Photoacid generator

Patent metadata

Field	Value
Publication number	US-2017192352-A1
Application number	US-201615387782-A
Country	US
Kind code	A1
Filing date	Dec 22, 2016
Priority date	Dec 31, 2015
Publication date	Jul 6, 2017
Grant date	—

Abstract

A photoacid generator compound having Formula (I):

wherein, EWG, Y, R, and M + are the same as described in the specification.

First claim

1 . A photoacid generator compound having Formula (I):

wherein:
EWG is 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 .

2 . A photoacid generator compound of claim 1 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, R, and M + are the same as in claim 1 ; and
each “ ” represents a partial double bond.

3 . The photoacid generator compound of claim 2 , wherein in Formula (III):
EWG is CN; 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 the same as in claim 1 .

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; Y is a single bond; and Z 1 , Z 2 , and M + are the same as in claim 1 .

5 . The photoacid generator compound of claim 1 , 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 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, which is a polymerization product of the photoacid generator compound of claim 1 .

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.

Assignees

• Rohm & Haas Elect Mat

Inventors

• Williams Iii William
• Aqad Emad
• Cameron James F

Classifications

• C07C381/12 Primary

  Sulfonium compounds · CPC title

• C07C25/18

  Polycyclic aromatic halogenated hydrocarbons · CPC title

• G03F7/0002

  Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping · CPC title

• C07C255/24

  containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton · CPC title

• C07C255/34

  with cyano groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains · CPC title