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Nat Commun. 2014 Apr 16;5:3573. doi: 10.1038/ncomms4573.

One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films.

Author information

1
Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.
2
1] Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia [2] Solar and Photovoltaic Engineering Research Center (SPERC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
3
Cornell High Energy Synchrotron Source (CHESS), Ithaca, New York 14853, USA.
4
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
5
School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, USA.
6
SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA.

Abstract

A crystal's structure has significant impact on its resulting biological, physical, optical and electronic properties. In organic electronics, 6,13(bis-triisopropylsilylethynyl)pentacene (TIPS-pentacene), a small-molecule organic semiconductor, adopts metastable polymorphs possessing significantly faster charge transport than the equilibrium crystal when deposited using the solution-shearing method. Here, we use a combination of high-speed polarized optical microscopy, in situ microbeam grazing incidence wide-angle X-ray-scattering and molecular simulations to understand the mechanism behind formation of metastable TIPS-pentacene polymorphs. We observe that thin-film crystallization occurs first at the air-solution interface, and nanoscale vertical spatial confinement of the solution results in formation of metastable polymorphs, a one-dimensional and large-area analogy to crystallization of polymorphs in nanoporous matrices. We demonstrate that metastable polymorphism can be tuned with unprecedented control and produced over large areas by either varying physical confinement conditions or by tuning energetic conditions during crystallization through use of solvent molecules of various sizes.

PMID:
24736391
DOI:
10.1038/ncomms4573
[Indexed for MEDLINE]
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