Removal composition for selectively removing hard mask and methods thereof
View Patent ↗The present disclosure relates to a removal composition for selectively removing an hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W relative to low-k dielectric material from a semiconductor substrate. The semiconductor substrate comprises a low-k dielectric material having a TiN, TaN, TiNxOy, TiW, W, Ti or alloy of Ti or W hard mask thereon. The removal composition comprises 0.1 wt % to 90 wt % of an oxidizing agent; 0.0001 wt % to 50 wt % of a carboxylate; and the balance up to 100 wt % of the removal composition comprising deionized water.
1. A removal composition for selectively removing a hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W relative to low-k dielectric material from a semiconductor substrate which comprises the low-k dielectric material having a TiN, TaN, TiNxOy, TiW, W, Ti or alloy of Ti or W hard mask thereon, the removal composition comprising:
(a) 0.1 wt % to 90 wt % of an oxidizing agent;
(b) 0.0001 wt % to 50 wt % of a carboxylate;
(c) 0.0001 wt % up to 50 wt % of a metal corrosion inhibitor; and
(d) the balance up to 100 wt % of the removal composition comprising deionized water;
wherein said metal corrosion inhibitor is one or more members selected from the group consisting of pyrrole and derivatives thereof, pyrazole and derivatives thereof, and indazole and derivatives thereof, and wherein said composition does not contain hydrofluoric acid.
2. The removal composition of claim 1 , wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide (H2O2), n-methylmorpholine oxide (NMMO or NMO), benzoyl peroxide, tetrabutylammonium peroxymonosulfate, ozone, ferric chloride, permanganate peroxoborate, perchlorate, persulfate, ammonium peroxydisulfate, urea hydroperoxide, nitric acid (HNO3), ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)25208), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammionium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)IO4), tetramethylammonium persulfate ((N(CH3)4)S2O8), ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), and mixtures thereof; and
the carboxylate is selected from the group consisting of potassium citrate tribasic monohydrate, potassium sodium tartrate tetrahydrate, potassium L-Lactate and mixtures thereof.
3. The removal composition of claim 2 further comprising: 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTNA).
4. The removal composition of claim 1 , wherein the metal corrosion inhibitor further comprising benzotriazole or tolyltriazole.
5. The removal composition of claim 2 further comprising: at least one base, at least one acid or mixture thereof; wherein the base is selected from the group consisting of quaternary ammonium salts, primary amines, secondary amines, tertiary amines, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA), tetrabutyphosphonium hydroxide (TBPH), and mixtures thereof; and wherein the acid is selected from the group consisting of inorganic acids, a carboxylic acid, an amino acid, a hydroxy carboxylic acid, a polycarboxylic acid, and a mixture thereof.
6. The removal composition of claim 2 further comprising: i) 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTHA).
7. The removal composition of claim 2 further comprising: i) 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTHA); and ii) at least one base, at least one acid or mixture thereof; wherein the base is selected from the group consisting of quaternary ammonium salts, primary amines, secondary amines, tertiary amines, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA), tetrabutyphosphonium hydroxide (TBPH), and mixtures thereof; and wherein the acid is selected from the group consisting of inorganic acids, a carboxylic acid, an amino acid, a hydroxy carboxylic acid, a polycarboxylic acid, and a mixture thereof.
8. The removal composition of claim 1 , wherein the carboxylate is an ammonium carboxylate.
9. The removal composition of claim 8 , wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide (H2O2), 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 (HNO3), ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S2O8), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammionium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)IO4), tetramethylammonium persulfate ((N(CH3)4)S2O8), ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), and mixtures thereof; and
the ammonium carboxylate is selected from the group consisting of ammonium oxalate, ammonium lactate, ammonium tartrate, ammonium citrate tribasic, ammonium acetate, ammonium carbamate, ammonium carbonate, ammonium benzoate, ammonium ethylenediaminetetraacetic acid, diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetic acid, tetraammonium ethylenediaminetetraacetic acid, ammonium succinate, ammonium formate, ammonium 1-H-pyrazole-3-carboxylate and mixtures thereof.
10. The removal composition of claim 9 , 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTNA).
11. The removal composition of claim 9 , wherein the metal corrosion inhibitor further comprising benzotriazole or tolyltriazole.
12. The removal composition of claim 9 further comprising: at least one base, at least one acid or mixture thereof; wherein the base is selected from the group consisting of quaternary ammonium salts, primary amines, secondary amines, tertiary amines, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA), tetrabutyphosphonium hydroxide (TBPH), and mixtures thereof; and wherein the acid is selected from the group consisting of inorganic acids, a carboxylic acid, an amino acid, a hydroxy carboxylic acid, a polycarboxylic acid, and a mixture thereof.
13. The removal composition of claim 9 further comprising: 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTHA).
14. The removal composition of claim 9 further comprising: i) 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 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); dioxaoctamethylene dinitrilo tetraacetic acid; and triethylenetetraamine hexaacetic acid (TTHA); and ii) at least one base, at least one acid or mixture thereof; wherein the base is selected from the group consisting of quaternary ammonium salts, primary amines, secondary amines, tertiary amines, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide (BTAH), monoethanol amine (MEA), diglycol amine (DGA), triethanolamine (TEA), tetrabutyphosphonium hydroxide (TBPH), and mixtures thereof; and wherein the acid is selected from the group consisting of inorganic acids, a carboxylic acid, an amino acid, a hydroxy carboxylic acid, a polycarboxylic acid, and a mixture thereof.
15. The removal composition of claim 9 further comprising: 0.001 wt % to 20 wt % 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid.
16. The removal composition of claim 15 , wherein the ammonium carboxylate is selected from ammonium tartrate.
17. The removal composition of claim 9 , wherein the ammonium carboxylate is selected from the group consisting of ammonium ethylenediaminetetraacetic acid, diammonium ethylenediaminetetraacetic acid, triammonium ethylenediaminetetraacetic acid, tetraammonium ethylenediaminetetraacetic acid and mixtures thereof.
18. The removal composition of claim 1 , wherein the pH is from 5 to 11.
19. The removal composition of claim 1 , wherein the pH is from 7.6 to 11.
20. A removal composition for selectively removing a hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W relative to low-k dielectric material from a semiconductor substrate which comprises the low-k dielectric material having a TiN, TaN, TiNxOy, TiW, W, Ti or alloy of Ti or W hard mask thereon, the removal composition comprising:
(a) 0.1 wt % to 90 wt % of an oxidizing agent;
(b) 0.0001 wt % to 50 wt % of a carboxylate;
(c) 0.0001 wt % up to 50 wt % of a metal corrosion inhibitor; and
(d) the balance up to 100 wt % of the removal composition comprising deionized water;
wherein said metal corrosion inhibitor is one or more members selected from the group consisting of pyrazole and derivatives thereof, and indazole and derivatives thereof.