In this thesis, I first describe the design and construction of a dual-tip millikelvin STM system. The STM is mounted on a dilution refrigerator and the setup includes vibration isolation, rf-filtered wiring, an ultra high vacuum (UHV) sample preparation chamber and sample transfer mechanism.

Next I describe a novel superconducting tip fabrication technique. My technique involves dry-etching sections of 250 μm diameter Nb wire with an SF₆ plasma in a reactive ion etcher. I present data taken with these tips on various samples at temperatures ranging from 30 mK to 9 K. My results demonstrate that the tips are superconducting, achieve good spectroscopic energy resolution, are mechanically robust over long time periods, and are atomically sharp.

I also show data characterizing the performance of our system. This data is in the form of atomic resolution images, spectroscopy, noise spectra and simultaneous scans taken with both tips of the STM. I used these to examine the tip-sample stability, cross talk between the two tips, and to extract the effective noise temperature (∼185 mK) of the sample by fitting the spectroscopy data to a voltage noise model.

Finally, I present spectroscopy data taken with a Nb tip on a Nb(100) sample at 30 mK. The enhanced spectroscopic resolution at this temperature allowed me to resolve peaks in the fluctuation-dominated supercurrent at sub-gap voltages. My analysis indicates that these peaks are due to the incoherent tunneling of Cooper pairs at resonant frequencies of the STM's electromagnetic environment. By measuring the response of the STM junction to microwaves, I identified the charge carriers in this regime as Cooper pairs with charge 2e. The amplitude of the response current scales as the square of the Bessel functions, indicating that the pair tunneling originates from photon assisted tunneling in the incoherent regime, rather than the more conventionally observed Shapiro steps in the coherent regime.