Charge transport materials constitute a relatively large portion of the cost in the production of perovskite solar cells (PSCs). Therefore, developing cheap and efficient charge transport materials is of great significance for the commercialization of PSCs. Herein, three low-cost hole transport materials (HTMs), specifically TP-H, TP-OMe and TP-F, were designed and synthesized by employing bulky groups substituted 2,2'-bithiophene core and methoxy- or F-functionalized triphenylamine derivatives. Compared to HTMs without F atoms, F substitution confers upon TP-F enhanced intermolecular packing, a lower highest occupied molecular orbital (HOMO) energy level, and increased hole mobility and conductivity. PSCs incorporating doped TP-F as hole transport layer achieved highest power conversion efficiency (PCE) of over 24% among the three devices. The high performance of TP-F can be attributed to the passivation effect of S and F atoms on uncoordinated Pb²⁺ within the perovskite (PVSK) film, which significantly reduces the density of defect states and the incidence of trap-mediated recombination in PSCs. This work demonstrates the effectiveness of the 3,3'-bis(4-methoxy-2,6-dimethylphenyl)-2,2'-bithiophene building block for constructing cost-effective HTMs and highlights the impact of F-substitution on enhancing the photovoltaic performance of PSCs.

Semi-transparent perovskite solar cells (ST-PSCs) have broad applications in building integrated photovoltaics. However, the stability of ST-PSCs needs to be improved, especially in n-i-p ST-PSCs since the doped 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (Spiro-OMeTAD) is unstable at elevated temperatures and high humidity. In this work, a π-conjugated polymer poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)] (PBDB-T) is selected to form a polymer composite hole transport layer (HTL) with Spiro-OMeTAD. The sulfur atom of the thiophene unit and the carbonyl group of the polymer interact with the undercoordinated Pb²⁺ at the perovskite surface, which stabilizes the perovskite/HTL interface and passivates the interfacial defects. The incorporation of the polymer also increases the glass transition temperature and the moisture resistance of Spiro-OMeTAD. As a result, we obtain ST-PSCs with a champion efficiency of 13.71% and an average visible light transmittance of 36.04%. Therefore, a high light utilization efficiency of 4.94% can be obtained. Moreover, the encapsulated device can maintain 84% of the initial efficiency after 751 h under continuous one-sun illumination (at 30% relative humidity) at the open circuit and the unencapsulated device can maintain 80% of the initial efficiency after maximum power tracking for more than 1250 h under continuous one-sun illumination.

Fullerene materials have been widely used to fabricate efficient and stable perovskite solar cells (PSCs) due to their excellent electron transport ability, defect passivation effect, and beyond. Recent studies have shown that fullerene-related chemical interaction has played a crucial role in determining device performance. However, the corresponding fullerene-related chemical interactions are yet well understood. Herein, a comprehensive review of fullerene materials in regulating carrier transport, passivating the surface and grain boundary defects, and enhancing device stability is provided. Specifically, the influence of the fullerene-related chemical interactions, including fullerene-perovskite, fullerene-inorganic electron transport layer (IETL), and fullerene-fullerene, on the device performance is well discussed. Finally, we outline some perspectives for further design and application of fullerene materials to enhance the performance and commercial application of PSCs.