Solution-processed organic photovoltaics (OPV) offer the attractive prospect of low-cost, light-weight and environmentally benign solar energy production. The highest efficiency OPV at present use low-bandgap donor polymers, many of which suffer from problems with stability and synthetic scalability. They also rely on fullerene-based acceptors, which themselves have issues with cost, stability and limited spectral absorption. Here we present a new non-fullerene acceptor that has been specifically designed to give improved performance alongside the wide bandgap donor poly(3-hexylthiophene), a polymer with significantly better prospects for commercial OPV due to its relative scalability and stability. Thanks to the well-matched optoelectronic and morphological properties of these materials, efficiencies of 6.4% are achieved which is the highest reported for fullerene-free P3HT devices. In addition, dramatically improved air stability is demonstrated relative to other high-efficiency OPV, showing the excellent potential of this new material combination for future technological applications.

Sequential doping is a promising new doping technique for semicrystalline polymers that has been shown to produce doped films with higher conductivity and more uniform morphology than conventional doping processes, and where the dopant placement in the film can be controlled. As a relatively new technique, however, much work is needed to understand the resulting polymer-dopant interactions upon sequential doping. A combination of infrared spectroscopy and theoretical simulations shows that the dopants selectively placed in the amorphous regions in the film via sequential doping result in highly localized polarons. We find that the presence of dopants within the amorphous regions of the film leads to an increase in conjugation length of the amorphous chains upon doping, increasing film connectivity and hence improving the overall conductivity of the film compared with the conventional doping processes.

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.

Doping of organic bulk heterojunction solar cells has the potential to improve their power conversion efficiency (PCE). Deconvoluting the effect of doping on charge transport, recombination, and energetic disorder remains challenging. It is demonstrated that molecular doping has two competing effects: on one hand, dopant ions create additional traps while on the other hand free dopant-induced charges fill deep states possibly leading to V OC and mobility increases. It is shown that molar dopant concentrations as low as a few parts per million can improve the PCE of organic bulk heterojunctions. Higher concentrations degrade the performance of the cells. In doped cells where PCE is observed to increase, such improvement cannot be attributed to better charge transport. Instead, the V OC increase in unannealed P3HT:PCBM cells upon doping is indeed due to trap filling, while for annealed P3HT:PCBM cells the change in V OC is related to morphology changes and dopant segregation.In PCDTBT:PC70BM cells, the enhanced PCE upon doping is explained by changes in the thickness of the active layer. This study highlights the complexity of bulk doping in organic solar cells due to the generally low doping efficiency and the constraint on doping concentrations to avoid carrier recombination and adverse morphology changes.

Barriers to charge transfer at electrode‐semiconductor contacts are ubiquitous and limit the applicability of organic semiconductors in electronic devices. Molecular or ionic doping near contacts can alleviate charge injection or extraction problems by enabling charge tunneling through contact barriers, but the soft nature of organic materials allows for small molecule dopants to diffuse and migrate, degrading the performance of the device and limiting effective interfacial doping. Here, it is demonstrated that contact doping in organic electronics is possible through ionic polymer dopants, which resist diffusion or migration due to their large size. Sub‐monolayer deposition of non‐conjugated strong polyelectrolytes, e.g., sulfonated poly(sulfone)s, at the anode‐semiconductor interface of organic photovoltaics enables efficient hole extraction at the anode. The performance of contact‐doped organic photo­voltaics nearly matches the performance of devices composed of traditional hole transport layers such as poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The degree of sulfonation of the dopant polymer and the thickness of the ionic dopant layer is shown to be critical for optimizing doping and the efficiency of the device.

Interfacial barriers at electrode−semiconductor contacts can greatly limit charge collection efficiency and hamper device performance. Doping of the semiconductor near the interface can mitigate charge extraction or injection problems by allowing charge tunneling through barriers with reduced width. Here we demonstrate that polymer acids can act as p-type dopants near electrode interfaces for active layers containing poly(3-hexylthiophene-2,5-diyl) (P3HT). By varying the pendant acidic groups between aromatic sulfonic acid, trifluoromethane sulfonimide, and perfluorosulfonic acid, we find the effectiveness of doping the conjugated polymer at the interface depends on the strength of the pendant acid group with stronger acid moieties being capable of creating more carriers in the doped system. Deposition of acidic polymeric dopants at the anode allows high carrier densities, of order 10 20 cm −3 , to be obtained in polymer semiconductors near the electrode interface. The charge carrier density also depends on the miscibility between polymeric dopants and conjugated polymers. The overall doping efficacy near electrodes therefore depends on the interplay between the strength of pendant acid groups and miscibility between polymeric dopants and conjugated polymers.

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We demonstrate room temperature mid-infrared photodetection using resonantly absorbing GeSn/Ge core/shell nanowire photonic crystals. For emission, we designed and characterized mid-infrared emission of resonantly scattering GeSn/Ge coreshell nanowires with 912% Sn.