Significant improvements to the thermoelectric figure of merit ZT have emerged in recent years, primarily due to the engineering of material composition and nanostructure in inorganic semiconductors (ISCs). However, many present high-ZT materials are based on low-abundance elements that pose challenges for scale-up, as they entail high material costs in addition to brittleness and difficulty in large-area deposition. Here we demonstrate a strategy to improve ZT in conductive polymers and other organic semiconductors (OSCs) for which the base elements are earth-abundant. By minimizing total dopant volume, we show that all three parameters constituting ZT vary in a manner so that ZT increases; this stands in sharp contrast to ISCs, for which these parameters have trade-offs. Reducing dopant volume is found to be as important as optimizing carrier concentration when maximizing ZT in OSCs. Implementing this strategy with the dopant poly(styrenesulphonate) in poly(3,4-ethylenedioxythiophene), we achieve ZT  =  0.42 at room temperature.

Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin–orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels–Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage.

A model for the Seebeck coefficient in the regime of hopping transport that includes the effects of Gaussian carrier density of states width and carrier localization allows these parameters to be derived independently of the attempt-to-jump rate, which can subsequently be derived from measured electrical conductivity. This model is applied to prototypical small molecular and polymer organic semiconductors to characterize carrier localization, quantify the role of dopants on the hopping transport parameters, and derive the effective dopant ionization fraction and activation energy.

The effects of exchange current density, Tafel slope, system resistance, electrode area, light intensity, and solar cell efficiency were systematically decoupled at the converter-assisted photovoltaic–water electrolysis system. This allows key determinants of overall efficiency to be identified. On the basis of this model, 26.5% single-junction GaAs solar cell was combined with a membrane-electrode-assembled electrolysis cell (EC) using the dc/dc converting technology. As a result, we have achieved a solar-to-hydrogen conversion efficiency of 20.6% on a prototype scale and demonstrated light intensity tracking optimization to maintain high efficiency. We believe that this study will provide design principles for combining solar cells, ECs, and new catalysts and can be generalized to other solar conversion chemical devices while minimizing their power loss during the conversion of electrical energy into fuel.

Low-noise thermoelectric and electrical measurements were used to derive the dependences of Seebeck coefficient and hole mobility on carrier concentration and grain size in the “bulk” regions of thermally evaporated pentacene thin films (in contrast to the channel field-effect mobility typically measured using thin-film transistor geometries). Distinct charge transport regimes were observed for larger (0.5 and 0.8 μm) and smaller (0.2 μm) grain sizes, attributed to carrier-dopant scattering and percolation, respectively.

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