Nanoscale Mapping of Wavelength-Selective Photovoltaic Responses in H- and J-Aggregates of Azo Dye-based Solar Cell Films

In the present study, nanoscale wavelength-selective photovoltaic activities in H- and J-aggregates of azo dye-based solar cell films were mapped by wavelength-dependent photoconductive noise microscopy. In this strategy, the local conductivities and charge traps in dye films were mapped by a conducting probe scanning the surface while illuminating the lights with selected wavelengths. We observed the formation of localized domains exhibiting wavelength-dependent photoconductivities. The individual domains could be identified as H- and J-aggregates, which showed dominant photoexcitations at wavelengths of 600 and 450 nm, respectively. Notably, the short-circuit currents Isc and photoconductivities ΔσPC of the film showed power-law dependencies with trap densities under illuminated conditions (NT_L) and the trap density change by the illumination (ΔNT), respectively, like ΔσPC ∝ |ΔNT|1/2 and Isc ∝ NT_L−3/4 for each wavelength illumination. These results revealed the carrier recombination process in cooperation with the traps which could be a major factor determining the performance of solar cells. Significantly, the J-aggregates showed lower trap densities than those of the H-aggregates, resulting in superior solar cell characteristics of the J-aggregates, such as a higher Isc and larger open circuit voltages. Since our method allows mapping the nanoscale photovoltaic activities of solar cell film aggregates, it can be a powerful tool for both basic research and in the application of photoelectronic devices.