Quasi-Phase Diagrams at Air/Oil Interfaces and Bulk Oil Phases for Crystallization of Small-Molecular Semiconductors by Adjusting Gibbs Adsorption

Satoshi Watanabe, Takahisa Ohta, Ryota Urata, Tetsuya Sato, Kazuto Takaishi, Masanobu Uchiyama, Tetsuya Aoyama, Masashi Kunitake

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The temperature and concentration dependencies of the crystallization of two small-molecular semiconductors were clarified by constructing quasi-phase diagrams at air/oil interfaces and in bulk oil phases. A quinoidal quaterthiophene derivative with four alkyl chains (QQT(CN)4) in 1,1,2,2-tetrachroloethane (TCE) and a thienoacene derivative with two alkyl chains (C8-BTBT) in o-dichlorobenzene were used. The apparent crystal nucleation temperature (Tn) and dissolution temperature (Td) of the molecules were determined based on optical microscopy examination in closed glass capillaries and open dishes during slow cooling and heating processes, respectively. Tn and Td were considered estimates of the critical temperatures for nuclear formation and crystal growth, respectively. The Tn values of QQT(CN)4 and C8-BTBT at the air/oil interfaces were higher than those in the bulk oil phases, whereas the Td values at the air/oil interfaces were almost the same as those in the bulk oil phases. These Gibbs adsorption phenomena were attributed to the solvophobic effect of the alkyl chain moieties. The temperature range between Tn and Td corresponds to suitable supercooling conditions for ideal crystal growth based on the suppression of nucleation. The Tn values at the water/oil and oil/glass interfaces did not shift compared with those of the bulk phases, indicating that adsorption did not occur at the hydrophilic interfaces. Promotion and inhibition of nuclear formation for crystal growth of the semiconductors were achieved at the air/oil and hydrophilic interfaces, respectively.

Original languageEnglish
Pages (from-to)8906-8913
Number of pages8
Issue number36
Publication statusPublished - Sep 12 2017


ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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