Solution coating of organic semiconductors offers great potential for achieving low-cost manufacturing of large-area and flexible electronics. However, the rapid coating speed needed for industrial-scale production poses challenges to the control of thin-film morphology. Here, we report an approach--termed fluid-enhanced crystal engineering (FLUENCE)--that allows for a high degree of morphological control of solution-printed thin films. We designed a micropillar-patterned printing blade to induce recirculation in the ink for enhancing crystal growth, and engineered the curvature of the ink meniscus to control crystal nucleation. Using FLUENCE, we demonstrate the fast coating and patterning of millimetre-wide, centimetre-long, highly aligned single-crystalline organic semiconductor thin films. In particular, we fabricated thin films of 6,13-bis(triisopropylsilylethynyl) pentacene having non-equilibrium single-crystalline domains and an unprecedented average and maximum mobilities of 8.1±1.2 cm(2) V(-1) s(-1) and 11 cm(2) V(-1) s(-1). FLUENCE of organic semiconductors with non-equilibrium single-crystalline domains may find use in the fabrication of high-performance, large-area printed electronics.

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.

Recently, confinement of polymers with different geometries has become a research hotspot. Here, we report the dramatic deviation of glass transition behaviors of poly(methyl methacrylate) (PMMA) confined in cylindrical nanopores with diameter significantly larger than chain’s radius of gyration (R g ). Fast cooling a PMMA melt in the nanopores results in a glass with one single glass transition temperature (T g). But two distinct T gs are detected after slow cooling the melt. The deviation in T g could be as large as 45 K. This phenomenon is interpreted by a two-layer model. During vitrification under slow cooling two distinct layers are formed: a strongly constrained interfacial layer showing an increased T g as compared to that of the bulk polymer and a core with a decreased T g. By thermal annealing experiments, we find that these two T gs are inherently correlated. In addition, the deviation of T g for PMMA confined in nanopores reveals a dependence on molecular weight.