Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors

Handle URI:
http://hdl.handle.net/10754/610559
Title:
Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors
Authors:
Ryno, Sean M.; Risko, Chad; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
The polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate their polarization energies in the bulk and at the organic-vacuum interface using a polarizable force field that accounts for induced-dipole and quadrupole interactions. Though both oligoacenes pack in a herringbone motif, the tetraphenyl substituents on the tetracene backbone of rubrene alter greatly the nature of the packing. The resulting change in relative orientations of neighboring molecules is found to reduce the bulk polarization energy of holes in rubrene by some 0.3 eV when compared to tetracene. The consideration of model organic-vacuum interfaces highlights the significant variation in the electrostatic environment for a charge carrier at a surface although the net change in polarization energy is small; interestingly, the environment of a charge even just one layer removed from the surface can be viewed already as representative of the bulk. Overall, it is found that in these herringbone-type layered crystals the polarization energy has a much stronger dependence on the intralayer packing density than interlayer packing density.
KAUST Department:
Solar and Photovoltaic Engineering Research Center (SPERC); Physical Sciences and Engineering (PSE) Division
Citation:
Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors 2016 ACS Applied Materials & Interfaces
Publisher:
American Chemical Society (ACS)
Journal:
ACS Applied Materials & Interfaces
Issue Date:
16-May-2016
DOI:
10.1021/acsami.6b02579
Type:
Article
ISSN:
1944-8244; 1944-8252
Sponsors:
This work has been supported by King Abdullah University of Science and Technology (KAUST), the KAUST Competitive Research Grant program, and the Office of Naval Research Global (Award N62909-15-1-2003). We acknowledge the IT Research Computing Team and Supercomputing Laboratory at KAUST for providing computational and storage resources. This work has also used the computing resources of the Garnet, Spirit, and Copper supercomputing systems through the DoD HPCMP. We thank Professor Dan Frisbie for most stimulating discussions and Professor Jay Ponder for invaluable assistance in troubleshooting the Tinker suite. C.R. thanks the University of Kentucky Vice President of Research for start-up funds.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acsami.6b02579
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorRyno, Sean M.en
dc.contributor.authorRisko, Chaden
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2016-05-23T08:03:15Z-
dc.date.available2016-05-23T08:03:15Z-
dc.date.issued2016-05-16-
dc.identifier.citationImpact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors 2016 ACS Applied Materials & Interfacesen
dc.identifier.issn1944-8244-
dc.identifier.issn1944-8252-
dc.identifier.doi10.1021/acsami.6b02579-
dc.identifier.urihttp://hdl.handle.net/10754/610559-
dc.description.abstractThe polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate their polarization energies in the bulk and at the organic-vacuum interface using a polarizable force field that accounts for induced-dipole and quadrupole interactions. Though both oligoacenes pack in a herringbone motif, the tetraphenyl substituents on the tetracene backbone of rubrene alter greatly the nature of the packing. The resulting change in relative orientations of neighboring molecules is found to reduce the bulk polarization energy of holes in rubrene by some 0.3 eV when compared to tetracene. The consideration of model organic-vacuum interfaces highlights the significant variation in the electrostatic environment for a charge carrier at a surface although the net change in polarization energy is small; interestingly, the environment of a charge even just one layer removed from the surface can be viewed already as representative of the bulk. Overall, it is found that in these herringbone-type layered crystals the polarization energy has a much stronger dependence on the intralayer packing density than interlayer packing density.en
dc.description.sponsorshipThis work has been supported by King Abdullah University of Science and Technology (KAUST), the KAUST Competitive Research Grant program, and the Office of Naval Research Global (Award N62909-15-1-2003). We acknowledge the IT Research Computing Team and Supercomputing Laboratory at KAUST for providing computational and storage resources. This work has also used the computing resources of the Garnet, Spirit, and Copper supercomputing systems through the DoD HPCMP. We thank Professor Dan Frisbie for most stimulating discussions and Professor Jay Ponder for invaluable assistance in troubleshooting the Tinker suite. C.R. thanks the University of Kentucky Vice President of Research for start-up funds.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acsami.6b02579en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acsami.6b02579.en
dc.titleImpact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductorsen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalACS Applied Materials & Interfacesen
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Chemistry and Biochemistry & Center for Organic Photonics and Electronics Georgia Institute of Technology Atlanta, Georgia 30332-0400en
dc.contributor.institutionDepartment of Chemistry & Center for Applied Energy Research University of Kentucky Lexington, Kentucky 40506-0055en
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorRyno, Sean Men
kaust.authorBredas, Jean-Lucen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.