Doping strategies for small molecule organic hole-transport materials: impacts on perovskite solar cell performance and stability

Hybrid organic/inorganic perovskite solar cells (PSCs) have dramatically changed the landscape of the solar research community over the past decade, but >25 year stability is likely required if they are to make the same impact in commercial photovoltaics and power generation more broadly. While every layer of a PSC has been shown to impact its durability in power output, the hole-transport layer (HTL) is critical for several reasons: (1) it is in direct contact with the perovskite layer, (2) it often contains mobile ions, like Li(+) – which in this case are hygroscopic, and (3) it usually has the lowest thermal stability of all layers in the stack. Therefore, HTL engineering is one method with a high return on investment for PSC stability and lifetime. Research has progressed in understanding design rules for small organic molecule hole-transport materials, yet, when implemented into devices, the same dopants, bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) and tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(iii) tri[bis(trifluoromethane)sulfonimide] (FK209), are nearly always required for improved charge-transport properties (e.g., increased hole mobility and conductivity). The dopants are notable because they too have been shown to negatively impact PSC stability and lifetime. In response, new research has targeted alternative dopants to bypass these negative effects and provide greater functionality. In this review, we focus on dopant fundamentals, alternative doping strategies for organic small molecule HTL in PSC, and imminent research needs with regard to dopant development for the realization of reliable, long-lasting electricity generation via PSCs.