Charge Transport Mechanisms in CuInSexS2-x Quantum Dot Films.

Colloidal quantum dots (QDs) have attracted considerable attention as promising materials for solution-processable electronic and optoelectronic devices. Copper indium selenium sulfide (CuInSexS2-x or CISeS) QDs are particularly attractive as an environmentally benign alternative to the much more extensively studied QDs containing toxic metals such as Cd and Pb. Carrier transport properties of CISeS-QD films, however, are still poorly understood. Here, we aim to elucidate the factors that control charge conductance in CISeS QD solids and, based on this knowledge, develop practical approaches for controlling the polarity of charge transport and carrier mobilities. To this end, we incorporate CISeS QDs into field-effect transistors (FETs) and perform detailed characterization of these devices as a function of the Se/(Se+S) ratio, surface treatment, thermal annealing, and the identity of source and drain electrodes. We observe that as-synthesized CuInSexS2-x QDs exhibit degenerate p-type transport, likely due to metal vacancies and/or CuIn'' anti-site defects (Cu1+ on an In3+ site) that act as acceptor states. Moderate-temperature annealing of the films in the presence of indium source and drain electrodes leads to switching of the transport polarity to non-degenerate n-type, which can be attributed to the formation of In-related defects such as InCu (an In3+ cation on a Cu1+ site) or Ini (interstitial In3+) acting as donors. We observe that the carrier mobilities increase dramatically (by three orders of magnitude) with increasing Se/(Se+S) ratio in both n- and p-type devices. To explain this observation, we propose a two-state conductance model, which invokes a high-mobility intrinsic band-edge state and a low-mobility defect-related intra-gap state. These states are thermally coupled, and their relative occupancies depend on both QD composition and temperature. Our observations suggest that the increase in the relative fraction of Se moves conduction- and valence band edges closer to low-mobility intra-gap levels. This results in increased relative occupancy of the intrinsic band-edge states and a corresponding growth of the measured mobility. Further improvement in charge-transport characteristics of the CISeS QD samples as well as their stability is obtained by infilling the QD films with amorphous Al2O3 using atomic layer deposition.