Influence of selenization pressure on the growth of Cu2ZnSnSe4 films from stacked metallic layers

Cu2ZnSnSe4 (CZTSe) is a p-type semiconductor with a high absorption coefficient, 104 to 105 cm-1, and is being seen as a possible replacement for Cu(In,Ga)Se2 in thin film solar cells. Yet, there are some fundamental properties of CZTSe that are not well known, one of them is its band gap. In order to resolve its correct value it is necessary to improve the growth conditions to ensure that single phase crystalline thin films are obtained. One of the problems encountered when growing CZTSe is the loss of Sn through evaporation of SnSe. Stoichiometric films are then difficult to obtain and usually there are other phases present. One possible way to overcome this problem is to increase the pressure of growth of CZTSe. This can be done by introducing an atmosphere of an inert gas like Ar or N2. In this work we report the results of morphological, structural and optical studies of the properties of CZTSe thin films grown by selenization of DC magnetron sputtered metallic layers under different Ar pressures. The films are analysed by SEM/EDS, Raman scattering and XRD.

Detection of ZnS phases in CZTS thin-films by EXAFS

Copper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.