Influence of Zn excess on compositional, structural and vibrational properties of Cu2ZnSn0.5Ge0.5Se4 thin films and their effect on solar cell efficiency

Abstract

This Accepted Manuscript will be available for reuse under a CC BY-NC-ND licence after 24 months of embargo periodThe effect of Zn content on compositional, structural and vibrational properties of Cu2ZnSn1-xGexSe4 (CZTGSe, x ~ 0.5) thin films is studied. Kesterite layer is deposited by co-evaporation onto 5 × 5 cm2 Mo/SLG substrate followed by a thermal treatment at maximum temperature of 480 °C, obtaining areas with different composition and morphology which are due to the sample position in the co-evaporation system and to the non-uniform temperature distribution across the substrate. Kesterite layers with higher Zn amounts are characterized by lower Cu and Ge contents; however, a uniform Ge distribution through the absorber layer is detected in all cases. The excess Zn concentration leads to the formation of ZnSe secondary phase on the surface and in the bulk of the absorber as determined by Raman spectroscopy. When higher Ge content and no ZnSe are present in the absorber layer, a compact structure is formed with larger grain size of kesterite. This effect could explain the higher Voc of the solar cell. The Zn content does not affect the bandgap energy significantly (Eg near 1.3 eV), although the observed effect of Zn excess in CZTGSe results in a decreased device performance from 6.4 to 4.2%. This investigation reveals the importance of the control of the off-stoichiometric CZTGSe composition during the deposition process to enhance solar cells propertiesThis work was supported by Spanish Ministry of Science, Innovation and Universities Project WINCOST (ENE2016-80788-C5-2-R) and European Project INFINITE CELL (H2020-MSCA-RISE-2017-777968). ARP also acknowledges financial support from Community of Madrid within Youth Employment Program (PEJD-2017-PRE/IND-4062). MG acknowledges the financial support from ACCIÓ-Generalitat de Catalunya within the TECNIOspring Plus fellowship (TECSPR18-1-0048