Tin dodecamers and radiation patternable coatings with strong EUV absorption
Patterning compositions are described based on organo tin dodecamers with hydrocarbyl ligands, oxo ligands, hydroxo ligands and carboxylato ligands. Alternative dodecamer embodiments have organo tin ligands in place of hydrocarbyl ligands. The organo tin ligands can be incorporated into the dodecamers from a monomer with the structure (RCC) 3 SnQ, where R is a hydrocarbyl group and Q is a alkyl tin moiety with a carbon bonded to the Sn atom of the monomer and with a Sn bonded as a replacement of a quaternary carbon atom with bonds to 4 carbon atoms. Some or all of the carboxylato and hydroxyl ligands can be replaced with fluoride ions. Good EUV patterning results are obtained with the dodecamer based patterning compositions.
1. A composition comprising a tin dodecamer represented by the formula (QSn) 12 O 14 (OH) 6 (RCO 2 ) 2 , where R is H or an alkyl group with 1 to 10 carbon atoms, Q is an alkyltin group with a structure —(CH 2 ) n Sn(R 1 R 2 R 3 ) with n=1 to 4 and with 4 to 15 total carbon atoms, and R 1 , R 2 , and R 3 are independently alkyl groups with 1 to 5 carbon atoms.
2. The composition of claim 1 wherein R 1 , R 2 , and R 3 are each methyl groups, —CH 3 .
3. The composition of claim 1 wherein Q is —CH 2 Sn(CH 3 ) 3 .
4. A solution for forming a radiation patternable coating, the solution comprising an organic solvent and the composition of claim 1 .
5. The solution of claim 4 wherein the concentration of tin atoms is from about 1 mM to about 1 M.
6. The solution of claim 5 wherein the organic solvent comprises chloroform.
7. The solution of claim 4 wherein the concentration of tin is from about 10 mM to about 200 mM.
8. The solution of claim 4 wherein Q is —CH 2 Sn(CH 3 ) 3 and wherein the concentration of tin is from about 10 mM to about 200 mM.
9. The solution of claim 4 further comprising 1-30 vol % formic acid, wherein the organic solvent comprises a ketone or an alkoxy alcohol with 4-10 C atoms.
10. The solution of claim 4 wherein the organic solvent comprises propylene glycol methyl ether acetate.
11. A composition comprising (QSn) n O 3n/2-1/2x-1/2y F x (OH) y , wherein 1≤n≤12, (0<x+y≤8), and x>0 and wherein Q is an alkyl group with 1 to 16 carbon atoms or an alkyltin group with a structure —CH 2 Sn(R 1 R 2 R 3 ) with 4 to 15 total carbon atoms, and R 1 , R 2 , and R 3 are independently alkyl groups with 1 to 5 carbon atoms.
12. The composition of claim 11 wherein R 1 , R 2 , and R 3 are each methyl groups, —CH 3 .
13. The composition of claim 11 wherein Q is —(CH 2 ) n C(R 1 R 2 R 3 ) with n=1 to 4.
14. The composition of claim 11 wherein Q is a tert-butyl group (—C(CH 3 ) 3 ).
15. The composition of claim 11 wherein Q is —CH 2 Sn(CH 3 ) 3 .
16. A solution for forming a radiation patternable coating, the solution comprising an organic solvent and the composition of claim 11 .
17. The solution of claim 16 wherein the concentration of tin atoms is from about 1 mM to about 1 M.
18. The solution of claim 16 the organic solvent comprises chloroform.
19. The solution of claim 16 wherein Q is a tert-group (—C(CH 3 ) 3 ) or a t-amyl group (—CH 2 C(CH 3 ) 3 ), and wherein the concentration of tin is from about 10 mM to about 200 mM.
20. The solution of claim 16 wherein Q is —CH 2 Sn(CH 3 ) 3 and wherein the concentration of tin is from about 10 mM to about 200 mM.
21. The solution of claim 16 further comprising 1-30 vol % formic acid, and wherein the solvent comprises a ketone or alkoxy alcohol with 4-10 C atoms.
22. The solution of claim 16 wherein the organic solvent comprises propylene glycol methyl ether acetate.
23. A method to fluorinate a dodecamer tin composition represented by the formula (QSn) 12 O 14 (OH) 6 (HCO 2 ) 2 , where Q is an alkyl group with 5 to 16 total carbon atoms, or Q is an alkyltin group with a structure —(CH 2 ) n Sn(R 1 R 2 R 3 ) with n=1 to 4 and with 4 to 15 total carbon atoms, and R 1 , R 2 , and R 3 independently alkyl groups with 1 to 10 carbon atoms, the method comprising:
reacting an alkyl tin hydroxide with trialkylamine trihydrofluoride.
24. The method of claim 23 wherein the trialkylamine trihydrofluoride is triethylamine trihydrofluoride.