Linear optical properties and electronic structures of poly(3- hexylthiophene) and poly(3-hexylselenophene) crystals from first principles

Takao Tsumuraya, Jung Hwan Song, Arthur J Freeman

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Linear optical properties of regio-regular-poly(3-hexythiophene) (rr-P3HT) and regio-regular-poly(3-hexyselenophene) (rr-P3HS) are investigated in relation to their anisotropic crystal structure by means of first-principles density functional calculations. The optical spectra are evaluated by calculating its dielectric functions, focusing on the frequency dependence of the imaginary part. The optical transition along the π conjugation-connecting backbone direction is found to be the most significant at the band edges. A group-theoretical analysis of the matrix elements is given to explain the interband transitions. The optical spectra, electronic structures, and structural stabilities are calculated using the all-electron full-potential linearized augmented plane wave (FLAPW) method within the local-density approximation. We proposed several possible crystal structures of rr-P3HT and performed structural optimizations to determine a stable structure. Comparing the total energy differences among these relaxed structures, a base-centered monoclinic structure belonging to the space group A2 is found to be the most stable structure. In the electronic structure, C and S orbitals belonging to polythiophene backbones are the biggest contributors at the valence band maximum and conduction band minimum, but there is almost no contribution from the hexyl side chains. Last, the differences in electronic and optical properties between rr-P3HT and rr-P3HS are discussed.

Original languageEnglish
Article number075114
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume86
Issue number7
DOIs
Publication statusPublished - Aug 8 2012

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Electronic structure
Optical properties
Crystal structure
electronic structure
optical properties
Local density approximation
Crystals
Optical transitions
optical spectrum
Structural optimization
Electron transitions
Valence bands
Conduction bands
Electronic properties
crystals
Density functional theory
crystal structure
structural stability
conjugation
optical transition

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Electronic, Optical and Magnetic Materials

Cite this

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title = "Linear optical properties and electronic structures of poly(3- hexylthiophene) and poly(3-hexylselenophene) crystals from first principles",
abstract = "Linear optical properties of regio-regular-poly(3-hexythiophene) (rr-P3HT) and regio-regular-poly(3-hexyselenophene) (rr-P3HS) are investigated in relation to their anisotropic crystal structure by means of first-principles density functional calculations. The optical spectra are evaluated by calculating its dielectric functions, focusing on the frequency dependence of the imaginary part. The optical transition along the π conjugation-connecting backbone direction is found to be the most significant at the band edges. A group-theoretical analysis of the matrix elements is given to explain the interband transitions. The optical spectra, electronic structures, and structural stabilities are calculated using the all-electron full-potential linearized augmented plane wave (FLAPW) method within the local-density approximation. We proposed several possible crystal structures of rr-P3HT and performed structural optimizations to determine a stable structure. Comparing the total energy differences among these relaxed structures, a base-centered monoclinic structure belonging to the space group A2 is found to be the most stable structure. In the electronic structure, C and S orbitals belonging to polythiophene backbones are the biggest contributors at the valence band maximum and conduction band minimum, but there is almost no contribution from the hexyl side chains. Last, the differences in electronic and optical properties between rr-P3HT and rr-P3HS are discussed.",
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