Electronic energy transfer (EET) has been the subject of intense research because of its significant contribution to the photophysical properties of various material systems. For π-conjugated polymers, it has long been accepted that a classical hopping mechanism is dominant in the energy transfer dynamics because of a weak electronic coupling. However, recent research reveals that conjugated polymers, in fact, can have an electronic coupling strong enough to preserve quantum-coherence. In this review, we summarize the main photophysical features of conjugated polymers. We discuss how electronic excited states evolve on various time scales from femtoseconds to hundreds of picoseconds in terms of exciton relaxation, localization, and electronic energy transfer. The F€ orster energy transfer model and modifications needed for describing energy transfer in conjugated polymers are described. We discuss how chain conformation and its disorder influence EET and the time scale of the evolution of electronic excited states, and demonstrate how quantum coherence contributes to energy transfer dynamics. Recent research on exciton diffusion in various kinds of polymers is summarized.

We utilize a time-dependent drift-diffusion model incorporating electron trapping and field-dependent charge separation to explore the device physics of organic bulk-heterojunction solar cells based on blends of poly(3-hexylthiophene) (P3HT) with a red polyfluorene copolymer. The model is used to reproduce experimental photocurrent transients measured in response to a step-function excitation of light of varied intensity. The experimental photocurrent transients are characterized by (i) a fast rise of order 1 μs followed by (ii) a slow rise of order 10–100 μs that evolves into a transient peak at high intensity, (iii) a fast decay component after turn-off and (iv) a long-lived tail with magnitude that does not scale linearly with light intensity or steady-state photocurrent. The fast rise and decay components are explained by the transport of mobile carriers while the slow rise and decay components are explained by slower electron trapping and detrapping processes. The transient photocurrent peak at high intensities with subsequent decay to the steady-state value is explained by trap-mediated space-charge effects. The build-up of trapped electrons in the device produces reduction in the strength of the electric field near the transparent anode that increases the likelihood of bimolecular recombination, and lowers the overall efficiency of charge dissociation in the device. Notably the model demonstrates that a reduction in free charge generation rate by space-charge effects is as significant as bimolecular recombination in this device assuming Langevin-type bimolecular recombination. The model is also used to explore the dynamics of charge separation with an upper bound of 50 ns set for the lifetime of electron-hole pairs, and to provide an estimate of the trap density of 1.3×1022 m−3.

We have studied photocurrent transients in all-polymer bulk-heterojunction solar cells based on poly(3-hexylthiophene) and poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl). By illuminating devices with square pulses of light of varying intensity, we reveal nonlinear photocurrent transients on the timescale of tens of microseconds. These microsecond photocurrent transients are attributed to the effects of trapping and detrapping of charges on this timescale, in particular, electrons. The buildup of trapped electrons results in the appearance of a peak in the photocurrent at high intensities at ∼10 μs after turn on. This trapped charge produces a local reduction in the strength of the internal electric field near the anode resulting in a net decrease in charge separation efficiency and an increase in the likelihood of bimolecular recombination due to increased and overlapping electron and hole densities. After turn off, a long photocurrent tail is observed with charge still being extracted after 0.5 ms consistent with the detrapping of deeply trapped charges. We are able to reproduce the observed transient photocurrent features using a time-dependent drift-diffusion model incorporating the trapping and detrapping of electrons.

Here, studies on the evolution of photophysics and device performance with annealing of blends of poly(3‐hexylthiophene) with the two polyfluorene copolymers poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2′′‐diyl) (F8TBT) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) are reported. In blends with F8TBT, P3HT is found to reorganize at low annealing temperatures (100 °C or below), evidenced by a redshift of both absorption and photoluminescence (PL), and by a decrease in PL lifetime. Annealing to 140 °C, however, is found to optimize device performance, accompanied by an increase in PL efficiency and lifetime. Grazing‐incidence small‐angle X‐ray scattering is also performed to study the evolution in film nanomorphology with annealing, with the 140 °C‐annealed film showing enhanced phase separation. It is concluded that reorganization of P3HT alone is not sufficient to optimize device performance but must also be accompanied by a coarsening of the morphology to promote charge separation. The shape of the photocurrent action spectra of P3HT:F8TBT devices is also studied, aided by optical modeling of the absorption spectrum of the blend in a device structure. Changes in the shape of the photocurrent action spectra with annealing are observed, and these are attributed to changes in the relative contribution of each polymer to photocurrent as morphology and polymer conformation evolve. In particular, in as‐spun films from xylene, photocurrent is preferentially generated from ordered P3HT segments attributed to the increased charge separation efficiency in ordered P3HT compared to disordered P3HT. For optimized devices, photocurrent is efficiently generated from both P3HT and F8TBT. In contrast to blends with F8TBT, P3HT is only found to reorganize in blends with F8BT at annealing temperatures of over 200 °C. The low efficiency of the P3HT:F8BT system can then be attributed to poor charge generation and separation efficiencies that result from the failure of P3HT to reorganize.

Through controlled annealing of planar heterojunction (bilayer) devices based on the polyfluorene copolymers poly(9,9‐dioctylfluorene‐co‐bis(N,N′‐(4,butylphenyl))bis(N,N′‐phenyl‐1,4‐phenylene)diamine) (PFB) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) we study the influence of interface roughness on the generation and separation of electron–hole pairs at the donor/acceptor interface. Interface structure is independently characterized by resonant soft X‐ray reflectivity with the interfacial width of the PFB/F8BT heterojunction observed to systematically increase with annealing temperature from 1.6 nm for unannealed films to 16 nm with annealing at 200 °C for ten minutes. Photoluminescence quenching measurements confirm the increase in interface area by the three‐fold increase in the number of excitons dissociated. Under short‐circuit conditions, however, unannealed devices with the sharpest interface are found to give the best device performance, despite the increase in interfacial area (and hence the number of excitons dissociated) in annealed devices. The decrease in device efficiency with annealing is attributed to decreased interfacial charge separation efficiency, partly due to a decrease in the bulk mobility of the constituent materials upon annealing but also (and significantly) due to the increased interface roughness. We present results of Monte Carlo simulations that demonstrate that increased interface roughness leads to lower charge separation efficiency, and are able to reproduce the experimental current‐voltage curves taking both increased interfacial roughness and decreased carrier mobility into account. Our results show that organic photovoltaic performance can be sensitive to interfacial order, and heterojunction sharpness should be considered a requirement for high performance devices.