Nanoscale Surface Photoreactions

Subnanometer-scale properties of molecules and materials have become extremely important to the development of nanoscale and molecular electronics devices, including advanced biological and chemical sensors. The energies (i.e., wavelengths) at which the LSPRs of individual nanoparticles are excited varies depending on their size, thickness, and shape, all of which can be controlled synthetically. Photon-coupled scanning tunneling microscopy uses a total internal reflection scheme to couple light into a tunneling junction, generating this specific LSPR in individual Au and Ag nanoprisms. By controlling and coupling this specific excitation to molecular assemblies, the effective photoreactivities and photoconductances of organic molecules can be measured and manipulated. Nanoparticle synthesis methods were developed to produce nanoprisms with appropriate dimensions and homogeneity. Functionalization of the sample surface using alkanedithiols and p-terphenyl-4,4"-dithiol enabled the adsorption dispersion of nanoprisms onto substrates with high density yet minimal stacking. Insertion into self-assembled monolayers was used to arrange single molecules on Au{111} and Ag{111} nanoprisms for selective surface plasmonic enhancement. Scanning tunneling microscopy measurements were collected for molecules adsorbed on the dispersed nanoprisms. Photon STM will be used to monitor the photoactivities of molecules on these substrates, such as photocurrent, photoconductance, and photoreaction