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

Gaurav Giri; Ruipeng Li; Detlef Matthias Smilgies; Erqiang Li; Ying Diao; Kristina M. Lenn; Melanie Chiu; Debora W. Lin; Ranulfo A. Allen; Julia A. Reinspach; Stefan C B Mannsfeld; Sigurdur T Thoroddsen; Paulette Clancy; Zhenan Bao; Aram Amassian

doi:10.1038/ncomms4573

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

Gaurav Giri, Ruipeng Li, Detlef Matthias Smilgies, Erqiang Li, Ying Diao, Kristina M. Lenn, Melanie Chiu, Debora W. Lin, Ranulfo A. Allen, Julia A. Reinspach, Stefan C B Mannsfeld, Sigurdur T Thoroddsen, Paulette Clancy, Zhenan Bao, Aram Amassian

Research output: Contribution to journal › Article › peer-review

124 Scopus citations

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. © 2014 Macmillan Publishers Limited.

Original language	English (US)
Journal	Nature Communications
Volume	5
Issue number	1
DOIs	https://doi.org/10.1038/ncomms4573
State	Published - Apr 16 2014

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.

ASJC Scopus subject areas

General Biochemistry, Genetics and Molecular Biology
General Chemistry
General Physics and Astronomy

Access to Document

10.1038/ncomms4573

Cite this

Giri, G., Li, R., Smilgies, D. M., Li, E., Diao, Y., Lenn, K. M., Chiu, M., Lin, D. W., Allen, R. A., Reinspach, J. A., Mannsfeld, S. C. B., Thoroddsen, S. T., Clancy, P., Bao, Z., & Amassian, A. (2014). One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films. Nature Communications, 5(1). https://doi.org/10.1038/ncomms4573

@article{c724a6a9de3b445e9586468d1d43417d,

title = "One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films",

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. {\textcopyright} 2014 Macmillan Publishers Limited.",

author = "Gaurav Giri and Ruipeng Li and Smilgies, {Detlef Matthias} and Erqiang Li and Ying Diao and Lenn, {Kristina M.} and Melanie Chiu and Lin, {Debora W.} and Allen, {Ranulfo A.} and Reinspach, {Julia A.} and Mannsfeld, {Stefan C B} and Thoroddsen, {Sigurdur T} and Paulette Clancy and Zhenan Bao and Aram Amassian",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.",

year = "2014",

month = apr,

day = "16",

doi = "10.1038/ncomms4573",

language = "English (US)",

volume = "5",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Nature Research",

number = "1",

}

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 Matthias

AU - Li, Erqiang

AU - Diao, Ying

AU - Lenn, Kristina M.

AU - Chiu, Melanie

AU - Lin, Debora W.

AU - Allen, Ranulfo A.

AU - Reinspach, Julia A.

AU - Mannsfeld, Stefan C B

AU - Thoroddsen, Sigurdur T

AU - Clancy, Paulette

AU - Bao, Zhenan

AU - Amassian, Aram

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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. © 2014 Macmillan Publishers Limited.

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. © 2014 Macmillan Publishers Limited.

UR - http://hdl.handle.net/10754/563500

UR - http://www.nature.com/articles/ncomms4573

UR - http://www.scopus.com/inward/record.url?scp=84898809383&partnerID=8YFLogxK

U2 - 10.1038/ncomms4573

DO - 10.1038/ncomms4573

M3 - Article

C2 - 24736391

SN - 2041-1723

VL - 5

JO - Nature Communications

JF - Nature Communications

IS - 1

ER -

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

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this