PHOTOACID GENERATORS, PHOTORESIST COMPOSITIONS, AND PATTERN FORMATION METHODS
A photoacid generator, including an organic cation; and an anion including an anionic core, wherein the anionic core includes a cyclopentadienide group, wherein the cyclopentadienide group is substituted with an organic group including a semi-metal element, and wherein the anion is substituted with one or more electron withdrawing groups.
1 . A photoacid generator, comprising:
an organic cation; and
an anion comprising an anionic core, wherein the anionic core comprises a cyclopentadienide group,
wherein the cyclopentadienide group is substituted with an organic group comprising a semi-metal element, and
wherein the anion is substituted with one or more electron withdrawing groups.
2 . The photoacid generator of claim 1 , wherein the organic cation is a sulfonium cation or an iodonium cation.
3 . The photoacid generator of claim 1 , wherein the anion is represented by one or more of Formulae (1) to (3):
wherein, in Formulae (1) to (3),
E 1 , E 2 , E 3 , E 4 , and E 5 are each independently an electron withdrawing group;
n1 is an integer from 1 to 4;
n2 is an integer from 0 to 4, and n3 is an integer from 0 to 2, provided that at least one of n2 and n3 is not 0;
n4 and n5 are each independently an integer from 0 to 4, provided that at least one of n4 and n5 is not 0;
m1 is an integer from 0 to 3;
m2 is an integer from 0 to 4, and m3 is an integer from 0 to 2;
m4 and m5 are each independently an integer from 0 to 4;
R 1 , R 2 , R 3 , R 4 , and R 5 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 heteroalkyl, substituted or unsubstituted C 4-30 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 heteroarylalkyl, or substituted or unsubstituted C 4-30 alkylheteroaryl;
each of R 2 , R 3 , R 4 , and R 5 optionally further comprises one or both of a divalent linking group or a polymerizable group as part of its structure;
L 1 , L 2 , and L 3 are each independently a single bond or a divalent linking group; and
Y 1 , Y 2 , and Y 3 are each independently the organic group comprising the semi-metal element,
wherein the semi-metal element is selected from B, Si, Ge, As, Te, Sb, Se, or a combination thereof.
4 . The photoacid generator of claim 1 , wherein each electron withdrawing group is independently selected from halogen, substituted or unsubstituted C 1-20 haloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 3-20 heteroaryl, —OR 6 , —NO 2 , —CN, —C(O)R 8 , —C(O)OR 9 , —C(O)NR 10 R 11 , —S(O) 2 OR 12 , —S(O) 2 R 13 , —OS(O) 2 R 14 , or a combination thereof, wherein R 6 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 alkylheteroaryl, or substituted or unsubstituted C 4-20 heteroarylalkyl,
wherein R 13 and R 14 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 alkylheteroaryl, or substituted or unsubstituted C 4-20 heteroarylalkyl,
provided that none of E 1 to E 5 comprises fluorine.
5 . The photoacid generator of claim 3 , wherein Y 1 , Y 2 , and Y 3 are each independently represented by one of Formulae (4) to (6):
wherein, in Formulae (4) to (6),
Z 1 is Se, Te, Se—Se, or Te—Te;
Z 2 is B, As, AsO, Sb, or SbO;
Z 3 is Si, Ge, or Te;
R 19 is cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl; wherein R 19 optionally further comprises a divalent linking group as part of its structure;
R 20 and R 21 are each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl; wherein R 20 and R 21 each optionally further comprises a divalent linking group as part of its structure;
provided that at least one of R 20 and R 21 is an organic group;
R 20 and R 21 are optionally connected to each other via a single bond or a divalent linking group to form a ring, wherein the ring is substituted or unsubstituted;
R 22 to R 24 are each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl;
provided that at least one of R 22 to R 24 is an organic group;
R 22 to R 24 each optionally further comprises a divalent linking group as part of its structure;
two or more of R 22 to R 24 are optionally connected to each other via a single bond or a divalent linking group to form a ring, wherein the ring is substituted or unsubstituted; and
* represents a binding site to L 1 for Y 1 , a binding site to L 2 for Y 2 , or a binding site to L 3 for Y 3 .
6 . The photoacid generator of claim 1 , wherein the anion comprises three or more —CN groups; and at least one Si atom.
7 . The photoacid generator of claim 1 , wherein
n1 is an integer of 3 or greater;
n2+n3 is an integer of 3 or greater; and
n4+n5 is an integer of 3 or greater.
8 . The photoacid generator of claim 1 , wherein the electron withdrawing group is —CN.
9 . The photoacid generator of claim 1 , wherein the photoacid generator is in the form of (i) a monomer comprising a polymerizable double bond or (ii) a polymer.
10 . A photoresist composition, comprising:
a polymer;
the photoacid generator of claim 1 , wherein the photoacid generator is optionally part of the polymer; and
a solvent.
11 . A method for forming a pattern, the method comprising:
(a) forming a photoresist layer from a photoresist composition of claim 10 on a substrate;
(b) pattern-wise exposing the photoresist layer to activating radiation; and
(c) developing the exposed photoresist layer to provide a resist relief image.
12 . The photoresist composition of claim 10 , wherein the organic cation is a sulfonium cation or an iodonium cation.
13 . The photoresist composition of claim 10 , wherein the anion is represented by one or more of Formulae (1) to (3):
wherein, in Formulae (1) to (3),
E 1 , E 2 , E 3 , E 4 , and E 5 are each independently an electron withdrawing group;
n1 is an integer from 1 to 4;
n2 is an integer from 0 to 4, and n3 is an integer from 0 to 2, provided that at least one of n2 and n3 is not 0;
n4 and n5 are each independently an integer from 0 to 4, provided that at least one of n4 and n5 is not 0;
m1 is an integer from 0 to 3;
m2 is an integer from 0 to 4, and m3 is an integer from 0 to 2;
m4 and m5 are each independently an integer from 0 to 4;
R 1 , R 2 , R 3 , R 4 , and R 5 are each independently substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 1-30 heteroalkyl, substituted or unsubstituted C 4-30 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 heteroarylalkyl, or substituted or unsubstituted C 4-30 alkylheteroaryl;
each of R 1 , R 2 , R 3 , R 4 , and R 5 optionally further comprises one or both of a divalent linking group or a polymerizable group as part of its structure;
L 1 , L 2 , and L 3 are each independently a single bond or a divalent linking group; and
Y 1 , Y 2 , and Y 3 are each independently the organic group comprising the semi-metal element,
wherein the semi-metal element is selected from B, Si, Ge, As, Te, Sb, Se, or a combination thereof.
14 . The photoresist composition of claim 10 , wherein each electron withdrawing group is independently selected from halogen, substituted or unsubstituted C 1-20 haloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 3-20 heteroaryl, —OR 6 , —SR 7 , —NO 2 , —CN, —C(O)R 8 , —C(O)OR 9 , —C(O)NR 10 R 11 , —S(O) 20 R 12 , —S(O) 2 R 13 , —OS(O) 2 R 14 , or a combination thereof,
wherein R 6 to R 12 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 alkylheteroaryl, or substituted or unsubstituted C 4-20 heteroarylalkyl,
wherein R 13 and R 14 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 3-20 heterocycloalkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 7-20 alkylaryl, substituted or unsubstituted C 7-20 arylalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 alkylheteroaryl, or substituted or unsubstituted C 4-20 heteroarylalkyl,
provided that none of E 1 to E 5 comprises fluorine.
15 . The photoresist composition of claim 10 , wherein Y′, Y 2 , and Y 3 are each independently represented by one of Formulae (4) to (6):
wherein, in Formulae (4) to (6),
Z 1 is Se, Te, Se—Se, or Te—Te;
Z 2 is B, As, AsO, Sb, or SbO;
Z 3 is Si, Ge, or Te;
R 19 is cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl; wherein R 19 optionally further comprises a divalent linking group as part of its structure;
R 20 and R 21 are each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl; wherein R 20 and R 21 each optionally further comprises a divalent linking group as part of its structure;
provided that at least one of R 20 and R 21 is an organic group;
R 20 and R 21 are optionally connected to each other via a single bond or a divalent linking group to form a ring, wherein the ring is substituted or unsubstituted;
R 22 to R 24 are each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkoxy, substituted or unsubstituted C 4-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 aryloxy, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 3-30 heteroaryloxy, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 heteroarylalkyl;
provided that at least one of R 22 to R 24 is an organic group;
R 22 to R 24 each optionally further comprises a divalent linking group as part of its structure;
two or more of R 22 to R 24 are optionally connected to each other via a single bond or a divalent linking group to form a ring, wherein the ring is substituted or unsubstituted; and
* represents a binding site to L 1 for Y 1 , a binding site to L 2 for Y 2 , or a binding site to L 3 for Y 3 .
16 . The photoresist composition of claim 10 , wherein the anion comprises three or more —CN groups; and at least one Si atom.
17 . The photoresist composition of claim 10 , wherein
n1 is an integer of 3 or greater;
n2+n3 is an integer of 3 or greater; and
n4+n5 is an integer of 3 or greater.
18 . The photoresist composition of claim 10 , wherein the electron withdrawing group is —CN.
19 . The photoresist composition of claim 10 , wherein the photoacid generator is in the form of (i) a monomer comprising a polymerizable double bond or (ii) a polymer.