Methods of etching articles via microcontact printing

• US 5,900,160 A
• Filed: 07/09/1996
• Issued: 05/04/1999
• Est. Priority Date: 10/04/1993
• Status: Expired due to Term

• Current Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Original Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Inventors: Kim, Enoch, Jackman, Rebecca J., Kumar, Amit, Whitesides, George M., Gorman, Christopher B., Xia, Younan, Wilbur, James L., Berggren, Karl K., Prentiss, Mara G., Biebuyck, Hans, Mrksich, Milan
• Primary Examiner(s): Nuzzolillo, M.
• Assistant Examiner(s): Weiner, Laura
• Application Number:
  US08/677,309
• Time in Patent Office: 1,029 Days
• Field of Search: 216/41, 216/33, 216/87, 216/13, 216/96, 216/36
• US Class Current: 216/41
• CPC Class Codes: B01J 2219/00382 Stamping
• CPC Class Codes: B01J 2219/00605 the compounds being directly bound or immobilised to solid supports
• CPC Class Codes: B01J 2219/00612 the surface being inorganic
• CPC Class Codes: B01J 2219/00637 by coating it with another layer
• CPC Class Codes: B01J 2219/00659 Two-dimensional arrays
• CPC Class Codes: B01L 2300/0654 Lenses; Optical fibres
• CPC Class Codes: B01L 2300/0819 Microarrays; Biochips
• CPC Class Codes: B01L 2300/0851 Bottom walls
• CPC Class Codes: B01L 3/5085 for multiple samples, e.g. microtitration plates
• CPC Class Codes: B01L 3/5088 confining liquids at a location by surface tension, e.g. virtual wells on plates, wires B01L3/50857 takes precedence
• CPC Class Codes: B05D 1/283 Transferring monomolecular layers or solutions of molecules adapted for forming monomolecular layers from carrying elements
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C40B 60/14 for creating libraries
• CPC Class Codes: G02B 2006/12102 Lens
• CPC Class Codes: G02B 2006/12104 Mirror; Reflectors or the like
• CPC Class Codes: G02B 2006/12107 Grating
• CPC Class Codes: G02B 5/1857 using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
• CPC Class Codes: G02B 6/124 Geodesic lenses or integrated gratings
• CPC Class Codes: G02B 6/136 : by etching
• 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: G03F 7/165 : Monolayers, e.g. Langmuir-Blodgett
• CPC Class Codes: H01L 21/4867 : Applying pastes or inks, e.g. screen printing H01L21/486 takes precedence
• CPC Class Codes: H01L 21/768 : Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics

Abstract

Improved methods of forming a patterned self-assembled monolayer on a surface and derivative articles are provided. According to one method, an elastomeric stamp is deformed during and/or prior to using the stamp to print a self-assembled molecular monolayer on a surface. According to another method, during monolayer printing the surface is contacted with a liquid that is immiscible with the molecular monolayer-forming species to effect controlled reactive spreading of the monolayer on the surface. Methods of printing self-assembled molecular monolayers on nonplanar surfaces and derivative articles are provided, as are methods of etching surfaces patterned with self-assembled monolayers, including methods of etching silicon. Optical elements including flexible diffraction gratings, mirrors, and lenses are provided, as are methods for forming optical devices and other articles using lithographic molding. A method for controlling the shape of a liquid on the surface of an article is provided, involving applying the liquid to a self-assembled monolayer on the surface, and controlling the electrical potential of the surface.

Claims

1. A method of etching an article having a surface, comprising:

contacting a first, nonplanar portion of the surface with a stamp to transfer to the first, nonplanar portion a self-assembled monolayer of a molecular species in a first pattern, the self-assembled monolayer being contiguous with an exposed portion of the surface in a second pattern; and

contacting the article with an etchant that reacts chemically with the article thereby degrading a portion of the article in a pattern dictated by the pattern of the self-assembled monolayer.

2. A method as in claim 1, wherein the article is a fiber.

3. A method as in claim 1, wherein the article is cylindrical.

4. A method as in claim 1 comprising, prior to the contacting step, coating a surface of the stamp with a self-assembled monolayer forming molecular species.

5. A method as in claim 4, wherein the surface of the stamp includes indentations and protrusions, the outward-facing surfaces of which define a stamping surface, the contacting step involving contacting the first, non-planar portion of the surface with the stamping surface.

6. A method as in claim 5, the contacting step comprising transferring the self-assembled monolayer to the nonplanar portion of the material by rolling the first, nonplanar portion of the surface of the article over the stamping surface of the stamp.

7. A method as in claim 1, wherein the article is selected from the group consisting of silicon, titanium, zirconium, germanium, aluminum, copper, oxides of these or glass.

8. A method as in claim 1, wherein the article is selected from the group consisting of gold, silver, nickel, cadmium, zinc, palladium, platinum, iron, chromium, alloys of these or alloys of copper.

9. A method as in claim 1, wherein the etchant is a first etchant.

10. A method as in claim 9, further comprising contacting the article with a second etchant.

11. A method as in claim 9, wherein the self-assembled monolayer resists the first etchant.

12. A method as in claim 1, comprising applying a protecting species to the self-assembled monolayer.

13. A method as in claim 12, wherein the protecting species is inert with respect to the first etchant.

14. A method comprising:

providing a nonplanar article with a layer of a material on a surface thereof;

forming, on a first portion of a surface of the material, a self-assembled monolayer of a molecular species in a first pattern, the self-assembled monolayer being contiguous with an exposed portion of the surface in a second pattern; and

contacting a portion of the surface of the material with a first etchant that reacts chemically with the material thereby degrading a portion of the material in a pattern dictated by the pattern of the self-assembled monolayer.

15. A method as in claim 14, further comprising contacting the article with a second etchant.

16. A method as in claim 15, wherein the second etchant reacts chemically with the article and is inert with respect to the material.

17. A method as in claim 14, wherein the article is cylindrical.

18. A method as in claim 14, comprising applying the self-assembled monolayer to the material with a stamp.

19. A method as in claim 18, comprising coating a stamping surface of the stamp with a self-assembled monolayer forming molecular species prior to applying the self-assembled monolayer to the material with the stamp.

20. A method as in claim 19, wherein the surface of the stamp includes indentations and protrusions, the outward-facing surfaces of which define the stamping surface.

21. A method as in claim 20, comprising transferring the self-assembled monolayer to the first portion of the surface of the material by rolling the first, nonplanar portion of the surface of the material over the stamping surface of the stamp.

22. A method as in claim 14, wherein the article is selected from the group consisting of silicon, titanium, zirconium, germanium, aluminum, copper, oxides of these or glass.

23. A method as in claim 14, wherein the material is selected from the group consisting of gold, silver, copper, nickel, cadmium, zinc, palladium, platinum, iron, chromium, or alloys of these.

24. A method as in claim 14, wherein the self-assembled monolayer resists the first etchant.

25. A method as in claim 14, wherein the self-assembled monolayer does not resist the first etchant.

26. A method as in claim 14, comprising applying a protecting species that is inert with respect to the first etchant to the self-assembled monolayer.

27. A method as in claim 14 further comprising, subsequent to the forming step and prior to the contacting step, applying a protecting species that is inert with respect to the first etchant a portion of the surface of the material complementary to the first portion of the surface of the material, the contacting step comprising degrading the self-assembled monolayer and the first portion of the surface of the material.