Multiphoton Microscopy of π-Conjugated Copolymers and Copolymer/Fullerene Blends for Organic Photovoltaic Applications

Organic photovoltaic (OPV) cells based on π-conjugated copolymer/fullerene blends are devices with the highest power conversion efficiencies within the class of organic semiconductors. Although a number of image microscopies have been applied to films of π-conjugated copolymers and their fullerene blends, seldom have they been able to detect microscopic defects in the blend films. We have applied multiphoton microscopy (MPM) using a 65 fs laser at 1.56 μm for spectroscopy and mapping of films of various π-conjugated copolymers and their fullerene blends. All pristine copolymer films have shown third harmonic generation (THG) and two-photon or three-photon photoluminescence that could be used for mapping the films with micrometer spatial resolution. Since the fullerenes have much weaker THG efficiency than those of the copolymers, we could readily map the copolymer/fullerene blend films that showed interpenetrating micron-sized grains of the two constituents. In addition, we also found second harmonic generation from various micron-sized defects in the films that are formed during film deposition or light illumination at ambient conditions, which do not possess inversion symmetry. The MPM method is therefore beneficial for organic films and devices for investigating the properties and growth of copolymer/fullerene blends for OPV applications.