Method and composition for selectively removing metal hardmask and other residues from semiconductor device substrates comprising low-k dielectric material and copper

A method for selectively removing an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, or an alloy of Ti or W relative to low-k materials from a semiconductor substrate comprising said low-k materials having an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, or an alloy of Ti or W thereon wherein the method comprises contacting the substrate with a removal composition comprising:

• (a) from 0.1 wt % to 90 wt % at least one oxidizing agent,
• (b) from 0.0001 wt % to 50 wt % of an ammonium carboxylate;
• and
• (c) the balance up to 100 wt % of said removal composition comprising deionized water
• at a temperature in the range of from room temperature up to 80° C. and at a pH in the range of from 3 to 13 for a time wherein said removal composition selectively removes said TiN, TaN, TiNxOy, TiW, W, or alloy of Ti or W etching mask relative to said low-k materials, and the achievable etch rate of the composition remains substantially constant over an extended period of time.

A method for selectively removing an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, or an alloy of Ti or W relative to low-k materials from a semiconductor substrate comprising said low-k materials having an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, or an alloy of Ti or W thereon wherein the method comprises contacting the substrate with a removal composition comprising:

• (a) from 0.1 wt % to 90 wt % of hydrogen peroxide;
• (b) from 0.0001 wt % to 50 wt % of an ammonium carboxylate selected from the group comprising ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, tetraammonium EDTA, ethylenediaminetetraacetic acid diammonium salt, ammonium succinate, ammonium formate, ammonium 1-H-pyrazole-3-carboxylate, and mixtures thereof;
• (c) from 0.001 wt % to 20 wt % of an amino acid, an aminopolycarboxylic acid, a carboxylic acid, a polycarboxylic acid, or a mixture thereof selected from the group consisting essentially of 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid;
• ethylenediaminetetraacetic acid;
• nitrilotriacetic acid;
• diethylene triamine pentaacetic acid;
• 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid;
• ethylene glycol tetraacetic acid (EGTA);
• and 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid;
• and
• (d) the balance up to 100 wt % of said removal composition comprising deionized water
• at a temperature in the range of from room temperature up to 80° C. and at a pH in the range of from 3 to 13 for a time wherein said removal composition selectively removes said TiN, TaN, TiNxOy, TiW, W, or alloy of Ti or W etching mask relative to said low-k materials whereby the etching mask is selectively removed and the achievable removal rate for the etching mask remains substantially constant over an extended period of time.