Photoinduced electrochemiluminescence (PECL) allows the electrochemically assisted conversion of low-energy photons into high-energy photons at an electrode surface. This concept is expected to have important implications, however, it is dramatically limited by the stability of the surface, impeding future developments. Here, a series of metal-insulator-semiconductor (MIS) junctions, using photoactive n-type Si (n-Si) as a light absorber covered by a few-nanometerthick protective SiO x /metal (SiO x /M, with M = Ru, Pt, and Ir) overlayers are investigated for upconversion PECL of the model co-reactant system involving the simultaneous oxidation of tris(bipyridine)ruthenium(II) and tri-n-propylamine. We show that n-Si/SiO x /Pt and n-Si/SiO x /Ir exhibit high photovoltages and record stabilities in operation (35 h for n-Si/SiO x /Ir) for the generation of intense PECL with an anti-Stokes shift of 218 nm. We also demonstrate that these surfaces can be employed for spatially localized PECL. These unprecedented performances are extremely promising for future applications of PECL.

Mitochondria are the subcellular bioenergetic organelles. The analysis of their morphology and topology is essential to provide useful information on their activity and metabolism. Herein, we report a label‐free shadow electrochemiluminescence (ECL) microscopy based on the spatial confinement of the ECL‐emitting reactive layer to image single living mitochondria deposited on the electrode surface. The ECL mechanism of the freely‐diffusing [Ru(bpy)3]2+ dye with the sacrificial tri‐n‐propylamine coreactant restrains the light‐emitting region to a micrometric thickness allowing to visualize individual mitochondria with a remarkable sharp negative optical contrast. The imaging approach named “shadow ECL” (SECL) reflects the negative imprint of the local diffusional hindrance of the ECL reagents by each mitochondrion. The statistical analysis of the colocalization of the shadow ECL spots with the functional mitochondria revealed by classical fluorescent biomarkers, MitoTracker Deep Red and the endogenous intramitochondrial NADH, validates the reported methodology. The versatility and extreme sensitivity of the approach are further demonstrated by visualizing single mitochondria, which remain hardly detectable with the usual biomarkers. Finally, by alleviating problems of photobleaching and phototoxicity associated with conventional microscopy methods, SECL microscopy should find promising applications in the imaging of subcellular structures.