Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

TL;DR

This study uses resonant Raman scattering to identify and analyze the electronic states of trans-polyacetylene, PPV, and sp-hybridised carbon in amorphous hydrogenated carbon films, revealing how excitation energy affects their spectral features.

Contribution

It demonstrates the ability of resonant Raman scattering to differentiate and probe various carbon hybridizations and conjugation lengths within amorphous carbon materials, highlighting their spectral behavior across excitation energies.

Findings

Resonant Raman spectra reveal inhomogeneity of trans-(CH)x chains.

PPV and sp segments show distinct dispersion with excitation energy.

Raman features of trans-(CH)x in amorphous carbon match bulk properties.

Abstract

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR - UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy \hbar{\omega}L is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to \hbar{\omega}L probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to \hbar{\omega}L probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.