Organometallic solution based high resolution patterning compositions

• US 10,025,179 B2
• Filed: 12/29/2015
• Issued: 07/17/2018
• Est. Priority Date: 08/22/2013
• Status: Active Grant

• Current Assignee: Inpria Corporation (JSR Corporation)
• Original Assignee: Inpria Corporation (JSR Corporation)
• Inventors: Meyers, Stephen T., Keszler, Douglas A., Jiang, Kai, Anderson, Jeremy T., Grenville, Andrew
• Primary Examiner(s): McPherson, John A
• Application Number:
  US14/983,220
• Publication Number:
  US 20160216606A1
• Time in Patent Office: 931 Days
• Field of Search: 430 9, 430 17, 4302701, 430325, 430326
• 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 precursor solution comprising an organic liquid and metal polynuclear oxo/hydroxo cations with branched alkyl ligands having metal carbon bonds with a metal concentration from about 0.01M to about 1.4M, and wherein the polynuclear oxo/hydroxo cations have M-OH linkages and M-O-M linkages.

2. The precursor solution of claim 1 wherein the organic liquid comprises an alcohol.

3. The precursor solution of claim 1 wherein the organic liquid comprises an ester or a ketone.

4. The precursor solution of claim 1 wherein the branched alkyl ligands comprise t-butyl ligands.

5. The precursor solution of claim 1 wherein the metal is tin.

6. 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 metal oxo-hydroxo network and branched alkyl ligands with metal cations having organic ligands with metal carbon bonds and/or with metal carboxylate bonds, wherein the first coating is soluble in at least one organic liquid, and wherein the oxo-hydroxo network comprises M-OH linkages and M-O-M linkages, where M represent the metal.

7. The patterned substrate of claim 6 wherein the branched alkyl ligands comprise t-butyl ligands.

8. The patterned substrate of claim 6 wherein the first coating has an average thickness of no more than about 10 microns and a thickness variation of no more than about 50% from the average at any point along the coating.

9. The patterned substrate of claim 6 wherein a mole ratio between the organic ligands bound to the metal cations with metal-carbon bonds and the metal cations is from about 0.5 to about 3.

10. The patterned substrate of claim 6 wherein the metal comprises tin.

11. The patterned substrate of claim 6 wherein the first coating is effectively soluble in at least some organic liquids selected from aromatic compounds, esters, alcohols, ketones, ethers, and combinations thereof, and the patterned coating 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.

12. A precursor solution comprising an organic liquid and metal polynuclear oxo carboxylate having metal carbon bonds to an organic ligand or metal carboxylate bonds, and M-O-M linkages and M-OH linkages, wherein the precursor solution has a metal concentration from about 0.01M to about 1.4M.

13. The precursor solution of claim 12 wherein the precursor solution has a viscosity from about 0.5 centipoises (cP) to about 150 cP.

14. The precursor solution of claim 12 wherein the organic liquid has a flash point of at least 10°

C. and a vapor pressure at 20°

C. less than about 10 kPa.

15. The precursor solution of claim 12 wherein the carboxylate group bridges two metal atoms.

16. The precursor solution of claim 12 wherein the carboxylate-to-metal ratio is less than 2.

17. A coated substrate comprising a radiation sensitive coating, the coating comprising metal oxo-hydroxo network with metal cations having organic ligands with a metal carbon bonds and/or with metal carboxylate bonds, and wherein the oxo-hydroxo network comprises M-OH linkages and M-O-M linkages, where M represent the metal,

wherein the coated substrate can be stored for 39 days in a dark, room-temperature environment under an atmospheric ambient and then patterned with a 30-kV electron beam and developed without observable degradation in image fidelity under SEM imaging when compared to a reference coated substrate prepared in the same way that is immediately patterned with a 30-kV electron beam and developed in the same way as the coated substrate.

18. A precursor solution comprising an organic liquid and from about 0.01M to about 1.4M metal ion concentration with organic ligands having a metal carbon bonds and/or with metal carboxylate bonds, wherein the metal with organic ligands forms an oxo-hydroxo network, and wherein the oxo-hydroxo network comprises M-OH linkages and M-O-M linkages, where M represent the metal,

wherein when the precursor solution can be stored for 39 days in a dark, room-temperature environment under an atmospheric ambient, and after storage is spin coated onto a wafer substrate, then baked on a hot plate for 2 minutes at 100°

C. creating a coated substrate, the coated substrate is then patterned with a 30-kV electron beam, developed for 30 seconds in PGMEA, rinsed and hard baked at 200°

C. for 2 minutes without observable degradation in image fidelity under SEM imaging when compared to a reference patterned substrate formed with an equivalent precursor solution that is processed the same way through patterning without storage of the precursor solution.

19. 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 that comprises a metal oxo-hydroxo network with organic ligands with metal carbon bonds and/or metal carboxylate bonds, wherein the oxo-hydroxo network comprises M-OH linkages and M-O-M linkages, where M represent the metal; and

selectively developing the irradiated structure to remove a substantial portion of the irradiated coating with an aqueous acid developer to form a patterned substrate.

20. The method of claim 19 wherein the aqueous acid developer comprises HF or oxalic acid.