Simultaneous Spectroscopic and Topographic Imaging of Single-Molecule Interfacial Electron-Transfer Reactivity and Local Nanoscale Environment.

The fundamental information related to the energy flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure is critical for understanding interfacial electron-transfer (ET) dynamics. The inhomogeneous nanoscale molecule-surface and molecule-molecule interactions are presumably the origins of the complexity in interfacial ET dynamics; thus, identifying the environment of molecules at nanoscale is crucial. We have developed atomic force microscopy (AFM) correlated single-molecule fluorescence intensity/lifetime imaging microscopy (AFM-SMFLIM) capable of identifying and characterizing individual molecules distributed across the heterogeneous surface at the nanometer length scale. Using the novel AFM-SMFLIM imaging, we are able to obtain nanoscale morphology and interfacial ET dynamics at a single-molecule level. Moreover, the observed blinking behavior and lifetime of each molecule in combination with the topography of the environment at nanoscale provide the location of each molecule on the surface (TiO2 vs cover glass) at nanoscale and the coupling strength of each molecule with TiO2 nanoparticles.