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Molecular doping of organic semiconductors is often used to enhance their charge transport characteristics. Despite its success, however, most studies to date concern p‐doping with considerably fewer reports involving n‐dopants. Here, n‐doping of organic thin‐film transistors (OTFTs) based on several non‐fullerene acceptor (NFA) molecules using the recently developed diquat (DQ) as a soluble molecular dopant is reported. The low ionization potential of DQ facilitates efficient electron transfer and subsequent n‐doping of the NFAs, resulting in a consistent increase in the electron field‐effect mobility. Solution‐processed BTP‐eC9 and N3‐based OTFTs exhibit significant increase in the electron mobility upon DQ doping, with values increasing from 0.02 to 0.17 cm2 V–1 s–1 and from 0.2 to 0.57 cm2 V–1 s–1, respectively. A remarkable electron mobility of >1 cm2 V–1 s–1 is achieved for O‐IDTBR transistors upon optimal doping with DQ. The enhanced performance originates primarily from synergistic effects on electronic transport and changes in morphology, including: i) significant reduction of contact resistances, ii) formation of larger crystalline domains, iii) change of preferred crystal orientation, and iv) alteration in molecular packing motif. This work demonstrates the universality of DQ as an electronic additive for improving electron transport in OTFTs. [ABSTRACT FROM AUTHOR]

Molecular doping is often used in organic semiconductors to tune their (opto)electronic properties. Despite its versatility, however, its application in organic photovoltaics (OPVs) remains limited and restricted to p‐type dopants. In an effort to control the charge transport within the bulk‐heterojunction (BHJ) of OPVs, the n‐type dopant benzyl viologen (BV) is incorporated in a BHJ composed of the donor polymer PM6 and the small‐molecule acceptor IT‐4F. The power conversion efficiency (PCE) of the cells is found to increase from 13.2% to 14.4% upon addition of 0.004 wt% BV. Analysis of the photoactive materials and devices reveals that BV acts simultaneously as n‐type dopant and microstructure modifier for the BHJ. Under optimal BV concentrations, these synergistic effects result in balanced hole and electron mobilities, higher absorption coefficients and increased charge‐carrier density within the BHJ, while significantly extending the cells' shelf‐lifetime. The n‐type doping strategy is applied to five additional BHJ systems, for which similarly remarkable performance improvements are obtained. OPVs of particular interest are based on the ternary PM6:Y6:PC71BM:BV(0.004 wt%) blend for which a maximum PCE of 17.1%, is obtained. The effectiveness of the n‐doping strategy highlights electron transport in NFA‐based OPVs as being a key issue. [ABSTRACT FROM AUTHOR]

A simple approach that enables a consistent enhancement of the electron extracting properties of the widely used small‐molecule Phen‐NaDPO and its application in organic solar cells (OSCs) is reported. It is shown that addition of minute amounts of the inorganic molecule Sn(SCN)2 into Phen‐NaDPO improves both the electron transport and its film‐forming properties. Use of Phen‐NaDPO:Sn(SCN)2 blend as the electron transport layer (ETL) in binary PM6:IT‐4F OSCs leads to a remarkable increase in the cells' power conversion efficiency (PCE) from 12.6% (Phen‐NaDPO) to 13.5% (Phen‐NaDPO:Sn(SCN)2). Combining the hybrid ETL with the best‐in‐class organic ternary PM6:Y6:PC70BM systems results to a similarly remarkable PCE increase from 14.2% (Phen‐NaDPO) to 15.6% (Phen‐NaDPO:Sn(SCN)2). The consistent PCE enhancement is attributed to reduced trap‐assisted carrier recombination at the bulk‐heterojunction/ETL interface due to the presence of new energy states formed upon chemical interaction of Phen‐NaDPO with Sn(SCN)2. The versatility of this hybrid ETL is further demonstrated with its application in perovskite solar cells for which an increase in the PCE from 16.6% to 18.2% is also demonstrated. [ABSTRACT FROM AUTHOR]