Coordination nanosheets are an emerging class of 2D, bottom‐up materials having fully π‐conjugated, planar, graphite‐like structures with high electrical conductivities. Since their discovery, great effort has been devoted to expand the variety of coordination nanosheets; however, in most cases, their low crystallinity in thick films hampers practical device applications. In this study, mixtures of nickel and copper ions are employed to fabricate benzenehexathiolato (BHT)‐based coordination nanosheet films, and serendipitously, it is found that this heterometallicity preferentially forms a structural phase with improved film crystallinity. Spectroscopic and scattering measurements provide evidence for a bilayer structure with in‐plane periodic arrangement of copper and nickel ions with the NiCu2BHT formula. Compared with homometallic films, heterometallic films exhibit more crystalline microstructures with larger and more oriented grains, achieving higher electrical conductivities reaching metallic behaviors. Low dependency of Seebeck coefficient on the mixing ratio of nickel and copper ions supports that the large variation in the conductivity data is not caused by change in the intrinsic properties of the films. The findings open new pathways to improve crystallinity and to tune functional properties of 2D coordination nanosheets.
Organic thermoelectrics offer the potential to deliver flexible, low-cost devices that can directly convert heat to electricity. Previous studies have reported high conductivity and thermoelectric power factor in the conjugated polymer poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT). Here, we investigate the thermoelectric properties of PBTTT films in which the polymer chains were aligned uniaxially by mechanical rubbing, and the films were doped by a recently developed ion exchange technique that provides a choice over the counterions incorporated into the film, allowing for more optimized morphology and better stability than conventional charge transfer doping. To optimize the polymer alignment process, we took advantage of two Design of Experiment (DOE) techniques: regular two-level factorial design and central composite design. Rubbing temperature T rub and post-alignment annealing temperature T anneal were the two factors that were most strongly correlated with conductivity. We were able to achieve high polymer alignment with a dichroic ratio >15 and high electrical conductivities of up to 4345 S/cm for transport parallel to the polymer chains, demonstrating that the ion exchange method can achieve conductivities comparable/higher than conventional charge transfer doping. While the conductivity of aligned films increased by a factor of 4 compared to unaligned films, the Seebeck coefficient (S) remained nearly unchanged. The combination of DOE methodology, high-temperature rubbing, and ion exchange doping provides a systematic, controllable strategy to tune structure-thermoelectric property relationships in semiconducting polymers.
The migration of ionic defects and electrochemical reactions with metal electrodes remains one of the most important research challenges for organometal halide perovskite optoelectronic devices. There is still a lack of understanding of how the formation of mobile ionic defects impact charge carrier transport and operational device stability, particularly in perovskite field‐effect transistors (FETs), which tend to exhibit anomalous device characteristics. Here, the evolution of the n‐type FET characteristics of one of the most widely studied materials, Cs0.05FA0.17MA0.78PbI3, is investigated during repeated measurement cycles as a function of different metal source–drain contacts and precursor stoichiometry. The channel current increases for high work function metals and decreases for low work function metals when multiple cycles of transfer characteristics are measured. The cycling behavior is also sensitive to the precursor stoichiometry. These metal/stoichiometry‐dependent device non‐idealities are correlated with the quenching of photoluminescence near the positively biased electrode. Based on elemental analysis using electron microscopy the observations can be understood by an n‐type doping effect of metallic ions that are created by an electrochemical interaction at the metal–semiconductor interface and migrate into the channel. The findings improve the understanding of ion migration, contact reactions, and the origin of non‐idealities in lead triiodide perovskite FETs.
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