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Abstract Self‐doping is a particular doping method that has been applied to a wide range of organic semiconductors. However, there is a lack of understanding regarding the relationship between dopant structure and function. A structurally diverse series of self‐n‐doped perylene diimides (PDIs) is investigated to study the impact of steric encumbrance, counterion selection, and dopant/PDI tether distance on functional parameters such as doping, stability, morphology, and charge‐carrier mobility. The studies show that self‐n‐doping is best enabled by the use of sterically encumbered ammoniums with short tethers and Lewis basic counterions. Additionally, water is found to inhibit doping, which concludes that thermal degradation is merely a phenomenological feature of certain dopants, and that residual solvent evaporation is the primary driver of thermally activated doping. In situ grazing‐incidence wide‐angle X‐ray scattering studies show that sample annealing increases the π–π stacking distance and shrinks grain boundaries for improved long‐range ordering. These features are then correlated to contactless carrier‐mobility measurements with time‐resolved microwave conductivity before and after thermal annealing. The collective relationships between structural features and functionality are finally used to establish explicit self‐n‐dopant design principles for the future design of materials with improved functionality.
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Concepts and principles of self-n-doping in perylene diimide chromophores for applications in biochemistry, energy harvesting, energy storage, and catalysis
Self-doping is an essential method of increasing carrier concentrations in organic electronics that eliminates the need to tailor host—dopant miscibility, a necessary step when employing molecular dopants. Self-n-doping can be accomplished using amines or ammonium counterions as an electron source, which are being incorporated into an ever-increasingly diverse range of organic materials spanning many applications. Self-n-doped materials have demonstrated exemplary and, in many cases, benchmark performances in a variety of applications. However, an in-depth review of the method is lacking. Perylene diimide (PDI) chromophores are an important mainstay in the semiconductor literature with well-known structure-function characteristics and are also one of the most widely utilized scaffolds for self-n-doping. In this review, we describe the unique properties of self-n-doped PDIs, delineate structure-function relationships, and discuss self-n-doped PDI performance in a range of applications. In particular, the impact of amine/ammonium incorporation into the PDI scaffold on doping efficiency is reviewed with regard to attachment mode, tether distance, counterion selection, and steric encumbrance. Self-n-doped PDIs are a unique set of PDI structural derivatives whose properties are amenable to a broad range of applications such as biochemistry, solar energy conversion, thermoelectric modules, batteries, and photocatalysis. Finally, we discuss challenges and the future outlook of self-n-doping principles.
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- PAR ID:
- 10333084
- Date Published:
- Journal Name:
- Materials Horizons
- ISSN:
- 2051-6347
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2mh00279e
