Pressure-Driven Reversible Switching between n- and p-Type Conduction in Chalcopyrite CuFeS2

Temperature-dependent switching between p- and n-type conduction is a newly observed phenomenon in very few Ag-based semiconductors, which may promote fascinating applications in modern electronics. Pressure, as an efficient external stimulus that has driven collective phenomena such as spin-crossover and Mott transition, is also expected to initialize a conduction-type switching in transition metal-based semiconductors. Herein, we report the observation of a pressure-driven dramatic switching between p- and n-type conduction in chalcopyrite CuFeS2 associated with a structural phase transition. Under compression around 8 GPa, CuFeS2 undergoes a phase transition with symmetry breakdown from space group I-42d to space group I-4 accompanying with a remarkable volume shrinkage of the FeS4 tetrahedra. A high-to-low spin-crossover of Fe2+ (S = 2 to S = 0) is manifested along with this phase transition. Instead of pressure-driven metallization, a surprising semiconductor-to-semiconductor transition is observed a...