Methods of improving long range order in self-assembly of block copolymer films with ionic liquids

• US 8,425,982 B2
• Filed: 03/21/2008
• Issued: 04/23/2013
• Est. Priority Date: 03/21/2008
• Status: Active Grant

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Regner, Jennifer Kahl
• Primary Examiner(s): CAMERON, ERMA C
• Application Number:
  US12/053,006
• Publication Number:
  US 20090240001A1
• Time in Patent Office: 1,859 Days
• Field of Search: None
• US Class Current: 427/372.2
• CPC Class Codes: B05D 1/34 Applying different liquids or other fluent materials simultaneously
• CPC Class Codes: B05D 3/0254 After-treatment
• CPC Class Codes: B05D 5/00 Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• CPC Class Codes: B05D 5/12 to obtain a coating with specific electrical properties
• CPC Class Codes: B81C 1/00031 Regular or irregular arrays of nanoscale structures, e.g. etch mask layer photomechanical, e.g. photolithographic, production of textured or patterned surfaces G03F7/00; lithographic processes for making patterned surfaces using printing and stamping G03F7/0002
• CPC Class Codes: B81C 2201/0149 Forming nanoscale microstructures using auto-arranging or self-assembling material
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/005 Modified block copolymers
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• CPC Class Codes: H01L 21/0337 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H01L 21/0338 Process specially adapted to improve the resolution of the mask
• CPC Class Codes: H01L 21/3086 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H01L 21/3088 Process specially adapted to improve the resolution of the mask
• CPC Class Codes: H01L 21/31144 using masks
• CPC Class Codes: Y10T 428/24182 Inward from edge of web or sheet

Abstract

Methods for fabricating arrays of nanoscaled alternating lamellar or cylinders in a polymer matrix having improved long range order utilizing self-assembling block copolymers, and films and devices formed from these methods are provided.

Claims

1. A method of forming a nanostructured polymer material on a substrate, comprising:

depositing a self-assembling lamellar-phase block copolymer composition within a trench in a material on a substrate, the trench having a length, a floor that is neutral wetting to both blocks of a block copolymer material of the self-assembling lamellar-phase block copolymer composition, and opposing sidewalls and ends that are preferentially wetting to a first block of the block copolymer material, and the self-assembling lamellar-phase block copolymer composition comprising a blend of the block copolymer material and an ionic liquid; and

annealing the self-assembling lamellar-phase block copolymer composition to self-assemble the self-assembling lamellar-phase block copolymer composition into alternating lamellar domains of the first block and a second block of the block copolymer material oriented perpendicular to the floor of the trench and extending the length of the trench.

2. The method of claim 1, wherein the self-assembling lamellar-phase block copolymer composition comprises about 0.1%-50% by wt of the ionic liquid, with the balance as the block copolymer material.

3. The method of claim 1, wherein the ionic liquid comprises an organic cation selected from the group consisting of substituted imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, ammoniums, guanidiniums, uroniums, isouroniums, thiouroniums, and sulfoniums.

4. The method of claim 1, wherein the ionic liquid comprises an anion selected from the group consisting of halogens, formate, sulfates, sulfonates, amides, imides, methanes, borates, phosphates, glycolates, antimonates, cobalt tetracarbonyl, trifluoroacetate, decanoate, alkylsulfate, alkylphosphate, and glycolate.

5. The method of claim 2, wherein the self-assembling lamellar-phase block copolymer composition further comprises about 0.1%-10% by wt of water.

6. The method of claim 1, wherein the block copolymer material comprises polystyrene and at least one of poly(methyl methacrylate), poly(ethylene oxide) and poly(vinylpyridine).

7. A method of forming a nanostructured polymer material on a substrate, comprising:

depositing a block copolymer composition within a trench in a material on a substrate, the trench having a length, a floor that is neutral wetting to both blocks of a block copolymer material of the block copolymer composition, and opposing sidewalls and ends that are preferentially wetting to a first block of the block copolymer material, and the block copolymer composition comprising a blend of the block copolymer material and an ionic liquid; and

annealing the block copolymer composition to self-assemble the block copolymer composition into polymer domains oriented perpendicular to the floor of the trench and in an array extending the length of the trench.

8. The method of claim 7, wherein the block copolymer composition comprises a lamellar-phase block copolymer material that microphase separates into alternating polymer domains of perpendicular-oriented lamellae.

9. The method of claim 7, wherein the block copolymer composition comprises a cylindrical-phase block copolymer material that microphase separates into perpendicular-oriented cylindrical domains of a minority polymer block within a matrix of a majority polymer block.

10. The method of claim 7, wherein one of the polymer domains comprises an inorganic component.

11. The method of claim 10, wherein the inorganic component comprises an inorganic heat resistant material or precursors thereof.

12. The method of claim 10, wherein the inorganic component is selected from the group consisting of metal salts, organic metal salts, metal oxide gels, metal alkoxide polymers, metal oxide precursors, metal nitride precursors and metal particles.

13. The method of claim 12, wherein the inorganic component comprises a metal selected from the group consisting of silicon, chromium, titanium, aluminum, molybdenum, gold, platinum, ruthenium, zirconium, tungsten, vanadium, lead and zinc.

14. The method of claim 7, wherein the block copolymer composition comprises a copolymer selected from the group consisting of poly(styrene)-b-poly(dimethylsiloxane), poly(isoprene)-b-poly(dimethylsiloxane), poly(styrene)-b-poly(ferrocenylmethylsilane), poly(isoprene)-b-poly(ferrocenylmethylethylsilane), poly(styrene)-b-poly(vinylmethylsiloxane), poly(styrene)-b-poly(butadiene), and poly(styrene)-b-poly(vinylpyridine).

15. The method of claim 7, further comprising:

selectively removing one of the polymer domains to form openings exposing the substrate.

16. The method of claim 15, further comprising, prior to removing one of the polymer domains, selectively crosslinking another of the polymer domains.

17. The method of claim 7, wherein one of the polymer domains comprises a metal selected from the group consisting of silicon, chromium, titanium, aluminum, molybdenum, gold, platinum, ruthenium, zirconium, tungsten, vanadium, lead and zinc.

18. The method of claim 7, wherein one of the polymer domains comprises a metal component, the method further comprises selectively removing one of the polymer domains to form openings exposing the substrate and forming the metal component into an inorganic metal material such that the inorganic metal material forms a plurality of lines on the substrate.

19. A method of forming a nanostructured polymer material on a substrate, comprising:

depositing a block copolymer material within a trench in a material overlying a substrate, the trench having opposing sidewalls and ends that are preferentially wetting to one block of the block copolymer material, a floor that is neutral wetting to both blocks of the block copolymer material, a width and a length;

blending the block copolymer material with an ionic liquid; and

causing a microphase separation in the block copolymer material to form a polymer material comprising self-assembled polymer domains oriented perpendicular to the floor of the trench and aligned parallel to the sidewalls for the length of the trench.

20. A method of forming a nanostructured polymer material on a substrate, comprising:

annealing a block copolymer material situated in a trench in a material overlying a substrate, the trench having opposing sidewalls and ends that are preferentially wetting to one block of the block copolymer material, a floor that is neutral wetting to both blocks of the block copolymer material, a width and a length, the block copolymer material blended with an ionic liquid,

wherein the block copolymer material forms an array of domains of a minority polymer block and a majority polymer block for the length of the trench.

21. The method of claim 20, further comprising selectively removing the minority polymer block to form openings exposing the substrate.

22. The method of claim 21, further comprising, prior to selectively removing the minority polymer block, selectively crosslinking the majority polymer block.

23. A method of forming a nanostructured polymer material on a substrate, comprising:

annealing a lamellar-phase block copolymer material situated in a trench in a material overlying a substrate, the trench having opposing sidewalls and ends that are preferentially wetting to one block of the lamellar-phase block copolymer material, a floor that is neutral wetting to both blocks of the lamellar-phase block copolymer material, a width and a length, the lamellar-phase block copolymer material blended with an ionic liquid,

wherein the lamellar-phase block copolymer material forms perpendicular-oriented lamellae spanning the width and extending the length of the trench.