Polymorphic Ga₂S₃ nanowires: phase-controlled growth and crystal structure calculations

The polymorphism of nanostructures is of paramount importance for many promising applications in high-performance nanodevices. We report the chemical vapor deposition synthesis of Ga₂S₃ nanowires (NWs) that show the consecutive phase transitions of monoclinic (M) → hexagonal (H) → wurtzite (W) → zinc blende (C) when lowering the growth temperature from 850 to 600 °C. At the highest temperature, single-crystalline NWs were grown in the thermodynamically stable M phase. Two types of H phase exhibited 1.8 nm periodic superlattice structures owing to the distinctively ordered Ga sites. They consisted of three rotational variants of the M phase along the growth direction ([001]_M = [0001]_H/W) but with different sequences in the variants. The phases shared the same crystallographic axis within the NWs, producing novel core-shell structures to illustrate the phase evolution. The relative stabilities of these phases were predicted using density functional theory calculations, and the results support the successive phase evolution. Photodetector devices based on the p-type M and H phase Ga₂S₃ NWs showed excellent UV photoresponse performance.