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Efficient charge generation from triplet excitons in metal-organic heterojunctions

The success of many emerging molecular electronics concepts hinges on an atomistic understanding of the underlying electronic dynamics. We employ picosecond time-resolved x-ray photoemission spectroscopy (tr-XPS) to elucidate the roles of singlet and triplet excitons for photoinduced charge generation at a copper-phthalocyanine–C 60 heterojunction. Contrary to common belief, fast intersystem crossing to triplet excitons after photoexcitation is not a loss channel but contributes to a signiﬁcantly larger extent to the time-integrated interfacial charge generation than the initially excited singlet excitons. The tr-XPS data provide direct access to the diffusivity of the triplet excitons D CuPc = (1 . 8 ± 1 . 2) × 10 − 5 cm 2 / s (where CuPc is copper-phthalocyanine) and their diffusion length L diff = (8 ± 3)nm.