Understanding crystal polymorphism is a long-standing challenge relevant to many fields, such as pharmaceuticals, organic semiconductors, pigments, food, and explosives. Controlling polymorphism of organic semiconductors (OSCs) in thin films is particularly important given that such films form the active layer in most organic electronics devices and that dramatic changes in the electronic properties can be induced even by small changes in the molecular packing. However, there are very few polymorphic OSCs for which the structure-property relationships have been elucidated so far. The major challenges lie in the transient nature of metastable forms and the preparation of phase-pure, highly crystalline thin films for resolving the crystal structures and evaluating the charge transport properties. Here we demonstrate that the nanoconfinement effect combined with the flow-enhanced crystal engineering technique is a powerful and likely material-agnostic method to identify existing polymorphs in OSC materials and to prepare the individual pure forms in thin films at ambient conditions. With this method we prepared high quality crystal polymorphs and resolved crystal structures of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), including a new polymorph discovered via in situ grazing incidence X-ray diffraction and confirmed by molecular mechanic simulations. We further correlated molecular packing with charge transport properties using quantum chemical calculations and charge carrier mobility measurements. In addition, we applied our methodology to a [1]benzothieno[3,2-b][1]1benzothiophene (BTBT) derivative and successfully stabilized its metastable form.

A series of bulky end-capped [1]benzothieno[3,2-b]benzothiophenes (BTBTs) are developed in order to tune the packing structure via terminal substitution. A coupled theoretical and experimental study allows us to identify 2,7-di-tert-butylBTBT as a new high-performance organic semiconductor with large and well-balanced transfer integrals, as evidenced by quantum-chemical calculations. Single-crystal field-effect transistors show a remarkable average saturation mobility of 7.1 cm(2) V(-1) s(-1) .

Core‐chlorinated naphthalene tetracarboxylic diimides (NDIs) with fluoroalkyl chains are synthesized and employed for n‐channel organic thin‐film transistors (OTFTs). Structural analyses of the single crystals and thin films are performed and their charge‐transport behavior is investigated in terms of structure–property relationships. NDIs with two chlorine substituents are shown to exhibit a herringbone structure with a very close π‐plane distance (3.3–3.4 Å), a large π‐stack overlap (slipping angle ca. 62°), and high crystal densities (2.046–2.091 g cm−3). These features result in excellent field‐effect mobilities of up to 1.43 cm2 V−1 s−1 with minimal hysteresis and high on–off ratios (ca. 107) in air. This is similar to the highest n‐channel mobilities in air reported so far. Despite the repulsive interactions of bulky Cl substituents, tetrachlorinated NDIs adopt a slip‐stacked face‐to‐face packing with an interplanar distance of around 3.4 Å, resulting in a high mobility (up to 0.44 cm2 V−1 s−1). The air‐stability of dichlorinated NDIs is superior to that of tetrachlorinated NDIs, despite of their higher LUMO levels. This is closely related to the denser packing of the fluorocarbon chains of dichlorinated NDIs, which serves as a kinetic barrier to the diffusion of ambient oxidants. Interestingly, these NDIs show an optimal performance either on bare SiO2 or on octadecyltrimethoxysilane (OTS)‐treated SiO2, depending on the carbon number of the fluoroalkyl chains. Their synthetic simplicity and processing versatility combined with their high performance make these semiconductors highly promising for practical applications in flexible electronics.

Developing organic photovoltaic systems that possess high efficiency, high reproducibility, and low cost remains a topic of keen investigation. From a molecular design perspective, developing a “multicomponent” copolymerization synthetic approach could potentially afford macromolecular materials encompassing all of the aforementioned desired parameters. Herein, we describe the synthesis of a series of poly(isoindigo-dithiophene)-based conjugated polymers with varying amounts of low molecular weight polystyrene (PS) side chains (M n = 1300 g/mol) via random copolymerization. We observed better solubility with polymers containing the PS side chains (when compared to their non-PS-side-chain counterparts), hence leading to better batch-to-batch reproducibility in terms of molecular weights. Furthermore, the PS-side-chain-decorated copolymers also demonstrated better thin film processability, without affecting the electronic and optical properties, when the molar percentage of the PS-containing repeating units were ≤10%. Bulk heterojunction solar cell devices fabricated with these PS-containing copolymers demonstrated significantly improved performances [maximum power conversion efficiencies (PCE) > 7% and open circuit voltages (V OC) ≥ 0.95 V], compared to the highest reported performance (PCE = 6.3% and V OC = 0.70) based on similar isoindigo-containing polymers. Taken together, the synthesis, processing, and device performances of PS-containing copolymers represent a new approach in molecular engineering to achieve a balance between the optical/electronic properties and solubility/processability of reproducible polymeric systems.