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

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.