Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

María José Aliaga-Gosalvez; Nicola Demitri; Michael Dohr; Juan Carlos Roldao; Sang Kyu Park; Sangyoon Oh; Shinto Varghese; Soo Young Park; Yoann Olivier; Begoña Milián-Medina; Roland Resel; Johannes Gierschner

doi:10.1002/adom.201900749

Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

María José Aliaga-Gosalvez
, Nicola Demitri
, Michael Dohr
, Juan Carlos Roldao
, Sang Kyu Park
, Sangyoon Oh
, Shinto Varghese
, Soo Young Park
, Yoann Olivier
, Begoña Milián-Medina
, Roland Resel
, Johannes Gierschner

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

Abstract

Polymorphs of organic semiconductors are of great interest as they shed light to structure-property relationships. The full X-ray thin film structure analysis of two polymorphs (B, G) of an important n-type semiconducting dicyano-distyrylbenzene based small molecule (CN-TFPA) is reported. Drastically different structures of the monotropic phases are revealed, that is an uncommon 2D crossed π-stacked arrangement for the B-phase versus a 1D slipped π-stack for G. Both phases exhibit a layered structure in the (100) plane with high structural integrity, driven by the hydrophobic contacts of the terminal CF₃ groups; as (100) coincides with the film surface, this allows for exfoliation by scotch tape. An in-depth time-dependent density functional theory (TD-DFT) based quantum mechanics/molecular mechanics (QM/MM) study reveals all subsequent significantly differing optical and electronic responses which result from the different arrangements: the B film shows little excitonic interaction with strong blue fluorescence, amplified spontaneous emission (ASE), and good 2D n-type transport. The G film forms H-aggregates with strong green fluorescence, no ASE, and 1D n-type charge transport. The established structure-property relationships are seen as a crucial step for computer-aided device analysis.

Original language	English
Article number	1900749
Journal	Advanced Optical Materials
Volume	7
Issue number	21
DOIs	https://doi.org/10.1002/adom.201900749
Publication status	Published - 1 Nov 2019

Funding

The work in Madrid and Valencia was supported by the Spanish Ministerio de Economía y Competitividad (MINECO-FEDER projects CTQ2014-58801 and CTQ2017-87054); the work in Madrid was further supported by the “Severo Ochoa” program for Centers of Excellence in R&D of the MINECO (SEV-2016-0686) and by the Campus of International Excellence (CEI) UAM+CSIC. The authors thank Michael Wykes, Cambridge, for technical support in the QM/MM calculations, and Fabrizio Santoro, CNR Pisa, for assistance with the FCClasses calculations. M.J.A.G thanks Benoit Sklenard, CEA Leti, for fruitful discussions. The work at Seoul National University was supported in parts by the Creative Research Initiative Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (MSIP; Grant No. 2009-0081571[RIAM0417-20150013]) and by the Basic Science Research Program through the NRF funded by the Ministry of Science, ICT and Future Planning (Grant No. 2017R1E1A1A01075372). The large scale facility Elettra, Trieste, Italy, provided synchrotron radiation for single crystal diffraction experiments at the beamline XRD1. The work in Mons was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreement No. 646176 (EXTMOS project). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the Grant Agreement n1117545.

Funders	Funder number
Fabrizio Santoro
Fonds de la Recherche Scientifiques de Belgique	2.5020.11
Waalse Gewest	n1117545
Fédération Wallonie-Bruxelles
Ministerio de Economía y Competitividad
Ministry of Science, ICT and Future Planning	2017R1E1A1A01075372, RIAM0417-20150013, 2009-0081571
National Research Foundation of Korea
Consiglio Nazionale delle Ricerche
Horizon 2020	646176
European Regional Development Fund	CTQ2017-87054, CTQ2014-58801, SEV-2016-0686

Keywords

fluorescent materials
organic optoelectronics
organic semiconductor
photophysics
thin film polymorphism
two-dimensional (2D) charge transport

Access to Document

10.1002/adom.201900749

Cite this

Aliaga-Gosalvez, M. J., Demitri, N., Dohr, M., Roldao, J. C., Park, S. K., Oh, S., Varghese, S., Park, S. Y., Olivier, Y., Milián-Medina, B., Resel, R., & Gierschner, J. (2019). Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response. Advanced Optical Materials, 7(21), Article 1900749. https://doi.org/10.1002/adom.201900749

@article{890e5c15158e401b8fadd7a2f3e58337,

title = "Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response",

abstract = "Polymorphs of organic semiconductors are of great interest as they shed light to structure-property relationships. The full X-ray thin film structure analysis of two polymorphs (B, G) of an important n-type semiconducting dicyano-distyrylbenzene based small molecule (CN-TFPA) is reported. Drastically different structures of the monotropic phases are revealed, that is an uncommon 2D crossed π-stacked arrangement for the B-phase versus a 1D slipped π-stack for G. Both phases exhibit a layered structure in the (100) plane with high structural integrity, driven by the hydrophobic contacts of the terminal CF3 groups; as (100) coincides with the film surface, this allows for exfoliation by scotch tape. An in-depth time-dependent density functional theory (TD-DFT) based quantum mechanics/molecular mechanics (QM/MM) study reveals all subsequent significantly differing optical and electronic responses which result from the different arrangements: the B film shows little excitonic interaction with strong blue fluorescence, amplified spontaneous emission (ASE), and good 2D n-type transport. The G film forms H-aggregates with strong green fluorescence, no ASE, and 1D n-type charge transport. The established structure-property relationships are seen as a crucial step for computer-aided device analysis.",

keywords = "fluorescent materials, organic optoelectronics, organic semiconductor, photophysics, thin film polymorphism, two-dimensional (2D) charge transport",

author = "Aliaga-Gosalvez, \{Mar{\'i}a Jos{\'e}\} and Nicola Demitri and Michael Dohr and Roldao, \{Juan Carlos\} and Park, \{Sang Kyu\} and Sangyoon Oh and Shinto Varghese and Park, \{Soo Young\} and Yoann Olivier and Bego{\~n}a Mili{\'a}n-Medina and Roland Resel and Johannes Gierschner",

note = "Funding Information: The work in Madrid and Valencia was supported by the Spanish Ministerio de Econom{\'i}a y Competitividad (MINECO-FEDER projects CTQ2014-58801 and CTQ2017-87054); the work in Madrid was further supported by the “Severo Ochoa” program for Centers of Excellence in R\&D of the MINECO (SEV-2016-0686) and by the Campus of International Excellence (CEI) UAM+CSIC. The authors thank Michael Wykes, Cambridge, for technical support in the QM/MM calculations, and Fabrizio Santoro, CNR Pisa, for assistance with the FCClasses calculations. M.J.A.G thanks Benoit Sklenard, CEA Leti, for fruitful discussions. The work at Seoul National University was supported in parts by the Creative Research Initiative Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT \& Future Planning (MSIP; Grant No. 2009-0081571[RIAM0417-20150013]) and by the Basic Science Research Program through the NRF funded by the Ministry of Science, ICT and Future Planning (Grant No. 2017R1E1A1A01075372). The large scale facility Elettra, Trieste, Italy, provided synchrotron radiation for single crystal diffraction experiments at the beamline XRD1. The work in Mons was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreement No. 646176 (EXTMOS project). Computational resources were provided by the Consortium des {\'E}quipements de Calcul Intensif (C{\'E}CI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 as well as the Tier-1 supercomputer of the F{\'e}d{\'e}ration Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the Grant Agreement n1117545. Publisher Copyright: {\textcopyright} 2019 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2019",

month = nov,

day = "1",

doi = "10.1002/adom.201900749",

language = "English",

volume = "7",

journal = "Advanced Optical Materials",

publisher = "John Wiley \& Sons Inc.",

number = "21",

}

Aliaga-Gosalvez, MJ, Demitri, N, Dohr, M, Roldao, JC, Park, SK, Oh, S, Varghese, S, Park, SY, Olivier, Y, Milián-Medina, B, Resel, R & Gierschner, J 2019, 'Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response', Advanced Optical Materials, vol. 7, no. 21, 1900749. https://doi.org/10.1002/adom.201900749

TY - JOUR

T1 - Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films

T2 - Impact on the Electronic and Optical Response

AU - Aliaga-Gosalvez, María José

AU - Demitri, Nicola

AU - Dohr, Michael

AU - Roldao, Juan Carlos

AU - Park, Sang Kyu

AU - Oh, Sangyoon

AU - Varghese, Shinto

AU - Park, Soo Young

AU - Olivier, Yoann

AU - Milián-Medina, Begoña

AU - Resel, Roland

AU - Gierschner, Johannes

N1 - Funding Information: The work in Madrid and Valencia was supported by the Spanish Ministerio de Economía y Competitividad (MINECO-FEDER projects CTQ2014-58801 and CTQ2017-87054); the work in Madrid was further supported by the “Severo Ochoa” program for Centers of Excellence in R&D of the MINECO (SEV-2016-0686) and by the Campus of International Excellence (CEI) UAM+CSIC. The authors thank Michael Wykes, Cambridge, for technical support in the QM/MM calculations, and Fabrizio Santoro, CNR Pisa, for assistance with the FCClasses calculations. M.J.A.G thanks Benoit Sklenard, CEA Leti, for fruitful discussions. The work at Seoul National University was supported in parts by the Creative Research Initiative Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (MSIP; Grant No. 2009-0081571[RIAM0417-20150013]) and by the Basic Science Research Program through the NRF funded by the Ministry of Science, ICT and Future Planning (Grant No. 2017R1E1A1A01075372). The large scale facility Elettra, Trieste, Italy, provided synchrotron radiation for single crystal diffraction experiments at the beamline XRD1. The work in Mons was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreement No. 646176 (EXTMOS project). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 as well as the Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under the Grant Agreement n1117545. Publisher Copyright: © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/11/1

Y1 - 2019/11/1

N2 - Polymorphs of organic semiconductors are of great interest as they shed light to structure-property relationships. The full X-ray thin film structure analysis of two polymorphs (B, G) of an important n-type semiconducting dicyano-distyrylbenzene based small molecule (CN-TFPA) is reported. Drastically different structures of the monotropic phases are revealed, that is an uncommon 2D crossed π-stacked arrangement for the B-phase versus a 1D slipped π-stack for G. Both phases exhibit a layered structure in the (100) plane with high structural integrity, driven by the hydrophobic contacts of the terminal CF3 groups; as (100) coincides with the film surface, this allows for exfoliation by scotch tape. An in-depth time-dependent density functional theory (TD-DFT) based quantum mechanics/molecular mechanics (QM/MM) study reveals all subsequent significantly differing optical and electronic responses which result from the different arrangements: the B film shows little excitonic interaction with strong blue fluorescence, amplified spontaneous emission (ASE), and good 2D n-type transport. The G film forms H-aggregates with strong green fluorescence, no ASE, and 1D n-type charge transport. The established structure-property relationships are seen as a crucial step for computer-aided device analysis.

AB - Polymorphs of organic semiconductors are of great interest as they shed light to structure-property relationships. The full X-ray thin film structure analysis of two polymorphs (B, G) of an important n-type semiconducting dicyano-distyrylbenzene based small molecule (CN-TFPA) is reported. Drastically different structures of the monotropic phases are revealed, that is an uncommon 2D crossed π-stacked arrangement for the B-phase versus a 1D slipped π-stack for G. Both phases exhibit a layered structure in the (100) plane with high structural integrity, driven by the hydrophobic contacts of the terminal CF3 groups; as (100) coincides with the film surface, this allows for exfoliation by scotch tape. An in-depth time-dependent density functional theory (TD-DFT) based quantum mechanics/molecular mechanics (QM/MM) study reveals all subsequent significantly differing optical and electronic responses which result from the different arrangements: the B film shows little excitonic interaction with strong blue fluorescence, amplified spontaneous emission (ASE), and good 2D n-type transport. The G film forms H-aggregates with strong green fluorescence, no ASE, and 1D n-type charge transport. The established structure-property relationships are seen as a crucial step for computer-aided device analysis.

KW - fluorescent materials

KW - organic optoelectronics

KW - organic semiconductor

KW - photophysics

KW - thin film polymorphism

KW - two-dimensional (2D) charge transport

UR - https://www.scopus.com/pages/publications/85070722942

U2 - 10.1002/adom.201900749

DO - 10.1002/adom.201900749

M3 - Article

AN - SCOPUS:85070722942

VL - 7

JO - Advanced Optical Materials

JF - Advanced Optical Materials

IS - 21

M1 - 1900749

ER -

Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

High Performance Computing Technology Platform

CCDC 1905198: Experimental Crystal Structure Determination

CCDC 1905199: Experimental Crystal Structure Determination

Cite this

Crossed 2D versus Slipped 1D π-Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Equipment

High Performance Computing Technology Platform

Datasets

CCDC 1905198: Experimental Crystal Structure Determination

CCDC 1905199: Experimental Crystal Structure Determination

Cite this