Surface-sensitive UHV dielectric studies of nanoscale organic thin films: Adsorption, crystallization, and sublimation

Nanoscale systems are small collections of atoms or molecules, which as a result of their limited extent, show measurable thermodynamic deviations from bulk samples of the same species. The deviations may result from purely finite-size effects, or may be due to an increased significance of the interaction between the nanoscale system and its container. Ultra-thin (<100 nm) films of organic molecules adsorbed on surfaces afford unique opportunities to study the interplay of forces relevant to nanoscale physics.;This thesis describes the development of a novel ultra-high vacuum apparatus to study the behavior of adsorbed polar molecules via dielectric spectroscopy (UHV-DS). Ultra-thin films are grown and characterized in-situ. The use of interdigitated electrode capacitors and a ratio-transformer bridge technique yields resolutions of ∼1 aF and ∼10-5 ppm in the capacitance and loss tangent, respectively. Typical sensitivity is 10 aF per monolayer at 80 K.;Results are given for studies on water, methanol, and Cp* (a synthetic molecular rotor). The desorption event in the dielectric spectra is correlated with thermal desorption spectroscopy. During growth of methanol films, we observe partial crystallization for temperatures above ≳ 100 K. Crystallization is also observed upon heating glassy films grown at 80 K. Finally, we discuss UHV-DS as a probe for solid thin-film vapor pressure measurements, and show that our data on methanol compare favorably with those in the literature.