Compositions and methods for selectively etching titanium nitride

Patent metadata

Field	Value
Publication number	US-2016130500-A1
Application number	US-201414896197-A
Country	US
Kind code	A1
Filing date	Jun 6, 2014
Priority date	Jun 6, 2013
Publication date	May 12, 2016
Grant date	—

Abstract

Compositions useful for the selective removal of titanium nitride and/or photoresist etch residue materials relative to metal conducting, e.g., cobalt, ruthenium and copper, 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.

First claim

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 at least one oxidizing agent, at least one etchant, at least one metal corrosion inhibitor, at least one chelating agent, and at least one solvent.

2 . The composition of claim 1 , wherein the 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), tris(2-hydroxyethyl)methyl ammonium hydroxide (THEMAH), 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), 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 or branched C 1 -C 6 alkyl groups, and combinations thereof.

3 . The composition of claim 1 , wherein the etchant comprises TMAH, choline hydroxide, potassium hydroxide, THEMAH, and any combination thereof.

4 . The composition of claim 1 , wherein the 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 ((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.

5 . The composition of claim 1 , wherein the oxidizing agent comprises hydrogen peroxide.

6 . The composition of claim 1 , wherein the at least one solvent comprises a species selected from the group consisting of water, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-1-hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, choline bicarbonate, dipropylene glycol, dimethylsulfoxide, sulfolane, tetrahydrofurfuryl alcohol (THFA), 1,2-butanediol, 1,4-butanediol, tetramethyl urea, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, 2,3-dihydrodecafluoropentane, ethyl perfluorobutylether, methyl perfluorobutylether, alkyl carbonates, 4-methyl-2-pentanol, and combinations thereof.

7 . The composition of claim 1 , wherein the at least one solvent comprises water.

8 . The composition of claim 1 , wherein the at least one metal corrosion inhibitor is selected from the group consisting of comprises a species selected from the group consisting of 5-amino-1,3,4-thiadiazole-2-thiol (ATDT), 2-amino-5-ethyl-1,3,4-thiadiazole, benzotriazole (BTA), 1,2,4-triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole (3-ATA), 5-amino-1,2,4-triazole (5-ATA), 3-amino-5-mercapto-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, ATA-SDS, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles (halo=F, Cl, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-methyltetrazole, 5-mercapto-1-methyl-tetrazole, 1-phenyl-1H-tetrazole-5-thiol, Ablumine O, 2-benzylpyridine, succinimide, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazoline thione, 4-methyl-4H-1,2,4-triazole-3-thiol, 4-amino-4H-1,2,4-triazole, benzothiazole, imidazole, benzimidazole, 2-bminobenzimidazole, 1-methylimidazole, indiazole, decyltrimethylammonium Chloride (DTAC), adenosine, adenine, succinimide, carbazole, saccharin, uric acid, benzoin oxime, cationic quaternary salts poly(ethylene glycol), poly(propylene glycol), ethylene oxide/propylene oxide block copolymers such, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monolaurate, polyoxypropylene/polyoxyethylene block copolymers, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate (SDS), dodecylphosphonic acid (DDPA), bis(2-ethylhexyl)phosphate, benzylphosphonic acid , diphenylphosphinic acid, 1,2-ethylenediphosphonic acid, phenylphosphonic acid, cinnamic acid, cetyltrimethylammonium bromide, myristyltrimethylammonium bromide and combinations thereof.

9 . The composition of claim 1 , wherein the metal corrosion inhibitor comprises 5-methyl-1H-benzotriazole, 3-ATA, 1,2,4-triazole, and/or DTAC.

10 . The composition of claim 1 , wherein the at least one chelating agent

Assignees

• Advanced Tech Materials

Inventors

• Chen Li-Min
• Lippy Steven
• Cooper Emanuel I
• Song Lingyan

Classifications

• H10P50/73

  using masks for insulating materials · CPC title

• H10P70/234

  the processing being the formation of vias or contact holes · CPC title

• H10P70/20

  Cleaning during device manufacture · CPC title

• H10P70/15

  by wet cleaning only (H10P70/52 takes precedence) · CPC title

• H10P50/667

  by liquid etching only · CPC title