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. An article comprising:
a substrate with a surface and a patterned coating,
wherein the patterned coating comprises a first material and/or a second material, wherein the first material comprises a first metal oxo-hydroxo network having first organic ligands associated with first metal cations, the first organic ligands forming metal carbon bonds and/or metal carboxylate bonds, wherein the first material is soluble in at least some organic liquids, wherein the second material comprises a second metal oxo-hydroxo network having second organic ligands associated with second metal cations, the second organic ligands forming metal carbon bonds and/or metal carboxylate bonds, wherein the second material is soluble in aqueous bases and/or aqueous acids and wherein the second material is chemically different from the first material:
A) wherein the patterned coating comprises the first material at selected regions along the surface and absent at other regions along the surface,
and alternatively 1) wherein the substrate surface is exposed at the regions of the substrate where the first material is absent or 2) wherein the patterned coating further comprises the second material along the surface of the substrate at the regions of the substrate where the first material is absent, or
B) wherein the patterned coating comprises the second material at selected regions along the surface and absent at other regions along the surface, wherein the substrate surface is exposed at the regions of the substrate where the second material is absent.
2. The article of claim 1 wherein the first metal oxo-hydroxo network and/or the second metal oxo-hydroxo network has both M-O—H linkages and M-O-M linkages.
3. The article of claim 1 wherein the patterned coating comprises the first material and the substrate surface is exposed at the regions of the substrate where the first material is absent.
4. The article of claim 1 wherein the first metal cations and/or the second metal cations independently comprise tin, antimony, indium or a combination thereof and wherein the first and/or the second organic ligands form a radiation sensitive 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 having 1 to 16 carbon atoms and/or wherein the first and/or the second organic ligands form a radiation sensitive metal carboxylate bond and wherein the ligand forming the metal carboxylate bond comprises an alkyl carboxylate ligand, alkenyl carboxylate ligand, aryl carboxylate ligand or a combination thereof, each ligand having 1 to 16 carbon atoms.
5. The article of claim 1 wherein the first and/or the second organic ligands forming metal carbon bonds comprise branched alkyl ligands.
6. The article of claim 1 wherein the first and/or the second organic ligands forming metal carbon bonds comprise t-butyl ligands.
7. The article of claim 1 wherein the first metal cations comprise tin, antimony, indium or a combination thereof, and a combination of different alkyl ligands are bound to the metal.
8. The article of claim 1 wherein the first metal cations comprise tin and the first material comprises Sn—O—H and Sn—O—Sn bonds and radiation sensitive Sn—C bonds and/or radiation sensitive Sn-carboxylate bonds.
9. The article of claim 1 wherein the first material and/or the second material comprise one or more compositions with tin and non-tin metals in a blend.
10. The article of claim 1 wherein the first material and/or the second material are free of peroxide ligands and wherein the second material comprises an enhanced metal oxo-hydroxo network.
11. The article of claim 1 wherein alternatively the patterned coating comprises the first material and the substrate surface is exposed at the regions of the substrate where the first material is absent or the patterned coating comprises the second material and the substrate surface is exposed at the regions of the substrate where the second material is absent, and wherein the patterned coating comprises features with an average pitch of no more than about 60 nm, average widths of no more than about 30 nm, and/or average line-width roughness of no more than about 3.0 nm.
12. The article of claim 1 wherein the substrate comprises a semiconductor wafer.
13. The article of claim 1 wherein the organic liquids comprise an aromatic compound, an ester, an alcohol, a ketone, an ether, or a combination thereof, optionally with up to 10% by weight additive.
14. The article of claim 1 wherein the wherein the aqueous bases comprise a quaternary ammonium hydroxide composition, optionally with up to 10% by weight additive.
15. The article of claim 1 wherein the patterned coating further comprises the second material along the surface of the substrate at regions where the first material is absent and wherein the article can be alternatively subjected to positive tone imaging or negative tone imaging.
16. The article of claim 1 wherein the second organic ligands are the same as the first organic ligands and the second metal cations are the same as the first metal cations and wherein the first metal oxo-hydroxo network has a higher carbon to metal ratio than the second metal oxo-hydroxo network.
17. The article of claim 1 wherein the patterned coating comprises the second material and the substrate surface is exposed at the regions of the substrate where the second material is absent and further comprising a layer of a third material over the patterned coating, wherein the third material comprises a third metal oxo-hydroxo network and third organic ligands with third metal cations, the third organic ligands forming metal carbon bonds and/or metal carboxylate bonds, and wherein the second material is not soluble in at least some organic liquids.
18. The article of claim 1 wherein the patterned coating comprises the second material and the substrate surface is exposed at the regions of the substrate where the second material is absent.
19. The article of claim 1 wherein the second material is resistant to dissolving by organic solvents.
20. The article of claim 1 wherein the first metal cations and/or the second metal cations independently consist of tin, antimony, indium or a combination thereof.
21. The article of claim 1 wherein the first and/or the second metal cations consist of tin.
22. The article of claim 1 wherein the first material and/or the second material independently comprise a first metal consisting of Sn, Sb, In or a combination thereof and a second metal consisting of one or more metal other than Sn, Sb or In, wherein the one or more metal other than Sn, Sb or In comprises Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, Lu or combinations thereof, and wherein the mole ratio of the second metal to the first metal is from about 0.1 to about 0.75.