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The Energy of Charge‐Transfer States in Electron Donor–Acceptor Blends: Insight into the Energy Losses in Organic Solar Cells
Author(s) -
Veldman Dirk,
Meskers Stefan C. J.,
Janssen René A. J.
Publication year - 2009
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200900090
Subject(s) - materials science , excited state , band gap , singlet state , acceptor , organic solar cell , atomic physics , singlet fission , electron , ground state , molecular physics , optoelectronics , physics , condensed matter physics , nuclear physics , composite material , polymer
Here, a general experimental method to determine the energy E CT of intermolecular charge‐transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that E CT correlates linearly with the open‐circuit voltage ( V oc ) of photovoltaic devices in D–A blends via eV oc = E CT − 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S 1 with energy E g ) in the blend to the CT state (S 1 → CT) occurs when E g − E CT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state ( E T ) of D or A (CT → T 1 ) can occur when E CT − E T > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable V oc is ultimately set by the optical band gap ( eV oc = E g − 0.6 eV) and ii) the singlet–triplet energy gap should be Δ E ST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.