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Nernstian proton-coupled electron transfer (PCET) is a fundamental process central to many physical and biological systems, such as electrocatalysis, enzyme operation, DNA biosynthesis, pH-/bio-sensors, and electrochemical energy storage devices. We report herein the discovery of super-Nernstian PCET behavior with two protons per electron transferred in the electrochemical doping of a redox conjugated polymer, phenazine-substituted ladder poly(benzimidazobenzophenanthroline) (BBL-P), in aqueous electrolyte. We show that the super-Nernstian response originates from existence of multiredox centers that have a gradient of p K a on the conjugated polymer. Our use of various pH-dependent in operando techniques to probe the nature of charge carriers in n-doped BBL-P found that polarons are the charge carriers at low to intermediate levels of doping (0.1-1.0 electron per repeat unit (eru)) whereas at higher doing levels (1.3 eru), polarons, polaron pairs, and bipolarons co-exist, which evolve into strongly coupled polaron pairs at the highest doping levels (>1.5 eru). We show that PCET-assisted n-doping of BBL-P results in very high redox capacity (>1200 F cm -3 ) in acidic electrolyte. Our results provide important new insights into PCET in organic materials and the nature of charge carriers in n-doped conjugated polymers while having implications for various electrochemical devices., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

We report the synthesis of two barbiturate end-capped non-fullerene acceptors and demonstrate their efficient function in high voltage output organic solar cells. The acceptor with the lower LUMO level is shown to exhibit suppressed geminate recombination losses, resulting in enhanced photocurrent generation and higher overall device efficiency.

Side chain engineering of an n-type polymer provides a means of maintaining solubility while increasing crystallinity and electron mobility, leading to enhanced photocurrent. Bulk heterojunction solar cells composed of a side chain engineered copolymer (PNDIS-30BO) as acceptor and PSEHTT as donor give 10.4 mA cm(-2) photocurrent and 4.4% efficiency.

Light scattering is a method that has been employed in dye-sensitized solar cells for optical absorption enhancement. In conventional dye-sensitized solar cells, large TiO(2) particles with sizes comparable to the wavelength of visible light are used as scatterers by either being mixed into the nanocrystalline film to generate light scattering or forming a scattering layer on the top of the nanocrystalline film to reflect the incident light, with the aim to extend the traveling distance of incident light within the photoelectrode film. Recently, hierarchical nanostructures, for example nanocrystallite aggregates (among others), have been applied to dye-sensitized solar cells. When used to form a photoelectrode film, these hierarchical nanostructures have demonstrated a dual function: providing large specific surface area; and generating light scattering. Some other merits, such as the capability to enhance electron transport, have been also observed on the hierarchically structured photoelectrode films. Hierarchical nanostructures possessing an architecture that may provide sufficient internal surface area for dye adsorption and meanwhile may generate highly effective light scattering, make them able to create photoelectrode films with optical absorption significantly more efficient than the dispersed nanoparticles used in conventional dye-sensitized solar cells. This allows reduction of the thickness of the photoelectrode film and thus lowering of the charge recombination in dye-sensitized solar cells, making it possible to increase further the efficiency of existing dye-sensitized solar cells.

A novel class of organic semiconductors aimed at improving the efficiency of organic photovoltaic devices is investigated by an ab initio electronic structure theory. Two conjugated block copolymers composed of chemically bound donor and acceptor blocks show substantial charge transfer upon photoexcitation, suggesting that the optically excited states are separated charge pairs rather than strongly interacting charges forming excitons. In contrast, little charge transfer is seen in the ground electronic state. The optical cross-sections of the charge separated states are quite high due to a good overlap of the tails of the ground and excited state wavefunctions. The absorption spectra of the systems cover visible spectrum and extend to the infrared, suggesting good prospects for light harvesting. The calculation results indicate that the proposed class of semiconducting molecular heterojunctions may overcome the exciton bottleneck problem in organic photovoltaic materials., (This journal is © the Owner Societies 2011)

A novel tetraphenylquinodimethane based on electron-deficient 4-phenylquinoline oligomer displayed an unusually low ionization potential and was used as a p-channel semiconductor in thin-film transistors and as an emitter to achieve very bright and high efficiency green light-emitting diodes.