Attachment of Polybutadienes to Hydrogen-Terminated Silicon and Post-Derivatization of the Adsorbed Species

We report the first attachment of polymers with pendant vinyl groups to hydrogen-terminated silicon(111) (Si(111)-H); 1,2-polybutadiene (M w = 3200−3500 g/mol) was attached to Si(111)-H under mild conditions at room temperature with visible light. We also report the partial functionalization, in solution, of 1,2-polybutadiene with various thiols using thiol−ene chemistry and the subsequent attachments of these compounds to Si(111)-H. The partially functionalized or unfunctionalized polybutadienes allow further functionalization at the surface through their unreacted carbon−carbon double bonds. We present this as a useful strategy for silicon surface modification. Surfaces were characterized with contact angle goniometry, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM).