Reduced interface recombination in Cu2ZnSnS4 solar cells with atomic layer deposition Zn1−xSnxOy buffer layers

Cu2ZnSnS4 (CZTS) solar cells typically include a CdS buffer layer in between the CZTS and ZnO front contact. For sulfide CZTS, with a bandgap around 1.5 eV, the band alignment between CZTS and CdS is not ideal (“cliff-like”), which enhances interface recombination. In this work, we show how a Zn1−xSnxOy (ZTO) buffer layer can replace CdS, resulting in improved open circuit voltages (Voc) for CZTS devices. The ZTO is deposited by atomic layer deposition (ALD), with a process previously developed for Cu(In,Ga)Se2 solar cells. By varying the ALD process temperature, the position of the conduction band minimum of the ZTO is varied in relation to that of CZTS. A ZTO process at 95 °C is found to give higher Voc and efficiency as compared with the CdS reference devices. For a ZTO process at 120 °C, where the conduction band alignment is expected to be the same as for CdS, the Voc and efficiency is similar to the CdS reference. Further increase in conduction band minimum by lowering the deposition temperature to 80 °C shows blocking of forward current and reduced fill factor, consistent with barrier formation at the junction. Temperature-dependent current voltage analysis gives an activation energy for recombination of 1.36 eV for the best ZTO device compared with 0.98 eV for CdS. We argue that the Voc of the best ZTO devices is limited by bulk recombination, in agreement with a room temperature photoluminescence peak at around 1.3 eV for both devices, while the CdS device is limited by interface recombination.