Enhanced bulk photovoltaic effect in two-dimensional ferroelectric CuInP₂S₆

The photocurrent generation in photovoltaics relies essentially on the interface of p-n junction or Schottky barrier with the photoelectric efficiency constrained by the Shockley-Queisser limit. The recent progress has shown a promising route to surpass this limit via the bulk photovoltaic effect for crystals without inversion symmetry. Here we report the bulk photovoltaic effect in two-dimensional ferroelectric CuInP₂S₆ with enhanced photocurrent density by two orders of magnitude higher than conventional bulk ferroelectric perovskite oxides. The bulk photovoltaic effect is inherently associated to the room-temperature polar ordering in two-dimensional CuInP₂S₆. We also demonstrate a crossover from two-dimensional to three-dimensional bulk photovoltaic effect with the observation of a dramatic decrease in photocurrent density when the thickness of the two-dimensional material exceeds the free path length at around 40 nm. This work spotlights the potential application of ultrathin two-dimensional ferroelectric materials for the third-generation photovoltaic cells.