IP Library Granted Patent US 10,373,842
Granted Patent B2
US 10,373,842 · App. 14/947,711 · Granted Aug 6, 2019

Composition and method used for chemical mechanical planarization of metals

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Quick Facts
Patent No.
US 10,373,842
App. No.
14/947,711
Granted
Aug 6, 2019
Kind
B2
Abstract

Compositions for use in CMP processing and methods of CMP processing. The composition utilizes low levels of particulate material, in combination with at least one amino acid, at least one oxidizer, and water to remove a metal layer such as one containing copper to a stop layer with high selectivity.

Claims (48)

1. A composition for use in removing copper from a surface of a wafer containing the copper laying above a stop layer consisting essentially of:

1) an oxidizing agent;

2) about 0.05% to about 5% by weight an amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof;

3) about 5 ppm to less than 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof;

4) at least one corrosion inhibitor; and

5) water;

wherein

the particulate material has a particle size in the range of about 4 nm to about 10,000 nm; and

the composition facilitates removal of copper from the wafer surface while maintaining a rate of removal of copper to stop layer of at least 50:1.

2. The composition of claim 1 wherein the oxidizing agent is hydrogen peroxide and the amino acid is aminoacetic acid.

3. The composition of claim 1 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof.

4. The composition of claim 1 having a pH in a range between about 3.5 and about 9.

5. The composition of claim 1 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm.

6. The composition of claim 1 , wherein the corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; I-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof.

7. The composition of claim 6 wherein the oxidizing agent is hydrogen peroxide; the amino acid is aminoacetic acid; and the corrosion inhibitor is 1,2,4-triazole.

8. A composition for use in removing copper from a surface of a wafer containing the copper laying above a stop layer consisting of:

hydrogen peroxide;

about 0.05% to about 5% by weight at least one amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof;

about 5 ppm to about 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof;

about 0.05% to about 5% by weight a corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; l-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof; and

water;

wherein the particulate material has a particle size in the range of about 4 nm to about 1000 nm;

the composition has a pH in a range between about 3.5 and about 9; and

the composition facilitates removal of the copper from the wafer surface while maintaining a rate of removal of copper to stop layer of at least 50:1.

9. The composition of claim 8 wherein the amino acid is aminoacetic acid.

10. The composition of claim 8 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof.

11. The composition of claim 8 wherein the composition maintains a rate of removal of copper to stop layer of at least 100:1.

12. The composition of claim 8 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm.

13. The composition of claim 8 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 100 ppm.

14. The composition of claim 8 wherein the particulate material has a particle size in the range of about 4 nm to about 400 nm.

15. A chemical mechanical planarization (CMP) system for polishing a wafer, comprising

1) the wafer having at least one surface comprising copper laying above a stop layer;

2) a polishing pad;

3) a CMP composition consisting essentially of:

a) an oxidizing agent;

b) about 0.05% to about 5% by weight at least one amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof;

c) about 5 ppm to about 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof;

d) about 0.05% to about 5% by weight a corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; l-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof; and

e) water;

wherein the particulate material has a particle size in the range of about 4 nm to about 1000 nm;

the composition has a pH in a range between about 3.5 and about 9; and

the composition facilitates removal of the copper from the surface of the wafer while maintaining a rate of removal of copper to stop layer of at least 50:1;

wherein the copper is in contact with the polishing pad and the CMP composition; and the CMP composition facilitates removal of copper while maintaining a rate of removal of copper to stop layer of at least 50:1.

16. The system of claim 15 wherein the oxidizing agent is hydrogen peroxide and the amino acid is aminoacetic acid.

17. The system of claim 15 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof.

18. The system of claim 15 having a pH in a range between about 3.5 and about 9.

19. The system of claim 15 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm.

20. The composition of claim 15 wherein the oxidizing agent is hydrogen peroxide; the amino acid is aminoacetic acid; and the corrosion inhibitor is 1,2,4-triazole.

Assignments (3)
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 →