Crystallization properties of Cu2ZnGeSe4

Abstract

We have studied the crystallization reaction of polycrystalline Cu2ZnGeSe4 solar cell absorbers fabricated by H2Se selenization of sequentially deposited metal layer stacks. We have executed a stop experiment, stopping the crystallization reaction at different times during the process, then analyzing the subsequent X-ray diffraction patterns. We have found that mainly Cu3Ge and ZnSe phases form very rapidly at temperatures below 350 °C. Depending on the order of the sequentially deposited metal layer stack, the formation reaction proceeds at different speeds. Putting the Ge layer in the bottom and the Cu layer on top leads to a very fast nucleation reaction of Cu2ZnGeSe4, leading to small grains that have obtained their final size already after 3 min of selenization at 460 °C. The inverse stack with Ge on top and Cu in the bottom delays the nucleation of Cu2ZnGeSe4, leading to a somewhat slower formation reaction and larger Cu2ZnGeSe4 grains, which obtain their final grain size only after 15 min of selenization at 460 °C.