Fullerenes
The present disclosure relates to novel fullerene derivatives, positive and negative photoresist compositions prepared therefrom and methods of using them. The derivatives, their photoresist compositions and the methods are ideal for high speed, fine pattern processing using, for example, ultraviolet radiation, extreme ultraviolet radiation, beyond extreme ultraviolet radiation, X-rays, electron beam and other charged particle rays.
1. A photoresist composition comprising at least one fullerene compound comprising the general formula:
a
wherein Z forms a ring structure with the C2x fullerene chosen from A, B, and C below:
wherein x is at least 10, y is 1 -6, R 1 is a C 1 to C 30 branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, heterocyclic, alkylheterocyclic substituent or a substituent which coordinates with a least one metal, and R 2 is a substituent which coordinates with at least one metal, and wherein R 3 , R 4 and R 5 is, each independently, a 1-6, R 1 is a C 1 to C 30 branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, heterocyclic, alkylheterocyclic substituent or a substituent which coordinates with a least one metal,
b. at least one solvent,
c. at least one photoacid generator, and
d. optionally, at least one of a component chosen from a crosslinker, an alkali soluble and polymer protected by an acid-labile group.
2. The composition of claim 1 , wherein the acid-labile group comprises an alkoxycarbonyl group.
3. The composition of claim 1 , wherein, when y >2, at least one of the R1, R3, R4 and/or R5 substituents is a —COO-alkyl-aryl-(CH2)n-O—R o substituent, wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1-16carbons with or without one or more heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, heteroaromatic group, or fused aromatic or fused heteroaromatic group, and R o is H or an acid labile group.
4. The composition of claim 3 , wherein the metal is comprised of non-fullerene bonded ligands.
5. The composition of claim 3 , wherein the heteroatoms are one or more of oxygen, nitrogen, sulfur, or oxides of sulfur.
6. The composition of claim 1 , wherein the metal is chosen from a transition metal, alkali metal, alkaline earth metal, a lanthanide metal, an actinide metal, metalloids, metals from groups 13, 14 and 15 of the periodic table and their respective cations.
7. The composition of claim 1 , further comprising at least one fullerene comprising the general formula:
wherein x is at least 10, y is 1-6, n is 0 -1, alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1-16carbons with or without one or more heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, heteroaromatic group, or fused aromatic or fused heteroaromatic group, and R is the same or different and is H or an acid labile group.
8. The composition of claim 1 , wherein the substituent which coordinates with at least one metal is a monodentate or a polydentate ligand.
9. The composition of claim 8 , wherein the substituent which coordinates with at least one metal is at least one of a bipyridyl, a crown ether, an ethylene diamine monomer or oligomer, a porphyrines, an ethylene diamine tetraacrylate, a peptide, a polysaccharide, phosphine, phosphates, carboxylates, and/or ethylene oxide monomers or oligomers, cyclic polyamides and heterocycles.
10. The composition of claim 1 , further comprising at least one fullerene comprising the general formula:
C 2x (>C—(COO—(CH 2 CH 2 —O) a —R) 2 ) y
wherein x is at least 10, y is 1-6, a is 1-10 and R is H or an acid labile group and
wherein the —CH 2 CH 2 —O— may be optionally substituted with fluorine atoms.
11. The composition of claim 1 , wherein the at least one photoacid generator comprises an onium salt compound, a triphenylsulphonium salt compound, a sulfone imide compound, a halogen-containing compound, a sulfone compound, a sulfonate ester compound, a quinone-diazide compound, a diazomethane compound, an iodonium salt compound, an oxime sulfonate compound or a dicarboxylimide sulfonate compound.
12. A fullerene comprising the general formula:
wherein Z forms a ring structure with the C2x fullerene chosen from A, B, and C below:
wherein x is at least 10, y is 1 -6, R 1 is a C 1 to C 30 branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, heterocyclic, alkylheterocyclic substituent or a substituent which coordinates with a least one metal, and R 2 is a substituent which coordinates with at least one metal, and wherein R 3 , R 4 and R 5 is, each independently, a 1-6, R 1 is a C 1 to C 30 branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aryl, aralkyl, heterocyclic, alkylheterocyclic substituent or a substituent which coordinates with a least one metal, and wherein fullerene C is a nonmethanoyl fullerene.
13. The fullerenes of claim 12 , wherein, when y>2, at least one of the R1, R3, R4 and/or R5 substituents is a —COO-alkyl-aryl-(CH2)n-O—R o substituent, wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1- 16 carbons with or without one or more heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, heteroaromatic group, or fused aromatic or fused heteroaromatic group, and R o is H or an acid labile group.
14. The fullerenes of claim 13 , wherein the heteroatoms are one or more of oxygen, nitrogen, sulfur, or oxides of sulfur.
15. The fullerenes of claim 13 , wherein the acid labile group comprises an alkoxycarbonyl group.
16. The fullerenes of claim 12 , wherein the metal is chosen from a transition metal, alkali metal, alkaline earth metal, a lanthanide metal, an actinide metal, metalloids, metals from groups 13, 14 and 15 of the periodic table and their respective cations.
17. The fullerenes of claim 16 , wherein the metal is comprised of non-fullerene bonded ligands.
18. The composition of claim 12 , wherein the substituent which coordinates with at least one metal is a monodentate or a polydentate ligand.
19. The composition of claim 18 , wherein the substituent which coordinates with at least one metal is at least one of a bipyridyl, a crown ether, an ethylene diamine monomer or oligomer, a porphyrines, an ethylene diamine tetraacrylate, a peptide, a polysaccharide, phosphine, phosphates, carboxylates, and/or ethylene oxide monomers or oligomers, cyclic polyamides and heterocycles.