LAUSR

Abstract By combining the most successful heterojunctions (HJ) with interdigitated back contacts, crystalline silicon (c‐Si) solar cells (SCs) have recently demonstrated a record efficiency of 26.6%. However, such SCs still introduce optical/electrical losses and technological issues due to parasitic absorption/Auger recombination inherent to the doped films and the complex process of integrating discrete p+‐ and n+‐HJ contacts. These issues have motivated the search for alternative new functional materials and simplified deposition technologies, whereby carrier‐selective contacts (CSCs) can be formed directly with c‐Si substrates, and thereafter form IBC cells, via a dopant‐free method. Screening and modifying CSC materials in a wider context is beneficial for building dopant‐free HJ contacts with better performance, shedding new light on the relatively mature Si photovoltaic field. In this review, a significant number of achievements in two representative dopant‐free hole‐selective CSCs, i.e., poly(3,4‐ethylene dioxythiophene):poly(styrenesulfonate)/Si and transition metal oxides/Si, have been systemically presented and surveyed. The focus herein is on the latest advances in hole‐selective materials modification, interfacial passivation, contact resistivity, light‐trapping structure and device architecture design, etc. By analyzing the structure–property relationships of hole‐selective materials and assessing their electrical transport properties, promising functional materials as well as important design concepts for such CSCs toward high‐performance SCs have been highlighted.