IP Library Granted Patent US 9,299,573
Granted Patent B2
US 9,299,573 · App. 14/384,729 · Granted Mar 29, 2016

Polishing method

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Quick Facts
Patent No.
US 9,299,573
App. No.
14/384,729
Granted
Mar 29, 2016
Kind
B2
Abstract

Provided is a polishing method that polishes a substrate having (1) silicon nitride as a stopper, and, on the stopper, (2) at least a portion of a wiring metal, and (3) at least a portion of an insulating material. The method includes a step of supplying a CMP slurry, and thereby polishing the (2) wiring metal and (3) insulating material. The CMP slurry contains (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent and (b) a monomer containing a hydrophobic substituent; (B) an abrasive grain; (C) an acid; (D) an oxidizing agent; and (E) a liquid medium, the component (B) has a zeta potential of +10 mV or more in the CMP slurry, and the copolymerization ratio (a):(b) of the component (A) is 25:75 to 75:25 as a molar ratio, with the pH being 5.0 or less.

Claims (54)

1. A polishing method comprising the steps of:

preparing a substrate which has silicon nitride as a stopper, a wiring metal and an insulating material, and has at least a portion of the wiring metal and at least a portion of the insulating material parallel to a direction of a surface subjected to polishing;

supplying a CMP slurry in between the surface subjected to polishing and a polishing pad, and thereby polishing the wiring metal and the insulating material that are positioned parallel to the direction of the surface subjected to polishing; and

stopping polishing, after the silicon nitride is exposed and before the silicon nitride is completely removed,

wherein the CMP slurry contains:

(A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer containing a hydrophobic substituent;

(B) an abrasive grain comprising silica or modification products of the silica;

(C) an acid;

(D) an oxidizing agent; and

(E) a liquid medium,

the component (B) has a zeta potential of +10 mV or more in the CMP slurry,

the component (A) has a copolymerization ratio between (a) and (b), wherein ((a):(b)) is 25:75 to 75:25 as a molar ratio, and

a pH is 5.0 or less.

2. The polishing method according to claim 1 , wherein the CMP slurry has a ratio of the polishing rate for the insulating material with respect to the polishing rate for the silicon nitride (polishing rate for insulating material/polishing rate for silicon nitride) of 20 or more.

3. The polishing method according to claim 1 , wherein the (a) monomer that is anionic and does not contain a hydrophobic substituent is at least one selected from the group consisting of acrylic acid and maleic acid.

4. The polishing method according to claim 1 , wherein the (b) monomer containing a hydrophobic substituent is at least one selected from the group consisting of methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-butylacrylic acid.

5. The polishing method according to claim 1 , wherein the component (A) is a copolymer of acrylic acid and methacrylic acid.

6. The polishing method according to claim 1 , wherein the component (C) is an organic acid.

7. The polishing method according to claim 1 , wherein the CMP slurry further contains a metal corrosion inhibitor as a component (F).

8. The polishing method according to claim 1 , wherein the component (A) has a copolymerization ratio between (a) and (b) such that sedimentation of the abrasive grain is prevented.

9. The polishing method according to claim 1 , wherein the anionic monomer (a) has an anionic substituent selected from the group consisting of a hydroxyl group, an aldehyde group, a carbonyl group, a carboxyl group, a nitro group, a sulfone group and a phosphone group.

10. The polishing method according to claim 1 , wherein the zeta potential of the component (B) in the CMP slurry is less than +35 mV.

11. The polishing method according to claim 1 , wherein said pH is at least 1.0.

12. A polishing method comprising the steps of:

preparing a substrate which has silicon nitride as a stopper, a wiring metal, a barrier metal and an insulating material, and has at least a portion of the wiring metal, at least a portion of the barrier metal, and at least a portion of the insulating material parallel to a direction of a surface subjected to polishing;

supplying a CMP slurry in between the surface subjected to polishing and a polishing pad, and thereby polishing the wiring metal, the barrier metal and the insulating material that are positioned parallel to the direction of the surface subjected to polishing; and

stopping polishing, after the silicon nitride is exposed and before the silicon nitride is completely removed,

wherein the CMP slurry contains:

(A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer containing a hydrophobic substituent;

(B) an abrasive grain comprising silica or modification products of the silica;

(C) an acid;

(D) an oxidizing agent; and

(E) a liquid medium,

the component (B) has a zeta potential of +10 mV or more in the CMP slurry,

the component (A) has a copolymerization ratio between (a) and (b), wherein ((a):(b)) is 25:75 to 75:25 as a molar ratio, and

a pH is 5.0 or less.

13. The polishing method according to claim 12 , wherein the (a) monomer that is anionic and does not contain a hydrophobic substituent is at least one selected from the group consisting of acrylic acid and maleic acid.

14. The polishing method according to claim 12 , wherein the (b) monomer containing a hydrophobic substituent is at least one selected from the group consisting of methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylacrylic acid, 2-propylacrylic acid, and 2-butylacrylic acid.

15. The polishing method according to claim 12 , wherein the component (A) is a copolymer of acrylic acid and methacrylic acid.

16. The polishing method according to claim 12 , wherein the CMP slurry further contains a metal corrosion inhibitor as a component (F).

17. A polishing method comprising the steps of:

preparing a substrate which has silicon nitride as a stopper, a wiring metal, a barrier metal, and an insulating material, has at least a portion of the wiring metal, at least a portion of the barrier metal, and at least a portion of the insulating material to parallel to a direction of a surface subjected to polishing, and has a section in which the silicon nitride, the insulating material, the barrier metal, and the wiring metal are laminated in this order perpendicular to the direction of the surface subjected to polishing;

a first polishing step of removing at least a portion of the wiring metal positioned parallel to the direction of the surface subjected to polishing, and thereby exposing a portion of the barrier metal; and

a second polishing step of removing by CMP at least a portion of the barrier metal and a portion of the insulating material that are positioned parallel to the direction of the surface subjected to polishing, thereby exposing the silicon nitride, and stopping polishing before the silicon nitride is completely removed,

at least the second polishing step including supplying a CMP slurry in between the surface subjected to polishing of the substrate and a polishing pad,

wherein the CMP slurry contains:

(A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer containing a hydrophobic substituent;

(B) an abrasive grain comprising silica or modification products of the silica;

(C) an acid;

(D) an oxidizing agent; and

(E) a liquid medium,

the component (B) has a zeta potential of +10 mV or more in the CMP slurry,

the component (A) has a copolymerization ratio between (a) and (b), wherein ((a):(b)) is 25:75 to 75:25 as a molar ratio, and

a pH is 5.0 or less.

Assignments (4)
CHANGE OF ADDRESS Recorded Feb 14, 2024
From: RESONAC CORPORATION
To: RESONAC CORPORATION
Reel/Frame 066599/0037 →
CHANGE OF NAME Recorded Mar 3, 2023
From: SHOWA DENKO MATERIALS CO., LTD.
To: RESONAC CORPORATION
Reel/Frame 062946/0125 →
CHANGE OF NAME Recorded Mar 2, 2023
From: HITACHI CHEMICAL COMPANY, LTD.
To: SHOWA DENKO MATERIALS CO., LTD.
Reel/Frame 062917/0865 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 12, 2014
From: MISHIMA, KOUJI; FUKASAWA, MASATO; NISHIYAMA, MASAYA
To: HITACHI CHEMICAL COMPANY, LTD.
Reel/Frame 033727/0429 →