Copper precursors useful for depositing copper or copper-containing films on substrates, e.g., microelectronic device substrates or other surfaces. The precursors includes copper compounds of various classes, including copper borohydrides, copper compounds with cyclopentadienyl-type ligands, copper compounds with cyclopentadienyl-type and isocyanide ligands, and stabilized copper hydrides. The precursors can be utilized in solid or liquid forms that are volatilized to form precursor vapor for contacting with the substrate, to form deposited copper by techniques such as chemical vapor deposition (CVD), atomic layer deposition (ALD) or rapid vapor deposition (digital CVD).