Electrical conduction at the single molecule scale has been studied extensively with molecular nanojunctions. Measurements have revealed a wealth of interesting physics. I3owever; our understanding is hindered by a lack of methods for simultaneous local imaging or spectroscopy to determine the conformation and local environment of the molecule of interest. Optical molecular spectroscopies have made significant progress in recent years, with single molecule sensitivity achieved through the use of surface-enhanced spectroscopies. In particular surface-enhanced Raman spectroscopy (SERS) has been demonstrated to have single molecule sensitivity for specific plasmonic structures. Many unanswered quest ions remain about the SERS process, particularly the role of chemical enhancements of the Raman signal. The primary goal of the research presented here is to combine both electrical and optical characterization techniques to obtain a more complete picture of electrical conduction at the single or few molecule level. We have successfully demonstrated that nanojunctions are excellent SERS substrates with the ability to achieve single molecule sensitivity. This is a major accomplishment with practical applications in optical sensor design. We present a method for mass producing nanojunctions with SERS sensitivity optimized through computer modeling. We have demonstrated simultaneous optical and electrical measurements of molecular junctions with single molecule electrical and SERS sensitivity. Measurements show strong correlations between electrical conductance and changes to the SERS response of nanojunctions. These results allow for one of the most conclusive demonstrations of single molecule SERS to date. This measurement technique provides the framework for three additional studies discussed here as well as opening up the possibilities for numerous other experiments. One measurement examines heating in nanowires rather than nanojunctions. We observe that, the electromigration process used to turn Pt nanowires into nanojunctions heats the wires to temperatures in excess of 1000 K, indicating that thermal decomposition of molecules on the nanowire is a major problem. Another measurement studies optically driven currents in nanojunctions. The photocurrent is a result of rectification of the enhanced optical electric field in the nanogap. From low frequency electrical measurements we are able to infer the magnitude of the enhanced electric field, with inferred enhancements exceeding 1000. This work is significant to the field of plasmonics and shows the need for more complete quantum treatments of plasmonic structures. Finally we investigate electrical and optical heating in molecular nanojunctions. Our measurements show that molecular vibrations and conduction electrons in nano-junctions under electrical bias or laser illumination can be driven from equilibrium to temperatures greater than 600 K. We observe that individual vibrations are also not in thermal equilibrium with one another. Significant heating in the conduction electrons in the metal electrodes was observed which is not expected in the ballistic tunneling model for electrons in nanojunctions this indicates a need for a more completely energy dissipation theory for nanojunctions.

The effects of optical heating via infrared free carrier absorption on the electron magneto-transport properties of n-InSb at helium temperatures have been studied for the first time. Oscillatory photoconductivity (OPC) type structure is seen in the photon energy dependence of the transport properties. A C0₂ laser (hω = 115 to 135 meV) was used as the optical source. Concentrations between 1 x 10¹⁵ cm⁻³ and 2 x 10¹⁶ cm⁻³ were studied. The conclusions of this study are that the energy relaxation of high energy photoexcited electrons, generated by free carrier absorption of C0₂ laser radiation in degenerate n-InSb at liquid helium temperatures, is by emission of a maximum number of optical phonons, and that this relaxation mechanism produces OPC type structure in the photon energy dependence of the electron temperature of the conduction band electron gas. This structure is seen, therefore, in the transport properties of the sample, including the Shubnikovde Haas effect, the effective absorption coefficient, and the photoconductivity (mobility) response (lower concentrations only). In addition, the highest concentration studied, nₑ = ~2 x 10¹⁶ cm⁻³, sets an experimental lower limit on the concentration at which electron-electron scattering will become the dominant energy relaxation mechanism for the photoexcited electrons, since OPC effects were present in this sample.