Post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid

Patent metadata

Field	Value
Publication number	US-9458415-B2
Application number	US-201314376978-A
Country	US
Kind code	B2
Filing date	Jan 24, 2013
Priority date	Feb 6, 2012
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

A post chemical-mechanical-polishing (post-CMP) cleaning composition comprising: (A) at least one compound comprising at least one thiol (—SH), thioether (—SR 1 ) or thiocarbonyl (>C═S) group, wherein R 1 is alkyl, aryl, alkylaryl or arylalkyl, (B) at least one sugar alcohol which contains at least three hydroxyl (—OH) groups and does not comprise any carboxylic acid (—COOH) or carboxylate (—COO—) groups, and (C) an aqueous medium.

First claim

The invention claimed is:

1. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) at least one compound comprising at least one thiol (—SH), thioether —(SR 1 ) or thiocarbonyl (>C═S) group, wherein R 1 is alkyl, aryl, alkylaryl or arylalkyl,
(B) erythritol, threitol, a stereoisomer thereof, or a mixture thereof, and
(C) an aqueous medium; and
(E) at least one surfactant.

2. The composition according to claim 1 , wherein the compound (A) further comprises at least one amino (—NH 2 , —NHR 2 , or —NR 3 R 4 ) group, and wherein
R 1 , R 2 , R 3 and R 4 are, independently from each other, alkyl, aryl, alkylaryl, or arylalkyl.

3. The composition according to claim 2 , wherein the compound (A) is thiourea or a derivative thereof.

4. The composition according to claim 2 , wherein compound (A) is an amino acid comprising at least one thiol (—SH), thioether (—SR 1 ) group, or a derivative thereof,
wherein R 1 is alkyl, aryl, alkylaryl or arylalkyl.

5. The composition according to claim 4 , wherein the compound (A) is cysteine, cystine, glutathione, N-acetylcysteine, or a derivative thereof.

6. The composition according to claim 1 , wherein the composition further comprises
(D) at least one metal chelating agent.

7. The composition according to claim 6 , wherein at least one metal chelating agent (D) s selected from the group consisting of propane-1,2,3-tricarboxylic acid, citric acid, butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid, trimellitic acid, trimesinic acid, pyromellitic acid, mellitic acid and oligomeric and polymeric polycarboxylic acids.

8. The composition according to claim 1 , wherein at least one surfactant (E) is selected from the group consisting of:
(E1) amphiphilic nonionic, water-soluble or water-dispersible surfactants comprising
(e11) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms; and
(e12) at least one hydrophilic group consisting of oxyethylene monomer units;

(E2) amphiphilic nonionic, water-soluble or water-dispersible surfactants comprising
(e21) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms; and
(e22) at least one hydrophilic group selected from the group consisting polyoxyalkylene groups comprising
(e221) oxyethylene monomer units and
(e222) at least one type of substituted oxyalkylene monomer units wherein the substituents are selected from the group consisting of alkyl, cycloalkyl, aryl, alkyl-cycloalkyl, alkyl-aryl, cycloalkyl-aryl and alkyl-cycloalkyl-aryl groups; and
said polyoxyalkylene group of (e22) containing the monomer units (e221) and (e222) in random, alternating, gradient and/or blocklike distribution; and

(E3) amphiphilic nonionic, water-soluble or water-dispersible alkyl polyglucoside surfactants.

9. A method for removing residues and contaminants from the surface of a semiconductor substrate useful for manufacturing microelectronic devices, said method comprising
contacting said substrate with the post-CMP cleaning composition of claim 1 .

10. The method according to claim 9 , wherein the post-CMP cleaning composition has a pH value of from 4 to 8.

11. The method according to claim 9 , wherein the residues and contaminants comprise benzotriazole or a derivative thereof and wherein the surface is a copper-containing surface.

12. The method according to claim 9 , wherein the semiconductor substrate comprises
electrically conductive layers comprises copper,
electrically insulating dielectric layers comprising low-k or ultra-lox dielectric materials, and
barrier layers comprising tantalum, tantalum nitride, titanium nitride, cobalt, nickel, manganese, ruthenium, ruthenium-nitride, ruthenium-carbide, or ruthenium tungsten nitride.

13. A method for manufacturing microelectronic devices from semiconductor substrates, said method comprising
contacting the semiconductor substrate with the post-CMP cleaning composition of claim 1 to remove residues and contaminants from the surface of the substrate.

14. The method according to claim 13 , wherein the cleaning composition has a pH value of from 4 to 8.

15. The method according to claim 13 , wherein the residues and contaminants comprise benzotriazole or a derivative thereof and wherein the surface is a copper-containing surface.

16. The method according to claim 13 , wherein the semiconductor substrate comprises
electrically conductive layers comprising copper,
electrically insulating dielectric layers comprising low-k or ultra-low-k dielectric materials, and
barrier layers comprising tantalum, tantalum nitride, titanium nitride, cobalt, nickel, manganese, ruthenium, ruthenium-nitride, ruthenium-carbide, or ruthenium tungsten nitride.

17. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid, and
(C) an aqueous medium,
wherein (L) is an oligomeric or polymeric polycarboxylic acid comprising acrylic acid monomeric units.

18. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid, and
(C) an aqueous medium,
wherein (L) is an oligomeric or polymeric polycarboxylic acid having at least 20 carboxylic acid groups.

19. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid, and
(C) an aqueous medium,
wherein the weight average molecular weight of the oligomeric or polymeric polycarboxylic acid (L) is more than 2,000 Dalton as determined by gel permeation chromatography.

20. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid, and
(C) an aqueous medium,
wherein (L) is an oligomeric or polymeric polycarboxylic acid which is a copolymer comprising
(i) acrylic acid monomeric units, and
(ii) monomeric units derived from fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid or maleic anhydride.

21. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid, and
(C) an aqueous medium,
wherein (L) is an oligomeric or polymeric polycarboxylic acid which is a maleic acid/acrylic acid copolymer.

22. A post chemical-mechanical-polishing (post-CMP) cleaning composition, comprising:
(A) cysteine, glutathione, N-acetylcysteine, thiourea or a derivative thereof
(L) at least one oligomeric or polymeric polycarboxylic acid,
(C) an aqueous medium, and
(E) at least one surfactant (E) selected from the group consisting of:
(E1) amphiphilic nonionic, water-soluble or water-dispersible surfactants comprising
(e11) at least one hydrophobic group selected from the group consisting of branched alkyl groups having 5 to 20 carbon atoms; and
(e12) at least one hydrophilic g

Assignees

• Basf Se

Inventors

• Li Yuzhuo
• Venkataraman Shyam Sundar
• Zhong Mingjie

Classifications

• H10P70/277 Primary

  the processing being a planarisation of conductive layers · CPC title

• C11D3/2082

  Polycarboxylic acids-salts thereof · CPC title

• C11D3/3765

  in liquid compositions · CPC title

• C11D3/349

  additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea · CPC title

• C11D3/3427 Primary

  containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales · CPC title