Chemistry of organoaluminum compounds on silicon surfaces forms a foundation of chemical vapor deposition (CVD) for the formation of metal-semiconductor interconnects. We have applied multiple internal reflection Fourier-transform infrared spectroscopy and thermal desorption mass spectrometry to analyze the chemistry of one of the promising Al-CVD precursors, diethylaluminum hydride, on a Si(100)-2×1 surface. Diethylaluminum hydride adsorbs molecularly on this surface both at room temperature and at 100 K. Thermally induced surface reaction consumes the monolayer of adsorbed organoaluminum molecule. The only hydrocarbon product is ethylene desorbing from the silicon surface around 600 K. Despite a clean reaction that removes carbon from the surface, aluminum deposition is not significant because of the formation of alane products. © 2003 Elsevier B.V. All rights reserved.