Organometallic solution based high resolution patterning compositions
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.
1. A precursor solution comprising an organic liquid and metal polynuclear oxo/hydroxo species with alkenyl ligands having metal carbon bonds with a metal concentration from about 0.01M to about 1.4M.
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 alkenyl ligands comprise vinyl ligands.
5. The precursor solution of claim 1 wherein the alkenyl ligands comprise allyl ligands.
6. The precursor solution of claim 1 wherein the polynuclear oxo/hydroxo species have one or more M-OH linkages, M-O-M linkages, or a combination thereof.
7. The precursor solution of claim 1 wherein the metal is tin.
8. The precursor solution of claim 1 wherein the precursor solution has a viscosity from about 0.5 centipoises (cP) to about 150 cP.
9. The precursor solution of claim 1 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.
10. The precursor solution of claim 1 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.
11. A coated substrate comprising a radiation sensitive coating, the coating comprising metal oxo-hydroxo network with metal cations having alkenyl ligands with metal carbon bonds,
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.
12. 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 alkenyl ligands with metal cations having organic ligands with metal carbon bonds, wherein the first coating is soluble in at least one organic liquid.
13. The patterned substrate of claim 12 wherein the alkenyl ligands comprise vinyl ligands.
14. The patterned substrate of claim 12 wherein the alkenyl ligands comprise allyl ligands.
15. The patterned substrate of claim 12 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.
16. The patterned substrate of claim 12 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 and wherein the oxo-hydroxo network comprises M-OH linkages, M-O-M linkages, or a combination thereof, where M represent the metal.
17. The patterned substrate of claim 12 wherein the metal comprises tin.
18. The patterned substrate of claim 12 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.