Lithium salts have been shown to dramatically increase the conductivity in a broad range of polymeric and small molecule organic semiconductors (OSs). Here we demonstrate and identify the mechanism by which Li(+) p-dopes OSs in the presence of oxygen. After we established the lithium doping mechanism, we re-evaluate the role of lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI) in 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-Spirobifluorene (Spiro-OMeTAD) based solid-state dye-sensitized solar cells (ss-DSSCs). The doping mechanism consumes Li(+) during the device operation, which poses a problem, since the lithium salt is required at the dye-sensitized heterojunction to enhance charge generation. This compromise highlights that new additives are required to maximize the performance and the long-term stability of ss-DSSCs.

Rational approaches to engineering polydopamine films with tailored properties for surface coating and functionalization are currently challenged by the lack of detailed information about the polymer structure and the mechanism of buildup. Using an integrated chemical and spectroscopic approach enables the demonstration of: a) a three-component structure of polydopamine, comprising uncyclized (catecholamine) and cyclized (indole) units, as well as novel pyrrolecarboxylic acid moieties; b) remarkable variations in the relative proportions of the cyclized and uncyclized units with starting dopamine concentration; c) the occurrence of oligomer components up to the tetramer level; d) the covalent incorporation of Tris buffer; and e) the role of dopamine quinone as a crucial control point for directing the buildup pathways and tuning the properties. The importance of the uncyclized amine-containing units in polydopamine adhesion is also highlighted. The proper selection of substrate concentration and buffer is thus proposed as a practical means of tailoring polydopamine functionality via control of competing pathways downstream of dopamine quinon

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The black we wear: Why nature selected 5,6‐dihydroxyindole‐2‐carboxylic acid (DHICA) to synthesize (photo)protective eumelanin pigments is an enigma. Synthetic DHICA eumelanin has now been shown to be a highly efficient free‐radical scavenger in the solid state, which is due to a conformationally interrupted π‐electron network associated with atypical optical, paramagnetic, and aggregation properties.