Hydroxy-amino thermally cured undercoat for 193 nm lithography

• US 20020007018A1
• Filed: 07/09/2001
• Published: 01/17/2002
• Est. Priority Date: 03/12/1999
• Status: Active Grant

• Current Assignee: Arch Specialty Chemicals, Inc.
• Original Assignee: Arch Specialty Chemicals, Inc.
• Inventors: Foster, Patrick, Blakeney, Andrew J., Steinhausler, Thomas, Biafore, John Joseph, Slater, Sydney George
• Granted Patent: US 6,783,916 B2
• Time in Patent Office: Days
• US Class Current: 525/328.8
• CPC Class Codes: B41C 1/1008 by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
• CPC Class Codes: B41C 1/1016 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
• CPC Class Codes: B41C 2201/04 Intermediate layers
• CPC Class Codes: B41C 2201/14 characterised by macromolecular organic compounds, e.g. binder, adhesives
• CPC Class Codes: B41C 2210/02 Positive working, i.e. the exposed (imaged) areas are removed
• CPC Class Codes: B41C 2210/06 Developable by an alkaline solution
• CPC Class Codes: B41C 2210/24 characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
• CPC Class Codes: B41N 1/08 for lithographic printing B41N1/003, B41N3/03 take precedence; compositions of the image-forming layer B41C1/10
• CPC Class Codes: B41N 1/14 Lithographic printing foils B41N1/003, B41N3/03 take precedence; compositions of the image-forming layer B41C1/10
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 212/24 Phenols or alcohols
• CPC Class Codes: C08F 216/18 Acyclic compounds
• CPC Class Codes: C08F 220/18 with acrylic or methacrylic acids
• CPC Class Codes: C08F 4/04 Azo-compounds
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C08K 5/34922 Melamine; Derivatives thereof
• CPC Class Codes: C08K 5/42 Sulfonic acids; Derivatives thereof
• CPC Class Codes: C08L 25/08 Copolymers of styrene C08L29/08, C08L35/06, C08L55/02 take precedence
• CPC Class Codes: C08L 57/10 containing oxygen atoms
• CPC Class Codes: C09D 125/08 Copolymers of styrene C09D129/08, C09D135/06, C09D155/02 take precedence
• CPC Class Codes: C09D 125/18 : Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• CPC Class Codes: G03F 7/0392 : the macromolecular compound being present in a chemically amplified positive photoresist composition
• CPC Class Codes: G03F 7/0758 : with silicon- containing groups in the side chains
• 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: Y10T 428/31667 : Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers

Abstract

The present invention is directed to a thermally curable polymer composition, and a photolithographic substrate coated therewith, the composition comprising a hydroxyl-containing polymer, an amino cross-linking agent and a thermal acid generator. The thermally curable polymer composition may be dissolved in a solvent and used as an undercoat layer in deep UV lithography.

Claims

1. A thermally curable polymer composition comprising a hydroxyl-containing polymer, an amino cross-linking agent and a thermal acid generator, wherein said hydroxyl-containing polymer comprises monomer units selected from the group consisting of:

cyclohexanol, hydroxystyrene, hydroxyalkyl acrylate or methacrylate, hydroxycycloalkyl acrylate or methacrylate, hydroxyalkylcycloalkyl acrylate or methacrylate, arylalkyl alcohol, and allyl alcohol.

2. The composition of claim 1 wherein said hydroxyl-containing polymer comprises monomer units of cyclohexanol, hydroxystyrene, hydroxyalkyl acrylate or methacrylate, biphenyl acrylate or methacrylate and hydroxycycloalkyl acrylate or methacrylate and has a number average molecular weight between about 14,000 to 30,000.

3. The composition of claim 1 wherein said thermal acid generator has the general structure:

4. The composition of claim 1 wherein said amino cross-linking agent has the general formula:

5. The composition of claim 1 wherein said hydroxyl containing polymer comprises a monomer unit of allyl alcohol and has a polymer weight average molecular weight of 2000 to 20000.

6. The composition of claim 1 further comprising a monomer unit of a cycloaliphatic ester of acrylic or methacrylic acid.

7. The composition of claim 6 wherein said monomer unit of cycloaliphatic ester of acrylic or methacrylic acid is selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylates, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate adamantyl acrylates and methacrylates, dicyclopentenyl acrylates and methacrylates, 2-(dicylcopenteneyloxy)ethyl acrylates and methacrylates.

8. The composition of claim 1 wherein said hydroxyalkyl acrylate or methacrylate is selected from the group consisting of:

hydroxymethyl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, 4-hydroxybutyl acrylate or methacrylate, 5-hydroxypentyl acrylate or methacrylate and 6-hydroxyhexyl acrylate or methacrylate.

9. The composition of claim 1 wherein said hydroxyl-containing polymer comprises the following monomer units:

10. The composition of claim 9 wherein the mole % of monomer unit (A) is about 25 to 60 mole % and the mole % of monomer unit (B) is about 40 to 75 mole %.

11. The composition of claim 1 wherein said hydroxyl-containing polymer comprises the following monomer units:

13. The composition of claim 3 wherein said thermal acid generator is selected from the group consisting of:

cyclohexyl p-toluenesulfonate, menthyl p-toluenesulfonate, bornyl p-toluenesulfonate, cyclohexyl triisopropylbenzenesulfonate, cyclohexyl 4-methoxybenzenesulfonate.

12. The composition of claim 12 wherein the mole % of monomer unit (C) is about 39-60 mole % and the mole % of monomer unit (D) is about 40 to 61 mole %.

14. A photolithographic sensitive coated substrate comprising:

(a) a substrate;

(b) a thermally cured undercoat on the substrate; and

(c) a radiation-sensitive resist topcoat on the thermally cured undercoat;

wherein said thermally cured undercoat comprises a thermally cured composition comprising a hydroxyl-containing polymer, an amino cross-linking agent and a thermal acid generator.

15. The coated substrate of claim 14 wherein said hydroxyl-containing polymer comprises monomer units selected from the group consisting of:

cyclohexanol, hydroxystyrene, hydroxyalkyl acrylate or methacrylate, hydroxycycloalkyl acrylate or methacrylate, aryalkyl alcohols, and allyl alcohol monomer units.

16. The coated substrate of claim 14 wherein said thermal acid generator has the general structure:

17. The coated substrate of claim 15 wherein said hydroxyl-containing polymer comprises monomer units selected from the group consisting of:

hydroxyalkyl acrylate or methacrylate and allyl alcohol units.

18. The coated substrate of claim 14 wherein said hydroxyl-containing polymer further comprises monomer units of cycloaliphatic ester of acrylic or methacrylic acid units.

19. The coated substrate of claim 14 wherein said hydroxyl-containing polymer comprises the following monomer units:

20. The coated substrate of claim 19 wherein the mole % of monomer unit (A) is about 25 to 60 mole % and the mole % of monomer unit (B) is about 40 to 75 mole %.

21. The coated substrate of claim 14 wherein said hydroxyl-containing polymer comprises the following monomer units:

22. The coated substrate of claim 21 wherein the mole % of monomer unit (C) is about 39-60 mole % and the mole % of monomer unit (D) is about 40 to 61 mole %.

23. The coated substrate of claim 14 wherein said hydroxyl-containing polymer comprises biphenyl acrylate or methacrylate and hydroxyethyl acrylate or methacrylate.

24. The coated substrate of claim 23 wherein the amount of biphenyl acrylate or methacrylate is about 50 to 90 mole % and the amount of hydroxyethyl acrylate or methacrylate is about 10 to 50 mole %.

25. The coated substrate of claim 14 wherein the radiation-sensitive resist topcoat is a chemically amplified resist containing silicon.

26. The coated substrate of claim 23 wherein the wherein the radiation sensitive topcoat comprises a polymer comprising the following monomer units:

27. The coated substrate of claim 14 wherein said amino cross-linking agent has the general formula

29. The process of claim 26 wherein said hydroxyl-containing polymer comprises about 30 to 60 mole % of hydroxystyrene monomer units and 40 to 70 mole % of isobornyl acrylate or methacrylate monomer units.

30. The process of claim 26 wherein said hydroxyl-containing polymer comprises about 39 to 60 mole % of styrene monomer units and about 40 to 61 mole % of allyl alcohol monomer units.

31. The process of claim 26 wherein the amount of biphenyl acrylate or methacrylate is about 50 to 90 mole % and the amount of hydroxyethyl acrylate or methacrylate is about 10 to 50 mole %.

32. The process of claim 26 wherein said radiation sensitive resist topcoat comprises a polymer comprising the following monomer units:

33. The process of claim 26 further comprising the step of:

removing said thermally cured undercoat composition to form an image thereof.

28. A process for the production of relief structures comprising the steps of:

(a) forming a coated substrate;

wherein said coated substrate comprises a substrate;

a thermally cured undercoat disposed on said substrate; and

a radiation-sensitive resist topcoat disposed on said thermally cured undercoat; and

wherein said thermally cured undercoat comprises a thermally cured composition comprising a hydroxyl-containing polymer, an amino cross-linking agent and a thermal acid generator;

(b) imagewise exposing said radiation-sensitive resist topcoat to actinic radiation; and

(c) forming a resist image by developing said radiation-sensitive resist topcoat with a developer.