Compositions and methods for selectively etching titanium nitride

Patent metadata

Field	Value
Publication number	US-10920141-B2
Application number	US-201414896197-A
Country	US
Kind code	B2
Filing date	Jun 6, 2014
Priority date	Jun 6, 2013
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

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

What is claimed is:

1. A composition comprising from about 15 wt % to about 30 wt % of at least one oxidizing agent, from about 0.01 wt % to about 15 wt % of at least one etchant, from about 0.01 wt % to about 2 wt % of at least one metal corrosion inhibitor, from about 0.01 wt % to about 1 wt % of at least one chelating agent, and at least one solvent, wherein:
the etchant comprises a species selected from the group consisting of 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, and combinations thereof;
the corrosion inhibitor comprises a species selected from the group consisting of 2-amino-5-ethyl-1,3,4-thiadiazole, ATA-SDS, Ablumine O, 2-benzylpyridine, decyltrimethylammonium chloride (DTAC), carbazole, saccharin, benzoin oxime, polyoxypropylene/polyoxyethylene block copolymer, sodium dodecylbenzenesulfonate (SDS), benzylphosphonic acid, diphenylphosphinic acid, 1,2-ethylenediphosphonic acid, phenylphosphonic acid, cinnamic acid, and combinations thereof; and
wherein the composition has a pH in a range of from about 6 to about 10; and
wherein the composition removes titanium nitride and/or photoresist etch residue from a surface of a microelectronic device having the same thereon and wherein the composition is highly selective to cobalt.

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

3. The composition of claim 1 , wherein the oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, FeCl3, FeF3, Fe(NO3)3, Sr(NO3)2, CoF3, MnF3, oxone (2KHSO5.KHSO4.K2SO4), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV, V) oxide, ammonium vanadate, ammonium peroxomonosulfate, ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium nitrate (NH4NO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO), ammonium tungstate ((NH4)10H2(W2O7)), sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO), sodium perborate, potassium iodate (KIO3), potassium permanganate (KMnO4), potassium persulfate, nitric acid (HNO3), potassium persulfate (K2S2O8), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium 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), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate (Fe(NO3)3), urea hydrogen peroxide ((CO(NH2)2)H2O2), peracetic acid (CH3(CO)OOH), 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof.

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

5. 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.

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

7. The composition of claim 1 , wherein the metal corrosion inhibitor comprises one or more species selected from the group consisting of ATA-SDS, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monolaurate, polyoxypropylene/polyoxyethylene block copolymers, DTAC, and combinations thereof.

8. The composition of claim 1 , wherein the at least one chelating agent comprises a species selected from the group consisting of acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, iminodiacetic acid (IDA), malonic acid, oxalic acid, succinic acid, boric acid, nitrilotriacetic acid, malic acid, citric acid, acetic acid, maleic acid, ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid diammonium salt, (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), diethylenetriamine pentaacetic acid (DTPA), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), ethylendiamine disuccinic acid, propylenediamine tetraacetic acid, phosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonic acid) (NTMP), amino tri(methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid) (EDTMPA), ethylenediamine, 2,4-pentanedione, benzalkonium chloride, 1-imidazole, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine-2,4,6-thithiol trisodium salt solution, 1,3,5-triazine-2,4,6-thithiol triammonium salt solution, sodium diethyldithiocarbamate, disubstituted dithiocarbamates, sulfanilamide, monoethanolamine (MEA), 2-hydroxypyridine 1-oxide, sodium triphosphate penta basic, and combinations thereof.

9. The composition of claim 1 , wherein the at least one chelating agent comprises CDTA.

10. The composition of claim 1 , wherein the at least one chelating agent comprises a species selected from the group consisting of ammonium cation or a tetraalkylammonium cation of acetate, chloride, bromide, iodide, sulfate, benzoate, propionate, citrate, formate, oxalate, tartarate, succinate, lactate, maleate, malonate, fumarate, malate, ascorbate, mandelate, and phthalate, and combinations thereof.

11. The composition of claim 1 , wherein the at least one chelating agent comprises ammonium bromide and/or ammonium chloride.

12. The composition of claim 1 , further comprising at

Assignees

• Advanced Tech Materials Inc
• Entegris Inc

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