Ion-Exchange Polymer Network Enhanced Interfacial Compatibility for Stable and Efficient Inverted Perovskite Solar Cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a low-cost and water-processable hole transport material has been widely used in various optoelectronic devices. Although the incorporation of anionic polyelectrolyte PSS in PEDOT contributes to superior water solubility, the trade-off between efficiency and stability remains a challenging issue, limiting its reliable application in perovskite solar cells (PSCs). Herein, we proposed an ion-exchange (IE) strategy to effectively control the doping degree, interfacial charge dynamics, and reliability of PEDOT:PSS in PSCs. This IE approach based on hard cation-soft anion rules enabled effective anion exchange between PEDOT:PSS and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), which favored enhancing the film conductivity, regulating the perovskite crystallization, and reducing the carrier losses at the interfaces. Consequently, a notable increase of the open-circuit voltage from 0.88 to 1.02 V was realized, resulting in a champion efficiency of 18.7% compared to the control (15.4%) in inverted PSCs. More encouragingly, this IE strategy significantly promoted the thermal and environmental stability of unsealed devices by maintaining over 80% of initial efficiencies after 2000 h. This work provides an effective way to regulate the doping state of the PEDOT-based hole transport material and guides the development of robust polymeric conducting materials for efficient perovskite photovoltaics.