Organotin oxide hydroxide patterning compositions, precursors, and patterning

Patent metadata

Field	Value
Publication number	US-11809081-B2
Application number	US-202217832920-A
Country	US
Kind code	B2
Filing date	Jun 6, 2022
Priority date	Oct 13, 2015
Publication date	Nov 7, 2023
Grant date	Nov 7, 2023

Abstract

Organometallic precursors are described for the formation of high resolution lithography patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands readily hydrolysable by water vapor or other OH source composition under modest conditions. The organometallic precursors generally comprise a radiation sensitive organo ligand to tin that can result in a coating that can be effective for high resolution patterning at relatively low radiation doses and is particularly useful for EUV patterning. The precursors compositions are readily processable under commercially suitable conditions. Solution phase processing with in situ hydrolysis or vapor based deposition can be used to form the coatings.

First claim

What is claimed is:

1. A method for forming a radiation patternable organometallic coating, the method comprising:
depositing a tin composition having organic ligands and hydrolysable ligands to form a coating with a dry thickness from about 1 nanometers (nm) to about 50 nm,
wherein the organic ligands comprise radiation sensitive Sn—C bonds, and
wherein the depositing is by a vapor-based deposition process.

2. The method of claim 1 further comprising at least partially hydrolysing the hydrolysable ligands to form oxo/hydroxo ligands.

3. The method of claim 2 wherein the hydrolysis involves atmospheric water.

4. The method of claim 2 wherein the hydrolysis is performed following deposition of the coating.

5. The method of claim 2 wherein the hydrolysis is performed during deposition of the coating.

6. The method of claim 1 wherein the vapor-based deposition process is chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD).

7. The method of claim 1 wherein the coating comprises Sn—O—H and Sn—O—Sn bonds and the radiation sensitive Sn—C bonds.

8. The method of claim 1 wherein the organic ligands comprise an alkyl ligand, a branched alkyl ligand, a cyclic alkyl, an alkenyl ligand, an aryl ligand, heteroatom substituted derivatives thereof, or a combination thereof, each ligand containing 1 to 31 carbon atoms.

9. The method of claim 8 wherein the organic ligands comprise a ligand substituted with cyano, thio, silyl, ether, keto, ester, or halogenated groups, or combinations thereof.

10. The method of claim 1 wherein the organic ligands comprise methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, t-amyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, 1-adamantyl, 2-adamantyl, phenyl, benzyl, allyl, or combinations thereof.

11. The method of claim 1 wherein the tin composition comprises at least one branched alkyl ligand.

12. The method of claim 1 wherein the tin composition comprises one or more compositions with different organic ligands in a blend.

13. The method of claim 1 wherein the tin composition comprises a blend of different organic ligands, different hydrolysable ligands, or a combination thereof.

14. The method of claim 1 wherein the tin composition comprises a combination of two or more different hydrolysable ligands.

15. The method of claim 1 wherein the hydrolysable ligands comprise a halide, an alkoxide, an alkylamide, an alkylnide, an azide, a dialkylamide, a siloxide, a silylamide, disilylamide, an aryloxide, an amidato, an amidinato, an imido, fluorinated analogues thereof, or a mixture thereof.

16. The method of claim 1 wherein the tin composition comprises t-butyl tris(dimethylamido) tin, i-propyl (dimethylamido) tin, t-butyl tris(diethylamido)tin, i-propyl tin trichloride, or combinations thereof.

17. The method of claim 1 wherein the coating has a thickness variation of no more than 50% from the average at any point along the coating as measurable by ellipsometry and/or x-ray reflectivity.

18. The method of claim 1 further comprising heating the deposited tin composition to temperatures from about 45° C. to about 250° C. for 0.1 minute to 30 minutes to form the radiation patternable organometallic coating.

19. The method of claim 1 wherein the depositing is onto a substrate comprising a silicon wafer.

20. The method of claim 1 further comprising irradiating the radiation patternable organometallic coating using patterned radiation to form a latent image.

21. The method of claim 20 wherein the irradiating comprises EUV, UV, or e-beam radiation exposure.

22. The method of claim 20 wherein the irradiating causes a reaction in the exposed portion of the latent image, the reaction comprising condensing of the tin composition and cleaving of Sn—C bonds.

23. The method of claim 22 wherein the exposed portion of the latent image is not soluble in organic solvents.

24. The method of claim 20 wherein the irradiating comprises EUV radiation at a dose from 3 mJ/cm 2 to 150 mJ/cm 2 .

25. The method of claim 20 further comprising a developing step after the irradiating step.

26. The method of claim 1 wherein the tin composition further comprises a blend of one or more non-tin metals.

27. A method for forming a radiation patternable organometallic coating, the method comprising:
depositing a tin composition having organic ligands and hydrolysable ligands to form a coating with a dry thickness from 1 nanometers (nm) to 50 nm,
wherein the organic ligands comprise radiation sensitive Sn—C bonds, and wherein the hydrolysable ligands comprise an alkoxide, an alkylamide, an alkylnide, an azide, a dialkylamide, a siloxide, a silylamide, disilylamide, an aryloxide, an amidato, an amidinato, an imido, fluorinated analogues thereof, or a mixture thereof.

28. The method of claim 27 wherein the tin composition comprises a blend of different organic ligands, different hydrolysable ligands, or a combination thereof.

29. The method of claim 27 wherein the tin composition comprises at least one branched alkyl ligand.

Assignees

• Inpria Corp

Inventors

• Meyers Stephen T
• Anderson Jeremy T
• Cardineau Brian J
• Edson Joseph B
• Jiang Kai
• Keszler Douglas A
• Telecky Alan J

Classifications

• C07F7/22

  Tin compounds · CPC title

• G03F7/168 Primary

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• C23C14/086

  of zinc, germanium, cadmium, indium, tin, thallium or bismuth · CPC title

• C23C16/407

  of zinc, germanium, cadmium, indium, tin, thallium or bismuth · CPC title

• C23C16/45523

  Pulsed gas flow or change of composition over time · CPC title