IP Library Granted Patent US 9,765,288
Granted Patent B2
US 9,765,288 · App. 14/648,815 · Granted Sep 19, 2017

Compositions for cleaning III-V semiconductor materials and methods of using same

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Quick Facts
Patent No.
US 9,765,288
App. No.
14/648,815
Granted
Sep 19, 2017
Kind
B2
Abstract

Liquid compositions useful for the cleaning of residue and contaminants from a III-V microelectronic device material, such as InGaAs, without substantially removing the III-V material. The liquid compositions are improvements of the SC1 and SC2 formulations.

Claims (19)

1. A liquid composition for cleaning the surface of a III-V microelectronic device material, said composition comprising at least one acid, at least one oxidizing agent, at least one corrosion inhibitor, and water, wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of 5-methyl-benzotriazole, 4-phenyl-1,2,3-triazole, 5-mercapto-4H-[1,2,4]triazol-3-ol, 4-ethyl-5-mercapto-4H-1,2,4-triazol-3-ol, 4-ethyl-4H-1,2,4-triazol-3-thiol, 5-ethyl-4H-1,2,4-triazol-3-thiol, (3-mercapto-5-propyl-4H-1,2,4-triazol-4-yl)acetic acid, 4-(5-sulfanyl-1H-tetraazol-1-yl)benzoic acid, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 2-benzylpyridine, succinimide, adenosine, carbazole, saccharin, benzoin oxime, DL-dithiothreitol (DTT), cystaminum dichloride, di-n-propyldisulfide, ammonium sulfide, ethyl thioglycolate, 2-mercaptoethanol, 1,2-ethanedithiol, cysteine, methionine, dibenzothiophene, S-adenosylmethionine, taurine, glutathione, thiolactic acid, mercaptosuccinic acid, thiosalicylic acid, 4-mercaptobenzoic acid, 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, thioglycolic acid, dithiodiglycolic acid, 2,2′-(ethylenedithio)diacetic acid, ethyl 2-mercaptoacetate, 3-methoxybutyl thioglycolate, methyl thioglycolate, dodecylphosphonic acid (DDPA), benzylphosphonic acid, phenylphosphonic acid, and combinations thereof, wherein the at least one acid comprises hydrochloric acid.

2. The liquid composition of claim 1 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, nitric acid, perchloric acid, peroxyacetic acid, FeCl 3 , oxone, periodic acid, iodic acid, ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium nitrate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium persulfate, sodium hypochlorite, potassium iodate, potassium peimanganate, potassium persulfate, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmotpholine N-oxide, trimethylamine N-oxide, pyridine-N-oxide, t-butyl-hydroperoxide, and combinations thereof.

3. The liquid composition of claim 1 , wherein the pH is in a range from about 0 to about 4.

4. The liquid composition of claim 1 , wherein the liquid composition is substantially devoid of fluoride sources.

5. The liquid composition of claim 1 , wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, thioglycolic acid, dithiodiglycolic acid, 2,2′-(ethylenedithio)diacetic acid, ethyl 2-mercaptoacetate, 3-methoxybutyl thioglycolate, methyl thioglycolate, benzylphosphonic acid, phenylphosphonic acid, and combinations thereof.

6. A liquid composition for cleaning the surface of a III-V microelectronic device material, said composition comprising at least one base, at least one oxidizing agent, and water, with the proviso that (a) the at least one oxidizing agent comprises an oxidant that is milder than hydrogen peroxide, (b) the liquid composition comprises a base other than ammonium hydroxide, or (c) both (a) and (b), wherein the pH of the liquid composition is in a range from about 9 to about 14.

7. The liquid composition of claim 6 , wherein the liquid composition is substantially devoid of hydrogen peroxide and the at least one oxidizing agent that is milder than hydrogen peroxide comprises a species selected from the group consisting of nitric acid, perchloric acid, peroxyacetic acid, FeCl 3 , oxone, periodic acid, iodic acid, ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium nitrate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium persulfate, sodium hypochlorite, potassium iodate, potassium permanganate, potassium persulfate, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, pyridine-N-oxide, t-butyl-hydroperoxide, and combinations thereof.

8. The liquid composition of claim 7 , wherein the at least one base is not ammonium hydroxide.

9. The liquid composition of claim 8 , wherein the at least one base comprises a species selected from the group consisting of monoethanolamine (MEA), diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, 2-amino-2-methyl-1-propanol, N-(aminoethyl)ethanolamine, N,N-dimethyl-2-aminoethanol, 2-(2-aminoethoxy)ethanol, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), hydroxyamine, trimethylethylammonium hydroxide, diethyldimethylammonium hydroxide, choline hydroxide, tetrabutylphosphonium hydroxide, guanidine acetate, 1,1,3,3-tetramethylguanidine, guanidine carbonate, arginine, and combinations thereof.

10. The liquid composition of claim 6 , wherein the at least one oxidizing agent comprises hydrogen peroxide and the at least one base comprises a species selected from the group consisting of monoethanolamine (MEA), diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, 2-amino-2-methyl-1-propanol, N-(aminoethyl)ethanolamine, N,N-dimethyl-2-aminoethanol, 2-(2-aminoethoxy)ethanol, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), hydroxyamine, trimethylethylammonium hydroxide, diethyldimethylammonium hydroxide, choline hydroxide, tetrabutylphosphonium hydroxide, guanidine acetate, 1,1,3,3-tetramethylguanidine, guanidine carbonate, arginine, and combinations thereof.

11. The liquid composition of claim 6 , wherein the composition further comprises at least one corrosion inhibitor.

12. A method of cleaning a surface of a III-V microelectronic device material, said method comprising contacting the surface with a liquid composition of claim 1 at time and temperature to at least partially clean the device structure comprising the III-V material without substantially removing the III-V material.

13. The method of claim 12 , wherein the III-V microelectronic device material comprises a species selected from the group consisting of InP, InAs, GaAs, AsP, InGaAs, InGaAsP, GaP, GaSb, InSb, AlAs, AlGaAs, InAlAs, InAlGaAs, InAlGaP, and InGaP.

14. The method of claim 12 , wherein residue and contaminants are cleaned from the surface of the III-V microelectronic device material without substantial removal of the III-V material of a substantial change in the stoichiometry of the III-V material.

15. A method of cleaning a surface of a III-V microelectronic device material, said method comprising contacting the surface with a liquid composition of claim 6 at time and temperature to at least partially clean the device structure comprising the III-V material without substantially removing the III-V material.

16. The method of claim 15 , wherein the III-V microelectronic device material comprises a species selected from the group consisting of InP, InAs, GaAs, AsP, InGaAs, InGaAsP, GaP, GaSb, InSb, AlAs, AlGaAs, InAlAs, InAlGaAs, InAlGaP, and InGaP.

17. The method of claim 15 , wherein residue and contaminants are cleaned from the surface of the III-V microelectronic device material without substantial removal of the III-V material of a substantial change in the stoichiometry of the III-V material.

18. The liquid composition of claim 1 , wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, nitric acid, perchloric acid, peracetic acid, and combinations thereof.

19. A liquid composition for cleaning the surface of a III-V microelectronic device material, said composition comprising at least one acid, at least one oxidizing agent, at least one corrosion inhibitor, and water, wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of 5-methyl-benzotriazole, 4-phenyl-1,2,3-triazole, 5-mercapto-4H-[1,2,4]triazol-3-ol, 4-ethyl-5-mercapto-4H-1,2,4-triazol-3-ol, 4-ethyl-4H-1,2,4-triazol-3-thiol, 5-ethyl-4H-1,2,4-triazol-3-thiol, (3-mercapto-5-propyl-4H-1,2,4-triazol-4-yl)acetic acid, 4-(5-sulfanyl-1H-tetraazol-1-yl)benzoic acid, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 2-benzylpyridine, succinimide, adenosine, carbazole, saccharin, benzoin oxime, DL-dithiothreitol (DTT), cystaminum dichloride, di-n-propyldisulfide, ammonium sulfide, ethyl thioglycolate, 2-mercaptoethanol, 1,2-ethanedithiol, cysteine, methionine, dibenzothiophene, S-adenosylmethionine, taurine, glutathione, thiolactic acid, mercaptosuccinic acid, thiosalicylic acid, 4-mercaptobenzoic acid, 2,2′-thiodiacetic acid, 3,3′-thiodipropionic acid, thioglycolic acid, dithiodiglycolic acid, 2,2′-(ethylenedithio)diacetic acid, ethyl 2-mercaptoacetate, 3-methoxybutyl thioglycolate, methyl thioglycolate, dodecylphosphonic acid (DDPA), benzylphosphonic acid, phenylphosphonic acid, and combinations thereof, wherein the pH is in a range from about 0 to about 4.

Assignments (5)
SECURITY INTEREST Recorded Jul 8, 2022
From: ENTEGRIS, INC.; ENTEGRIS GP, INC.; POCO GRAPHITE, INC.; CMC MATERIALS, INC.; INTERNATIONAL TEST SOLUTIONS, LLC; QED TECHNOLOGIES INTERNATIONAL, INC.
To: TRUIST BANK, AS NOTES COLLATERAL AGENT
Reel/Frame 060613/0072 →
ASSIGNMENT OF PATENT SECURITY INTEREST RECORDED AT REEL/FRAME 048811/0679 Recorded Nov 5, 2019
From: GOLDMAN SACHS BANK USA
To: MORGAN STANLEY SENIOR FUNDING, INC.
Reel/Frame 050965/0035 →
SECURITY INTEREST Recorded Nov 13, 2018
From: ENTEGRIS, INC.; SAES PURE GAS, INC.
To: GOLDMAN SACHS BANK USA
Reel/Frame 048811/0679 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 12, 2016
From: COOPER, EMANUEL I.; CHEN, LI-MIN
To: ENTEGRIS, INC.
Reel/Frame 039704/0156 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 12, 2016
From: WU, HSING-CHEN; YANG, MIN-CHIEH; TU, SHENG-HUNG
To: ATMI TAIWAN CO., LTD.
Reel/Frame 039704/0196 →