Organometallic solution based high resolution patterning compositions

• US 9,310,684 B2
• Filed: 08/22/2013
• Issued: 04/12/2016
• Est. Priority Date: 08/22/2013
• Status: Active Grant

• Current Assignee: Inpria Corporation
• Original Assignee: Inpria Corporation
• Inventors: Meyers, Stephen T., Keszler, Douglas A., Jiang, Kai, Anderson, Jeremy, Grenville, Andrew
• Primary Examiner(s): McPherson, John A
• Application Number:
  US13/973,098
• Publication Number:
  US 20150056542A1
• Time in Patent Office: 964 Days
• Field of Search: 430/9, 430/17, 430/270.1, 430/325, 430/326
• US Class Current: 1/1
• CPC Class Codes: G03F 7/0042 with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists G03F7/075 takes precedence
• CPC Class Codes: G03F 7/0043 Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof G03F7/0044 takes precedence
• CPC Class Codes: G03F 7/09 characterised by structural details, e.g. supports, auxiliary layers supports for printing plates in general B41N
• CPC Class Codes: G03F 7/20 Exposure; Apparatus therefor photographic printing apparatus for making copies G03B27/00
• CPC Class Codes: G03F 7/2002 with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
• CPC Class Codes: G03F 7/2037 Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
• CPC Class Codes: G03F 7/30 Imagewise removal using liquid means
• CPC Class Codes: G03F 7/32 Liquid compositions therefor, e.g. developers
• CPC Class Codes: G03F 7/322 Aqueous alkaline compositions
• CPC Class Codes: G03F 7/325 Non-aqueous compositions

Abstract

Organometallic solutions have been found to provide high resolution radiation based patterning using thin coatings. The patterning can involve irradiation of the coated surface with a selected pattern and developing the pattern with a developing agent to form the developed image. The patternable coatings may be susceptible to positive-tone patterning or negative-tone patterning based on the use of an organic developing agent or an aqueous acid or base developing agent. The radiation sensitive coatings can comprise a metal oxo/hydroxo network with organic ligands. A precursor solution can comprise an organic liquid and metal polynuclear oxo-hydroxo cations with organic ligands having metal carbon bonds and/or metal carboxylate bonds.

Claims

1. A method for patterning a substrate with radiation, the method comprising:

irradiating a coated substrate along a selected pattern to form an irradiated structure with a region of irradiated coating and a region with un-irradiated coating, wherein the coated substrate comprises a coating having an average thickness from about 5 nm to about 200 nm and that comprises a metal oxo-hydroxo network with organic ligands with metal carbon bonds and/or with metal carboxylate bonds and free of peroxide ligands;

heating the irradiated structure at a temperature from about 45°

C. to about 250°

C. for 0.1 minutes to about 30 minutes to form an annealed irradiated structure; and

selectively developing the annealed irradiated structure to remove a substantial portion of the irradiated coating or of the un-irradiated coating to form a patterned substrate

wherein the metal oxo-hydroxo network comprises both M-O—

H linkages and M-O-M linkages.

2. The method of claim 1 wherein the irradiated structure has irradiated coating that is soluble in aqueous base and non-irradiated coating soluble in organic solvents such that the irradiated structure can be alternatively subjected to positive tone imaging or negative tone imaging.

3. The method of claim 1 wherein the development is performed with an organic solvent to remove the non-irradiated coating.

4. The method of claim 1 wherein the selective development is performed with an aqueous base.

5. The method of claim 1 wherein the irradiation is performed with an electron beam, ultraviolet light, extreme ultraviolet light, irradiation from an ArF laser, irradiation from a KrF laser, or a UV lamp.

6. The method of claim 1 wherein the patterned substrate comprises features with an average pitch of no more than about 60 nm.

7. The method of claim 1 wherein the un-irradiated coating has a mole ratio between the organic ligands and the metal cations from about 0.1 to about 4 and has an average coating thickness of no more than about 1 micron.

8. The method of claim 1 wherein the metal comprises a tin ion, antimony ion, indium ion or a combination thereof and wherein the organic ligand forms a metal carbon bond and wherein the ligand forming the metal carbon bond comprises an alkyl ligand, alkenyl ligand, aryl ligand, or a combination thereof, each ligand containing 1 to 16 carbon atoms and/or organic ligands form a metal-carboxyl bond and wherein the metal-carboxyl bond is formed by an alkyl carboxylate ligand, alkenyl carboxylate ligand, aryl carboxylate ligand or a combination thereof, each ligand having 1 to 16 carbon atoms.

9. The method of claim 1 further comprising forming the coating by depositing a liquid precursor solution and evaporating the solvent to solidify the coating.

10. A coated substrate comprising a radiation sensitive coating having an average thickness from about 5 nm to about 200 nm and a thickness variation of no more than about 50% from the average at any point along the coating, the coating comprising a metal oxo-hydroxo network with metal cations having organic ligands with metal carbon bonds and/or with metal carboxylate bonds, wherein the oxo-hydroxo network has both M-O—

H linkages and M-O-M linkages.

11. The coated substrate of claim 10 wherein a mole ratio between the organic ligands and the metal cations is from about 0.1 to about 4.

12. The coated substrate of claim 10 wherein a mole ratio between the organic ligands and the metal cations is from about 0.5 to about 3.

13. The coated substrate of claim 10 having an average coating thickness from about 5 nm to about 50 nm.

14. The coated substrate of claim 10 having an average coating thickness from about 5 nm to about 150 nm.

15. The coated substrate of claim 10 wherein the metal ion comprises a tin ion, antimony ion, indium ion or a combination thereof.

16. The coated substrate of claim 15 wherein the metal cations further comprise a cation of another metal element and/or metalloid element at no more than about 50 mole % of total metal+metalloid content.

17. The coated substrate of claim 10 wherein the organic ligand forms a metal carbon bond and wherein the ligand forming the metal carbon bond comprises an alkyl ligand, alkenyl ligand, aryl ligand or combinations thereof, each containing 1 to 16 carbon atoms.

18. The coated substrate of claim 10 wherein the organic ligand forms a metal carboxyl bond and wherein the metal carboxyl bond is formed by an alkyl carboxylate ligand, alkenyl carboxylate ligand, an aryl carboxylate ligand or a combination thereof, each having 1 to 16 carbon atoms.

19. The coated substrate of claim 10 wherein the radiation sensitive coating is free of peroxide ligands.

20. A patterned substrate comprising a substrate with a surface and a first coating at selected regions along the surface and absent at other regions along the surface, the first coating comprising a metal oxo-hydroxo network and organic ligands with metal cations having organic ligands with metal carbon bonds and/or with metal carboxylate bonds, wherein the oxo-hydroxo network has both M-O—

H linkages and M-O-M linkages, wherein alternatively the first coating is soluble in at least some organic liquids or the first coating is soluble in aqueous bases.

21. The patterned substrate of claim 20 wherein the substrate surface is exposed at the regions of the substrate where the coating is absent.

22. The patterned substrate of claim 20 wherein the first coating is effectively soluble in at least some organic liquids and further comprising a second coating along the surface at regions where the first coating is absent wherein the second coating is soluble in aqueous bases.

23. The patterned substrate of claim 20 wherein the patterned coating comprises features with an average pitch of no more than about 60 nm.

24. The patterned substrate of claim 20 wherein the first coating is free of peroxide ligands.

25. The patterned substrate of claim 20 wherein features of the pattern have average widths of no more than about 30 nm.

26. The patterned substrate of claim 20 wherein features of the pattern have average line-width roughness of no more than about 3.0 nm.

27. A precursor solution comprising an organic liquid and from about 0.01M to about 1.4M metal polynuclear oxo/hydroxo cation with organic ligands having metal carbon bonds and/or with metal carboxylate bonds, wherein the metal polynuclear oxo/hydroxo cation with organic ligands forms an oxo-hydroxo network, wherein the oxo-hydroxo network has both M-O—

H linkages and M-O-M linkages, the precursor solution having a viscosity from about 0.5 centipoises (cP) to about 150 cP and the organic liquid having a flash point of at least 10°

C. and a vapor pressure at 20°

C. less than about 10 kPa.

28. The precursor solution of claim 27 wherein the metal comprises tin and the organic liquid is an alcohol.

29. The precursor solution of claim 27 wherein the solution is free of peroxide ligands.