Efficiency Enhancement of Single‐Walled Carbon Nanotube‐Silicon Heterojunction Solar Cells Using Microwave‐Exfoliated Few‐Layer Black Phosphorus

Abstract Carbon nanotube‐silicon (CNT‐Si)‐based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few‐layer black phosphorus (FL‐BP) sheets are produced in N‐methyl‐2‐pyrrolidone (NMP) using microwave‐assisted liquid‐phase exfoliation and introduced into the CNTs‐Si‐based HJSCs for the first time. The NMP‐based FL‐BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p‐type dominated conduction, the FL‐BP/NMP incorporated CNT‐Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT‐Si cell) to 9.37%. Our density‐functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL‐BP is higher in energy than that of single‐walled CNT. Therefore, we observed a reduction in the orbitals localized on FL‐BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next‐generation PVs.