Very small tail state formation in Cu2ZnGeSe4

We find that coevaporated Cu2ZnGeSe4 has an ideal bandgap for solar cells (1.39 ± 0.01 eV) and shows quite reduced tail state absorption with a very low Urbach energy of 28 meV, which is far smaller than those of more studied Cu2ZnSnSe4 and Cu2ZnSnS4. The small tail states in Cu2ZnGeSe4 are found to originate from almost perfect cation ordering, while unusual tail state generation occurs in the Sn-based quaternary compounds by extensive cation substitution. Quite remarkably, the crystal total energy derived from first-principles calculations reveals a unified rule for the cation disordering, confirming that the lighter group-IV element (i.e., Ge) is essential for eliminating the tail state generation induced by cation mixing.