Structural and Solar Cell Properties of a Ag-Containing Cu₂ZnSnS₄ Thin Film Derived from Spray Pyrolysis

A silver (Ag)-incorporated kesterite Cu₂ZnSnS₄ (CZTS) thin film was fabricated by a facile spray pyrolysis method. Crystallographic analyses indicated successful incorporation of various amounts of Ag up to a Ag/(Ag + Cu) ratio of ca. 0.1 into the crystal lattice of CZTS in a homogeneous manner without formation of other impurity compounds. From the results of morphological investigations, Ag-incorporated films had larger crystal grains than the CZTS film. The sample with a relatively low Ag content (Ag/(Ag + Cu) of ca. 0.02) had a compact morphology without appreciable voids and pinholes. However, an increase in the Ag content in the CZTS film (Ag/(Ag + Cu) ca. 0.10) induced the formation of a large number of pinholes. As can be expected from these morphological properties, the best sunlight conversion efficiency was obtained by the solar cell based on the film with Ag/(Ag + Cu) of ca. 0.02. Electrostructural analyses of the devices suggested that the Ag-incorporated film in the device achieved reduction in the amounts of unfavorable copper on zinc antisite defects compared to the bare CZTS film. Moreover, the use of a Ag-incorporated film improved band alignment at the CdS(buffer)-CZTS interface. These alterations should also contribute to enhancement of device properties.