Photogeneration

in Organic Solar
Cells
PRESENTED BY:
LEONAR JUN R. GABIANA

Exciton Binding Energy

For PPVs, estimates for the exciton binding energy
range from less than 0.1 eV to over 1 eV while in
polydiacetylenes, EBexc has been estimated at 0.5
eV by a comparison of the onset of the ground-state
absorption (1.8-1.9 eV) and the onset of
photoconductivity (2.3-2.5 eV)
For PPV, absorption and photoconductivity occur at

Experimental estimates of the exciton binding energy have often been based
upon estimates of the minimum LUMO level offset required to separate excitons at
organic donor/ acceptor interfaces.
It has been suggested in the literature that a LUMO level offset of 0.3 eV is
sufficient for efficient charge separation and this value is used in many other
studies as a justification for lowering the polymer LUMO in order to achieve a
smaller band-gap material without sacrificing VOC (by raising the donor HOMO
instead)
Direct experimental measures of the magnitude of Ebexc remain controversial.
The source of this dissension results in part from the disordered nature
of conjugated polymers, which prevents parameters such as the exciton
binding energy from being well defined.

Charge Transfer State

Binding Energy
The energy of the CT state, ECT, is approximated as the difference in
energy between the electron affinity of the acceptor and the ionization
potential of the donor (IPD - EAA) plus another term to account for the
binding energy of the CT state, EBCT
For a CT state that is emissive (i.e., geminate recombination back to the
ground state is a radiative process), its energy can be estimated directly
from the photoluminescence spectrum.
The binding energy of a CT state is usually estimated to be lower than the
singlet exciton (due to the increased electron-hole separation distance)
and is typically estimated at approximately 0.1-0.5 eV

The energy of the CT state can be tuned by altering

the composition of the blend. This was noted by Loi
et al.,
As the concentration of PCBM in the
blend was increased, the red shift of the CT
emission (compared to the pristine components
emission) became larger.
The energy of the CT state also appears to be
sensitive to film processing

The nature of binding

energy
Most discussions of binding energies focus only
upon the Coulomb attraction energy and therefore
address only potential rather than free energy
Potential energy approach is relevant to consideration of
the energy barrier impending exciton or CT-state
separation.
A free energy analysis is necessary where reverse
process is considered.

The importance of CT state

From the study of Janssen et al., it was concluded that only
minimal driving force is required to generate the CT state , G CT
< 0.1 3ev, as such the principal energy loss required for charge
separation ooccurs after the initial creation of the CT state.
The conclusion was consistent with the report by Ohkita et al.,
and suggests that majority of the of free energy required for
driving the generation of free charge carriers is associated with
the dissociation of the CT state.

Interfacial Energetics: Singlet and Triplet

Exciton Energies versus CT-State Energies
A fundamental requirement for the energy levels presented
in Figure 9 is a downhill energetic driving force such that
the donor is capable of transferring an electron to the
acceptor.
A second fundamental thermodynamic requirement for
efficient charge photogeneration is that the chargeseparated state must be the lowest energy excited state in
the system.

Energy Transfer vs. Electron

Transfer
The concept of energy versus electron transfer was examined by Halls
et al.,
One blend system, MEH-PPV:CN-PPV, demonstrated electron transfer
while DMOS-PPV:CN-PPV, on the other hand, exhibited energy transfer.
Theoretical calculations on both systems indicated that the energy of
the charge-separated state is lower than the S1 state of CN-PPV only
for MEH-PPV:CNPPV. In DMOS-PPV:CN-PPV the energies of these two
states are reversed; therefore, energy transfer is the preferred
pathway instead of electron transfer.

Benson-Smith et al. studied a series of polyfluorene

polymers in blends with PCBM and found that those with a
high ionization potential (above 5.5 eV) produced
evidence of PCBM triplets instead of the desired charge
carriers.

The photoluminescence spectrum of the

polyfluorene blends (with 5 wt % PCBM) revealed
total quenching of the polymer emission and a
PCBM singlet peak at 710 nm, thereby indicating an
efficient energy transfer process from the polymer
exciton to the PCBM.

one polymer (RedF, a fluorene/benzodithiazolebased polymer) with an intermediate IP of 5.3 eV

produced both polarons and PCBM triplets,
depending upon the blend composition.

Triplets were present at low PCBM concentrations

(5 wt %), while polarons were measured at high
concentrations (50 wt %).

Conclusions
Therefore, the energy of the charge-separated state is of great
importance in achieving efficient charge photogeneration.
Lowering the polymer HOMO to achieve a higher VOC should
therefore be treated with caution as this may raise the energy
of the charge-separated state to the point where it is no longer
thermodynamically accessible and alternative pathways to
lower energy triplet states may be activated instead.

Thank you!