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Controlling organic semiconductor self-assembly through cylindrical nanoconfinement
Citation Link: https://doi.org/10.15480/882.15950
Publikationstyp
Preprint
Date Issued
2025-09-30
Sprache
English
TORE-DOI
Citation
chemrxiv: rzjg4 (2025)
Publisher DOI
Publisher
American Chemical Society (ACS)
Peer Reviewed
false
Controlling the self-assembly of organic semiconductors at the nanoscale is critical for advancing high-performance electronic and photonic devices, yet remains challenging due to their intrinsic anisotropic crystallization and sensitivity to processing conditions. Here, we demonstrate that cylindrical nanoconfinement within anodic aluminum oxide membranes provides a versatile platform to precisely tune the molecular orientation and phase behavior of the prototypical organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). Combining temperature-dependent high-resolution synchrotron X-ray scattering with optical birefringence measurements, we uncover that confinement geometries (pore diameters 25–180 nm) and surface chemistry govern the emergence of distinct smectic A textures, featuring molecular layers either parallel or perpendicular to the pore axis. The competition between axial and radial smectic layering is modulated by pore size, surface hydrophilicity, and thermal history, enabling reversible control over domain orientations and transitions between liquid crystalline and crystalline states. Notably, nanoconfinement stabilizes the smectic phase over an expanded temperature range compared to bulk, while inducing complex multi-domain configurations owing to geometric constraints and anchoring conditions. Our results elucidate fundamental mechanisms by which anisotropic nanoscale confinement directs the self-organization of highly conjugated organic molecules, with implications for optimizing directional charge transport and anisotropic optical responses in organic–inorganic hybrid nanoarchitectures. This study establishes nanoconfinement as a powerful strategy to engineer morphology and functional properties in organic semiconducting materials with nanoscale precision.
Subjects
smectic liquid crystal
nanoporous material
X-ray scattering
optical birefringence
DDC Class
541.3: Physical Chemistry
Publication version
draft
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