Macroscopic versus microscopic photovoltaic response of heterojunctions based on mechanochemically prepared nanopowders of kesterite and n-type semiconductors

Mechanochemically prepared nanopowder of selenium-free kesterite
Cu2ZnSnS4 (CZTS) in combination with n-type semiconductors, i.e., CdS, ZnO and
TiO2, was tested in planar and bulk-heterojunction solar cells. The samples have been
studied by macroscopic current-voltage (I-V) measurements and Kelvin-probe atomicforce microscopy (KPFM). KPFM images taken under light illumination showed the
distribution of the potential across the surface, with negative potential on the n-type
semiconductor domains and positive potential on the CZTS domains, which indicated
charge separation at the interface of the counterparts. The best result was found for the
CdS-CZTS composition, which showed a potential difference between the domains up to
250 mV. These results were compared with the planar heterojunctions of CdS/CZTS and
TiO2/CZTS, where CZTS nanopowder was pressed/deposited directly onto the surface of
films of the corresponding n-type semiconductors. Again, I-V characteristics showed that
cells based on CdS/CZTS heterojunctions have the best performance, with a
photovoltage up to 200 mV and photocurrent densities up to 0.1 mA/cm2
. However, the
carrier generation was found to occur mainly in the CdS semiconductor, while CZTS
showed no photo-response and served as the hole-transporting layer only. It is concluded
that sensitization of the kesterite powder obtained by mechanochemical method is
necessary to improve the performance of the corresponding solar cells.