Iodine-containing photoacid generators and compositions comprising the same
A photoacid generator compound having formula (I): wherein, in formula (I), groups and variables are the same as described in the specification.
1. A photoacid generator compound having formula (I):
wherein, in formula (I):
“I” represents iodine;
V is OR 1 or C(═O)OR 1 , wherein R 1 is independently H or a substituted or unsubstituted C 1-30 hydrocarbyl group optionally comprising 1 to 5 heteroatoms selected from O, S, N, P, and F, and optionally comprising an acid-cleavable group, a polymerizable group, or a combination thereof;
W is a single bond or a group selected from —(C═O)O—, —O(SO 2 )—, —(SO 2 )O—, —NH(SO 2 )—, —(SO 2 )NH—, —NH(CO)—, —(CO)NH—, —SO 2 —, and —SO—;
m is an integer of 0 or greater;
n is an integer of 0 or greater;
L is a single bond or a group having formula —(CH 2 ) n1 —(CR 2 R 3 ) n2 —, wherein R 2 and R 3 are selected from hydrogen and fluorine, provided that at least one of R 2 and R 3 in each —(CR 2 R 3 )— is fluorine, n1 is an integer of 0 to 10, and n2 is an integer of 2 to 10;
represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 arylene group or a monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene group, wherein each “*” indicates a point of attachment to a neighboring group or atom;
G + has formula (II):
wherein, in formula (II):
X is S or I,
each R c is unsubstituted or substituted, halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; or a polycyclic or monocyclic C 4-30 aryl group,
wherein when X is S, one of the R c is optionally attached to one adjacent R c to form a ring, and the photoacid generator compound having formula (I) comprises at least two iodine atoms, and G + comprises at least one iodine, and
wherein when X is I, n is an integer of 1 or greater,
wherein when X is S, n is an integer of 0 or greater, provided the photoacid generator having formula (I) comprises at least two iodine atoms,
z is 2 or 3, wherein when X is I, z is 2, or when X is S, z is 3; and
Y is SO 3 , CO 2 , NHSO 3 , or O.
2. The photoacid generator compound of claim 1 , wherein W is a single bond or —(C═O)O—.
3. The photoacid generator compound of claim 1 , wherein L a is a single bond.
4. The photoacid generator compound of claim 1 , wherein
is a C 6 aryl group and n is 1, 2, 3, 4, or 5 when X═I, and n is 0, 1, 2, 3, 4, or 5 when X═S.
5. The photoacid generator compound of claim 1 , wherein the photoacid generator compound I comprises, two, three, four, or five iodine atoms.
6. The photoacid generator compound of claim 1 , wherein G + has formula (III), (IV), or (V):
X is I or S,
R h , R i , R j , R k and R l are unsubstituted or substituted and are each independently hydroxy, nitrile, halogen selected from fluorine, chlorine, bromine, and iodine, a C 1-30 alkyl group, a C 1-30 fluoroalkyl group, a C 3-30 cycloalkyl group, a C 1-30 fluorocycloalkyl group, a C 1-30 alkoxy group, a C 3-30 alkoxycarbonylalkyl group, a C 3-30 alkoxycarbonylalkoxy group, a C 3-30 cycloalkoxy group, C 5-30 a cycloalkoxycarbonylalkyl group, a C 5-30 cycloalkoxycarbonylalkoxy group, a C 1-30 fluoroalkoxy group, a C 3-30 fluoroalkoxycarbonylalkyl group, a C 3-30 fluoroalkoxycarbonylalkoxy group, a C 3-30 fluorocycloalkoxy group, a C 5-30 fluorocycloalkoxycarbonylalkyl group, a C 5-30 fluorocycloalkoxycarbonylalkoxy group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 6-30 aryloxy group, a C 6-30 fluoroaryloxy group, or a C 2-30 acetal group comprising —O—C(R 11 R 12 )—O— (wherein R 11 and R 12 are each independently hydrogen or a C 1-30 alkyl group), each of which is unsubstituted or substituted;
wherein at least one of R i , R j , R k and R l is optionally substituted with an acid-sensitive group, a polymerizable group, or a combination thereof,
Ar 1 and Ar 2 are independently C 10-30 fused or singly bonded polycyclic aryl groups;
wherein X is S or I;
p is an integer of 2 or 3,
wherein when X is I, p is 2, and wherein when X is S, p is 3,
q and r are each independently an integer from 0 to 5,
u is an integer from 0 to 1, wherein when u is 0, X is I, and wherein when u is 1, X is S, and
s and t are each independently an integer from 0 to 4.
7. A photoresist composition comprising the photoacid generator compound of any of claims 1 to 6 and a copolymer.
8. The photoresist composition of claim 7 , wherein the copolymer comprises the acid-deprotectable monomer represented by formula (VI), the base-soluble monomer represented by formula (VII), and the lactone-containing monomer represented by formula (VIII):
wherein
each R a is independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl;
each R b is independently H, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 3-20 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group, or a substituted or unsubstituted C 7-20 aralkyl group, and each R b is separate or at least one R b is bonded to an adjacent R b to form a cyclic structure;
Q 1 is an ester-containing or non-ester containing group selected from a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 3-20 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group, and a substituted or unsubstituted C 7-20 aralkyl group;
W 1 is a base-reactive group comprising at least one selected from —C(═O)—OH; —C(CF 3 ) 2 OH; —NH—SO 2 —Y 1 where Y 1 is F or a C 1-4 perfluoroalkyl group; an aromatic —OH;
and an adduct of any of the foregoing with a vinyl ether;
a is an integer of 1 to 3; and
L 1 is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group.
9. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition of claim 7 over the one or more layers to be patterned.
10. A method of forming an electronic device, comprising:
(a) applying a layer of the photoresist composition of claim 7 over a surface of the substrate;
(b) pattern-wise exposing the photoresist composition layer to activating radiation; and
(c) developing the exposed photoresist composition layer to provide a resist relief image.
11. A photoacid generator compound having formula (I):
wherein, in formula (I):
“I” represents iodine;
V is OR 1 or C(═O)OR 1 , wherein R 1 is independently H or a substituted or unsubstituted C 1-30 hydrocarbyl group optionally comprising 1 to 5 heteroatoms selected from O, S, N, P, and F, and optionally comprising an acid-cleavable group, a polymerizable group, or a combination thereof,
W is a single bond or a group selected from —(C═O)O—, —O(C═O)—, —O(SO 2 )—, —(SO 2 )O—, —NH(SO 2 )—, —(SO 2 )NH—, —NH(CO)—, —(CO)NH—, —SO 2 —, and —SO—;
m is an integer of 0 or greater;
n is an integer of 0 or greater;
L is a single bond, an unsubstituted C 1-20 heteroalkylene group, a substituted or unsubstituted C 3-20 cycloalkylene group, a substituted or unsubstituted C 3-20 heterocycloalkylene group, a substituted or unsubstituted C 7-20 aralkylene group, or a group having formula —(CH 2 ) n1 —(CR 2 R 3 ) n2 —, wherein R 2 and R 3 are selected from hydrogen and fluorine, provided that at least one of R 2 and R 3 in each —(CR 2 R 3 )— is fluorine, n1 is an integer of 0 to 10, and n2 is an integer of 1 to 10;
represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 arylene group or a monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene group, wherein each “*” indicates a point of attachment to a neighboring group or atom;
G + has formula (II):
wherein, in formula (II):
X is S or I,
each R c is unsubstituted or substituted, halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; or a polycyclic or monocyclic C 4-30 aryl group,
wherein when X is S, one of the R c is optionally attached to one adjacent R c to form a ring, and the photoacid generator compound having formula (I) comprises at least two iodine atoms, and
wherein when X is I, n is an integer of 1 or greater,
wherein when X is S, n is an integer of 0 or greater, provided the photoacid generator having formula (I) comprises at least two iodine atoms,
z is 2 or 3, wherein when X is I, z is 2, or when X is S, z is 3; and
Y is CO 2 .
12. A photoacid generator compound having formula (I):
wherein, in formula (I):
“I” represents iodine;
V is OR 1 or C(═O)OR 1 , wherein R 1 is independently H or a substituted or unsubstituted C 1-30 hydrocarbyl group optionally comprising 1 to 5 heteroatoms selected from O, S, N, P, and F, and optionally comprising an acid-cleavable group, a polymerizable group, or a combination thereof;
W is a single bond or a group selected from —(C═O)O—, —O(SO 2 )—, —(SO 2 )O—, —NH(SO 2 )—, —(SO 2 )NH—, —NH(CO)—, —(CO)NH—, —SO 2 —, and —SO—;
m is an integer of 0 or greater;
L is a single bond or a group having formula —(CH 2 ) n1 —(CR 2 R 3 ) n2 —, wherein R 2 and R 3 are selected from hydrogen and fluorine, provided that at least one of R 2 and R 3 in each —(CR 2 R 3 )— is fluorine, n1 is an integer of 0 to 10, and n2 is an integer of 2 to 10;
represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 arylene group or a monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene group, wherein each “*” indicates a point of attachment to a neighboring group or atom;
G + has formula (II):
wherein, in formula (II):
X is I,
each R c is unsubstituted or substituted, halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; or a polycyclic or monocyclic C 4-30 aryl group, and
n is an integer of 1 or greater,
z is 2; and
Y is SO 3 , CO 2 , NHSO 3 , or O.
13. A photoacid generator compound having formula (I):
wherein, in formula (I):
“I” represents iodine;
V is OR 1 or C(═O)OR 1 , wherein R 1 is independently H or a substituted or unsubstituted C 1-30 hydrocarbyl group optionally comprising 1 to 5 heteroatoms selected from O, S, N, P, and F, and optionally comprising an acid-cleavable group, a polymerizable group, or a combination thereof,
W is a single bond or a group selected from —(C═O)O—, —O(C═O)—, —O(SO 2 )—, —(SO 2 )O—, —NH(SO 2 )—, —(SO 2 )NH—, —NH(CO)—, —(CO)NH—, —SO 2 —, and —SO—;
m is an integer of 0 or greater;
n is an integer of 0 or greater;
L is a single bond, a substituted or unsubstituted C 1-20 alkylene group, a substituted or unsubstituted C 1-20 heteroalkylene group, a substituted or unsubstituted C 3-20 cycloalkylene group, a substituted or unsubstituted C 3-20 heterocycloalkylene group, a substituted or unsubstituted C 6-20 arylene group, or a substituted or unsubstituted C 7-20 aralkylene group;
represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 arylene group or a monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene group, wherein each “*” indicates a point of attachment to a neighboring group or atom;
G + has formula (II):
wherein, in formula (II):
X is S or I,
each R c is unsubstituted or substituted, halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; or a polycyclic or monocyclic C 4-30 aryl group,
wherein when X is S, one of the R c is optionally attached to one adjacent R c to form a ring, the photoacid generator compound having formula (I) comprises at least two iodine atoms, n is an integer of 1 or greater, and G + comprises at least one iodine,
z is 2 or 3, wherein when X is I, z is 2, or when X is S, z is 3; and
Y is SO 3 , CO 2 , NHSO 3 , or O,
wherein when X is I, G + comprises at least one iodine in addition to the positively charged iodonium cation.