Probing dark exciton diffusion using photovoltage.

The migration of weakly and non-luminescent (dark) excitons remains an understudied subset of exciton dynamics in molecular thin films. Inaccessible via photoluminescence, these states are often probed using photocurrent methods that require efficient charge collection. Here we probe exciton harvesting in both luminescent and dark materials using a photovoltage-based technique. Transient photovoltage permits a real-time measurement of the number of charges in an organic photovoltaic cell, while avoiding non-geminate recombination losses. The extracted exciton diffusion lengths are found to be similar to those determined using photocurrent. For the luminescent material boron subphthalocyanine chloride, the photovoltage determined diffusion length is less than that extracted from photoluminescence. This indicates that while photovoltage circumvents non-geminate losses, geminate recombination at the donor-acceptor interface remains the primary recombination pathway. Photovoltage thus offers a general approach for extracting a device-relevant diffusion length, while also providing insight in to the dominant carrier recombination pathways.

Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films.

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 ± 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H2Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale. By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10(4) times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H2Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H2Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.

Directing energy transport in organic photovoltaic cells using interfacial exciton gates.

Exciton transport in organic semiconductors is a critical, mediating process in many optoelectronic devices. Often, the diffusive and subdiffusive nature of excitons in these systems can limit device performance, motivating the development of strategies to direct exciton transport. In this work, directed exciton transport is achieved with the incorporation of exciton permeable interfaces. These interfaces introduce a symmetry-breaking imbalance in exciton energy transfer, leading to directed motion. Despite their obvious utility for enhanced exciton harvesting in organic photovoltaic cells (OPVs), the emergent properties of these interfaces are as yet uncharacterized. Here, directed exciton transport is conclusively demonstrated in both dilute donor and energy-cascade OPVs where judicious optimization of the interface allows exciton transport to the donor-acceptor heterojunction to occur considerably faster than when relying on simple diffusion. Generalized systems incorporating multiple exciton permeable interfaces are also explored, demonstrating the ability to further harness this phenomenon and expeditiously direct exciton motion, overcoming the diffusive limit.

Connecting molecular structure and exciton diffusion length in rubrene derivatives.

Connecting molecular structure and exciton diffusion length in rubrene derivatives demonstrates how the diffusion length of rubrene can be enhanced through targeted functionalization aiming to enhance self-Förster energy transfer. Functionalization adds steric bulk, forcing the molecules farther apart on average, and leading to increased photoluminescence efficiency. A diffusion length enhancement greater than 50% is realized over unsubstituted rubrene.