Method of producing nanopatterned articles, and articles produced thereby

1. A method of preparing a nanopatterned surface, comprising:

forming a block copolymer film on an annealed, miscut surface of a crystalline substrate;

annealing the block copolymer film; and

surface reconstructing the annealed block copolymer film.

2. The method of claim 1 , wherein the annealed block copolymer film comprises a hexagonal array of cylindrical microdomains.

3. The method of claim 2 , wherein the hexagonal array of cylindrical microdomains exhibits an orientation order of at least 0.9 over an area of at least 1 centimeter.

4. The method of claim 2 , wherein the cylindrical microdomains are separated by a nearest-neighbor distance of about 10 to about 100 nanometers.

5. The method of claim 1 , wherein the annealed block copolymer film comprises a linear array of micro domains.

6. The method of claim 1 , wherein the block copolymer comprises a first block having a first Hildebrand solubility parameter and a second block having a second Hildebrand solubility parameter, and wherein the first Hildebrand solubility parameter and the second Hildebrand solubility parameter differ by at least 0.4 megapascal 1/2 .

7. The method of claim 6 , wherein the first block and the second block differ in number average molecular weight by at least a factor of 1.5.

8. The method of claim 1 , wherein the block copolymer is a polystyrene-poly(4-vinylpyridine) or polystyrene-poly(2-vinylpyridine) diblock copolymer.

9. The method of claim 1 , wherein the block copolymer is a polystyrene-poly(ethylene oxide) diblock copolymer.

10. The method of claim 1 , wherein the block copolymer film has a thickness of about 10 to about 100 nanometers.

11. The method of claim 1 , wherein the crystalline substrate consists essentially of a single crystal.

12. The method of claim 1 , wherein the crystalline substrate is selected from the group consisting of crystalline silicon, doped crystalline silicon, and crystalline aluminum oxide.

13. The method of claim 1 , wherein the crystalline substrate comprises crystalline silicon.

14. The method of claim 1 , wherein the crystalline substrate comprises crystalline aluminum oxide.

15. The method of claim 1 , wherein the miscut crystalline surface is at least one degree removed from any crystallographic plane of the crystalline substrate.

16. The method of claim 1 , wherein the annealed, miscut surface of the crystalline substrate exhibits a saw-tooth pattern characterized by a peak-to-peak separation of about 24 to about 200 nanometers and a peak-to-valley separation of about 3 to about 20 nanometers.

17. The method of claim 1 , wherein the annealed, miscut surface of the crystalline substrate exhibits a grooved pattern characterized by a groove depth of about 3 to about 20 nanometers and a groove-to-groove separation of about 24 to about 200 nanometers.

18. The method of claim 1 , wherein the annealed, miscut surface of the crystalline substrate is chemically homogeneous.

19. The method of claim 1 , wherein the block copolymer is a polystyrene-poly(4-vinylpyridine) diblock copolymer, and wherein the surface reconstructing the annealed block copolymer film comprises immersing the block copolymer film in a lower alkanol solvent selected from the group consisting of methanol, ethanol, and mixtures thereof.

20. The method of claim 1 , further comprising coating an etch-resistant layer on the surface reconstructed block copolymer film to form a resist-coated block copolymer film.

21. The method of claim 20 , wherein the coating the etch-resistant layer on the surface reconstructed block copolymer film comprises depositing gold onto the surface reconstructed block copolymer film.

22. The method of claim 20 , further comprising etching through the resist-coated block copolymer film and into the substrate to create an etched article comprising a nanopatterned substrate.

23. The method of claim 22 , further comprising separating the etch-resistant layer and the block copolymer film from the nanopatterned substrate.

24. The method of claim 1 ,

wherein the surface-reconstructed block copolymer film defines a hexagonal array of cylindrical voids extending through the surface-reconstructed block copolymer film; and

wherein the method further comprises coating a magnetic material on the surface reconstructed block copolymer film and into the voids defined by the surface reconstructed block copolymer film.

25. The method of claim 24 , wherein the magnetic material is selected from the group consisting of nickel, cobalt, chromium, and alloys of iron and platinum.

26. The method of claim 24 , further comprising separating the magnetic material-coated, reconstructed block copolymer film from the crystalline substrate to form a miscut surface decorated with a hexagonal array of magnetic islands.

27. The method of claim 1 ,

wherein the crystalline substrate consists essentially of a single crystal of crystalline aluminum oxide or doped silicon;

wherein the block copolymer film comprises a polystyrene-block-poly(4-vinylpyridine) diblock copolymer comprising a polystyrene block having a number average molecular weight of about 6,000 to about 30,000 atomic mass units and a poly(4-vinylpyridine) or poly(2-vinylpyridine) block having a number average molecular weight of about 2,000 to about 10,000 atomic mass units;

wherein a ratio of the number average molecular weight of the polystyrene block to the number average molecular weight of the poly(4-vinylpyridine) or poly(2-vinylpyridine) block is about 2 to about 6;

wherein the annealing the block copolymer film comprises exposing the block copolymer film to an annealing solvent vapor comprising toluene and tetrahydrofuran;

wherein the annealed block copolymer film comprises a hexagonal array of cylindrical poly(4-vinylpyridine) or poly(2-vinylpyridine) microdomains;

wherein the hexagonal array of cylindrical microdomains exhibits an orientation order of at least 0.9 over an area of at least 1 centimeter 2 ; and

wherein the surface reconstructing the annealed block copolymer film comprises immersing the annealed block copolymer film in a solvent comprising a C 1 -C 3 alkanol.

28. The method of claim 1 ,

wherein the crystalline substrate consists essentially of a single crystal of crystalline aluminum oxide or doped silicon;

wherein the block copolymer film comprises a polystyrene-block-poly(ethylene oxide) diblock copolymer comprising a polystyrene block having a number average molecular weight of about 6,000 to about 30,000 atomic mass units and a poly(ethylene oxide) block having a number average molecular weight of about 2,000 to about 10,000 atomic mass units;

wherein a ratio of the number average molecular weight of the polystyrene block to the number average molecular weight of the poly(ethylene oxide) block is about 2 to about 6;

wherein the annealing the block copolymer film comprises exposing the block copolymer film to an annealing solvent vapor comprising toluene and tetrahydrofuran;

wherein the annealed block copolymer film comprises a hexagonal array of cylindrical poly(ethylene oxide) microdomains;

wherein the hexagonal array of cylindrical microdomains exhibits an orientation order of at least 0.9 over an area of at least 1 centimeter; and

wherein the surface reconstructing the annealed block copolymer film comprises immersing the annealed block copolymer film in a solvent comprising a C 1 -C 3 alkanol.

29. The method of claim 1 , wherein the surface reconstructing the annealed block copolymer film comprises exposing the annealed block copolymer film to a solvent that preferentially dissolves a minor phase of the block copolymer film and effects transfer of the minor phase to a surface of the block copolymer film opposite the substrate.