Metal inks, methods of making the same, and methods for printing and/or forming metal films

A method of printing a metal or metal alloy film on a substrate, comprising:

• a) coating or printing a formulation onto at least part of an exposed silicon-containing surface of said substrate, the formulation consisting essentially of (i) one or more salts and/or complexes of a silicide forming Group 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal, (ii) one or more organic solvents, and (iii) one or more anion source additives selected from the group consisting of HX and NH4X to form the formulation, where X is a halide, nitrate, sulfate, formate, acetate, cyanate, isocyanate, and/or alkoxide, the organic solvent(s) are present in an amount of at least 50% by volume of the formulation, at least 20% by volume of the formulation is a low volatility solvent having a viscosity of at least 2 cP, a boiling point of at least 150 ° C., and a surface tension of at least 20 dynes/cm, and each component of the formulation, including said salt(s) and/or complex(es) of said silicide forming Group 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal, said solvent(s), and said anion source additive(s) form gaseous or volatile byproducts upon reduction of the metal salt(s) and/or metal complex(es) to an elemental metal or alloy thereof;
• b) removing said one or more solvents to form a metal-containing precursor film;
• c) reducing said metal-containing precursor film to form said metal or metal alloy film;
• and
• d) annealing the substrate and said metal or metal alloy film at a temperature sufficiently high and for a time sufficiently long to form a metal.