Direct assembly of molecules onto silicon surfaces is of particular interest for potential employment in hybrid organic-semiconductor devices. In the study we report here, aryl diazonium salts were used to assemble covalently bound molecular groups on a hydride-passivated, oxide-free n-type Si(111) surface. The reaction of 4-(trimethylsilylethynyl)benzenediazonium tetrafluoroborate generates a molecular layer of 4-(trimethylsilylethynyl)phenylene (TMS-EP) on the n++-Si(111) surface. The monolayer modifies the electrical properties of the interface and exhibits nonlinear current-voltage characteristics, as compared with the ohmic behavior observed from metal-n++-Si(111) junctions. The result of current-voltage measurements at variable temperatures (from 300 to 10 K) on samples made with the TMS-EP molecule does not show significant thermally-activated transport, indicating that tunneling is the dominant transport mechanism. The measured data is compared to a tunneling model.