POLISHING COMPOSITION CONTAINING CERIA ABRASIVE

• US 20160257856A1
• Filed: 03/05/2015
• Published: 09/08/2016
• Est. Priority Date: 03/05/2015
• Status: Active Grant

• Current Assignee: CMC Materials LLC (Fujifilm Holdings Corporation)
• Original Assignee: Cabot Microelectronics Corporation (Entegris Incorporated)
• Inventors: SAUTER VAN NESS, Dana, HAINS, Alexander, REISS, Brian, LAM, Viet, KRAFT, Steven, JIA, Renhe
• Granted Patent: US 9,505,952 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B24B 1/00 Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
• CPC Class Codes: B24B 37/044 characterised by the composition of the lapping agent
• CPC Class Codes: B24B 37/20 Lapping pads for working plane surfaces
• CPC Class Codes: C09G 1/00 Polishing compositions French polish C09F11/00; detergents C11D
• CPC Class Codes: C09G 1/02 containing abrasives or grinding agents abrasives as such C09K3/14; polishing of semi-conductors H01L
• CPC Class Codes: C09G 1/04 Aqueous dispersions C09G1/02 takes precedence
• CPC Class Codes: C09G 1/06 Other polishing compositions
• CPC Class Codes: C09K 13/06 with organic material
• CPC Class Codes: C09K 3/1409 Abrasive particles per se preparation of diamond C01B32/25
• CPC Class Codes: C09K 3/1454 Abrasive powders, suspensions and pastes for polishing
• CPC Class Codes: C09K 3/1463 Aqueous liquid suspensions
• CPC Class Codes: H01L 21/30625 With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
• CPC Class Codes: H01L 21/31053 involving a dielectric removal step
• CPC Class Codes: H01L 21/3212 by chemical mechanical polishing [CMP]

Abstract

The invention provides a chemical-mechanical polishing composition including first abrasive particles, wherein the first abrasive particles are wet-process ceria particles, have a median particle size of about 40 nm to about 100 nm, are present in the polishing composition at a concentration of about 0.005 wt. % to about 2 wt. %, and have a particle size distribution of at least about 300 nm, a functionalized heterocycle, a pH-adjusting agent, and an aqueous carrier, and wherein the pH of the polishing composition is about 1 to about 6. The invention also provides a method of polishing a substrate, especially a substrate comprising a silicon oxide layer, with the polishing composition.

Claims

1. A chemical-mechanical polishing composition comprising:

(a) first abrasive particles, wherein the first abrasive particles are wet-process ceria particles, have a median particle size of about 40 nm to about 100 nm, are present in the polishing composition at a concentration of about 0.005 wt. % to about 2 wt. %, and have a particle size distribution of at least about 300 nm, wherein the first abrasive particles have a surface that comprises tridentate hydroxyl groups, and wherein the first abrasive particles have a surface coverage of tridentate hydroxyl groups that is about 2.0×

10<sup>−

5</sup> moles/m² or more,

(b) a functionalized heterocycle selected from a functionalized nitrogen-containing heterocycle, a functionalized sulfur-containing heterocycle, a naphthoic acid, and combinations thereof, wherein the functionalized heterocycle is present in the polishing composition at a concentration of about 100 ppm to about 1500 ppm,

(c) a pH-adjusting agent, and

(d) an aqueous carrier,

wherein the pH of the polishing composition is about 1 to about 6.

3. The chemical-mechanical polishing composition of claim 1, wherein a Raman spectrum of the first abrasive particles comprises a peak at about 458 cm⁻

1 and a peak at about 583 cm<sup>−

1</sup>, and wherein the ratio of the intensity of the peak at about 458 cm<sup>−

1</sup> to the intensity of the peak at about 583 cm<sup>−

1</sup> is about 100 or less.

4. The chemical-mechanical polishing composition of claim 1, wherein the first abrasive particles are present in the polishing composition at a concentration of about 0.1 wt. % to about 0.5 wt. %.

5. The chemical-mechanical polishing composition of claim 1, wherein the functionalized heterocycle comprises a functionalized nitrogen-containing heterocycle selected from picolinic acid, quinaldic acid, and combinations thereof.

6. The chemical-mechanical polishing composition of claim 1, wherein the pH-adjusting agent is selected from an alkyl amine, an alcohol amine, a quaternary amine hydroxide, ammonia, and combinations thereof.

7. The chemical-mechanical polishing composition of claim 6, wherein the pH-adjusting agent is triethanolamine.

8. The chemical-mechanical polishing composition of claim 1, wherein the pH of the polishing composition is about 3.5 to about 5.

9. The chemical-mechanical polishing composition of claim 1, wherein the polishing composition further comprises an additive selected from

an anionic copolymer of a carboxylic acid monomer, a sulfonated monomer, or a phosphonated monomer, and an acrylate, a polyvinylpyrrolidone, or a polyvinylalcohol,

a nonionic polymer, wherein the nonionic polymer is polyvinylpyrrolidone or polyethylene glycol,

a silane, wherein the silane is an amino silane, an ureido silane, or a glycidyl silane,

an N-oxide of a functionalized pyridine,

a starch,

a cyclodextrin, and

combinations thereof,

wherein the additive is present in the chemical-mechanical polishing composition at a concentration of about 25 ppm to about 500 ppm.

10. The chemical-mechanical polishing composition of claim 9, wherein the additive is selected from a copolymer of 2-hydroxyethylmethacrylic acid and methacrylic acid, polyvinylpyrrolidone, aminopropylsilanetriol, picolinic acid N-oxide, starch, alpha-cyclodextrin, beta-cyclodextrin, and combinations thereof.

11. The chemical-mechanical polishing composition of claim 1, wherein the polishing composition further comprises:

a cationic polymer, wherein the cationic polymer is a quaternary amine, and wherein the cationic polymer is present in the polishing composition at a concentration of about 1 ppm to about 250 ppm, and

a carboxylic acid, wherein the pKa of the carboxylic acid is about 1 to about 6, and wherein the carboxylic acid is present in the polishing composition at a concentration of about 25 ppm to about 500 ppm,

wherein the pH of the polishing composition is within about 2 units of the pKa of the carboxylic acid.

12. The chemical-mechanical polishing composition of claim 11, wherein the cationic polymer is poly(vinylimidazolium).

13. The chemical-mechanical polishing composition of claim 11, wherein the pKa of the carboxylic acid is about 3.5 to about 5.

14. The chemical-mechanical polishing composition of claim 11, wherein the carboxylic acid is acetic acid.

15. The chemical-mechanical polishing composition of claim 1, wherein the polishing composition further comprises a cationic polymer selected from a cationic polyvinyl alcohol and a cationic cellulose, and wherein the cationic polymer is present in the polishing composition at a concentration of about 1 ppm to about 250 ppm.

16. A method of polishing a substrate comprising:

(i) providing a substrate;

(ii) providing a polishing pad;

(iii) providing the chemical-mechanical polishing composition of claim 1;

(iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition; and

(v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to abrade at least a portion of the substrate to polish the substrate.

2. (canceled)

17. A method of polishing a substrate comprising:

(i) providing a substrate, wherein the substrate comprises a silicon oxide layer;

(ii) providing a polishing pad;

(iii) providing a chemical-mechanical polishing composition comprising;

(a) first abrasive particles, wherein the first abrasive particles are wet-process ceria particles, have a median particle size of about 40 nm to about 100 nm, are present in the polishing composition at a concentration of about 0.005 wt. % to about 2 wt. %, and have a particle size distribution of at least about 300 nm,

(b) a functionalized heterocycle selected from a functionalized nitrogen-containing heterocycle, a functionalized sulfur-containing heterocycle, a naphthoic acid, and combinations thereof, wherein the functionalized heterocycle is present in the polishing composition at a concentration of about 100 ppm to about 1500 ppm,

(c) a pH-adjusting agent, and

(d) an aqueous carrier,

wherein the pH of the polishing composition is about 1 to about 6;

(iv) contacting the substrate with the polishing pad and the chemical-mechanical polishing composition; and

(v) moving the polishing pad and the chemical-mechanical polishing composition relative to the substrate to abrade at least a portion of the silicon oxide layer on a surface of the substrate to polish the substrate.

18. The method of claim 17, wherein the first abrasive particles have a surface that comprises tridentate hydroxyl groups, and wherein the first abrasive particles have a surface coverage of tridentate hydroxyl groups that is about 2.0×

10<sup>−

5</sup> moles/m² or more.

19. The method of claim 17, wherein a Raman spectrum of the first abrasive particles comprises a peak at about 458 cm⁻

1 and a peak at about 583 cm<sup>−

1</sup>, and wherein the ratio of the intensity of the peak at about 458 cm<sup>−

1</sup> to the intensity of the peak at about 583 cm<sup>−

1</sup> is about 100 or less.

20. The method of claim 17, wherein the first abrasive particles are present in the polishing composition at a concentration of about 0.1 wt. % to about 0.5 wt. %.

21. The method of claim 17, wherein the functionalized heterocycle comprises a functionalized nitrogen-containing heterocycle selected from picolinic acid, quinaldic acid, and combinations thereof.

22. The method of claim 17, wherein the pH-adjusting agent is selected from an alkyl amine, an alcohol amine, a quaternary amine hydroxide, ammonia, and combinations thereof.

23. The method of claim 22, wherein the pH-adjusting agent is triethanolamine.

24. The method of claim 17, wherein the pH of the polishing composition is about 3.5 to about 5.

25. The method of claim 17, wherein the polishing composition further comprises an additive selected from

an anionic copolymer of a carboxylic acid monomer, a sulfonated monomer, or a phosphonated monomer, and an acrylate, a polyvinylpyrrolidone, or a polyvinylalcohol,

a nonionic polymer, wherein the nonionic polymer is polyvinylpyrrolidone or polyethylene glycol,

a silane, wherein the silane is an amino silane, an ureido silane, or a glycidyl silane, an N-oxide of a functionalized pyridine,

a starch,

a cyclodextrin, and

combinations thereof,

wherein the additive is present in the chemical-mechanical polishing composition at a concentration of about 25 ppm to about 500 ppm.

26. The method of claim 25, wherein the additive is selected from a copolymer of 2-hydroxyethylmethacrylic acid and methacrylic acid, polyvinylpyrrolidone, aminopropylsilanetriol, picolinic acid N-oxide, starch, alpha-cyclodextrin, beta-cyclodextrin, and combinations thereof.

27. The method of claim 17, wherein the polishing composition further comprises:

a cationic polymer, wherein the cationic polymer is a quaternary amine, and wherein the cationic polymer is present in the polishing composition at a concentration of about 1 ppm to about 250 ppm, and

a carboxylic acid, wherein the pKa of the carboxylic acid is about 1 to about 6, and wherein the carboxylic acid is present in the polishing composition at a concentration of about 25 ppm to about 500 ppm,

wherein the pH of the polishing composition is within about 2 units of the pKa of the carboxylic acid.

28. The method of claim 27, wherein the cationic polymer is poly(vinylimidazolium).

29. The method of claim 27, wherein the pKa of the carboxylic acid is about 3.5 to about 5.

30. The method of claim 29, wherein the carboxylic acid is acetic acid.

31. The method of claim 17, wherein the polishing composition further comprises a cationic polymer selected from a cationic polyvinyl alcohol and a cationic cellulose, wherein the cationic polymer is present in the polishing composition at a concentration of about 1 ppm to about 250 ppm.