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We report an microbeam grazing incidence X-ray scattering study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C-BTBT) organic semiconductor thin film deposition by hollow pen writing. Multiple transient phases are observed during the crystallization for substrate temperatures up to ≈93 °C. The layered smecticliquid-crystalline phase of C-BTBT initially forms and preceedes inter-layer ordering, followed by a transient crystalline phase for temperature >60 °C, and ultimately the stable phase. Based on these results, we demonstrate a method to produce extremely large grain size and high carrier mobility during high-speed processing. For high writing speed (25 mm/s), mobility up to 3.0 cm2/V-s has been observed.


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