The design and performance of organic photovoltaic cells is dictated, in part, by the magnitude of the exciton diffusion length (LD). Despite the importance of this parameter, there have been few investigations connecting LD and materials purity. Here, we investigate LD for the organic small molecule N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine as native impurities are systematically removed from the material. Thin films deposited from the as-synthesized material yield a value for LD, as measured by photoluminescence quenching, of (3.9 ± 0.5) nm with a corresponding photoluminescence efficiency (ηPL) of (25 ± 1)% and thin film purity of (97.1 ± 1.2)%, measured by high performance liquid chromatography. After purification by thermal gradient sublimation, the value of LD is increased to (4.7 ± 0.5) nm with a corresponding ηPL of (33 ± 1)% and purity of (98.3 ± 0.8)%. Interestingly, a similar behavior is also observed as a function of the deposition boat temperature. Films deposited from the purified material at a high temperature give LD = (5.3 ± 0.8) nm with ηPL = (37 ± 1)% for films with a purity of (99.0 ± 0.3)% purity. Using a model of diffusion by Förster energy transfer, the variation of LD with purity is predicted as a function of ηPL and is in good agreement with measurements. The removal of impurities acts to decrease the non-radiative exciton decay rate and increase the radiative decay rate, leading to increases in both the diffusivity and exciton lifetime. The results of this work highlight the role of impurities in determining LD, while also providing insight into the degree of materials purification necessary to achieve optimized exciton transport.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation (NSF) under DMR-1307066. I.J.C. also acknowledges support from the Robert and Beverly Sundahl Fellowship. All materials synthesis and HPLC were performed at The Dow Chemical Company. RJH is a member of the Dow Chemical Company Technical Advisory Board.