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 compound represented by the formula (RCC) 3 SnQ, wherein R is a hydrocarbyl group with 1 to 15 carbon atoms and wherein Q is an alkyltin group with a structure —(CH 2 ) n Sn(R 1 R 2 R 3 ) wherein n=1 to 4 and R 1 , R 2 , and R 3 are independently alkyl groups with 1 to 5 carbon atoms, with the proviso that Q has 4 to 15 total carbon atoms.
2. The composition of claim 1 wherein Q is represented by (CH 2 ) n Sn(CH 3 ) 3 , where n=1 to 4.
3. The composition of claim 1 wherein Q is represented by CH 2 Sn(CH 3 ) 3 .
4. A method of forming an organo tin compound, the method comprising:
gradually adding tin dihalide to a solution comprising an organic solvent, alkylacetylene having the formula HC≡CR, and alkylmagnesium halide to form a tin intermediate solution; and
combining XCH 2 Sn(R 1 R 2 R 3 ), where X is a halide and R 1 , R 2 , and R 3 are independently alkyl groups with 1 to 5 carbon atoms, to the tin intermediate solution to form a solid compound, (RCC) 3 SnCH 2 Sn(R 1 R 2 R 3 ).
5. The method of claim 4 wherein the tin dihalide is SnCl 2 and the alkyl magnesium halide is alkyl magnesium chloride, wherein the alkyl group has 1 to 4 carbon atoms.
6. The method of claim 4 wherein the solvent is tetrahydrofuran.
7. The method of claim 4 wherein the alkylacetylene is phenylacetylene.
8. The composition of claim 1 wherein R 1 and R 2 form a cyclic alkyl moiety.
9. The composition of claim 1 wherein R 1 , R 2 , and R 3 form a cyclic moiety.
10. The composition of claim 1 wherein R comprises an alkyl group, an alkenyl group, an aromatic groups, or corresponding halogenated derivatives thereof.
11. The composition of claim 1 wherein the tin compound comprises (C 6 H 5 CC) 3 SnCH 2 Sn(CH 3 ) 3 .
12. The method of claim 4 wherein X is a chlorine atom.
13. The method of claim 4 wherein the solvent comprises an aprotic polar solvent.