Chemical bath deposited PbS thin films on ZnO nanowires for photovoltaic applications

Photovoltaic devices usually exploit mid-range band-gap semiconductors which absorb in the visible range of the solar spectrum. However, much energy is lost in the IR and near-IR range. We combined the advantages of small band-gap, bulk-like PbS deposited by facile, cheap and direct chemical bath deposition (CBD), with the good electronic properties of ZnO and the large surface area of nanowires, towards low cost photovoltaic devices utilizing IR and near-IR light. Surprisingly, CBD of PbS on ZnO, and particularly on ZnO nanowires, was not studied hitherto. Therefore, the mechanism of PbS growth by chemical bath deposition on ZnO nanowires was studied in details. A visible proof is shown for a growth mechanism starting from amorphous Pb(OH)₂ layer, that evolved into the 'ion-by-ion' growth mechanism. The growth mechanism and the resulting morphology at low temperatures were controlled by the thiourea concentration. The grain size affected the magnitude of the band-gap and was controlled by the deposition temperatures. Deposition above 40 C resulted in bulk-like PbS with an optical band-gap of 0.4 eV. Methods were demonstrated for achieving complete PbS coverage of the complex ZnO NW architecture, a crucial requirement in optoelectronic devices to prevent shorts. Measurements of photocurrents under white and near-IR (784 nm) illumination showed that despite a 200 meV barrier for electron transfer at the PbS/ZnO interface, extraction of photo-electrons from PbS to the ZnO was feasible. The ability to harvest electrons from a narrow band-gap semiconductor deposited on a large surface-area electrode can advance the field towards high efficiency, low cost IR and near-IR sensors and third generation solar cells.