设计具有DA型分子框架的HTM，然后选择二苯胺和/或咔唑作为构建树突的基础。所有HTM均显示出良好的热稳定性和出色的薄膜形态，并且可以通过改变树枝状结构来微调关键的光电性能。其中，MPA-Cz-BTI和MCz-Cz-BTI与钙钛矿活性层的界面接触得到改善，并且可以有效地抑制非辐射复合损失和电荷传输损失。因此，基于MPA-Cz-BTI和MCz-Cz-BTI的设备分别实现了20.8％和21.35％的高功率转换效率（PCE），并具有出色的长期存储稳定性。更令人鼓舞的是，两种器件的超高填充率分别达到85.2％和83.5％，是迄今为止报告的最高值之​​一。这项工作证明了树枝状材料作为一种新型的无掺杂HTM的巨大潜力，这种HTM适用于具有出色FF的高性能PVSC。两种设备均记录了5％的数据，这是迄今为止报告的最高值。这项工作证明了树枝状材料作为一种新型的无掺杂HTM的巨大潜力，这种HTM适用于具有出色FF的高性能PVSC。两种设备均记录了5％的数据，这是迄今为止报告的最高值。这项工作证明了树枝状材料作为一种新型的无掺杂HTM的巨大潜力，这种HTM适用于具有出色FF的高性能PVSC。