TY - JOUR
T1 - One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films
AU - Giri, Gaurav
AU - Li, Ruipeng
AU - Smilgies, Detlef M.
AU - Li, Er Qiang
AU - Diao, Ying
AU - Lenn, Kristina M.
AU - Chiu, Melanie
AU - Lin, Debora W.
AU - Allen, Ranulfo
AU - Reinspach, Julia
AU - Mannsfeld, Stefan C.B.
AU - Thoroddsen, Sigurdur T.
AU - Clancy, Paulette
AU - Bao, Zhenan
AU - Amassian, Aram
N1 - Funding Information:
This work was partially supported by the National Science Foundation (DMR-1303178), the Air Force Office of Scientific Research (FA9550-12-1-0190), and an Intel Foundation/ SRCEA Masters Scholarship (for K.M.L.) supported in part by the Office of Competitive Research Funding (OCRF) of the King Abdullah University of Science and Technology (KAUST) under CRG and AEA awards. CHESS is supported by the NSF and NIH/NIGMS via NSF award DMR-0936384. Y.D. and S.C.B.M. acknowledge the support from Laboratory Directed Research and Development (LDRD). We acknowledge travel support from the KAUST sponsored Stanford Center for Advanced Photovoltaics. We thank Dr Jeffery Tok for helpful reading and corrections of the manuscript. E.Q.L. is grateful for a SABIC Postdoctoral Fellowship.
PY - 2014/4/16
Y1 - 2014/4/16
N2 - 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.
AB - 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.
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U2 - 10.1038/ncomms4573
DO - 10.1038/ncomms4573
M3 - Article
C2 - 24736391
AN - SCOPUS:84898809383
SN - 2041-1723
VL - 5
JO - Nature communications
JF - Nature communications
M1 - 3573
ER -