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

Abstract

An aqueous removal composition having a pH in the range of from 2 to 14 and method for selectively removing an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, or alloy of Ti or W relative to low-k materials from a semiconductor substrate comprising said low-k materials having a TiN, TaN, TiNxOy, TiW, W, or alloy of Ti or W etching mask thereon wherein the removal composition comprises at least one oxidizing agent and a carboxylate compound.

What is claimed is: 
     
         1 . A removal composition having a pH in the range of from 2 to 14 for selectively removing an etching mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, and alloys of Ti and W relative to low-k dielectric material from a semiconductor device substrate which comprises said low-k dielectric material having a TiN, TaN, TiNxOy, TiW, W, or alloy of Ti or W etching mask thereon, wherein said removal composition comprises:
 (a) from 0.1 wt % to 90 wt % of an 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.   
     
     
         2 . The removal composition of  claim 1  further comprising an organic cosolvent that is miscible with water. 
     
     
         3 . The removal composition of  claim 1  or  claim 2  wherein (a) said oxidizing agent is selected from the group consisting essentially of hydrogen peroxide (H 2 O 2 ), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate peroxoborate, perchlorate, persulfate, ammonium peroxydisulfate, per acetic acid, urea hydroperoxide, nitric acid (HNO 3 ), ammonium chlorite (NH 4 CIO 2 ), ammonium chlorate (NH 4 CIO 3 ), ammonium iodate (NH 4 IO 3 ), ammonium perborate (NH 4 BO 3 ), ammonium perchlorate (NH 4 CIO 4 ), ammonium periodate (NH 4 IO 3 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), tetramethylammonium chlorite ((N(CH 3 ) 4 )CIO 2 ), tetramethylammionium chlorate ((N(CH 3 ) 4 )CIO 3 ), tetramethylammonium iodate ((N(CH 3 ) 4 )IO 3 ), tetramethylammonium perborate ((N(CH 3 ) 4 )BO 3 ), tetramethylammonium perchlorate ((N(CH 3 ) 4 )CIO 4 ), tetramethylammonium periodate ((N(CH 3 ) 4 )IO 4 ), tetramethylammonium persulfate ((N(CH 3 ) 4 )S 2 O 8 ), ((CO(NH 2 ) 2 )H 2 O 2 ), peracetic acid (CH 3 (CO)OOH), and mixtures thereof; and
 (b) said ammonium carboxylate is 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. 
 
     
     
         4 . The removal composition of  claim 3  wherein said oxidizing agent is hydrogen peroxide. 
     
     
         5 . The removal composition of  claim 1  further comprising 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); 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid; N-{2-[bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA); and ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid) (EDDHA). 
     
     
         6 . The removal composition of  claim 1  further comprising from 0.0001 wt % up to 50 wt % of a metal corrosion inhibitor. 
     
     
         7 . The removal composition of  claim 1  wherein the pH is in the range of from 3 to 13 and said oxidizing agent is hydrogen peroxide. 
     
     
         8 . The removal composition of  claim 7  wherein the pH is in the range of from 7 to 12. 
     
     
         9 . 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.   
     
     
         10 . The method of  claim 9  wherein:
 (a) said oxidizing agent is selected from the group consisting essentially of hydrogen peroxide (H 2 O 2 ), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate peroxoborate, perchlorate, persulfate, ammonium peroxydisulfate, per acetic acid, urea hydroperoxide, nitric acid (HNO 3 ), ammonium chlorite (NH 4 CIO 2 ), ammonium chlorate (NH 4 CIO 3 ), ammonium iodate (NH 4 IO 3 ), ammonium perborate (NH 4 BO 3 ), ammonium perchlorate (NH 4 CIO 4 ), ammonium periodate (NH 4 IO 3 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), tetramethylammonium chlorite ((N(CH 3 ) 4 )CIO 2 ), tetramethylammionium chlorate ((N(CH 3 ) 4 )CIO 3 ), tetramethylammonium iodate ((N(CH 3 ) 4 )IO 3 ), tetramethylammonium perborate ((N(CH 3 ) 4 )BO 3 ), tetramethylammonium perchlorate ((N(CH 3 ) 4 )CIO 4 ), tetramethylammonium periodate ((N(CH 3 ) 4 )IO 4 ), tetramethylammonium persulfate ((N(CH 3 ) 4 )S 2 O 8 ), ((CO(NH 2 ) 2 )H 2 O 2 ), peracetic acid (CH 3 (CO)OOH), and mixtures thereof; and 
 (b) said ammonium carboxylate is 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. 
 
     
     
         11 . The method of  claim 10  wherein said removal composition further comprises from 0.0001 wt % up to 20 wt % of a copper corrosion inhibitor. 
     
     
         12 . The method of  claim 10  wherein said removal composition further comprises 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); 1,2-bis(o-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid; N-{2-[bis(carboxymethyl)amino]ethyl}-N-(2-hydroxyethyl)glycine (HEDTA); and ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid) (EDDHA) whereby the achievable removal rate for the etching mask remains substantially constant over an extended period of time up to at least thirty five hours. 
     
     
         13 . 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.