Photoactive molecular junctions, based on 4 nm thick diarylethene (DAE) and 5 nm thick bisthienylbenzene (BTB) layers, were fabricated by electrochemical deposition. Total thickness was around 9 nm, that is, above the direct tunneling limit and in the hopping regime. The DAE units were switched between their open and closed forms. The DAE/BTB bilayer structure exhibits new electronic functions combining photoswitching and photorectification. The open form of DAE/BTB shows low conductance and asymmetric - curves while the closed form shows symmetric - curves and high conductance. More importantly, unprecedented ON/OFF current ratios of over 10 000 at 1 V were reproducibly measured.
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