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Copper metallization is an ideal choice for use in semiconductor devices and packages. The metal’s desirable properties are low resistivity, good electromigration resistance, solderability, and low cost. Microstructural differences in copper deposited by four techniques commonly used in the microelectronics industry are determined. These differences were measured using optical microscopy, x‐ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and secondary‐ion mass spectroscopy. The results were compared to clearly define the differences in microstructure among the different copper films providing a basis for interpreting the effects of copper film deposition method on film microstructure and those physical properties influenced by microstructure. Finally the microstructural rather than chemical differences are used to predict how each copper sample will react to the same wet etchant.