Phase-change materials exhibiting tristability: Interconverting forms of crystalline α-, β-, and glassy K ₂ZnSn ₃S ₈

We show that K ₂ZnSn ₃S ₈ is a phase-change system that exhibits tristability. Kinetic and thermodynamic forms of different compounds in the K/Zn/Sn/S system have been synthesized and thoroughly characterized. We report an example where slow and rapid cooling of a melt of K ₂CO ₃/S/Sn/Zn leads to different kinetically stable products (crystalline layered α-K ₂ZnSn ₃S ₈, 1, and glassy K ₂ZnSn ₃S ₈, A, respectively). These forms convert to a thermodynamically stable compound (crystalline cubic β-K ₂ZnSn ₃S ₈, 2) upon annealing below their melting points. The band gaps of compounds 1, A, and 2 are 2.30, 2.15, and 2.55 eV, respectively.