Electronic and optical spectroscopy of molecular junctions

Electronic transport through molecules has been intensively studied in recent years, due to scientific interest in fundamental questions about charge transport and the technological promise of nanoscale circuitry. A wide range of range of experimental platforms have been developed to electronically probe both single molecules and molecular monolayers. However, it remains challenging to fabricate reliable electronic contacts to molecules, and the vast majority of molecular electronic architectures are not amenable to standard characterization techniques, such as optical spectroscopy. Thus the field of molecular electronics has been hampered with problems of reproducibility, and many fundamental questions about electronic transport remain unanswered.;This thesis describes four significant contributions towards the fabrication and characterization of molecular electronic devices: (1) The development of a new method for creating robust, large area junctions where the electronic transport is through a single monolayer of molecules. This method utilizes atomic layer deposition (ALD) to grow an ultrathin oxide layer on top of a molecular monolayer, which protects the molecules against subsequent processing. (2) A new method for rapid imaging and analysis of single defects in molecular monolayers. This method also electrically passivates defects as it labels them. (3) Hot carrier spectroscopy of molecular junctions. Using optically excited hot carriers, we demonstrate the ability to probe the energy level lineup inside buried molecular junctions. (4) Efficient coupling of optical fields to metal-insulator-metal (MIM) surface plasmon modes. We show both theoretical and experimental work illustrating the ability to create very intense optical fields inside MIM systems. The intense fields generated in this manner have natural extensions to a variety of applications, such as photon assisted tunneling in molecular junctions, optical modulators, and ultrafast optoelectronic switches.