High structural quality of crystalline organic semiconductors is the basis of their superior electrical performance. Recent progress in quasi two-dimensional (2D) organic semiconductor films challenges bulk single crystals because both demonstrate competing charge-carrier mobilities. As the thinnest molecular semiconductors, monolayers offer numerous advantages such as unmatched flexibility and light transparency as well they are an excellent platform for sensing. Oligothiophene-based materials are among the most promising ones for light-emitting applications because of the combination of efficient luminescence and decent charge-carrier mobility. Here, we demonstrate single-crystal monolayers of unprecedented structural order grown from four alkyl-substituted thiophene and thiophene–phenylene oligomers. The monolayer crystals with lateral dimensions up to 3 mm were grown from the solution on substrates with various surface energies and roughness by drop or spin-casting with subsequent slow solvent evaporation. Our data indicate that 2D crystallization resulting in single-crystal monolayers occurs at the receding gas–solution–substrate contact line. The structural properties of the monolayers were studied by grazing-incidence X-ray diffraction/reflectivity, atomic force and differential interference contrast microscopies, and imaging spectroscopic ellipsometry. These highly ordered monolayers demonstrated an excellent performance in organic field-effect transistors approaching the best values reported for the thiophene or thiophene–phenylene oligomers. Our findings pave the way for efficient monolayer organic electronics highlighting the high potential of simple solution-processing techniques for the growth of large-size single-crystal monolayers with excellent structural order and electrical performance competing against bulk single crystals.
Abstract2D organic semiconductor single crystals comprising one or a few molecular layers of macroscopic lateral sizes are ideal materials for ultrathin, flexible, and transparent field‐effect devices—a platform for transistors and sensors. In recent years, these 2D materials have demonstrated high performance not inferior to their 3D counterparts. However, light emissive properties of 2D organic semiconductor single crystals have not yet been reported, and a combination of high charge‐carrier mobility and bright luminescence in one material is still a challenge for 2D organic optoelectronics. Emissive high‐mobility 2D organic semiconductor based on a [1]benzothieno[3,2‐b]benzothiophene (BTBT)‐derivative, 2,7‐bis(4‐decylphenyl)[1]benzothieno[3,2‐b][1]benzothiophene (DPBTBT), is presented here. DPBTBT molecules self‐organize in large‐area ultrathin single‐crystalline films consisting of one or a few molecular layers. These 2D single crystals perfectly suit as an active layer of organic field‐effect transistors in full accordance with Shockley's model and uniquely combine the high charge‐carrier mobility reaching 7.5 cm2 V–1 s–1 with prominent light emissive properties, which allow a demonstration of the first 2D organic light‐emitting transistor. The high charge‐carrier mobility and thermal stability of the crystalline phases, pronounced luminescence, and good shelf‐life stability suggest that emissive BTBT‐type molecules are a promising avenue for 2D organic optoelectronics.
Recently developed ultrathin two-dimensional (2D) organic semiconductor crystals are a promising platform for advanced organic electronic devices. Remarkable quality of such crystals results in charge-carrier mobilities comparable to those of bulk crystals, but their structure and orientation are hard to study because of their extremely small thickness. Here, we applied surface-enhanced Raman spectroscopy (SERS) to investigate the structure of the thinnest 2D single crystalsmonolayers, which are based on thiophene-phenylene co-oligomers: 1,4-bis(5′-decyl-2,2′-bithiene-5-yl)benzene and 1,4-bis(5′-hexyl-2,2′-bithiene-5-yl)benzene. Their Raman spectra were calculated as a function of the molecule orientation and SERS microscopy maps were acquired. High sensitivity of SERS allowed us to study monolayer single-crystal domains with the optical spatial resolution. Raman anisotropy was used to probe the orientations of single-crystal domains and the molecule orientation within them. Notably, the SERS microscopy detected the presence of a submonolayeramorphous material between the crystalline domains, which is practically inaccessible to optical or conventional atomic force microscopies (AFMs). The submonolayer was also studied by lateral-force AFM, which showed notably higher friction and adhesion. We found that the measured Raman anisotropy significantly reduced by the metal-covered substrate still allowing us to distinguish orientations of molecules in the 2D crystals and in the submonolayer. Anisotropy-sensitive SERS was shown to be promising for studying 2D organic semiconductor crystals.
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