IP Library Granted Patent US 10,604,678
Granted Patent B1
US 10,604,678 · App. 16/270,725 · Granted Mar 31, 2020

Chemical mechanical polishing of tungsten using a method and composition containing quaternary phosphonium compounds

Inventors: Lin-Chen Ho (Taipei, TW); Wei-Wen Tsai (Taichung, TW); Cheng-Ping Lee (Miaoli County, TW)
Assignee: Rohrn and Haas Electronic Materials CMP Holdings, Inc.
C09G1/02B24B37/044
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Quick Facts
Patent No.
US 10,604,678
App. No.
16/270,725
Granted
Mar 31, 2020
Kind
B1
Abstract

A process and composition are disclosed for polishing tungsten containing select quaternary phosphonium compounds at low concentrations to at least reduce corrosion rate of tungsten. The process and composition include providing a substrate containing tungsten; providing a stable polishing composition, containing, as initial components: water; an oxidizing agent; select quaternary phosphonium compounds at low concentrations to at least reduce corrosion rate; a dicarboxylic acid, a source of iron ions; a colloidal silica abrasive; and, optionally a pH adjusting agent; providing a chemical mechanical polishing pad, having a polishing surface; creating dynamic contact at an interface between the polishing pad and the substrate; and dispensing the polishing composition onto the polishing surface at or near the interface between the polishing pad and the substrate; wherein some of the tungsten is polished away from the substrate, and corrosion rate of tungsten is reduced.

Claims (34)

1. A method of chemical mechanical polishing tungsten, comprising:

providing a substrate comprising tungsten and a dielectric;

providing a chemical mechanical polishing composition, comprising, as initial components:

water;

an oxidizing agent;

a colloidal silica abrasive;

a dicarboxylic acid, salt thereof or mixtures thereof,

a source of iron (III) ions; and,

optionally, a pH adjusting agent;

a quaternary phosphonium compound in amounts of less than 1000 ppm but greater than 0 ppm, wherein the quaternary phosphonium compound has a formula:

wherein R 1 , R 2 , R 3 and R 4 independently comprise hydrogen; linear or branched alkyl; linear or branched hydroxyalkyl; linear or branched alkoxy; linear or branched, aminoalkyl; linear or branched haloalkyl; linear or branched carboxyalkyl; acetonyl; allyl; substituted or unsubstituted aryl; substituted or unsubstituted arylalkyl; substituted or unsubstituted arylalkoxy; phosphoniumalkyl moiety; or a heterocyclic alkyl moiety; with the proviso that R 1 , R 2 , R 3 and R 4 are not all hydrogen at the same instance and not all are butyl at the same instance; and X − is a halide ion or hydroxide ion;

providing a chemical mechanical polishing pad, having a polishing surface;

creating dynamic contact at an interface between the chemical mechanical polishing pad and the substrate; and

dispensing the chemical mechanical polishing composition onto the polishing surface of the chemical mechanical polishing pad at or near the interface between the chemical mechanical polishing pad and the substrate to remove at least some of the tungsten.

2. The method of claim 1 , wherein the chemical mechanical polishing composition provided has a tungsten removal rate of ≥1,000 Å/min with a platen speed of 80 revolutions per minute, a carrier speed of 81 revolutions per minute, a chemical mechanical polishing composition flow rate of 125 mL/min, a nominal down force of 21.4 kPa on a 200 mm polishing machine; and, wherein the chemical mechanical polishing pad comprises a polyurethane polishing layer containing polymeric hollow core microparticles and a polyurethane impregnated non-woven subpad.

3. The method of claim 1 , wherein the chemical mechanical polishing composition, provided comprises, as initial components:

the water;

0.01 to 10 wt % of the oxidizing agent, wherein the oxidizing agent is hydrogen peroxide;

0.01 to 10 wt % of the colloidal silica abrasive;

1 to 1,400 ppm of the dicarboxylic acid, salt thereof or mixtures thereof, wherein the dicarboxylic acid, salt thereof or mixtures thereof is malonic acid, salt thereof or mixtures thereof;

100 to 1,000 ppm of the source of iron (III) ions, wherein the source of iron (III) ions is ferric nitrate nonahydrate; and,

optionally, the pH adjusting agent;

wherein the chemical mechanical polishing composition has a pH of 1 to 7; and,

wherein the quaternary phosphonium compound is in amounts of 5 ppm to 500 ppm and wherein R 1 , R 2 , R 3 and R 4 independently comprise hydrogen; linear or branched (C 1 -C 16 )alkyl; linear or branched hydroxy(C 1 -C 4 )alkyl; linear or branched (C 1 -C 4 )alkoxy; linear or branched, amino(C 1 -C 4 )alkyl; linear or branched halo(C 1 -C 4 )alkyl; linear or branched carboxy(C 1 -C 4 )alkyl; substituted or unsubstituted phenyl; substituted or unsubstituted phenyl(C 1 -C 4 )alkyl; substituted or unsubstituted phenyl(C 1 -C 4 )alkoxy; (C 2 -C 4 )alkylphosphonium moiety; or a heterocyclic(C 1 -C 3 )alkyl moiety; with the proviso that R 1 , R 2 , R 3 , R 4 are not all hydrogen at the same instance and are not all butyl at the same instance; and X − is bromide, chloride or fluoride.

4. The method of claim 3 , wherein the chemical mechanical polishing composition provided has a tungsten removal rate of ≥1,000 Å/min with a platen speed of 80 revolutions per minute, a carrier speed of 81 revolutions per minute, a chemical mechanical polishing composition flow rate of 125 mL/min, a nominal down force of 21.4 kPa on a 200 mm polishing machine; and, wherein the chemical mechanical polishing pad comprises a polyurethane polishing layer containing polymeric hollow core microparticles and a polyurethane impregnated non-woven subpad.

5. The method of claim 1 , wherein the chemical mechanical polishing composition, provided comprises, as initial components:

the water;

1 to 3 wt % of the oxidizing agent, wherein the oxidizing agent is hydrogen peroxide;

0.2 to 4 wt % of the colloidal silica abrasive;

120 to 1,350 ppm of the dicarboxylic acid, wherein the dicarboxylic acid is malonic acid or salt thereof;

250 to 400 ppm of the source of iron (III) ions, wherein the source of iron (III) ions is ferric nitrate nonahydrate; and,

optionally, the pH adjusting agent; and,

wherein the chemical mechanical polishing composition has a pH of 2 to 3; and wherein the quaternary phosphonium compound is in amounts of 10 ppm to 100 ppm, wherein R 1 , R 2 , R 3 and R 4 independently comprise hydrogen; linear or branched (C 4 -C 16 )alkyl; linear or branched hydroxy(C 1 -C 4 )alkyl; linear or branched, amino(C 1 -C 4 )alkyl; linear or branched halo(C 1 -C 4 )alkyl; substituted or unsubstituted phenyl; or substituted or unsubstituted phenyl(C 1 -C 4 )alkyl; with the proviso that R 1 , R 2 , R 3 , R 4 are not all hydrogen at the same instance and are not all butyl at the same instance; and X − is bromide or chloride.

6. The method of claim 5 , wherein the chemical mechanical polishing composition provided has a tungsten removal rate of ≥1,000 Å/min with a platen speed of 80 revolutions per minute, a carrier speed of 81 revolutions per minute, a chemical mechanical polishing composition flow rate of 125 mL/min, a nominal down force of 21.4 kPa on a 200 mm polishing machine; and, wherein the chemical mechanical polishing pad comprises a polyurethane polishing layer containing polymeric hollow core microparticles and a polyurethane impregnated non-woven subpad.

Assignments (4)
SECURITY INTEREST Recorded Nov 3, 2025
From: QNITY ELECTRONICS, INC.
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 073515/0243 →
SECURITY INTEREST Recorded Nov 3, 2025
From: QNITY ELECTRONICS, INC.
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 073517/0298 →
CHANGE OF NAME Recorded Oct 29, 2024
From: ROHM & HAAS ELECTRONIC MATERIALS CMP HOLDINGS INC.
To: DUPONT ELECTRONIC MATERIALS HOLDING, INC.
Reel/Frame 069274/0160 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 8, 2019
From: HO, LIN-CHEN; TSAI, WEI-WEN; LEE, CHENG-PING
To: ROHM AND HAAS ELECTRONIC MATERIALS CMP HOLDINGS, INC.
Reel/Frame 048274/0347 →
Cited By (1)
US 12,291,655