Abstract Atomic-scale control of photochemistry facilitates extreme miniaturisation of optoelectronic devices. Localised surface plasmons, which provide strong confinement and enhancement of electromagnetic fields at the nanoscale, secure a route to achieve sub-nanoscale reaction control. Such local plasmon-induced photochemistry has been realised only in metallic structures so far. Here we demonstrate controlled plasmon-induced single-molecule switching of peryleneanhydride on a silicon surface. Using a plasmon-resonant tip in low-temperature scanning tunnelling microscopy, we can selectively induce the dissociation of the O–Si bonds between the molecule and surface, resulting in reversible switching between two configurations within the nanojunction. The switching rate can be controlled by changing the tip height with 0.1-Å precision. Furthermore, the plasmon-induced reactivity can be modified by chemical substitution within the molecule, suggesting the importance of atomic-level design for plasmon-driven optoelectronic devices. Thus, metal–single-molecule–semiconductor junctions may serve as a prominent controllable platform beyond conventional nano-optoelectronics.
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