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We demonstrate that solvent vapor annealing of small molecular weight organic heterojunctions can be used to independently control the interface and bulk thin-film morphologies, thereby modifying charge transport and exciton dissociation in these structures. As an example, we anneal diphenyl-functionalized squaraine (DPSQ)/C(60) heterojunctions before or after the deposition of C(60). Solvent vapor annealing of DPSQ before C(60) deposition results in molecular order at the heterointerface. Organic photovoltaics based on this process have reduced open circuit voltages and power conversion efficiencies relative to as-cast devices. In contrast, annealing following C(60) deposition locks in interface disorder found in unannealed junctions while improving order in the thin-film bulk. This results in an increase in short circuit current by30% while maintaining the open circuit voltage of the as-cast heterojunction device. These results are analyzed in terms of recombination dynamics at excitonic heterojunctions and demonstrate that the optimal organic photovoltaic morphology is characterized by interfacial disorder to minimize polaron-pair recombination, while improved crystallinity in the bulk increases exciton and charge transport efficiency in the active region.

Squaraine (SQ) dyes are notable for their exceptionally high absorption coefficients extending from the green to the near-infrared. In this work, we utilize the functionalized SQ donor: 2,4-bis [4-(N-phenyl-1-naphthylamino)-2,6-dihydroxyphenyl] squaraine (1-NPSQ) by substitution of isobutylamines in the common "parent SQ" with arylamines to improve stacking and hence exciton and charge transport. The strong electron-withdrawing arylamine group results in a highest occupied molecular orbital energy of 5.3 eV, compared to 5.1 eV for the parent SQ, making 1-NPSQ a suitable donor when used with a C(60) acceptor in an organic photovoltaic cell. Optimized and thermally annealed, nanocrystalline heterojunction 1-NPSQ/C(60)/bathocuproine solar cells with an open circuit voltage of 0.90 ± 0.01 V, fill factor of 0.64 ± 0.01, and short circuit current of 10.0 ± 1.1 mA/cm(2) at 1 sun, AM1.5G illumination (solar spectrally corrected) result in a power conversion efficiency of 5.7 ± 0.6%. Crystallograpnic data suggest that the intermolecular stacking of 1-NPSQ molecules is closer than that of the parent SQ, thereby reducing the device series resistance and increasing its fill factor.

Spin-cast 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine (SQ) thin films only 62 A thick are converted from amorphous to polycrystalline via postannealing at elevated temperatures. The surface roughness of the SQ films increases by a factor of 2, while selected area electron diffraction spectra indicate an increase in the extent of postannealed film crystallinity. Dichloromethane solvent annealing is also demonstrated to increase the exciton diffusion length of SQ by a factor of 3 over thermally annealed SQ films as a result of further enhancement in crystalline order. We find that the roughened surface features have a length scale on the order of the exciton diffusion length. Hence, coating the donor SQ with the acceptor, C(60), results in a nearly optimum controlled bulk heterojunction solar cell structure. Optimized SQ/C(60) photovoltaic cells have a power conversion efficiency of eta(p) = 4.6 +/- 0.1% (correcting for solar mismatch) at 1 sun (AM1.5G) simulated solar intensity, and a corresponding peak external quantum efficiency of EQE = 43 +/- 1% even for the very thin SQ layers employed.