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 (II):
wherein:
X 1 , X 2 , X 3 and X 4 are each independently an electron-withdrawing group;
Y is a single bond or a linking group;
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 ; and
each “ ” represents a partial double bond.
2. A photoacid generator compound having Formula (III):
wherein:
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 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;
Z 1 and Z 2 are each 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 linking group;
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 ,
wherein when X 5 and X 6 are both C(CN) 2 , Z 1 and Z 2 are not connected to each other to form a ring.
3. The photoacid generator compound of claim 2 , wherein in Formula (III):
X 5 and X 6 are each C(CN) 2 ;
R is a polycyclic C 3-20 cycloalkyl group; and
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.
4. The photoacid generator compound of claim 2 , wherein in Formula (III):
X 5 and X 6 are each C(CN) 2 ;
R is hydrogen; and
Y is a single bond.
5. The photoacid generator compound of claim 2 , having Formula (IV):
wherein,
X 5 , X 6 , and M + are the same as in claim 2 ;
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 is 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; and
k is an integer of 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 photoacid generator compound of claim 1 , wherein
when M + is an organic sulfonium cation, the organic sulfonium cation has the following formula:
wherein X is 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, or 5; and m is 3; and
when M + is an organic iodonium cation, the organic iodonium cation has the following formula:
wherein X is I; each R 3 is independently a halogen, a C 3-10 cycloalkyl group, or a C 3-10 fluorocycloalkyl group; each n is an integer of 0, 1, 2, 3, 4, or 5, provided that at least one n is not 0; and m is 2.
8. The photoacid generator 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, or 5, and
s and t are each independently an integer of 0, 1, 2, 3, or 4.
9. The photoacid generator compound of claim 1 , wherein R is a polymerizable group.
10. The photoacid generator compound of claim 2 , wherein R is a polymerizable group.
11. An acid-sensitive polymer comprising a unit formed from a photoacid generator compound having Formula (II):
wherein:
X 1 , X 2 , X 3 and X 4 are each independently an electron-withdrawing group;
Y is a single bond or a linking group;
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 ; and
each “ ” represents a partial double bond.
12. A photoresist composition, comprising:
an acid-sensitive polymer,
a solvent, and
a photoacid generator compound of claim 1 .
13. A photoresist composition, comprising:
the acid-sensitive polymer of claim 11 , and
a solvent.
14. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 12 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.
15. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 13 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.
16. An acid-sensitive polymer comprising a unit formed from a photoacid generator compound having Formula (II):
wherein:
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 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;
Z 1 and Z 2 are each 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 linking group;
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 ,
wherein when X 5 and X 6 are both C(CN) 2 , Z 1 and Z 2 are not connected to each other to form a ring.
17. A photoresist composition, comprising:
an acid-sensitive polymer,
a solvent, and
a photoacid generator compound of claim 2 .
18. A photoresist composition, comprising:
the acid-sensitive polymer of claim 16 , and
a solvent.
19. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 17 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.
20. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 18 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.