Chemical modifications suppress anharmonic effects in the lattice dynamics of organic semiconductors

Maor Asher, Rémy Jouclas, Marco Bardini, Yael Diskin-Posner, Nitzan Khan, Roman Korobko, Alan R. Kennedy, Lygia Silva de Moraes, Guillaume Schweicher, Jie Liu, David Beljonne, Yves Geerts, Omer Yaffe

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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.

Original languageEnglish
Pages (from-to)699-708
Number of pages10
JournalACS Materials Au
Issue number6
Early online date5 Jul 2022
Publication statusPublished - 9 Nov 2022


  • small-molecule organics semiconductors
  • organic crystals
  • lattice dynamics
  • temperature and polarization-dependent Raman spectroscopy
  • vibrational anharmonicity
  • density functional theory
  • temperature-dependent X-ray diffraction


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