Pressure-induced bandgap engineering and photoresponse enhancement of wurtzite CuInS ₂ nanocrystals

Wurtzite CuInS₂ exhibits great potential for optoelectronic applications because of its excellent optical properties and good stability. However, exploring effective strategies to simultaneously optimize its optical and photoelectrical properties remains a challenge. In this study, the bandgap of wurtzite CuInS₂ nanocrystals is successfully extended and the photocurrent is enhanced synchronously using external pressure. The bandgap of wurtzite CuInS₂ increases with pressure and reaches an optimal value (1.5 eV) for photovoltaic solar energy conversion at about 5.9 GPa. Surprisingly, the photocurrent simultaneously increases nearly 3-fold and reaches the maximum value at this critical pressure. Theoretical calculation indicates that the pressure-induced bandgap extention in wurtzite CuInS₂ may be attributed to an increased charge density and ionic polarization between the In-S atoms. The photocurrent preserves a relatively high photoresponse even at 8.8 GPa, but almost disappears above 10.3 GPa. The structural evolution demonstrates that CuInS₂ undergoes a phase transformation from the wurtzite phase (P6₃mc) to the rock salt phase (Fm3̄m) at about 10.3 GPa, which resulted in a direct to indirect bandgap transition and fianlly caused a dramatic reduction in photocurrent. These results not only map a new route toward further increase in the photoelectrical performance of wurtzite CuInS₂, but also advance the current research of A^I-B^III-CVI2 materials.