Organotin patterning materials with ligands having silicon/germanium; precursor compositions; and synthesis methods

Patent metadata

Field	Value
Publication number	US-12032291-B2
Application number	US-202217682639-A
Country	US
Kind code	B2
Filing date	Feb 28, 2022
Priority date	Jun 15, 2021
Publication date	Jul 9, 2024
Grant date	Jul 9, 2024

Abstract

As described herein, photosensitive composition comprises RSnL 3 , where R is a hydrocarbyl ligand with 1-20 carbon atoms and one or more silicon and/or germanium heteroatoms and L is an acetylide ligand (—C≡CA, where A is a silyl group with 0 to 6 carbon atoms or an organo group with 1 to 10 carbon atoms). Methods are described wherein photosensitive compositions are synthesized by reacting RX, where X is a halide, and MSnL 3 , where M is an alkali metal, alkali earth metal or a pseudo-alkali earth metal, L is an acetylide or a dialkylamide. The radiation sensitive compositions are effective for radiation based patterning, such as with EUV light.

First claim

What we claim is:

1. A photosensitive composition comprising RSnL 3 , where R is a hydrocarbyl ligand with 1-20 carbon atoms and one or more silicon and/or germanium heteroatoms and L is an acetylide ligand represented by the formula —C≡CA, where A is a silyl group with 0 to 6 carbon atoms or an organo group with 1 to 10 carbon atoms.

2. The photosensitive composition of claim 1 wherein the one or more silicon or germanium heteroatoms atoms are bonded to a carbon atom that is directly bonded to the tin atom.

3. The photosensitive composition of claim 1 wherein the hydrocarbyl ligand has the formula R 1 R 2 R 3 C—, wherein R 1 comprises a silicon or germanium atom and 0-10 carbon atoms, and wherein R 2 and R 3 are independently hydrogen or a hydrocarbyl group with 1-10 carbon atoms.

4. The photosensitive composition of claim 3 wherein R 1 comprises a silyl group.

5. The photosensitive composition of claim 3 wherein R 2 and R 3 are methyl groups.

6. The photosensitive composition of claim 1 wherein R comprises cyano, thio, ether, keto, ester, halogenated groups, or combinations thereof.

7. The photosensitive composition of claim 1 wherein L comprises TMSA.

8. The photosensitive composition of claim 1 wherein RSnL 3 comprises ethyltrimethylsilyltin tris(trimethylsilylacetylide).

9. The photosensitive composition of claim 1 wherein the RSnL 3 is thermally stable as determined by a coating of the RSnL 3 on a wafer retaining at least 90% of the normalized CH peak area measured by FTIR analysis after heating at 200° C. for 120 seconds.

10. A solution comprising an organic solvent and the photosensitive composition of claim 1 .

11. The solution of claim 10 wherein the organic solvent comprises an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester, an ether, a ketone, or combinations thereof, and wherein the solution has a concentration from about 0.005 M to about 1.4 M based on tin concentration.

12. The solution of claim 11 wherein the organic solvent comprises 4-methyl-2-pentanol.

13. A photosensitive composition comprising RSnL 3 , where R is (R 4 ) 3 Si(CH 2 ) n CR 5 2− , where n is 0 to 8, R 4 and R 5 are independently hydrogen, a halide, or a hydrocarbyl group with 1 to 4 carbon atoms and L is a hydrolysable ligand.

14. The photosensitive composition of claim 13 wherein n=0 to 2 and R 4 are methyl groups (CH 3 ).

15. The photosensitive composition of claim 13 wherein L comprises an alkoxide, an acetylide, an amide moiety, or a combination thereof.

16. The photosensitive composition of claim 13 wherein L comprises —NR′ 2 , —OR′, —CCR″, or a combination thereof, wherein R′ is a hydrocarbyl group having no more than 12 carbon atoms and R″ is a silyl group or a hydrocarbyl group having no more than 12 carbon atoms.

17. The photosensitive composition of claim 13 wherein L comprises —NMe 2 , —NEt 2 , —OiPr, —OtBu, —OtAmyl, —CC(Si(CH 3 ) 3 ), or a combination thereof.

18. The photosensitive composition of claim 13 further comprising R″SnL′ 3 , where R″ is an hydrocarbyl ligand different from R and with 1-20 carbon atoms and L′ is a hydrolysable ligand that is the same or different from L.

19. A precursor solution comprising an organic solvent and the photosensitive composition of claim 13 .

20. The solution of claim 19 wherein the organic solvent comprises an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester, an ether, a ketone, or combinations thereof, and wherein the solution has a concentration from about 0.005 M to about 1.4 M based on tin concentration.

21. The solution of claim 19 wherein the organic solvent comprises 4-methyl-2-pentanol.

22. The solution of claim 19 further comprising R″SnL′ 3 , where R″ is an hydrocarbyl ligand different from R and with 1-20 carbon atoms and L′ is a hydrolysable ligand that is the same or different from L.

23. A method for production of RSnL 3 , wherein R is a hydrocarbyl group with 1-20 carbon atoms and one or more silicon or germanium heteroatoms, and L is a hydrolysable ligand, the method comprising:
reacting RX, where X is a halide, and MSnL 3 , where M is an alkali metal, alkali earth metal or a pseudo-alkali earth metal, L is an acetylide, represented by the formula —C≡CA, where A is a silyl group with 0 to 6 carbon atoms or an organo group with 1 to 10 carbon atoms, or a dialkylamide with 1 to 10 carbon atoms, wherein the reaction forms RSnL 3 with a Sn—C bond wherein R is a hydrocarbyl ligand with 1-20 carbon atoms and one or more silicon and/or germanium heteroatoms.

24. The method of claim 23 further comprising reacting the RSnL 3 with an alcohol HOR′ to form RSn(OR′) 3 .

25. The method of claim 23 wherein reacting of RX with MSnL 3 to form RSnL 3 comprises reacting at a temperature from about −78.5° C. to about 10° C.

26. The method of claim 23 wherein M═K and the RX and the KSnL 3 are provided in a molar ratio from about 1:1 to about 3:1.

27. The method of claim 23 wherein the R moiety is ethyltrimethylsilyl.

28. The method of claim 23 wherein the MSnL 3 is KSn(TMSA) 3 .

29. The method of claim 23 further comprising preparing the MSnL 3 prior to reacting to form the RSnL 3 , wherein the preparing comprises reacting an alkyl lithium having the formula R″Li, a tin dihalide having the formula SnX′ 2 , a reactant having the formula KZ, and a reactant having the formula HL to form the KSnL 3 , wherein KZ comprises a potassium alkoxide or a potassium halide.

30. The method of claim 29 wherein the alkyl lithium and the alkyl/silyl acetylene are provided in stoichiometric amounts or the alkyl acetylene is provided in an excess of about 1 mol % to about 50 mol % over the stoichiometric amount.

31. The method of claim 29 wherein the tin dihalide comprises SnCl 2 and the reactant having the formula KZ comprises potassium t-butoxide, and wherein the reaction is performed at a temperature of less than 0° C. in a dry organic solvent.

Assignees

• Inpria Corp

Inventors

• Jilek Robert E
• Jiang Kai
• Narasimhan Amrit K

Classifications

• G03F7/0042

  with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence) · CPC title

• G03F7/11

  having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)} · CPC title

• G03F7/168

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

• C07F7/2224

  Compounds having one or more tin-oxygen linkages · CPC title

• C07F7/2208

  Compounds having tin linked only to carbon, hydrogen and/or halogen · CPC title