density functional theory; lattice dynamics; organic crystals; small-molecule organics semiconductors; temperature and polarization-dependent Raman spectroscopy; temperature-dependent X-ray diffraction; vibrational anharmonicity; Electronic, Optical and Magnetic Materials; Biomaterials; Polymers and Plastics; Materials Chemistry
Abstract :
[en] The lattice dynamics of organic semiconductors has a significant role in determining their electronic and mechanical properties. A common technique to control these macroscopic properties is to chemically modify the molecular structure. These modifications are known to change the molecular packing, but their effect on the lattice dynamics is relatively unexplored. Therefore, we investigate how chemical modifications to a core [1]benzothieno[3,2-b]benzothiophene (BTBT) semiconducting crystal affect the evolution of the crystal structural dynamics with temperature. Our study combines temperature-dependent polarization-orientation (PO) low-frequency Raman measurements with first-principles calculations and single-crystal X-ray diffraction measurements. We show that chemical modifications can indeed suppress specific expressions of vibrational anharmonicity in the lattice dynamics. Specifically, we detect in BTBT a gradual change in the PO Raman response with temperature, indicating a unique anharmonic expression. This anharmonic expression is suppressed in all examined chemically modified crystals (ditBu-BTBT and diC8-BTBT, diPh-BTBT, and DNTT). In addition, we observe solid-solid phase transitions in the alkyl-modified BTBTs. Our findings indicate that π-conjugated chemical modifications are the most effective in suppressing these anharmonic effects.
Disciplines :
Chemistry
Author, co-author :
Asher, Maor ; Department of Chemical and Biological Physics, Weizmann Institute of Science, Rehovot 76100, Israel
Jouclas, Rémy; Laboratoire de Chimie des Polymères, Université Libre de Bruxelles (ULB), 1050 Brussels, Belgium
Bardini, Marco ; Université de Mons - UMONS > Faculté des Science > Service de Chimie des matériaux nouveaux
Diskin-Posner, Yael ; Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel
Kahn, Nitzan; Department of Chemical and Biological Physics, Weizmann Institute of Science, Rehovot 76100, Israel
Korobko, Roman ; Department of Chemical and Biological Physics, Weizmann Institute of Science, Rehovot 76100, Israel
Kennedy, Alan R ; Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, United Kingdom
Silva de Moraes, Lygia ; Laboratoire de Chimie des Polymères, Université Libre de Bruxelles (ULB), 1050 Brussels, Belgium
Schweicher, Guillaume ; Laboratoire de Chimie des Polymères, Université Libre de Bruxelles (ULB), 1050 Brussels, Belgium
Liu, Jie ; Laboratoire de Chimie des Polymères, Université Libre de Bruxelles (ULB), 1050 Brussels, Belgium
Beljonne, David ; Université de Mons - UMONS > Faculté des Science > Service de Chimie des matériaux nouveaux
Geerts, Yves ; Université de Mons - UMONS ; Laboratoire de Chimie des Polymères, Université Libre de Bruxelles (ULB), 1050 Brussels, Belgium ; International Solvay Institutes for Physics and Chemistry, 1050 Brussels, Belgium
Yaffe, Omer ; Department of Chemical and Biological Physics, Weizmann Institute of Science, Rehovot 76100, Israel
R400 - Institut de Recherche en Science et Ingénierie des Matériaux Complexys
Funders :
F?d?ration Wallonie-Bruxelles H2020 Marie Sklodowska-Curie Actions Fonds De La Recherche Scientifique - FNRS H2020 European Research Council
Funding text :
We thank Lior Segev for software development. O.Y. acknowledges funding from the European Research Counsel (850041, ANHARMONIC). Y.G. is thankful to the Belgian National Fund for Scientific Research (FNRS) for financial support through research projects BTBT No. 2.4565.11, Phasetrans No. T.0058.14, Pi-Fast No. T.0072.18, 2D to 3D No. 30489208, and DIFFRA No. U.G001.19. Financial support from the French Community of Belgian (ARC No. 20061) is also acknowledged. G.S. is a FNRS Research Associate. D.B. is a FNRS research director. The work in Mons has been supported by the Marie Curie ITN projects UHMob (GA-811284) and the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 811284 (UHMob).
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