The present invention provides a method for purifying ruthenium sources to obtain high purity ruthenium metal and form a ruthenium metal pattern on a semiconductor substrate without the need for high temperature processing or a complex series of wet processes. A gas stream including ozone (O.sub.3) is brought into contact with a ruthenium source in one or more reaction vessels to form ruthenium tetraoxide (RuO.sub.4), a compound that is a gas at the reaction conditions. The ruthenium tetraoxide, along with unreacted ozone and the remainder of the gas stream is then fed into a collection vessel where the gaseous ruthenium tetraoxide is reduced to form a ruthenium dioxide (RuO.sub.2) layer on a semiconductor substrate. The deposited ruthenium dioxide is then reduced, preferably with hydrogen, to produce highly pure ruthenium metal that may be, in turn, patterned and dry etched using ozone as an etchant gas.

The invention includes methods of forming a substrate having a surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms. In one implementation, a substrate is provided which has a first substrate surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms. The first substrate surface has a first degree of roughness. Within a chamber, the first substrate surface is exposed to a PF.sub.3 comprising atmosphere under conditions effective to form a second substrate surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms which has a second degree of roughness which is greater than the first degree of roughness. The substrate having the second substrate surface with the second degree of roughness is ultimately removed from the chamber.

The present invention provides methods for the preparation of compounds of the formula (Formula I): wherein M is Ru or Os, each L is independently a neutral ligand, y=1-4, and z=1-5. These methods involve the reaction of Ru.sub.3 (CO).sub.12 or Os.sub.3 (CO).sub.12 with a neutral ligand in a solvent system having a boiling point higher than that of benzene at atmospheric pressure.

The invention includes methods of forming a substrate having a surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms. In one implementation, a substrate is provided which has a first substrate surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms. The first substrate surface has a first degree of roughness. Within a chamber, the first substrate surface is exposed to a PF.sub.3 comprising atmosphere under conditions effective to form a second substrate surface comprising at least one of Pt, Pd, Co and Au in at least one of elemental and alloy forms which has a second degree of roughness which is greater than the first degree of roughness. The substrate having the second substrate surface with the second degree of roughness is ultimately removed from the chamber.

A method is provided for forming a film of ruthenium or ruthenium oxide to the surface of a substrate by employing the techniques of chemical vapor deposition to decompose ruthenium precursor formulations. The ruthenium precursor formulations of the present invention include a ruthenium precursor compound and a solvent capable of solubilizing the ruthenium precursor compound. A method is further provided for making a vaporized ruthenium precursor for use in the chemical vapor deposition of ruthenium and ruthenium-containing materials onto substrates, wherein a ruthenium precursor formulation having a ruthenium-containing precursor compound and a solvent capable of solubilizing the ruthenium-containing precursor compound is vaporized.