An unexpected substrate etching phenomenon during the sputtering of certain intermetallic compounds has been found to be caused by a large flux of negative metal ions from the sputtering target. The substrates directly under the target in a diode geometry are etched (eroded) rather than coated with a film. The occurrence of this substrate etching has been correlated with negative ion yields measured by secondary ion mass spectroscopy(SIMS). We find a high yield of negative metal ions from several intermetallic compounds in addition to the highly ionic compounds previously reported. A model based on electron charge transfer is presented which predicts when negative ion formation will be important, and the dependence of etch rate on target voltage is also treated. We predict that negative ion effects will be found in the sputtering of a wide range of compounds.