Removal composition for selectively removing hard mask and methods thereof

1. A method for removing a hard mask consisting essentially of TiN, TaN, TiNxOy, TiW, W, Ti and alloys of Ti and W from a semiconductor substrate, the method comprising contacting the semiconductor substrate with a removal composition comprising:

(a) 0.1 wt % to 90 wt % at least one oxidizing agent,

(b) 0.0001 wt % to 50 wt % of a carboxylate;

(c) from 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.

2. The method 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, 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 carboxylate is selected from the group consisting of potassium citrate tribasic monohydrate, potassium sodium tartrate tetrahydrate, potassium L-Lactate and mixtures thereof.

3. The method of claim 2 , wherein the 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 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 method of claim 2 , wherein the removal composition further comprises 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, organic acids or mixtures thereof.

5. The method of claim 2 , wherein the removal composition further comprises: 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).

6. The method of claim 2 , wherein the removal composition further comprises: 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.

7. The method of claim 1 , wherein the carboxylate is an ammonium carboxylate.

8. The method of claim 7 , 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.

9. The method of claim 8 , wherein the 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 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).

10. The method of claim 8 , wherein the removal composition further comprises 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, organic acids or mixtures thereof.

11. The method of claim 8 , wherein the removal composition further comprises: 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).

12. The method of claim 8 , wherein the removal composition further comprises: 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.

13. The method of claim 8 , wherein the removal composition further comprises 0.001 wt % to 20 wt % 1,2-cyclohexanediamine-N, N, N′, N′-tetraacetic acid.

14. The method of claim 8 , wherein the ammonium carboxylate is selected from ammonium tartrate.

15. The method of claim 8 , 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.

16. The method of claim 8 , wherein etch rate of a hard mask is stabilized up to at least 35 hours.

17. The method of claim 1 , additionally comprising heating the removal composition up to 60° C.

18. The method of claim 1 , wherein the removal composition further comprising benzotriazole.

19. The method of claim 1 , wherein the removal composition further comprising tolyltriazole.