Dynamics of Excitation Transfer and Charge Separation in Polymeric Semiconductors

Arvydas Ruseckas

Research output: ThesisDoctoral Thesis (compilation)


Dynamics of optically excited electronic states have been studied in solid films and solutions of semiconducting polymers and model compounds. Transient absorption, monitored in the spectral range from 0.9 eV to 2.5 eV with a time resolution of about 100 fs, was the main experimental technique. Transient anisotropy, obtained from different polarizations of light, was employed to trace the dipole moment dynamics of the probed optical transitions.

Dynamics of electron-hole pairs created by direct photoexcitation to the charge transfer state of electron donor-acceptor complexes was studied in sensitised films of a photoconducting polymer poly(epoxypropyl-carbazole) and in model solutions. Fast hole transfer (within 100 fs) from the parent carbazolyl moiety to the neighbouring carbazolyls in films is concluded from transient anisotropy measurements. This is supported by the charge recombination dependence on excitation photon energy and acceptor concentration. Comparison of charge recombination kinetics with Monte Carlo simulations suggests the separation distance between the thermalized charge pairs to be in the range of 10-20 Å. Correlation is observed between the charge separation distance and the probability of radiative recombination.

Emissive intra-chain singlet states are found to be the predominant primary excitations in polythiophene conjugated polymers. A red - shift of emission spectra with time and a gradual decay of the anisotropy indicate excitation transfer to the lower energy sites in the bulk films and in the isolated polymer chains in solution. Very fast excitation transfer between adjacent chains on a time scale of 100 fs is observed in films with dense packing. Short inter-chain distance (about 4 Å) allows for the formation of inter-chain charge pairs, which are generated on a femtosecond time scale with about 20% efficiency. Mixed inter-chain exciton – charge transfer states are proposed to be precursors for charge pairs.

Finally, electron transfer from the excited model molecule terthiophene into an electron accepting TiO2-SiO2 hybrid polymer matrix is found to proceed on a time scale of 1 ps. Charge separation is slower than in polymer systems. That result is explained by a fact that the primary excited state is localized on a single molecule, while it is considered delocalized in conjugated polymer systems at early time after excitation.
Original languageEnglish
Awarding Institution
  • Chemical Physics
  • [unknown], [unknown], Supervisor, External person
Award date1999 Nov 2
Publication statusPublished - 1999

Bibliographical note

Defence details

Date: 1999-11-02
Time: 10:15
Place: Lecture hall D, Kemicentrum, Lund

External reviewer(s)

Name: Samuel, I.D.W.
Title: Dr
Affiliation: Department of Physics, University of Durham, South Road, Durham, DH1 3LE, United Kingdom


Article: 1. A. Ruseckas, V. Gulbinas, V. Sundström, A. Undzenas and L. Valkunas “Charge separation and recombination in a photoconducting polymer with electron donor-acceptor complexes” Journal of Physical Chemistry B 102 (1998) 7365-7370.

Article: 2. D. Abramavicius, V. Gulbinas, A. Ruseckas, A. Undzenas and L. Valkunas “Geminate charge pair recombination in a sensitized photoconducting polymer” Journal of Chemical Physics 111 (1999) 5611-5616.

Article: 3. A. Ruseckas, M. Theander, L. Valkunas, M. R. Andersson, O. Inganäs and V. Sundström “Energy transfer in a conjugated polymer with reduced inter-chain coupling” Journal of Luminescence 76&77 (1998) 474-477.

Article: 4. A. Ruseckas, M. Theander, M. R. Andersson, M. Prato, O. Inganäs and V. Sundström “Ultrafast photogeneration of inter-chain charge pairs in polythiophene films”, manuscript, to be submitted to Chemical Physics Letters.

Article: 5. M. Helbig, A. Ruseckas, M.M.-L. Grage, E. Birckner, S. Rentsch and V. Sundström, “Resolving the radical cation formation from the lowest-excited singlet (S1) state of terthiothene in a TiO2-SiO2 hybrid polymer matrix” Chemical Physics Letters 302 (1999) 587-594.

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Chemical Physics (S) (011001060)

Subject classification (UKÄ)

  • Atom and Molecular Physics and Optics

Free keywords

  • Anisotropy
  • Photoinduced absorption
  • Femtosecond spectroscopy
  • Polythiophene
  • Conjugated polymers
  • Donor-Acceptor Complexes
  • Carbazole
  • Charge separation
  • Excitation transfer
  • Recombination
  • Physics
  • Fysik


Dive into the research topics of 'Dynamics of Excitation Transfer and Charge Separation in Polymeric Semiconductors'. Together they form a unique fingerprint.

Cite this