Chemistry of olefin-terminated homogeneous and mixed monolayers on scribed silicon

We describe the preparation of homogeneous olefin-terminated monolayers on scribed silicon made from 1,9-decadiene, and mixed monolayers with varying degrees of olefin termination prepared from 1,9-decadiene and 1-decene or 1-octene, and their subsequent reactions with bromine, osmium tetroxide, dicholorocarbene, and Grubbs' catalyst. Each of these reagents contains a heteroatom, which allows straightforward monitoring of the surface reactions by X-ray photoelectron spectroscopy (XPS). Surface reactions of mixed monolayers made from 1,9-decadiene and 1-octene are consistently more efficient than surface reactions of mixed monolayers made from 1,9-decadiene and 1-decene, presumably because of steric effects. After chemisorbtion of Grubbs' catalyst, ring-opening metathesis polymerization (ROMP) of norbornene is demonstrated. The kinetics of Grubbs' catalyst adsorption and of polynorbornene growth is monitored by XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS). A principal components analysis (PCA) of the ToF-SIMS data is presented. Autoscaling is shown to be a relatively ineffective preprocessing method for this data. Polynorbornene features on patterned substrates effectively resist and direct the electroless deposition of copper.