Anti-reflective coatings using vinyl ether crosslinkers

• US 9,110,372 B2
• Filed: 12/20/2010
• Issued: 08/18/2015
• Est. Priority Date: 04/29/2004
• Status: Active Grant

• Current Assignee: Brewer Science Inc.
• Original Assignee: Brewer Science Inc.
• Inventors: Guerrero, Douglas J., Cox, Robert Christian, Weimer, Marc W.
• Primary Examiner(s): Hamilton, Cynthia
• Application Number:
  US12/973,552
• Publication Number:
  US 20120156613A1
• Time in Patent Office: 1,702 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 43/166 having unsaturation outside the aromatic rings
• CPC Class Codes: G03F 7/039 Macromolecular compounds which are photodegradable, e.g. positive electron resists G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023
• CPC Class Codes: G03F 7/0392 the macromolecular compound being present in a chemically amplified positive photoresist composition
• CPC Class Codes: G03F 7/091 characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• CPC Class Codes: G03F 7/094 Multilayer resist systems, e.g. planarising layers
• CPC Class Codes: G03F 7/11 having cover layers or intermediate layers, e.g. subbing layers G03F7/091 - G03F7/093, B41N3/03 take precedence
• CPC Class Codes: G03F 7/168 Finishing the coated layer, e.g. drying, baking, soaking
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking
• CPC Class Codes: Y10S 438/952 Utilizing antireflective layer
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

Novel, wet developable anti-reflective coating compositions and methods of using those compositions are provided. The compositions comprise a polymer and/or oligomer having acid functional groups and dissolved in a solvent system along with a crosslinker and a photoacid generator. The preferred acid functional group is a carboxylic acid, while the preferred crosslinker is a vinyl ether crosslinker. In use, the compositions are applied to a substrate and thermally crosslinked. Upon exposure to light, the cured compositions will decrosslink, rendering them soluble in typical photoresist developing solutions (e.g., alkaline developers).

Claims

1. A method of forming a microelectronic structure, said method comprising the steps of:

providing a substrate having a surface;

applying a composition to said surface, said composition comprising;

a compound selected from the group consisting of polymers, oligomers, and mixtures thereof, said compound comprising acid groups other than phenolic groups, and having protected acid groups and unprotected acid groups, wherein the molar ratio of protected acid groups to unprotected acid groups is from about 1;

3 to about 3;

1;

a chromophore;

a vinyl ether crosslinker; and

a solvent system, said compound, chromophore, and crosslinker being dissolved or dispersed in said solvent system; and

crosslinking the compound in said composition to yield a crosslinked composition having a k value of about 0.1-0.8 at a wavelength selected from the group consisting of 157 nm, 193 nm, 248 nm, and 365 nm.

2. The method of claim 1, further comprising:

forming a photoresist layer on said crosslinked composition;

exposing said composition to light to yield an exposed portion of said composition; and

contacting said composition with a developer so as to remove said exposed portion from said surface.

3. The method of claim 1, wherein said crosslinking yields crosslinked compounds comprising linkages having the formula

4. The method of claim 2, wherein said exposing step results in the breaking of the bond (*) of the linkage having the formula

5. The method of claim 1, wherein said chromophore is bonded with said compound.

6. The method of claim 1, wherein said chromophore is not bonded with said compound.

7. The method of claim 1, said composition comprising from about 95-99% by weight of said solvent system, based upon the total weight of the composition taken as 100% by weight.

8. The method of claim 1, said composition having a solids content of about 3% by weight, based upon the total weight of the composition taken as 100% by weight.

9. The method of claim 1, wherein said polymers and oligomers are selected from the group consisting of aliphatic polymers, acrylates, methacrylates, polyesters, polycarbonates, novolaks, polyamic acids, isocyanurates, glycidyl ethers, and mixtures thereof.

10. The method of claim 1, wherein said chromophore is selected from the group consisting of naphthalenes, heterocyclic chromophores, carbazoles, anthracenes, substituted and unsubstituted phenyls.

11. The method of claim 1, wherein said chromophore is selected from the group consisting of naphthoic acid methacrylate, 3,7-dihydroxynaphthoic acid, 9-anthracene methyl methacrylate, 9-anthracenecarboxylic acid, furan rings, and thiophene rings.

12. A method of forming a microelectronic structure, said method comprising the steps of:

providing a substrate having a surface;

applying a composition to said surface, said composition comprising;

a compound selected from the group consisting of polymers, oligomers, and mixtures thereof, said compound comprising acid groups, and having protected acid groups and unprotected acid groups, wherein the molar ratio of protected acid groups to unprotected acid groups is from about 1;

3 to about 3;

1;

a chromophore;

a vinyl ether crosslinker; and

from about 95-99% by weight of a solvent system, based upon the total weight of the composition taken as 100% by weight, said compound, chromophore, and crosslinker being dissolved or dispersed in said solvent system; and

crosslinking the compound in said composition to yield a crosslinked composition having a k value of about 0.1-0.8 at a wavelength selected from the group consisting of 157 nm, 193 nm, 248 nm, and 365 nm.

13. A method of forming a microelectronic structure, said method comprising the steps of:

providing a substrate having a surface;

applying a composition to said surface, said composition comprising;

a compound selected from the group consisting of polymers, oligomers, and mixtures thereof, said compound comprising acid groups other than phenolic groups, and having protected acid groups and unprotected acid groups, wherein the molar ratio of protected acid groups to unprotected acid groups is from about 1;

3 to about 3;

1;

from about 20 to about 40% by weight of a chromophore, based upon the total weight of the compound taken as 100% by weight;

a vinyl ether crosslinker; and

a solvent system, said compound, chromophore, and crosslinker being dissolved or dispersed in said solvent system; and

crosslinking the compound in said composition.