IP Library Granted Patent US 10,446,389
Granted Patent B2
US 10,446,389 · App. 15/669,238 · Granted Oct 15, 2019

Formulations for the removal of particles generated by cerium-containing solutions

Inventors: Emanuel I. Cooper (Scarsdale, NY); Jeffery A. Barnes (Bethlehem, CT)
Assignee: ENTEGRIS, INC.
H01L21/02076H01L21/02057H01L21/31133
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 10,446,389
App. No.
15/669,238
Granted
Oct 15, 2019
Kind
B2
Abstract

Compositions and methods for removing lanthanoid-containing solids and/or species from the surface of a microelectronic device or microelectronic device fabrication hardware. Preferably, the lanthanoid-containing solids and/or species comprise cerium. The composition is preferably substantially devoid of fluoride ions.

Claims (24)

1. An aqueous composition comprising:

an acid having a pKa of less than 4, wherein the acid is a strong acid having a pKa of less than 1.5 selected from the group consisting of nitric acid, sulfuric acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, methanesulfonic acid, and combinations thereof, and is present in an amount ranging from 0.1 to 15 wt. % based on the total weight of the composition;

a reducing agent, wherein the reducing agent is present in an amount ranging from 0.1 to 10 wt. % based on the total weight of the composition;

a salt of the strong acid; and

at least 65 wt. % water, the composition substantially devoid of fluoride ions, wherein when in contact with a surface of a microelectronic device including metal gate material and having lanthanoid-containing solids present thereon, the composition dissolves at least some of the lanthanoid-containing solids without substantially removing metal gate material present on the substrate.

2. The aqueous composition of claim 1 , wherein the strong acid is nitric acid, sulfuric acid, or a combination of nitric acid and sulfuric acid.

3. The aqueous composition of claim 1 , wherein the acid is present in an amount ranging from 0.1 to 5 wt. % based on the total weight of the composition.

4. An aqueous composition comprising:

an acid having a pKa of less than 4, wherein the acid is present in an amount ranging from 0.1 to 15 wt. % based on the total weight of the composition;

a reducing agent, wherein the reducing agent is present in an amount ranging from 0.1 to 10 wt. % based on the total weight of the composition; and

at least 65 wt. % water,

wherein the acid is a weak acid having a pKa in a range from about 1.5 to about 4, wherein the weak acid is selected from the group consisting of nitrous acid, phosphorous acid, cyanic acid, formic acid, glyceric acid, glycolic acid, lactic acid, pyruvic acid, mandelic acid, succinic acid, malonic acid, and combinations thereof, and

wherein when in contact with a surface of a microelectronic device having lanthanoid-containing solids present thereon, the composition dissolves at least some of the lanthanoid-containing solids.

5. The aqueous composition of claim 4 , wherein the weak acid is formic acid.

6. The aqueous composition of claim 1 , wherein the reducing agent is present in an amount ranging from 0.1 to 5 wt. % based on the total weight of the composition.

7. The aqueous composition of claim 1 , wherein the reducing agent is selected from the group consisting of ascorbic acid, borane-pyridine, borane-morpholine, hydroxylamine sulfate, hydroxylamine hydrochloride, ammonium nitrite, ammonium sulfite, ammonium hydrogen sulfite, hydrazine sulfate, hydrazine hydrochloride, ammonium hydrogen sulfide, diethyl malonate, hydroquinone, ammonium metabisulfite, polyphenon 60, glucose, ammonium citrate, hydrogen, formic acid, oxalic acid, acetaldehyde, hydrogen iodide, ammonium phosphite, ammonium hydrogen phosphite, hypophosphorous acid, and combinations thereof.

8. The aqueous composition of claim 1 , wherein the reducing agent is ascorbic acid.

9. The aqueous composition of claim 1 , wherein the reducing agent is polyphenon 60.

10. The aqueous composition of claim 1 , wherein the lanthanoid-containing solids comprises cerium-containing solids, and wherein when in contact with the surface of a microelectronic device having cerium-containing solids present thereon, the composition dissolves at least some of the cerium-containing solids.

11. The aqueous composition of claim 4 , wherein the reducing agent is present in an amount ranging from 0.1 to 5 wt. % based on the total weight of the composition.

12. The aqueous composition of claim 4 , wherein the reducing agent is selected from the group consisting of ascorbic acid, borane-pyridine, borane-morpholine, hydroxylamine sulfate, hydroxylamine hydrochloride, ammonium nitrite, ammonium sulfite, ammonium hydrogen sulfite, hydrazine sulfate, hydrazine hydrochloride, ammonium hydrogen sulfide, diethyl malonate, hydroquinone, ammonium metabisulfite, polyphenon 60, glucose, ammonium citrate, hydrogen, formic acid, oxalic acid, acetaldehyde, hydrogen iodide, ammonium phosphite, ammonium hydrogen phosphite, hypophosphorous acid, and combinations thereof.

13. The aqueous composition of claim 4 , wherein the reducing agent is ascorbic acid.

14. The aqueous composition of claim 4 , wherein the reducing agent is polyphenon 60.

15. The aqueous composition of claim 4 , wherein the lanthanoid-containing solids comprises cerium-containing solids, and wherein when in contact with the surface of a microelectronic device having cerium-containing solids present thereon, the composition dissolves at least some of the cerium-containing solids.

Assignments (6)
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 Oct 19, 2018
From: COOPER, EMANUEL I.; BARNES, JEFFREY A.
To: ENTEGRIS, INC.
Reel/Frame 047233/0701 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 19, 2018
From: COOPER, EMANUEL I.; BARNES, JEFFREY A.
To: ADVANCED TECHNOLOGY MATERIALS, INC.
Reel/Frame 047233/0713 →
MERGER Recorded Oct 19, 2018
From: ADVANCED TECHNOLOGY MATERIALS, INC.
To: ENTEGRIS, INC.
Reel/Frame 047233/0785 →
Continuity (3)
Continuation 13978825
Provisional Application 61432370 · Jan 13, 2011
Related Publication 20170338104A1 · Nov 23, 2017
Cited By (1)
US 12,675,044