Synthesis of photoresist polymers
View Patent ↗The present invention is directed to the preparation of photoresist polymers via living free radical polymerization techniques. Sterically bulky ester monomers are utilized as the polymerization components. Use of chain transfer agents is included in polymerization processing conditions. Cleavage of polymer terminal end groups that include a heteroatom are described.
1. A method of free radical polymerization to form a polymer comprising the formula:
wherein R 1 represents a hydrogen atom or a methyl group, each R 2 , individually, represents a linear or branched, non-substituted or substituted, alkyl group having 1-4 carbon atoms or a bridged or non-bridged, non-substituted or substituted, monovalent alicyclic hydrocarbon group having 4-20 carbon atoms, provided that at least one R 2 group is a linear or branched alkyl group having 1-4 carbon atoms, or any two R 2 groups form, in combination and together with the carbon atoms to which the two R 2 groups bond, a bridged or non-bridged, non-substituted or substituted, divalent alicyclic hydrocarbon group having 4-20 carbon atoms, with the remaining R 2 groups being a linear or branched, non-substituted or substituted, alkyl group having 1-4 carbon atoms or —C(R 2 ) 3 , is one of
wherein the polymer is prepared by a living free radical process (LFRP) in the presence of a chain transfer agent (CTA) having the formula
wherein R x is a group that is sufficiently labile to be expelled as its free radical form, T is carbon or phosphorus, and Z is any group that activates the C═S double bond towards a reversible free radical addition fragmentation reaction.
2. The method of claim 1 , wherein Z is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof.
3. The method of claim 1 , wherein Z is selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted, aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl, and optionally substituted arylphosphonyl.
4. The method of claim 1 , wherein the —C(R 2 ) 3 structure in the recurring unit (1) is a 2-methyl-2-tricyclodecanyl group, 2-ethyl-2-tricyclodecanyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, or 1-ethylcyclohexyl group.
5. The method of any of claims 1 - 4 , wherein the polymerization process further comprises addition of a monomer that results in at least a second recurring unit selected from
wherein R 3 represents a hydrogen atom or a methyl group, R 4 is a linear or branched alkyl group having 1-6 carbon atoms or a linear or branched alkyl group having 1-6 carbon atoms substituted with one or more alkyloxy, alkylcarbonyloxy or oxo groups, two or more R 4 groups, if present, being either the same or different, i is an integer of 0−(3+k), j is 0 or 1, k is an integer of 1-3, R 5 represents a hydrogen atom or a methyl group, B is a methylene group, an oxygen atom, or a sulfur atom, R 6 represents a hydrogen atom, a linear or branched alkyl group having 1-6 carbon atoms, or a linear or branched alkyl group having 1-6 carbon atoms substituted with one or more alkyloxy, alkylcarbonyloxy or oxo groups, R 7 represents a hydrogen atom or a methyl group, and R 8 represents a hydrogen atom, a linear or branched alkyl group having 1-6 carbon atoms, or a linear or branched alkyl group having 1-6 carbon atoms substituted with one or more alkyloxy, alkylcarbonyloxy or oxo groups.
6. The method of claim 5 , wherein the polymerization process further comprises addition of a monomer that results in a recurring having the formula:
wherein where E represents a group derived from non-bridged or bridged, non-substituted or substituted alicyclic hydrocarbons and R 9 is a hydrogen atom, trifluoromethyl or a methyl group.
7. The method of claim 1 , wherein the Mw is between about 2,000 and 30,000.
8. The method of claim 2 , wherein the Mw is between about 2,000 and 30,000.
9. The method of claim 3 , wherein the Mw is between about 2,000 and 30,000.
10. The method of claim 4 , wherein the Mw is between about 2,000 and 30,000.
11. The method of claim 5 , wherein the Mw is between about 2,000 and 30,000.
12. The method of claim 6 , wherein the Mw is between about 2,000 and 30,000.
13. The method of claim 1 , wherein the polydispersity is less than or equal to about 1.5.
14. The method of claim 2 , wherein the polydispersity is less than or equal to about 1.5.
15. The method of claim 3 , wherein the polydispersity is less than or equal to about 1.5.
16. The method of claim 4 , wherein the polydispersity is less than or equal to about 1.5.
17. The method of claim 5 , wherein the polydispersity is less than or equal to about 1.5.
18. The method of claim 6 , wherein the polydispersity is less than or equal to about 1.5.
19. The method of claim 1 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.
20. The method of claim 2 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.
21. The method of claim 3 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.
22. The method of claim 4 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.
23. The method of claim 5 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.
24. The method of claim 6 , wherein a terminal end group of the polymer with a CTA fragment is treated such that the CTA fragment is cleaved.