Effects of reduced dimensionality on the electronic structure and defect chemistry of semiconducting hybrid organic–inorganic PbS solids

Abstract

The combination of inorganic and organic frameworks to produce crystalline hybrid semiconductors offers a pathway for obtaining novel photovoltaic and optoelectronic materials. Taking an archetypal binary semiconductor, PbS (galena), we investigate the electronic effects of the reduced dimensionality in the PbS framework on transition from bulk PbS to three-dimensional and one-dimensional hybrid inorganic–organic networks. Analysis of density functional theory calculations reveals the substantial contribution of the organic (benzenehexathiol derivates) to the band-edge states. Implications for intrinsic defect formation and potential application in solar cell devices are discussed, as well as future design pathways for engineering the electronic properties of this new class of hybrid metal–organic framework.