IP Library Granted Patent US 11,530,356
Granted Patent B2
US 11,530,356 · App. 17/388,990 · Granted Dec 20, 2022

Compositions and methods for selectively etching silicon nitride films

Inventors: Steven M. Bilodeau (Fairfield, CT); Emanuel I. Cooper (Scarsdale, NY); Daniela White (Ridgefield, CT)
Assignee: ENTEGRIS, INC.
C09K13/06C09K13/08H01L21/0217H01L21/30604H01L21/311H01L21/31105H01L21/31111H01L21/32134
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Quick Facts
Patent No.
US 11,530,356
App. No.
17/388,990
Granted
Dec 20, 2022
Kind
B2
Abstract

Provided are wet etching compositions and methods for etching a surface of a microelectronic device that contains silicon nitride (SiN), silicon oxide, and polysilicon which in one embodiment is in contact with a surface comprising a compound which is electrochemically more noble than silicon, and optionally other materials which may include a conductive material, a semiconducting material, or an insulating material useful in a microelectronic device, or a processing material that is useful in preparing a microelectronic device.

Claims (28)

1. A method of etching silicon nitride on a microelectronic device substrate, said substrate comprising a surface comprising silicon nitride, a surface comprising silicon oxide, and a surface comprising polysilicon, the method comprising:

providing an etching composition comprising:

a. concentrated phosphoric acid, having at least about 80 weight percent phosphoric acid solids in about 20 weight percent water, in an amount of at least 60 weight percent, based on the total weight of the composition;

b. a polysilicon corrosion inhibitor compound chosen from chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids, and C 6 -C 16 alkyldiphenyl oxide disulfonic acids, C 6 -C 16 alkyldiphenyl sulfide disulfonic acids, or C 6 -C 16 alkyldiphenylamine disulfonic acids;

c. an aminoalkyl silanol; and

d. optionally a fluorine compound;

providing a substrate having a surface that comprises silicon nitride and a surface which comprises polysilicon, and

contacting the substrate with the composition under conditions effective to etch silicon nitride.

2. The method of claim 1 , wherein said surface comprising polysilicon is in contact with a surface comprising a composition which is more electrochemically noble than silicon.

3. The method of claim 2 , wherein the surface comprising a composition which is more noble than silicon is chosen from tungsten silicide, nickel silicide, platinum silicide, and titanium silicide.

4. The method of claim 1 , wherein the fluorine compound is present and is chosen from HF, ammonium fluoride, tetrafluoroboric acid, hexafluorosilicic acid, tetrabutylammonium tetrafluoroborate, tetra(C 1 -C 6 alkyl)ammonium fluorides, and combinations thereof.

5. The method of claim 4 , wherein the fluorine compound is HF.

6. The method of claim 5 , wherein the aminoalkyl silanol is formed in situ from an aminoalkoxy silane.

7. The method of claim 1 , wherein the fluorine compound is a fluorosurfactant.

8. The method of claim 1 , wherein the aminoalkyl silanol is chosen from 3-aminopropylsilanetriol, N-(6-aminohexyl)aminopropylsilanol, 3-aminopropyltriethoxide and 3-aminopropyltrimethoxide and (3-trimethoxysilylpropyl) diethylenetriamine.

9. The method of claim 1 , wherein the polysilicon corrosion inhibitor is chosen from linear and branched C 8 -C 16 alkylbenzenesulfonic acids.

10. The method of claim 1 , wherein the polysilicon corrosion inhibitor is chosen from C 6 -C 16 alkyldiphenyl oxide disulfonic acids, C 6 -C 16 alkyldiphenyl sulfide disulfonic acids, and C 6 -C 16 alkyldiphenylamine disulfonic acids.

11. The method of claim 1 , wherein the polysilicon corrosion inhibitor is chosen from hexyl diphenyl oxide disulfonic acid, dodecyl diphenyl oxide disulfonic acid, and dodecylbenzenesulfonic acid.

12. The method of claim 1 , wherein the substrate is contacted with the composition at a temperature of about 130° to about 180° C.

13. The method of claim 1 , wherein the composition is comprised of:

a. concentrated phosphoric acid, in an amount of at least 60 weight percent, based on the total weight of the composition;

b. dodecylbenzenesulfonic acid; and

c. 3-aminopropylsilanetriol.

14. The method of claim 1 , wherein the composition is comprised of

a. concentrated phosphoric acid, in an amount of at least 60 weight percent, based on the total weight of the composition;

b. a C 6 -C 16 alkyldiphenyl oxide disulfonic acid, C 6 -C 16 alkyldiphenyl sulfide disulfonic acid, or C 6 -C 16 alkyldiphenylamine disulfonic acid; and

c. 3-aminopropylsilanetriol.

15. The method of claim 1 , further comprising a fluorine compound.

Assignments (3)
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 →
SECURITY INTEREST Recorded Jul 8, 2022
From: ENTEGRIS, INC.; ENTEGRIS GP, INC.; POCO GRAPHITE, INC.
To: MORGAN STANLEY SENIOR FUNDING, INC., AS COLLATERAL AGENT
Reel/Frame 060614/0980 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 29, 2021
From: BILODEAU, STEVEN M.; WHITE, DANIELA; COOPER, EMANUEL I.
To: ENTEGRIS, INC.
Reel/Frame 057026/0211 →
Continuity (2)
Provisional Application 63058663 · Jul 30, 2020
Related Publication 20220033710A1 · Feb 3, 2022