IP Library Granted Patent US 10,032,644
Granted Patent B2
US 10,032,644 · App. 15/166,605 · Granted Jul 24, 2018

Barrier chemical mechanical planarization slurries using ceria-coated silica abrasives

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Quick Facts
Patent No.
US 10,032,644
App. No.
15/166,605
Granted
Jul 24, 2018
Kind
B2
Abstract

Chemical Mechanical Planarization (CMP) polishing compositions comprising composite particles, such as ceria coated silica particles, offer tunable polishing removal selectivity values between different films. Compositions enable high removal rates on interconnect metal and the silicon oxide dielectric while providing a polish stop on low-K dielectrics, a-Si and tungsten films. Chemical Mechanical Planarization (CMP) polishing compositions have shown excellent performance using soft polishing pad.

Claims (75)

1. A polishing composition comprising:

0.01 wt % to 20 wt % of ceria coated silica composite particles and silica abrasive particles and;

0.0001 wt % to 5 wt % of a pH-adjusting agent selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, quaternary organic ammonium hydroxide, nitric acid, sulfonic acid, phosphoric acid, hydrogen chloride, and mixtures thereof;

0.0005 wt % to 0.5 wt % of a corrosion inhibitor selected form the group consisting of benzotriazole, imidazole, triazole and combinations thereof;

a surfactant selected from the group consisting of acetylenic diol surfactant, alcohol ethoxylate surfactant and combination thereof;

potassium silicate; ammonium silicate; and

water;

wherein

the polishing composition has a pH of from about 2 to 11.

2. The polishing composition of claim 1 further comprises at least one of

(1) 0.0010 wt % to about 1.0 wt % of dispersing additive selected form the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, and phosphonic acid group in the same molecule of a copolymer; polyvinyl acid or its salt, polyethylene oxide; polypropylene oxide; and combinations thereof;

(2) 0.001 wt % to 5 wt % of an oxidizer selected from the group consisting of hydrogen peroxide, periodic acid, periodate salt, perbromic acid, perbromate salt, perchloric acid, perchloric salt, perboric acid, and perborate salt, permanganate, bromate, chlorate, chromate, iodate, iodic acid, and combinations thereof; and

(3) 0.001 wt % to 5 wt % of a chelating agent selected from the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, phosphoric acid, and pyridine acid in the same molecule of a copolymer; polyvinyl acid or its salt; inorganic polyethylene oxide; polypropylene oxide; pyridine or its derivative; bipyridine or its derivative; bipyridine or its derivative; and combinations thereof.

3. The polishing composition of claim 1 further comprises a dispersing additive selected from the group consisting of a polymeric acid or its salt, and combinations thereof; wherein the polymeric acid is selected from the group consisting of polyacrylic acid, poly-methacrylic acid, polystyrene sulfonic acid or its salt, and combinations thereof.

4. The polishing composition of claim 1 , wherein the pH-adjusting agent is ammonium hydroxide or potassium hydroxide.

5. The polishing composition of claim 1 , wherein the pH-adjusting agent is ammonium hydroxide or potassium hydroxide; and further comprises hydrogen peroxide.

6. A polishing method for chemical mechanical planarization of a semiconductor device comprising at least one surface having a first material selected from the group consisting of metallic or alloy form of Co, Cu, Al, and combinations, and a second material, comprising the steps of:

a) contacting the at least one surface with a polishing pad;

b) delivering a polishing composition to the at least one surface, the polishing composition comprising:

0.01 wt % to 20 wt % of ceria coated silica composite particles and silica abrasive particles and;

0.0001 wt % to 5 wt % of a pH-adjusting agent selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, quaternary organic ammonium hydroxide, nitric acid, sulfonic acid, phosphoric acid, hydrogen chloride, and mixtures thereof;

0.0005 wt % to 0.5 wt % of a corrosion inhibitor selected form the group consisting of benzotriazole, imidazole, triazole and combinations thereof;

a surfactant selected from the group consisting of acetylenic diol surfactant, alcohol ethoxylate surfactant and combination thereof; potassium silicate; ammonium silicate; and

water;

wherein

the polishing composition has a pH of from about 2 to 11;

and

C) polishing the at least one surface with the polishing composition.

7. The polishing method for of claim 6 , wherein polishing composition further comprises at least one of

(1) 0.0010 wt % to about 1.0 wt % of dispersing additive selected form the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, and phosphonic acid group in the same molecule of a copolymer; polyvinyl acid or its salt, polyethylene oxide; polypropylene oxide; and combinations thereof;

(2) 0.001 wt % to 5 wt % of an oxidizer selected from the group consisting of hydrogen peroxide, periodic acid, periodate salt, perbromic acid, perbromate salt, perchloric acid, perchloric salt, perboric acid, and perborate salt, permanganate, bromate, chlorate, chromate, iodate, iodic acid, and combinations thereof; and

(3) 0.001 wt % to 5 wt % of a chelating agent selected from the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, phosphoric acid, and pyridine acid in the same molecule of a copolymer; polyvinyl acid or its salt; inorganic polyethylene oxide; polypropylene oxide; pyridine or its derivative; bipyridine or its derivative; bipyridine or its derivative; and combinations thereof.

8. The polishing method for of claim 6 , wherein the polishing composition further comprises a dispersing additive selected from the group consisting of a polymeric acid or its salt, and combinations thereof; wherein the polymeric acid is selected from the group consisting of polyacrylic acid, poly-methacrylic acid, polystyrene sulfonic acid or its salt, and combinations thereof.

9. The polishing method for of claim 6 , wherein the pH-adjusting agent is ammonium hydroxide or potassium hydroxide.

10. The polishing method for of claim 6 , wherein the pH-adjusting agent is ammonium hydroxide or potassium hydroxide; and further comprises hydrogen peroxide.

11. The polishing method for of claim 6 , wherein

the polishing pad is a soft pad;

the first material is Co;

the second material is selected from the group consisting of Co, SiN, SiO 2 , W and combinations thereof;

the polishing composition has a pH of 8.0-11;

the polishing composition has removal rate selectivity of 1.0:4.0 to 4.0:1.0 for SiO 2 :Co; and 1.0:1.0 to 6.0:1.0 for Co:SiN; and

wherein the polishing composition has stop on polishing W.

12. The polishing method for of claim 6 , wherein

the polishing pad is a soft pad;

the second material is selected from the group consisting of Co, SiN, SiO 2 , and combinations thereof;

the polishing composition has a pH of 5.0-8.0; and

the polishing composition has removal rate selectivity of 1.0:4.0 to 4.0:1.0 for SiO 2 :Co; and 10:1 to 15:1.0 for Co:SiN.

13. The polishing method for of claim 6 , wherein

the polishing pad is a soft pad;

the first material is Co;

the second material is selected from the group consisting of Co, SiN, SiO 2 , a-Si, Organo Silicate Glass (OSG), silicon oxy carbide (SiOC), W, and combinations thereof;

the polishing composition has a pH of 5.0-9.0; and

the polishing composition has removal rate selectivity of 1.0:4.0 to 4.0:1.0 for SiO 2 :Co; and 10:1 to 15:1.0 for Co:SiN; and

wherein the polishing composition has stop on polishing a-Si, OSG, SiOC, and W.

14. A system for chemical mechanical planarization, comprising:

a semiconductor device comprising at least one surface having a first material selected from the group consisting of metallic or alloy form of Co, Cu, Al, and combinations, and a second material;

a polishing pad; and

a polishing composition comprising:

0.01 wt % to 20 wt % of ceria coated silica composite particles and silica abrasive particles and;

0.0001 wt % to 5 wt % of a pH-adjusting agent selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, quaternary organic ammonium hydroxide, nitric acid, sulfonic acid, phosphoric acid, hydrogen chloride, and mixtures thereof;

0.0005 wt % to 0.5 wt % of a corrosion inhibitor selected form the group consisting of benzotriazole, imidazole, triazole and combinations thereof;

a surfactant selected from the group consisting of acetylenic diol surfactant, alcohol ethoxylate surfactant and combination thereof;

potassium silicate; ammonium silicate; and

water;

wherein

the polishing composition has a pH of from about 2 to 11;

and

wherein the at least one surface is in contact with the polishing pad and the polishing composition.

15. The system of claim 14 , wherein the polishing composition further comprises at least one of

(1) 0.0010 wt % to about 1.0 wt % of dispersing additive selected form the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, and phosphonic acid group in the same molecule of a copolymer; polyvinyl acid or its salt, polyethylene oxide; polypropylene oxide; and combinations thereof;

(2) 0.001 wt % to 5 wt % of an oxidizer selected from the group consisting of hydrogen peroxide, periodic acid, periodate salt, perbromic acid, perbromate salt, perchloric acid, perchloric salt, perboric acid, and perborate salt, permanganate, bromate, chlorate, chromate, iodate, iodic acid, and combinations thereof; and

(3) 0.001 wt % to 5 wt % of a chelating agent selected from the group consisting of organic acid or its salt; polymeric acid or its salt; water soluble copolymer or its salt; copolymer or its salt containing at least two acid groups selected from the group consisting of carboxylic acid group, sulfonic acid group, phosphoric acid, and pyridine acid in the same molecule of a copolymer; polyvinyl acid or its salt; inorganic polyethylene oxide; polypropylene oxide; pyridine or its derivative; bipyridine or its derivative; bipyridine or its derivative; and combinations thereof.

16. The system of claim 15 , wherein the polishing composition further comprises (1) a dispersing additive selected from the group consisting of a polymeric acid or its salt, and combinations thereof; wherein the polymeric acid is selected from the group consisting of polyacrylic acid, poly-methacrylic acid, polystyrene sulfonic acid or its salt, and combinations thereof.

17. The system of claim 14 , wherein the pH adjusting agent is ammonium hydroxide or potassium hydroxide.

18. The system of claim 14 , wherein the pH adjusting agent is ammonium hydroxide or potassium hydroxide; and the polishing composition further comprises hydrogen peroxide.

Assignments (4)
RELEASE OF SECURITY INTEREST Recorded Oct 7, 2019
From: CITIBANK, N.A., AS AGENT
To: VERSUM MATERIALS US, LLC
Reel/Frame 050647/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 20, 2017
From: AIR PRODUCTS AND CHEMICALS, INC.
To: VERSUM MATERIALS US, LLC
Reel/Frame 041772/0733 →
PATENT SECURITY AGREEMENT Recorded Oct 27, 2016
From: VERSUM MATERIALS US, LLC
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 040503/0442 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 15, 2016
From: SHI, XIAOBO; SCHLUETER, JAMES ALLEN; O'NEILL, MARK LEONARD; TAMBOLI, DNYANESH CHANDRAKANT
To: AIR PRODUCTS AND CHEMICALS, INC.
Reel/Frame 038920/0387 →