Dehydrohalogenation Condensation Reaction of Phenylhydrazine with Cl-Terminated Si(111) Surfaces.

Formation of stable organic-inorganic contacts with silicon often requires oxygen- and carbon-free interfaces. Some of the general approaches to create such interfaces rely on the formation of a Si-N bond. A reaction of dehydrohalogenation condensation of Cl-terminated Si(111) surface with phenylhydrazine is investigated as a means to introduce a simple function to the surface using a -NH-NH(2) moiety as opposed to previously investigated approaches. The use of substituted hydrazine allows for the formation of a stable structure that is less strained compared to the previously investigated primary amines and leads to minimal surface oxidation. The process is confirmed by a combination of infrared studies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry investigations. Density functional theory is utilized to yield a plausible surface reaction mechanism and provide a set of experimental observables to compare with these data.