Polyfluorenes are also used in polymer solar cells because of their affinity for property tuning. Copolymerization of fluorene with other monomers allows researchers to optimize the absorption and electronic energy levels as a means to increase the photovoltaic performance. For instance, by lowering the band gap of polyfluorenes, the absorption spectrum of the polymer can be adjusted to coincide with the maximum photon flux region of the solar spectrum. This helps the solar cell absorb more of the sun's energy and to increase its energy conversion efficiency; donor-acceptor structured copolymers of fluorene have achieved efficiencies above 4% when their absorption edge was pushed to 700 nm.
The voltage of polymer solar cells has also been increased through the design of polyfluorenes. These devices are typically produced by blending electron accepting and electron donating molecules which help separate charge to produce power. In polymer blend solar cells, the voltage produced by the device is determined by the difference between the electron donating polymer’s highest occupied molecular orbital (HOMO) energy level and the electron accepting molecules lowest unoccupied molecular orbital (LUMO) energy level. By adding electron withdrawing pendant molecules to conjugated polymers, their HOMO energy level can be lowered. For instance by adding electronegative groups on the end of conjugated side chains, researchers lowered the HOMO of a polyfluorene copolymer to −5.30 eV and increased the voltage of a solar cell to 0.99 V.
Typical polymer solar cells utilize fullerene molecules as electron acceptors because of their low LUMO energy level (high electron affinity). However the tunability of polyfluorenes allows their LUMO to be lowered to a level appropriate for use as an electron acceptor. Thus, polyfluorene copolymers have also been used in polymer:polymer blend solar cells, where their electron accepting, electron conducting and light absorbing properties permit device performance.