Graphoepitaxial self-assembly of arrays of downward facing half-cylinders
Methods for fabricating sublithographic, nanoscale microstructures in line arrays utilizing self-assembling block copolymers, and films and devices formed from these methods are provided.
1. A method of forming a nanostructured polymer material on a substrate, comprising:
forming a self-assembling block copolymer material within a trench in a material layer on the substrate, the trench having a length, a neutral wetting floor, and opposing sidewalls and ends that are preferentially wetting to a minority block of the block copolymer;
applying a material preferentially wetting to the minority block over and in contact with the block copolymer material within the trench; and
annealing the block copolymer material such that the block copolymer material self-assembles into one or more rows of half cylinders of the minority block of the block copolymer within a matrix of a majority block of the block copolymer, the one or more rows of half cylinders oriented parallel to the trench floor and extending the length of the trench, with a face oriented toward and wetting the neutral wetting trench floor.
2. The method of claim 1 , wherein the minority block of the block copolymer comprises a metal.
3. The method of claim 2 , wherein the metal is selected from the group consisting of silicon, chromium, titanium, aluminum, molybdenum, gold, platinum, ruthenium, zirconium, tungsten, vanadium, lead, and zinc.
4. The method of claim 2 , wherein the minority block of the block copolymer is selected from the group consisting of poly(vinylpyridine), poly(methylmethacrylate), poly(lactide), poly(tert-butyl acrylate) poly(ethylene-co-butylene), poly(ethylene oxide), poly(butadiene), and polystyrene.
5. The method of claim 2 , wherein the minority block of the block copolymer is selected from the group consisting of polydimethylsiloxane, poly(vinylmethylsiloxane), and poly(ferrocenylmethylethylsilane).
6. The method of claim 1 , wherein the majority block of the block copolymer is selected from the group consisting of poly(styrene), poly(isoprene), poly(butadiene), and poly(ethylene-alt-propylene), and poly(methylmethacrylate).
7. The method of claim 1 , wherein applying the preferentially wetting material comprises contacting the block copolymer material within the trench with an elastomeric material.
8. The method of claim 7 , wherein the preferentially wetting material comprises poly(dimethylsiloxane) or poly(urethane).
9. The method of claim 8 , wherein the preferentially wetting material comprises poly(dimethylsiloxane) having a hydrophilic surface.
10. The method of claim 9 , wherein the preferentially wetting material comprises poly(dimethylsiloxane) comprising silanol groups on a surface.
11. The method of claim 1 , wherein applying the preferentially wetting material comprises depositing an inorganic material to form a layer over the block copolymer material within the trench.
12. The method of claim 11 , wherein the preferentially wetting material comprises a spin-on dielectric material.
13. The method of claim 1 , further comprising removing the preferentially wetting material to expose the annealed block copolymer material within the trench.
14. The method of claim 13 , wherein removing the preferentially wetting material comprises separating the preferentially wetting material from the annealed block copolymer material.
15. The method of claim 14 , further comprising, applying a solvent to the preferentially wetting material to enhance removal.
16. The method of claim 13 , wherein the preferentially wetting material comprises an oxide material and removing the preferential wetting material layer comprises applying a fluoride-based etchant.
17. The method of claim 1 , further comprising selectively removing the majority polymer block to expose the one or more rows of half cylinders and the substrate adjacent thereto.
18. The method of claim 1 , further comprising selectively removing polymeric material to expose the substrate and forming a metal component of the minority block into an inorganic metal material such that said inorganic metal material forms a line on the substrate.
19. A method of forming a nanostructured polymer material on a substrate, comprising:
forming a block copolymer material within a trench in a material layer overlying the substrate, the trench having a width, a length, a depth, a neutral wetting floor, and opposing sidewalls and ends that are preferentially wetting to a minority block of the block copolymer;
applying a material preferentially wetting to the minority block over and in contact with the block copolymer material within the trench; and
causing a microphase separation in the block copolymer material to form one or more rows of half-cylinders comprising the minority block of the block copolymer in a matrix of a majority block of the block copolymer, the one or more rows of half-cylinders oriented parallel to the trench floor and registered to the sidewalls in one or more lines extending the length of the trench, with a face situated on the neutral wetting trench floor.
20. The method of claim 19 , wherein the trench has a width of about 1.5-2 times the L value of the block copolymer, and a single row of a half-cylinder is formed within the trench having a width of about 0.5*L.
21. The method of claim 19 , wherein the trench has a width greater than about 2 times the L value of the block copolymer, and two or more rows of half-cylinders are formed within the trench at a center-to-center distance of about the L value of the block copolymer.
22. The method of claim 21 , wherein the trench has a width of about 3 or more times the L value of the block copolymer.
23. The method of claim 19 , wherein the neutral wetting floor comprises a blend of grafted homopolymers.
24. A method of forming a nanostructured polymer material on a substrate, comprising:
forming a self-assembling block copolymer material within a trench in a material layer on the substrate, the trench having a length, a neutral wetting floor, and opposing sidewalls and ends that are preferentially wetting to a minority block of the block copolymer;
applying an atmosphere preferentially wetting to the minority block over and in contact with the block copolymer material within the trench; and
annealing the block copolymer material such that the block copolymer material self-assembles into one or more rows of half-cylinders of the minority block of the block copolymer within a matrix of a majority block of the block copolymer, the one or more rows of half-cylinders being oriented parallel to the trench floor and extending the length of the trench, with a face oriented toward and wetting the neutral wetting trench floor, and the minority block forming a layer over the block copolymer material.
25. The method of claim 24 , wherein the preferentially wetting atmosphere is selected from the group consisting of clean dry air, humid air, and a near-saturated solvent atmosphere.
26. A method of forming a nanostructured polymer material on a substrate, comprising:
applying a material over and in contact with a block copolymer material within a trench, said material being preferentially wetting to a minority block of the block copolymer material, the trench having a length, a neutral wetting floor, and opposing sidewalls and ends that are preferentially wetting to said minority block of the block copolymer; and
annealing the block copolymer material such that one or more lines of parallel-oriented half-cylinders of said minority block form within the trench within a matrix of a majority block of the block copolymer, said one or more lines of half-cylinders extending the length of the trench and oriented parallel to the trench floor, with a face oriented toward and wetting the neutral wetting trench floor.
27. The method of claim 26 , wherein the minority block of the block copolymer comprises a metal.
28. The method of claim 26 , wherein the preferentially wetting material comprises poly(dimethylsiloxane) or poly(urethane).
29. The method of claim 26 , wherein the preferentially wetting material comprises an oxide material.
30. The method of claim 26 , wherein the preferentially wetting material is a preferentially wetting atmosphere selected from the group consisting of dry air, humid air, and a near-saturated solvent atmosphere.
31. The method of claim 30 , wherein the preferential wetting atmosphere is a near-saturated solvent atmosphere comprising ethanol or dimethylformamide.
32. The method of claim 26 , further comprising removing the preferentially wetting material from contact with the annealed block copolymer material.
33. The method of claim 32 , further comprising selectively removing the majority polymer block to expose said one or more lines of half-cylinders and the substrate adjacent thereto.
34. The method of claim 26 , further comprising removing a layer of the minority block overlying a surface of the annealed block copolymer material within the trench.