Methods and compositions for oxide production on copper

A method for oxide production on a Copper substrate, the method comprising:

• contacting a surface of a Copper substrate with an ammoniacal oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions:
• b) ammonium nitrate as a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of a Cuprous ligand;
• said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• wherein production of oxide on the Copper substrate produces a treated Copper surface that, when bonded to an organic substrate, produces an adhesive bond of enhanced strength relative to an untreated Copper substrate surface.

A method for oxide production on a Copper substrate, the method comprising:

• contacting a surface of a Copper substrate with an acidic oxide-producing composition comprising:
• a) Copper nitrate as a source of Cu++ (Cupric) ions;
• b) nitric acid as a strong acid that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• wherein production of oxide on the Copper substrate produces a treated Copper surface that, when bonded to an organic substrate, produces an adhesive bond of enhanced strength relative to an untreated Copper substrate surface.

A method for oxide production on a Copper substrate, the method comprising:

• contacting a surface of a Copper substrate with an ammoniacal oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions;
• b) ammonium nitrate as an ammonium salt of an acid that provides a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• wherein production of oxide on the Copper substrate produces a treated Copper surface that, when bonded to an organic substrate, produces an adhesive bond of enhanced strength relative to an untreated Copper substrate surface.

A method for adhering a polymeric resin to a surface of a Copper substrate, said process comprising:

• contacting a surface of a Copper substrate with an oxide-producing composition comprising:
• a) Cooper sulfate as a source of Cu++ (Cupric) ions;
• b) sulfuric acid as a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of a Cuprous ligand;
• wherein the source of primary electrolyte is chosen from a strong acid and an ammonium salt of an acid, and wherein said contacting is under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• and
• adhering a polymeric material to the surface of the Copper substrate.

An acidic oxide-producing composition comprising:

• a) Copper sulfate as a source of Cu++ (Cupric) ions;
• b) sulfuric acid a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• c) a source of a Cuprous ligand;
• and
• d) an organic compound chosen from a straight chain alkyne alcohol and a dicarboxylic acid;
• wherein each of a), b), and c) and d) are present in an amount such that contacting the oxide-producing composition with a Copper substrate in the presence of atmospheric oxygen results in production of Copper oxide on the Copper substrate.

An acidic oxide-producing composition comprising:

• a) copper nitrate as a source of Cu++ (Cupric) ions;
• b) nitric acid as a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• c) a source of a Cuprous ligand;
• and
• d) an organic compound chosen from a straight chain alkyne alcohol and a dicarboxylic acid;
• wherein each of a), b), c) and d) are present in an amount such that contacting the oxide-producing composition with a Copper substrate in the presence of atmospheric oxygen results in production of Copper oxide on the Copper substrate.

A method of replenishing an oxide producing chemical system, the method comprising;

• replenishing an oxide production bath by addition of a replenishing composition, wherein the oxide production bath comprises an acidic oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions;
• b) a strong acid as a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion, wherein the strong acid is sulfuric acid when the source of Cupric ions is Copper sulfate and the strong acid is nitric acid when the source of Cupric ions is Copper nitrate;
• c) a source of a Cuprous ligand;
• and
• d) an organic compound chosen from a straight chain alkyne alcohol and a dicarboxylic acid;
• wherein each of a), b) and c) are present in the oxide-producing composition in an amount such that contacting the oxide-producing composition with a Copper substrate in the presence of atmospheric oxygen results in production of Copper oxide on the Copper substrate, and
• wherein the replenishing composition comprises b) and c), and
• where addition of the replenishing composition to the oxide product bath restores the bath so as to have concentrations of Cupric ions, primary electrolyate, and Cuprous ligand similar to that of a bath prior to use in oxide production.

A method for oxide production on a Copper substrate, the method comprising:

• contacting a surface of a Copper substrate with an ammoniacal oxide-producing composition comprising:
• a) Copper Nitrate as a source of Cu++ (Cupric) ions;
• b) an ammonium salt of an acid that provides a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• wherein production of oxide on the Copper substrate produces a treated Copper surface that, when bonded to an organic substrate, produces an adhesive bond of enhanced strength relative to an untreated Copper substrate surface.

A method for oxide production on a Copper substrate, the method comprising:

• contacting a surface of a Copper substrate with an acidic oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions:
• b) a strong acid that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• wherein the oxide-producing composition contains no detectable amount of a polymeric compound, said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• wherein production of oxide on the Copper substrate produces a treated Copper surface that, when bonded to an organic substrate, produces an adhesive bond of enhanced strength relative to an untreated Copper substrate surface.

A method for adhering a polymeric resin to a surface of a Copper substrate, said process comprising:

• contacting a surface of a Copper substrate with an acidic oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions;
• b) a strong acid as a source of a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• wherein the oxide-producing compositions contains no detectable amount of a polymeric compound, said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• and
• adhering a polymeric material to the surface of the Copper substrate.

A method for adhering a polymeric resin to a surface of a Copper substrate, said process comprising:

• contacting a surface of a Copper substrate with an ammoniacal oxide-producing composition comprising:
• a) a source of Cu++ (Cupric) ions;
• b) ammonium nitrate as an ammonium salt of an acid that provides a primary electrolyte that is non-interactive with either of Cuprous or Cupric ion;
• and
• c) a source of halide ions;
• said contacting being under conditions and for a time sufficient for oxide production on the surface of the Copper substrate;
• and
• adhering a polymeric material to the surface of the Copper substrate.