Compositions and methods for selectively etching titanium nitride
View Patent ↗Compositions useful for the selective removal of titanium nitride and/or photoresist etch residue materials relative to metal conducting, e.g., tungsten, and insulating materials from a microelectronic device having same thereon. The removal compositions contain at least one oxidant and one etchant, may contain various corrosion inhibitors to ensure selectivity.
1. A composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon, said composition comprising (a) a concentrate comprising at least one etchant, at least one metal corrosion inhibitor, at least one oxidizing agent stabilizer, and at least one solvent, and (b) at least one oxidizing agent, wherein the at least one metal corrosion inhibitor comprises a species selected from the group consisting of 5-methyl-benzotriazole, benzotriazole carboxylic acid, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, oleic imidazoline, 2-benzylpyridine, succinimide, adenosine, carbazole, saccharin, benzoin oxime, poly(ethylene glycol), poly(propylene glycol), PEG-PPG copolymers, myristyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, and combinations thereof, and
wherein the at least one oxidizing agent stabilizer comprises a species selected from the group consisting of glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, diethylenetriamine pentaacetic acid, propylenediamine tetraacetic acid, ethylendiamine disuccinic acid, sulfanilamide, and combinations thereof.
2. The composition of claim 1 , wherein the composition comprises about 0.001 wt % to about 50 wt % of at least one oxidizing agent, about 0.01 wt % to about 10 wt % of at least one etchant, about 0.01 wt % to about 1 wt % of at least one metal corrosion inhibitor, about 0.0001 wt % to about 0.5 wt % of at least one oxidizing agent stabilizer, and about 39 wt % to about 99 wt % of at least one solvent.
3. The composition of claim 1 , wherein the at least one etchant comprises a species selected from the group consisting of H 2 ZrF 6 , H 2 TiF 6 , HPF 6 , HF, ammonium fluoride, tetrafluoroboric acid, hexafluorosilicic acid, tetrabutylammonium tetrafluoroborate (TBA-BF 4 ), ammonium hexafluorosilicate, ammonium hexafluorotitanate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), 1,1,3,3-tetramethylguanidine (TMG), guanidine carbonate, arginine, ammonium hydroxide, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine, cysteine, tetraalkylammonium fluoride (NR 1 R 2 R 3 R 4 F), and combinations thereof, where R 1 , R 2 , R 3 , R 4 may be the same as or different from one another and is selected from the group consisting of straight-chained C 1 -C 6 alkyl groups and branched C 1 -C 6 alkyl groups.
4. The composition of claim 1 , wherein the at least one etchant comprises TMAH.
5. The composition of claim 1 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, FeCl 3 , FeF 3 , Fe(NO 3 ) 3 , Sr(NO 3 ) 2 , CoF 3 , MnF 3 , oxone (2KHSO 5 .KHSO 4 .K 2 SO 4 ), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide, ammonium vanadate, ammonium peroxomonosulfate, ammonium chlorite (NH 4 ClO 2 ), ammonium chlorate (NH 4 ClO 3 ), ammonium iodate (NH 4 IO 3 ), ammonium nitrate (NH 4 NO 3 ), ammonium perborate (NH 4 BO 3 ), ammonium perchlorate (NH 4 ClO 4 ), ammonium periodate (NH 4 IO 3 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), ammonium hypochlorite (NH 4 ClO), ammonium tungstate ((NH 4 ) 10 H 2 (W 2 O 7 )), sodium persulfate (Na 2 S 2 O 8 ), sodium hypochlorite (NaClO), sodium perborate, potassium iodate (KIO 3 ), potassium permanganate (KMnO 4 ), potassium persulfate, nitric acid (HNO 3 ), potassium persulfate (K 2 S 2 O 8 ), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH 3 ) 4 /ClO 2 ), tetramethylammonium chlorate ((N(CH 3 ) 4 )ClO 3 ), tetramethylammonium iodate ((N(CH 3 ) 4 )IO 3 ), tetramethylammonium perborate ((N(CH 3 ) 4 )ClO 3 ), tetramethylammonium perchlorate ((N(CH 3 ) 4 /ClO 4 ), tetramethylammonium periodate ((N(CH 3 ) 4 )IO 4 ), tetramethylammonium persulfate ((N(CH 3 ) 4 /S 2 O 8 ), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate (Fe(NO 3 ) 3 ), urea hydrogen peroxide ((CO(NH 2 ) 2 )H 2 O 2 ), peracetic acid (CH 3 (CO)OOH), 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof.
6. The composition of claim 1 , wherein the at least one oxidizing agent comprises hydrogen peroxide.
7. The composition of claim 1 , wherein the at least one solvent comprises water.
8. The composition of claim 1 , further comprising at least one carboxylate salt.
9. The composition of claim 8 , wherein the at least one carboxylate salt comprises an ammonium cation and an anion selected from the group consisting of acetate, benzoate, citrate, formate, oxalate, tartarate, succinate, lactate, maleate, malonate, fumarate, malate, ascorbate, mandelate, and phthalate.
10. The composition of claim 8 , wherein the at least one carboxylate salt comprises ammonium acetate, ammonium benzoate, or a combination thereof.
11. The composition of claim 1 , wherein the at least one metal corrosion inhibitor comprises 5-methyl-1H-benzotriazole.
12. The composition of claim 1 , wherein the at least one oxidizing agent stabilizer comprises CDTA, sulfanilamide, or a combination thereof.
13. The composition of claim 1 , wherein the composition is substantially devoid of silicates, abrasive materials, chloride sources, metal halides, and combinations thereof.
14. The composition of claim 1 , wherein pH of the composition is in a range from about 5 to about 10.
15. A method of etching titanium nitride material from a surface of a microelectronic device having same thereon, said method comprising contacting the surface with a composition, wherein the composition selectively removes the titanium nitride material from the surface relative to metals and insulating materials, said composition comprising (a) a concentrate comprising at least one etchant, at least one metal corrosion inhibitor, at least one oxidizing agent stabilizer, and at least one solvent, and (b) at least one oxidizing agent, wherein the at least one metal corrosion inhibitor comprises a species selected from the group consisting of 5-methyl-benzotriazole, benzotriazole carboxylic acid, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, oleic imidazoline, 2-benzylpyridine, succinimide, adenosine, carbazole, saccharin, benzoin oxime, poly(ethylene glycol), poly(propylene glycol), PEG-PPG copolymers, myristyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, and combinations thereof, and
wherein the at least one oxidizing agent stabilizer comprises a species selected from the group consisting of glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, diethylenetriamine pentaacetic acid, propylenediamine tetraacetic acid, ethylendiamine disuccinic acid, sulfanilamide, and combinations thereof.
16. The method of claim 15 , wherein the contacting comprises time in a range from about 0.3 minute to about 30 minutes at temperature in a range of from about 20° C. to about 100° C.
17. The method of claim 15 , wherein the composition is rinsed from the surface following the desired etching action.
18. The method of claim 15 , wherein the at least one metal corrosion inhibitor comprises 5-methyl-1H-benzotriazole.
19. The method of claim 15 , wherein the at least one etchant comprises a species selected from the group consisting of H 2 ZrF 6 , H 2 TiF 6 , HPF 6 , HF, ammonium fluoride, tetrafluoroboric acid, hexafluorosilicic acid, tetrabutylammonium tetrafluoroborate (TBA-BF 4 ), ammonium hexafluorosilicate, ammonium hexafluorotitanate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), 1,1,3,3-tetramethylguanidine (TMG), guanidine carbonate, arginine, ammonium hydroxide, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine, cysteine, tetraalkylammonium fluoride (NR 1 R 2 R 3 R 4 F), and combinations thereof, where R 1 , R 2 , R 3 , R 4 may be the same as or different from one another and is selected from the group consisting of straight-chained C 1 -C 6 alkyl groups and branched C 1 -C 6 alkyl groups.
20. The method of claim 15 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, FeCl 3 , FeF 3 , Fe(NO 3 ) 3 , Sr(NO 3 ) 2 , CoF 3 , MnF 3 , oxone (2KHSO 5 .KHSO 4 .K 2 SO 4 ), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide, ammonium vanadate, ammonium peroxomonosulfate, ammonium chlorite (NH 4 ClO 2 ), ammonium chlorate (NH 4 ClO 3 ), ammonium iodate (NH 4 IO 3 ), ammonium nitrate (NH 4 NO 3 ), ammonium perborate (NH 4 BO 3 ), ammonium perchlorate (NH 4 ClO 4 ), ammonium periodate (NH 4 IO 3 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), ammonium hypochlorite (NH 4 ClO), ammonium tungstate ((NH 4 ) 10 H 2 (W 2 O 7 )), sodium persulfate (Na 2 S 2 O 8 ), sodium hypochlorite (NaClO), sodium perborate, potassium iodate (KIO 3 ), potassium permanganate (KMnO 4 ), potassium persulfate, nitric acid (HNO 3 ), potassium persulfate (K 2 S 2 O 8 ), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH 3 ) 4 )ClO 2 ), tetramethylammonium chlorate ((N(CH 3 ) 4 )ClO 3 ), tetramethylammonium iodate ((N(CH 3 ) 4 )IO 3 ), tetramethylammonium perborate ((N(CH 3 ) 4 )BO 3 ), tetramethylammonium perchlorate ((N(CH 3 ) 4 )ClO 4 ), tetramethylammonium periodate ((N(CH 3 ) 4 )IO 4 ), tetramethylammonium persulfate 4N(CH 3 ) 4 )S 2 O 8 ), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate (Fe(NO 3 ) 3 ), urea hydrogen peroxide ((CO(NH 2 ) 2 )H 2 O 2 ), peracetic acid (CH 3 (CO)OOH), 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof.