Spectroscopic characterization of samples of sputter‐deposited Al/Si/Cu very large scale integration metallization 1.3 μ thick having 1 wt. % Si and 0.0, 0.2, 0.4, and 0.8 wt. % Cu with and without a forming gas (N2/H2) 450 °C anneal for 1 h was performed as a function of deposition temperatures of 100, 163, 263, 363, and 463 °C. Secondary ion mass spectroscopic depth profiles of the metallization samples show a unique redistribution of the Si from the bulk to the metal/oxide interface at deposition temperatures between 263 and 363 °C. These data are correlated with scanning electron microscope micrographs of Si module precipitation on the silicon dioxide substrate surface after removal of the Al by an Al‐specific wet etch. In a subsequent paper, electrical and mechanical characterization results of these same metallization samples will be reported from resistivity and Knoop hardness measurements.