This progress report summarizes the numerous DPP-containing polymers recently developed for field-effect transistor applications including diphenyl-DPP and dithienyl-DPP-based polymers as the most commonly reported materials, but also difuranyl-DPP, diselenophenyl-DPP and dithienothienyl-DPP-containing polymers. We discuss the hole and electron mobilities that were reported in relation to structural properties such as alkyl substitution patterns, polymer molecular weights and solid state packing, as well as electronic properties including HOMO and LUMO energy levels. We moreover consider important aspects of ambipolar charge transport and highlight fundamental structure-property relations such as the relationships between the thin film morphologies and the charge carrier mobilities observed for DPP-containing polymers.

Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter θ, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor:acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor:acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination.

Over the last decade the performance of organic field-effect transistors (FETs) has seen a remarkable improvement, owing to advances in material development as well as device optimization. Field-effect mobilities on the order of 10 cm 2 V À1

The photoactive layer of organic solar cells consists of a nanoscale blend of electron-donating and electron-accepting organic semiconductors. Controlling the degree of phase separation between these components is crucial to reach efficient solar cells. In solution-processed polymer-fullerene solar cells, small amounts of co-solvents are commonly used to avoid the formation of undesired large fullerene domains that reduce performance. There is an ongoing discussion about the origin of this effect. To clarify the role of co-solvents, we combine three optical measurements to investigate layer thickness, phase separation and polymer aggregation in real time during solvent evaporation under realistic processing conditions. Without co-solvent, large fullerene-rich domains form via liquid-liquid phase separation at B20 vol% solid content. Under such supersaturated conditions, co-solvents induce polymer aggregation below 20 vol% solids and prevent the formation of large domains. This rationalizes the formation of intimately mixed films that give high-efficient solar cells for the materials studied.

A new class of diketopyrrolopyrrole conjugated acceptor polymer incorporating thiazoles with low-lying energy levels, high electron mobility, and broad absorption to the near infrared region provides a power conversion efficiency of 2.9% in solar cells with a second diketopyrrolo-pyrrole polymer as the donor.

Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined.

Wienk, M.M.; Turbiez, M.G.R.; Struijk, M.P.; Fonrodona, M.; Janssen, R.A.J.

One of the biggest challenges for the commercialization of polymer‐based and other printed photovoltaic (PV) technologies is to establish reliable up‐scaling processes that minimize the efficiency losses occurring during the transition from record laboratory cells to roll‐to‐roll (R2R) printed PV modules. This article reviews the latest advances in reducing the efficiency gap between record solar cells and large‐area organic PV modules. The major loss sources are identified for the most popular cell architectures and categorized into optical, electrical, and processing‐related contributions. Their relative shares in the overall efficiency drop are quantified through optical and electrical simulations. Further potential sources of efficiency loss, such as the replacement of halogenated by green solvents for active layer processing, are also addressed. Finally, the effect of reduced efficiency gaps on the production costs of R2R printed modules is discussed, demonstrating that values as low as € 0.5 Wp−1 (the nominal power of a solar module/cell) can be achieved.