Photoacid generator
A photoacid generator compound having Formula (I): wherein, EWG, Y, R, and M + are the same as described in the specification.
1. A photoacid generator compound having Formula (I):
wherein:
EWG is an electron-withdrawing group selected from the group consisting of a halogen, —CF 3 , —CCl 3 , —CN, —NO 2 , —C(═O)R 21 , —C(═O)OR 22 , —C(═O)NH 2 , —SO 3 H, and —SO 2 R 23 , wherein R 21 is a hydrogen, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group, and R 22 and R 23 are each independently a hydrogen, a C 1-30 aliphatic organic group, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group;
Y is a single bond, a C 1-30 linking group, an ether group, a carbonyl group, an ester group, a carbonate group, an amine group, an amide group, a urea group, a sulfate group, a sulfoxide group, an N-oxide group, a sulfonate group, a sulfonamide group, or a combination of at least two of the foregoing;
R is hydrogen, a straight chain or branched C 1-20 alkyl group, a straight chain or branched C 2-20 alkenyl group, a monocyclic or polycyclic C 3-20 cycloalkyl group, a monocyclic or polycyclic C 3-20 cycloalkenyl group, a monocyclic or polycyclic C 3-20 heterocycloalkyl group; a monocyclic or polycyclic C 3-20 heterocycloalkenyl group; a monocyclic or polycyclic C 6-20 aryl group, or a monocyclic or polycyclic C 1-20 heteroaryl group, each of which except hydrogen is substituted or unsubstituted; and
M + is an organic sulfonium cation or an organic iodonium cation having Formula (VII):
wherein,
R 0 is a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 1-30 heteroaryl group, a C 7-30 aralkyl group, a C 7-30 fluoroaralkyl group, a C 2-30 heteroaralkyl group, or a C 2-30 fluoroheteroaralkyl group, each of which is substituted or unsubstituted, and
Ar is a C 6-30 substituted aromatic organic group,
wherein Ar is optionally connected to R 0 .
2. A photoacid generator compound having Formulae (II) or (III):
wherein:
X 1 , X 2 , X 3 and X 4 are each independently an electron-withdrawing group;
X 5 and X 6 are each independently an electron withdrawing group selected from C(CN) 2 , C(NO 2 ) 2 , C(COR 27 ) 2 , C(CO 2 R 28 ) 2 , C(SO 2 R 29 ) 2 , and C(R f ) 2 , wherein R f is a C 1 -C 30 fluoroalkyl group;
Z 1 and Z 2 are each independently hydrogen, a straight chain or branched C 1-50 alkyl group, a monocyclic or polycyclic C 3-50 cycloalkyl group, a monocyclic or polycyclic C 3-50 heterocycloalkyl group; a monocyclic or polycyclic C 6-50 aryl group, a monocyclic or polycyclic C 5-20 heteroaryl group, or a combination thereof, wherein groups Z 1 and Z 2 are optionally connected to each other to form a ring;
Y is a single bond or a C 1-30 linking group;
R is a straight chain or branched C 1-20 alkyl group, a straight chain or branched C 2-20 alkenyl group, a monocyclic or polycyclic C 3-20 cycloalkyl group, a monocyclic or polycyclic C 3-20 cycloalkenyl group, a monocyclic or polycyclic C 3-20 heterocycloalkyl group; a monocyclic or polycyclic C 3-20 heterocycloalkenyl group; a monocyclic or polycyclic C 6-20 aryl group, or a monocyclic or polycyclic C 1-20 heteroaryl group, each of which except hydrogen is substituted or unsubstituted; and
M + is an organic sulfonium cation or an organic iodonium cation having Formula (VII):
wherein,
R 0 is a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 1-30 heteroaryl group, a C 7-30 aralkyl group, a C 7-30 fluoroaralkyl group, a C 2-30 heteroaralkyl group, or a C 2-30 fluoroheteroaralkyl group, each of which is substituted or unsubstituted, and
Ar is a C 6-30 substituted aromatic organic group,
wherein Ar is optionally connected to R 0 ; and
each “ ” represents a partial double bond.
3. A photoacid generator compound having Formula
wherein,
X 5 and X 6 are each C(CN) 2 ;
Z 1 and Z 2 are each independently hydrogen, a straight chain C 1-50 alkyl group, a branched C 3-50 alkyl group, a monocyclic C 3-50 cycloalkyl group, a polycyclic C 7-50 cycloalkyl group, a monocyclic or polycyclic C 3-50 heterocycloalkyl group; a monocyclic C 6-50 aryl group, a polycyclic C 10-50 aryl group, a monocyclic or polycyclic C 5-20 heteroaryl group, or a combination thereof, wherein groups Z 1 and Z 2 are optionally connected to each other to form a ring;
R is a polycyclic C 3-20 cycloalkyl group;
Y is a single bond, —C(R 30 ) 2 —, —N(R 31 )—, —O—, —S—, —S(═O) 2 —, —C(═O)—, or a combination thereof, wherein each R 30 and R 31 is independently hydrogen or a C 1-6 alkyl group; and
M + is an organic sulfonium cation or an organic iodonium cation having Formula (VII):
wherein,
R 0 is a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 1-30 heteroaryl group, a C 7-30 aralkyl group, a C 7-30 fluoroaralkyl group, a C 2-30 heteroaralkyl group, or a C 2-30 fluoroheteroaralkyl group, each of which is substituted or unsubstituted, and
Ar is a C 6-30 substituted aromatic organic group,
wherein Ar is optionally connected to R 0 .
4. The photoacid generator compound of claim 2 , wherein in Formula (III):
X 5 and X 6 are each C(CN) 2 ; and
Y is a single bond.
5. A photoacid generator compound having Formula (IV):
wherein,
X 5 and X 6 are each independently an electron withdrawing group selected from C(NO 2 ) 2 , C(COR 27 ) 2 , C(CO 2 R 28 ) 2 , C(SO 2 R 29 ) 2 , and C(R f ) 2 , wherein R 27 , R 28 , and R 29 are each independently a C 1-30 aliphatic organic group, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group, and wherein R f is a C 1 -C 30 fluoroalkyl group;
M + is an organic sulfonium cation, or M + is an organic iodonium cation having Formula (VII):
wherein,
R 0 is a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 1-30 heteroaryl group, a C 7-30 aralkyl group, a C 7-30 fluoroaralkyl group, a C 2-30 heteroaralkyl group, or a C 2-30 fluoroheteroaralkyl group, each of which is substituted or unsubstituted, and
Ar is a C 6-30 substituted aromatic organic group,
wherein Ar is optionally connected to R 0 ;
R 1 is a halogen, a C 1-10 alkyl group, a C 1-10 fluoroalkyl group, a C 1-10 alkoxy group, a C 1-10 fluoroalkoxy group, a C 3-10 cycloalkyl group, a C 3-10 fluorocycloalkyl group, a C 3-10 cycloalkoxy group, a C 3-10 fluorocycloalkoxy group, or an electron-withdrawing group selected from NO 2 , CN, C(R f ) 3 or CO 2 R, wherein R f is a C 1 -C 30 fluoroalkyl group; and
k is an integer of 0, 1, 2, 3, or 4.
6. The photoacid generator compound of claim 1 , wherein the organic sulfonium cation has Formula (V):
wherein,
each R 2 is independently a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-20 aryl group, a C 6-20 fluoroaryl group, a C 1-20 heteroaryl group, a C 7-20 aralkyl group, a C 7-20 fluoroaralkyl group, a C 2-20 heteroaralkyl group, or a C 2-20 fluoroheteroaralkyl group, each of which is substituted or unsubstituted,
wherein each R 2 is either separate or connected to the other group R 2 via a single bond or a linking group, and
Ar is a substituted or unsubstituted C 6-30 aromatic organic group.
7. The compound of claim 1 , wherein M + is an organic cation having Formula (VI):
wherein
X is I or S;
each R 3 is independently a halogen, a C 1-10 alkyl group, a C 1-10 fluoroalkyl group, a C 1-10 alkoxy group, a C 1-10 fluoroalkoxy group, a C 3-10 cycloalkyl group, a C 3-10 fluorocycloalkyl group, a C 3-10 cycloalkoxy group, a C 3-10 fluorocycloalkoxy group, or a C 6-10 alkoxycarbonylalkyleneoxy group;
each n is an integer of 0, 1, 2, 3, 4, and 5, provided that when X is I, at least one n is not 0; and
m is an integer of 2 or 3, provided that when X is I, m is 2, and where X is S, m is 3.
8. The compound of claim 1 , wherein M + is an organic cation having Formulae (VII) or (VIII):
wherein
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a halogen, —CN, —OH, a C 1-10 alkyl group, a C 1-10 fluoroalkyl group, a C 1-10 alkoxy group, a C 1-10 fluoroalkoxy group, a C 3-10 cycloalkyl group, a C 3-10 fluorocycloalkyl group, a C 3-10 cycloalkoxy group, or a C 3-10 fluorocycloalkoxy group, each of which except a halogen, —CN, and —OH is substituted or unsubstituted;
J is a single bond or a connecting group selected from S, O, and C═O,
p is each independently an integer of 0, 1, 2, 3, or 4;
r is an integer of 0, 1, 2, 3, 4, and 5, and
s and t are each independently an integer of 0, 1, 2, 3, and 4.
9. An acid-sensitive polymer comprising a unit formed from a photoacid generator compound having Formula (I):
wherein:
EWG is an electron-withdrawing group selected from the group consisting of a halogen, —CF 3 , —CCl 3 , —CN, —NO 2 , —C(═O)R 21 , —C(═O)OR 22 , —C(═O)NH 2 , —SO 3 H, and —SO 2 R 23 , wherein R 21 is a hydrogen, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group, and R 22 and R 23 are each independently a hydrogen, a C 1-30 aliphatic organic group, a C 6-30 aromatic organic group, or a C 1-30 heteroaromatic organic group;
Y is a single bond, a C 1-30 linking group, an ether group, a carbonyl group, an ester group, a carbonate group, an amine group, an amide group, a urea group, a sulfate group, a sulfoxide group, an N-oxide group, a sulfonate group, a sulfonamide group, or a combination of at least two of the foregoing;
R is a polymerizable group; and
M + is an organic sulfonium cation or an organic iodonium cation having Formula (VII):
wherein,
R 0 is a C 1-20 alkyl group, a C 1-20 fluoroalkyl group, a C 3-20 cycloalkyl group, a C 3-20 fluorocycloalkyl group, a C 2-20 alkenyl group, a C 2-20 fluoroalkenyl group, a C 6-30 aryl group, a C 6-30 fluoroaryl group, a C 1-30 heteroaryl group, a C 7-30 aralkyl group, a C 7-30 fluoroaralkyl group, a C 2-30 heteroaralkyl group, or a C 2-30 fluoroheteroaralkyl group, each of which is substituted or unsubstituted, and
Ar is a C 6-30 substituted aromatic organic group,
wherein Ar is optionally connected to R 0 .
10. A photoresist composition, comprising:
an acid-sensitive polymer,
a solvent, and
the photoacid generator compound of claim 1 .
11. A photoresist composition, comprising:
the acid-sensitive polymer of claim 9 , and
a solvent.
12. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 10 on a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image.