Site-specific chemical doping reveals electron atmospheres at the surfaces of organic semiconductor crystals

Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory. Organic semiconductor crystals can be selectively doped at the crystallographic step edges, deactivating shallow traps and recovering band-like transport. The space charge induced by chemical doping is observed by scanning Kelvin probe microscopy.