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Journal of Renewable and Sustainable Energy / Volume 1 / Issue 4 / REGULAR ARTICLES

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J. Renewable Sustainable Energy 1, 043110 (2009); doi:10.1063/1.3212827 (18 pages)

Light-induced EPR spectroscopy of charge carriers photoinduced in polymer/fullerene bulk heterojunctions

V. I. Krinichnyi and E. I. Yudanova

Institute of Problems of Chemical Physics, RAS, Semenov Avenue 1, Chernogolovka 142432, Russia

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(Received 22 February 2009; accepted 5 August 2009; published online 25 August 2009)

Composites of conjugated polymers with fullerenes are perspective materials for polymer photovoltaics. Light-induced EPR (LEPR) study of magnetic, relaxation, and dynamic parameters of polaron-fullerene radical pairs photoinduced in fullerene-modified poly(3-alkylthiophenes) is described. Weak interaction between positively charged polaron and negatively charged fullerene ion radical in the pairs allowed to determine separately all their magnetic, relaxation, and dynamics parameters. Paramagnetic susceptibility of charge carriers reflects their activation dynamics and spin exchange in the composite. Decay of long-living polaron and fullerene anion radical depends on a spatial distance between them and the energy of exciting photons. One-dimensional polaron diffusion along the polymer chain and fullerene rotation near its own main molecular axis were shown to follow the activation Elliot hopping model and to be governed by photon energy. The deviation in activation energies for dynamics of charge carriers and the difference in their dependence on the exciting photon energy prove the noninteracting character of charge carriers photoinduced in the polymer/fullerene composite. The dependence of the main magnetic, relaxation, and dynamics parameters of charge carriers on the phonon energy was ascribed to inhomogeneous distribution of polymer and fullerene domains in bulk heterojunctions. This inhomogeneity decreases by the annealing of the composite.

© 2009 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL
  3. RESULTS AND DISCUSSIONS
    1. Magnetic-resonance parameters
    2. Recombination of charge carriers
    3. Electron relaxation and dynamics of charge carriers
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

composite materials, conducting polymers, fullerenes, magnetic susceptibility, paramagnetic resonance, photovoltaic effects, polarons, weak interactions (molecular physics)

PACS

  • 71.38.-k

    Polarons and electron-phonon interactions

  • 73.61.Ph

    Polymers; organic compounds

  • 73.61.Wp

    Fullerenes and related materials

  • 73.50.Pz

    Photoconduction and photovoltaic effects

  • 76.30.-v

    Electron paramagnetic resonance and relaxation

  • 78.70.-g

    Interactions of particles and radiation with matter

  • 82.35.Lr

    Physical properties of polymers

  • 81.40.Rs

    Electrical and magnetic properties related to treatment conditions

ARTICLE DATA

Permalink
http://link.aip.org/link/doi/10.1063/1.3212827

PUBLICATION DATA

ISSN:

1941-7012 (print)  
1941-7012 (online)

Publisher:

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (7) Tables (2)

Figures (click on thumbnails to view enlargements)

FIG.1
Schematic band diagram of two semiconductors with different electron affinities before making between them a bulk heterojunction. The electron donor (AD) and electron acceptor (AA) affinities are defined vs the electron energy in vacuum at the same electrical potential. EgD and EgA are the band-gap energies of the electron donor and electron acceptor, respectively. In the top, the P3AT and PCBM are schematically shown as electron donor and electron acceptor, respectively. The appearance of a polaron quasiparticle with a spin and an elemental positive charge in the P3AT chain is shown as well.

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
LEPR spectra of radical pairs background photoinduced at 77 K in bulk heterojunctions of PCBM molecules with macromolecules of regioregular (a) P3DDT, (b) P3OT, and (c) P3HT as a function of the photon energy hνph (linewidth λph). The optical absorption spectrum of the P3HT/PCBM composite is shown by the dashed line. The positions of polaron P+• and fullerene anion radical C60−• are shown as well.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
(a) Paramagnetic susceptibility χ of the polarons P+• (open points) and fullerene anion radicals C60−• (filled points) photoinduced at 77 K in (1) the P3HT/PCBM and (2) P3DDT/PCBM composites as a function of the photon energy hνph. Spin susceptibilities determined for these charge carriers initiated by white light in the P3HT/PCBM sample are shown by the dashed and dotted line sections, respectively. Experimental points are connected by sight polynomial dotted lines. (b) Temperature dependence of the χ parameter determined for the P+• (open points) and C60−• (filled points) charge carriers photoinduced by white light in the (1) initial and (2) annealed at 400 K for 1 h P3HT/PCBM composites as well as by the photons with the energies of (3) 1.88 eV, (4) 2.22 eV, and (5) 2.75 eV in the P3DDT/PCBM composite. Some dependences calculated from Eq. ( 5 ) with different ΔEij are shown by dashed lines as an example. In the top are shown the temperature dependence of a typical LEPR spectrum of polymer/fullerene composite.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.4
(a) A lower limit of the peak-to-peak linewidth ΔBpp(0) of the polarons P+• (open points) and fullerene anion radicals C60−• (filled points) photoinduced at 77 K in the (1) P3HT/PCBM and (2) P3DDT/PCBM composites as a function of the photon energy hνph. The ΔBpp(0) values determined for polarons and fullerene anion radicals initiated by white light in the P3HT/PCBM sample are shown by the dashed and dotted line sections, respectively. Experimental points are connected by sight polynomial dotted lines. (b) Temperature dependence of the linewidth determined for the P+• and C60−• charge carriers photoinduced by white light in the (1) initial and (2) annealed at 400 K for 1 h P3HT/PCBM composites as well as by the photons with the energies of (3) 1.88 eV, (4) 2.22 eV, and (5) 2.75 eV in the P3DDT/PCBM composite. Some dependences calculated from Eq. ( 6 ) with different Ea presented in Table 2 are also shown as an example.

FIG.4 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.5
Typical time dependence of the concentration of polarons P+• (open points) and anion radicals C60−• (filled points) photoinduced in the P3AT/PCBM composite after the light irradiation blackout. The dashed and dotted lines show the dependences calculated from Eq. ( 10 ) with n0a3 = 2.21×10−4 and τ0 = 7.2×10−5 min and n0a3 = 1.4×10−3 and τ0 = 3.6×10−7 min, respectively. LEPR spectra of the P3HT/PCBM composite obtained at the respective delays are shown. The right insert demonstrates the change in the lifetime τ0 of charge carriers photoinduced in the P3HT/PCBM composite on the photon energy hνph.

FIG.5 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.6
Temperature dependency of the (a) spin-lattice T1 and (b) spin-spin T2 relaxation times of the polarons P+• (open points) and fullerene anion radicals C60−• (filled points) photoinduced by white light in the (1) initial and (2) annealed at 400 K for 1 h P3HT/PCBM composite as well as in the P3DDT/PCBM composite by the photons with the energies of (3) 1.88 eV, (4) 2.22 eV, and (5) 2.75 eV. Experimental points are connected by sight polynomial dotted lines.

FIG.6 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.7
(a) The coefficients of the polaron P+• hopping along (D1D, open points) and between (D3D, filled points) polymer chains and the coefficient of the fullerene anion radical C60−• rotation near main axis (Drot, semifilled points) in the (1) P3HT/PCBM and (2) P3DDT/PCBM composites at 77 K as a function of the photon energy hνph. The respective parameters determined for these charge carriers initiated by white light in the P3HT/PCBM sample are shown by the dashed, dashed-dotted, and dotted line sections, respectively. Experimental points are connected by sight polynomial dotted lines. (b) Temperature dependence of these parameters determined for the charge carriers photoinduced by white light in the (1) initial and (2) annealed at 400 K for 1 h P3HT/PCBM composites as well as by the photons with the energies of (3) 1.88 eV, (4) 2.22 eV, and (5) 2.75 eV in the P3DDT/PCBM composite. Some dependences calculated from Eqs. ( 13 , 14 ) with the respective Eph and Eb are also shown as an example.

FIG.7 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Tables

Table I. The terms ΔBppi of linewidth LEPR spectra of polarons and fullerene anion radicals used for simulation of the LEPR spectra of the P3DDT/PCBM composite obtained at different laser photon energies hνph and 77 K.

View Table
Table II. The ΔEij, Ea, Eph, and Ea values determined from Eqs. (5,6,13,14), respectively, for radical pairs photoinduced by white light in the initial and annealed P3HT/PCBM composites as well as by laser beam with different photon energies hνph in the P3DDT/PCBM system.

View Table


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