A Self-Doping, O2-Stable, n-Type Interfacial Layer for Organic Electronics

Solid films of a water‐soluble dicationic perylene diimide salt, perylene bis(2‐ethyltrimethylammonium hydroxide imide), Petma+OH−, are strongly doped n‐type by dehydration and reversibly de‐doped by hydration. The hydrated films consist almost entirely of the neutral perylene diimide, PDI, while the dehydrated films contain ∼50% PDI anions. The conductivity increases by five orders of magnitude upon dehydration, probably limited by film roughness, while the work function decreases by 0.74 V, consistent with an n‐type doping density increase of ∼12 orders of magnitude. Remarkably, the PDI anions are stable in dry air up to 120 °C. The work function of the doped film, ϕ (3.96 V vs. vacuum), is unusually negative for an O2‐stable contact. Petma+OH− is also characterized as an interfacial layer, IFL, in two different types of organic photovoltaic cells. Results are comparable to state of the art cesium carbonate IFLs, but may improve if film morphology can be better controlled. The films are stable and reversible over many months in air and light. The mechanism of this unusual self‐doping process may involve the change in relative potentials of the ions in the film caused by their deshielding and compaction as water is removed, leading to charge transfer when dry. A red dicationic perylene diimide film spontaneously turns blue upon dehydration, and its conductivity increases by five orders of magnitude. This transition is reversible and reproducible. Perylene diimide anions are formed by dehydration and the n‐type doping level increases by ∼12 orders of magnitude. Employed as n‐type interfacial layers (IFLs) in organic photovoltaic cells, these unoptimized films perform as well as the best current n‐type IFLs.