U.S. patent application number 11/566309 was filed with the patent office on 2008-06-05 for photoactive compounds.
Invention is credited to M. Dalil Rahman, David L. Rentkiewicz.
Application Number | 20080131810 11/566309 |
Document ID | / |
Family ID | 39415076 |
Filed Date | 2008-06-05 |
United States Patent
Application |
20080131810 |
Kind Code |
A1 |
Rahman; M. Dalil ; et
al. |
June 5, 2008 |
Photoactive Compounds
Abstract
The present application relates to a compound of formula Ai Xi
Bi where Ai and Bi are each individually an organic onium cation;
and Xi is anion of the formula
.sup.-O.sub.3S--CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--SO.sub.3.sup.-.
The compounds are useful as photoactive materials.
Inventors: |
Rahman; M. Dalil;
(Flemington, NJ) ; Rentkiewicz; David L.; (Roselle
Park, NJ) |
Correspondence
Address: |
Alan P. Kass;AZ Electronic Materials USA Corp.
70 Meister Avenue
Somervill
NJ
08876
US
|
Family ID: |
39415076 |
Appl. No.: |
11/566309 |
Filed: |
December 4, 2006 |
Current U.S.
Class: |
430/270.1 ;
430/322; 568/35 |
Current CPC
Class: |
Y10S 430/115 20130101;
C07C 43/225 20130101; C07C 309/06 20130101; G03F 7/0045 20130101;
C07C 381/12 20130101; Y10S 430/122 20130101; C07C 25/18 20130101;
C07C 2603/74 20170501; G03F 7/0397 20130101; Y10S 430/123 20130101;
C07D 333/76 20130101 |
Class at
Publication: |
430/270.1 ;
430/322; 568/35 |
International
Class: |
G03F 7/004 20060101
G03F007/004; G03F 7/26 20060101 G03F007/26; C07C 317/04 20060101
C07C317/04 |
Claims
1. A compound of the formula Ai Xi Bi, where Ai and Bi are each
individually an organic onium cation; and Xi is anion of the
formula O.sub.3S--CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--SO.sub.3--,
where each of Ai and Bi are selected from ##STR00018## and Y--Ar
where Ar is selected from ##STR00019## naphthyl, or anthryl; Y is
selected from ##STR00020## --I.sup.+-naphtyl, --I.sup.+-anthryl
where R.sub.1, R.sub.2, R.sub.3, R.sub.1A, R.sub.1B, R.sub.2A,
R.sub.2B, R.sub.3A, R.sub.3B, R.sub.4A, R.sub.4B, R.sub.5A, and
R.sub.5B are each independently selected from Z, hydrogen,
OSO.sub.2R.sub.9, OR.sub.20, straight or branched alkyl chain
optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
arylcarbonylmethyl group, alkoxyalkyl, alkoxycarbonylalkyl,
alkylcarbonyl, monocycloalkyl- or polycycloalkyloxycarbonylalkyl
with the cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, straight or branched
perfluoroalkyl, monocycloperfluoroalkyl or polycycloperfluoroalkyl,
straight or branched alkoxy chain, nitro, cyano, halogen, carboxyl,
hydroxyl, sulfate, tresyl, or hydroxyl; R.sub.6 and R.sub.7 are
each independently selected from straight or branched alkyl chain
optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
straight or branched perfluoroalkyl, monocycloperfluoroalkyl or
polycycloperfluoroalkyl, arylcarbonylmethyl group, nitro, cyano, or
hydroxyl or R.sub.6 and R.sub.7 together with the S atom to which
they are attached form a 5-, 6-, or 7-membered saturated or
unsaturated ring optionally containing one or more O atoms; R.sub.9
is selected from alkyl, fluoroalkyl, perfluoroalkyl, aryl,
fluoroaryl, perfluoroaryl, monocycloalkyl or polycycloalkyl group
with the cycloalkyl ring optionally containing one or more O atoms,
monocyclofluoroalkyl or polycyclofluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms, or
monocycloperfluoralkyl or polycycloperfluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms; R.sub.20
is alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyl, monocycloalkyl-
or polycycloalkyloxycarbonylalkyl with the cycloalkyl ring
optionally containing one or more O atoms, or monocycloalkyl- or
polycycloalkyloxyalkyl with the cycloalkyl ring optionally
containing one or more O atoms; T is a direct bond, a divalent
straight or branched alkyl group optionally containing one or more
O atoms, divalent aryl group, divalent aralkyl group, or divalent
monocycloalkyl or polycycloalkyl group optionally containing one or
more O atoms; Z is
--(V).sub.j--(C(X11)(X12)).sub.n--O--C(.dbd.O)--R.sub.8, where
either (i) one of X11 or X12 is straight or branched alkyl chain
containing at least one fluorine atom and the other is hydrogen,
halogen, or straight or branched alkyl chain or (ii) both of X11
and X12 are straight or branched alkyl chain containing at least
one fluorine atom; V is a linkage group selected from a direct
bond, a divalent straight or branched alkyl group optionally
containing one or more O atoms, divalent aryl group, divalent
aralkyl group, or divalent monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms; X2 is hydrogen, halogen,
or straight or branched alkyl chain optionally containing one or
more O atoms; R.sub.8 is a straight or branched alkyl chain
optionally containing one or more O atoms, a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms, or
aryl; X3 is hydrogen, straight or branched alkyl chain, halogen,
cyano, or --C(.dbd.O)--R.sub.50 where R.sub.50 is selected from
straight or branched alkyl chain optionally containing one or more
O atoms or --O--R.sub.51 where R.sub.51 is hydrogen or straight or
branched alkyl chain; each of i and k are independently 0 or a
positive integer; j is 0 to 10; m is 0 to 10; and n is 0 to 10, the
straight or branched alkyl chain optionally containing one or more
O atoms, straight or branched alkyl chain, straight or branched
alkoxy chain, monocycloalkyl or polycycloalkyl group optionally
containing one or more O atoms, monocycloalkyl- or
polycycloalkylcarbonyl group, alkoxyalkyl, alkoxycarbonylalkyl,
alkylcarbonyl, monocycloalkyl- or polycycloalkyloxycarbonylalkyl
with the cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, aralkyl, aryl, naphthyl,
anthryl, 5-, 6-, or 7-membered saturated or unsaturated ring
optionally containing one or more O atoms, or arylcarbonylmethyl
group being unsubstituted or substituted by one or more groups
selected from the group consisting of Z, halogen, alkyl, C.sub.1-8
perfluoroalkyl, monocycloalkyl or polycycloalkyl, OR.sub.20,
alkoxy, C.sub.3-20 cyclic alkoxy, dialkylamino, dicyclic
dialkylamino, hydroxyl, cyano, nitro, tresyl, oxo, aryl, aralkyl,
oxygen atom, CF.sub.3SO.sub.3, aryloxy, arylthio, and groups of
formulae (II) to (VI): ##STR00021## wherein R.sub.10 and R.sub.11
each independently represent a hydrogen atom, a straight or
branched alkyl chain optionally containing one or more O atoms, or
a monocycloalkyl or polycycloalkyl group optionally containing one
or more O atoms, or R.sub.10 and R.sub.11 together can represent an
alkylene group to form a five- or six-membered ring; R.sub.12
represents a straight or branched alkyl chain optionally containing
one or more O atoms, a monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms, or aralkyl, or R.sub.10
and R.sub.12 together represent an alkylene group which forms a
five- or six-membered ring together with the interposing --C--O--
group, the carbon atom in the ring being optionally substituted by
an oxygen atom; R.sub.13 represents a straight or branched alkyl
chain optionally containing one or more O atoms or a monocycloalkyl
or polycycloalkyl group optionally containing one or more O atoms;
R.sub.14 and R.sub.15 each independently represent a hydrogen atom,
a straight or branched alkyl chain optionally containing one or
more O atoms or a monocycloalkyl or polycycloalkyl group optionally
containing one or more O atoms; R.sub.16 represents a straight or
branched alkyl chain optionally containing one or more O atoms, a
monocycloalkyl or polycycloalkyl group optionally containing one or
more O atoms, aryl, or aralkyl; and R.sub.17 represents straight or
branched alkyl chain optionally containing one or more O atoms, a
monocycloalkyl or polycycloalkyl group optionally containing one or
more O atoms, aryl, aralkyl, the group
--Si(R.sub.16).sub.2R.sub.17, or the group
--O--Si(R.sub.16).sub.2R.sub.17, the straight or branched alkyl
chain optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
aryl, and aralkyl being unsubstituted or substituted as above.
2. The compound of claim 1 wherein each of Ai and Bi are selected
from ##STR00022##
3. The compound of claim 1 where Ai and Bi are each ##STR00023##
where R.sub.6 and R.sub.7 are each independently unsubstituted or
substituted straight or branched alkyl chain optionally containing
one or more O atoms or unsubstituted or substituted aryl, or
R.sub.6 and R.sub.7 together with the S atom to which they are
attached form a 5-, 6-, or 7-membered saturated or unsaturated ring
optionally containing one or more O atoms; T is a direct bond or a
divalent straight or branched alkyl group optionally containing one
or more O atoms optionally substituted with oxo.
4. The compound of claim 3 wherein R.sub.6 and R.sub.7 are each
independently unsubstituted or substituted aryl; and T is a direct
bond.
5. The compound of claim 4 wherein the aryl of R.sub.6 and R.sub.7
are each substituted by OSO.sub.2R.sub.9, OR.sub.20, hydroxy, or
alkoxy.
6. The compound of claim 3 wherein R.sub.3A is selected from
hydroxy and straight or branched alkoxy chain and each of R.sub.2A
and R.sub.4A is selected from hydrogen and straight or branched
alkyl chain optionally containing one or more O atoms.
7. The compound of claim 3 wherein R.sub.6 and R.sub.7 together
with the S atom to which they are attached form a 5-, 6-, or
7-membered saturated or unsaturated ring optionally containing one
or more O atoms; and T is a divalent straight or branched alkyl
group optionally containing one or more O atoms optionally
substituted with oxo.
8. The compound of claim 1 wherein Ai and Bi are each
##STR00024##
9. The compound of claim 6 wherein each of R.sub.3A and R.sub.3B is
selected from hydrogen, straight or branched alkyl chain optionally
containing one or more O atoms, and straight or branched alkoxy
chain.
10. The compound of claim 1 selected from the group bis
[di(4-t-butyl phenyl) iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis [di(4-octyloxyphenyl) iodonium]di-(tetrafluoroethyl
sulfonate) ether, bis [(4-octyloxyphenyl) phenyl
iodonium]di-(tetrafluoroethyl sulfonate) ether, bis
[(4-methylphenyl) phenyl iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis [(4-t-butylphenyl) phenyl iodonium]di-(tetrafluoroethyl
sulfonate) ether, bis [(4-methoxyphenyl) phenyl
iodonium]di-(tetrafluoroethyl sulfonate) ether,
bis(4-methoxyphenyl) iodonium di-(tetrafluoroethyl sulfonate)
ether, bis(4-octyloxyphenyl) phenyl sulfonium di-(tetrafluoroethyl
sulfonate) ether, bis(4-t-butylphenyl diphenyl sulfonium)
di-(tetrafluoroethyl sulfonate) ether, bis(4-t-butylphenyl
iodonium) di-(tetrafluoroethyl sulfonate) ether,
bis(4-t-butylphenyl iodonium) triphenyl sulfonium
di-(tetrafluoroethyl sulfonate) ether,
bis(benzoyltetramethylenesulfonium) di-(tetrafluoroethyl sulfonate)
ether, bis (triphenyl sulfonium) di-(tetrafluoroethyl sulfonate)
ether, bis(tris(4-t-butyl phenyl) sulfonium) di-(tetrafluoroethyl
sulfonate) ether, bis
[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]di-(tetrafl-
uoroethyl sulfonate) ether, bis
[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfonium-
]di-(tetrafluoroethyl sulfonate) ether, bis
[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmethox-
yphenyl]phenyl sulfonium]di-(tetrafluoroethyl sulfonate) ether, and
bis
[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]di-(tetrafluor-
oethyl sulfonate) ether.
11. A photoresist composition useful for imaging in deep UV
comprising; a) a polymer containing an acid labile group; b) a
compound of claim 1; and c) one or more additional photoacid
generators.
12. The composition of claim 11, wherein c) the one or more
additional photoacid generators are selected from (a) a compound of
the formula Ai Xi1 Bi, where Ai and Bi are each individually an
organic onium cation as previously defined; Xi1 is an anion of the
formula Q-R.sub.500--SO.sub.3.sup.- where Q is selected from
.sup.-O.sub.3S and .sup.-O.sub.2C; R.sub.500 is a group selected
from linear or branched alkyl, cycloalkyl, aryl, or combinations
thereof, optionally containing a catenary S or N, where the alkyl,
cycloalkyl, and aryl groups are unsubstituted or substituted by one
or more groups selected from the group consisting of halogen,
unsubstituted or substituted alkyl, unsubstituted or substituted
C.sub.1-8 perfluoroalkyl, hydroxyl, cyano, sulfate, and nitro; and
(b) a compound having the formula Ai Xi2, where Ai is an organic
onium cation as previously defined and Xi2 is an anion; and
mixtures of (a) and (b) thereof.
13. The composition of claim 12, wherein Xi2 is selected from
CF.sub.3SO.sub.3.sup.-, CHF.sub.2SO.sub.3.sup.-,
CH.sub.3SO.sub.3.sup.-, CC1.sub.3SO.sub.3.sup.-,
C.sub.2F.sub.5SO.sub.3.sup.-, C.sub.2HF.sub.4SO.sub.3.sup.-,
C.sub.4F.sub.9SO.sub.3.sup.-, camphor sulfonate, perfluorooctane
sulfonate, benzene sulfonate, pentafluorobenzene sulfonate, toluene
sulfonate, perfluorotoluene sulfonate, (Rf1SO.sub.2).sub.3C.sup.-
and (Rf1SO.sub.2).sub.2N.sup.-, wherein each Rf1 is independently
selected from the group consisting of highly fluorinated or
perfluorinated alkyl or fluorinated aryl radicals and may be
cyclic, when a combination of any two Rf1 groups are linked to form
a bridge, further, the Rf1 alkyl chains contain from 1-20 carbon
atoms and may be straight, branched, or cyclic, such that divalent
oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the
skeletal chain, further when Rf1 contains a cyclic structure, such
structure has 5 or 6 ring members, optionally, 1 or 2 of which are
heteroatoms, and Rg-O--Rf2-SO.sub.3.sup.-, where Rf2 is selected
from the group consisting of linear or branched (CF.sub.2).sub.j
where j is an integer from 4 to 10 and C.sub.1-C.sub.12
cycloperfluoroalkyl divalent radical which is optionally
perfluoroC.sub.1-10alkyl substituted, Rg is selected from the group
consisting of C.sub.1-C.sub.20 linear, branched, monocycloalkyl or
polycycloalkyl, C.sub.1-C.sub.20 linear, branched, monocycloalkenyl
or polycycloalkenyl, aryl, and aralkyl, the alkyl, alkenyl, aralkyl
and aryl groups being unsubstituted, substituted, optionally
containing one or more catenary oxygen atoms, partially fluorinated
or perfluorinated.
14. The composition of claim 12 wherein the anion Xi2 is selected
from include (C.sub.2F.sub.5SO.sub.2).sub.2N.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.2N.sup.-,
(C.sub.8F.sub.17SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.3C.sup.-, (CF.sub.3SO.sub.2).sub.2N.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.4F.sub.9SO.sub.2)C.sup.-,
(C.sub.2F.sub.5SO.sub.2).sub.3C.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.2F.sub.5SO.sub.2)C.sup.-,
(C.sub.4F.sub.9SO.sub.2)(C.sub.2F.sub.5SO.sub.2).sub.2C.sup.-,
(CF.sub.3SO.sub.2)(C.sub.4F.sub.9SO.sub.2)N.sup.-,
[(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2].sub.2N.sup.-,
(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2C.sup.-
(SO.sub.2CF.sub.3).sub.2,
(3,5-bis(CF.sub.3)C.sub.6H.sub.3)SO.sub.2N.sup.-O.sub.2CF.sub.3,
C.sub.6F.sub.5SO.sub.2C.sup.-(SO.sub.2CF.sub.3).sub.2,
C.sub.6F.sub.5SO.sub.2N.sup.-SO.sub.2CF.sub.3, ##STR00025##
CF.sub.3CHFO(CF.sub.2).sub.4SO.sub.3.sup.-,
CF.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3O(CF.sub.2).sub.4SO.sub.3,
C.sub.2H.sub.5O(CF.sub.2).sub.4SO.sub.3,
C.sub.4H.sub.9O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.6H.sub.5CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.2H.sub.5OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
CH.sub.2.dbd.CHCH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.4H.sub.9OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.8H.sub.17O(CF.sub.2).sub.2SO.sub.3.sup.-, and
C.sub.4H.sub.9O(CF.sub.2).sub.2SO.sub.3.sup.-.
15. The composition of claim 11, wherein c) the one or more
additional photoacid generators are selected from the group
bis(4-t-butylphenyl) iodonium triphenyl sulfonium
perfluorobutane-1,4-disulfonate, bis(4-t-butylphenyl) iodonium
triphenyl sulfonium perfluoropropane-1,3-disulfonate,
bis(4-t-butylphenyl) iodonium triphenyl sulfonium
perfluoropropane-1-carboxylate-3-sulfonate, bis(4-t-butylphenyl)
iodonium triphenyl sulfonium
perfluorobutane-1-carboxylate-4-sulfonate, bis(4-t-butylphenyl)
iodonium triphenyl sulfonium perfluoromethane disulfonate,
bis(4-t-butylphenyl) iodonium triphenyl sulfonium methane
disulfonate, bis(4-t-butylphenyl) iodonium triphenyl sulfonium
perfluoroethane disulfonate, bis(4-t-butylphenyl) iodonium
triphenyl sulfonium ethane disulfonate, bis(triphenyl sulfonium)
perfluorobutane-1,4-disulfonate, bis(triphenyl sulfonium)
perfluoropropane-1,3-disulfonate,
bis(benzoyltetramethylenesulfonium)
perfluoropropane-1,3-disulfonate,
bis(benzoyltetramethylenesulfonium)
perfluorobutane-1,4-disulfonate, bis(tris(4-t-butylphenyl)
sulfonium) perfluorobutane-1,4-disulfonate,
bis(tris(4-t-butylphenyl) sulfonium)
perfluoropropane-1,3-disulfonate, bis(4-t-butylphenyldiphenyl
sulfonium) perfluorobutane-1,4-disulfonate,
bis(4-t-butylphenyldiphenyl sulfonium)
perfluoropropane-1,3-disulfonate, bis(triphenyl sulfonium)
perfluoropropane-1-carboxylate-3-sulfonate, bis(triphenyl
sulfonium) perfluorobutane-1-carboxylate-4-sulfonate,
bis(benzoyltetramethylenesulfonium)
perfluoropropane-1-carboxylate-3-sulfonate,
bis(benzoyltetramethylenesulfonium)
perfluorobutane-1-carboxylate-4-sulfonate, bis(tris(4-t-butyl
phenyl) sulfonium) perfluoropropane-1-carboxylate-3-sulfonate,
bis(tris(4-t-butyl phenyl) sulfonium)
perfluorobutane-1-carboxylate-4-sulfonate, bis(4-t-butylphenyl
diphenyl sulfonium) perfluoropropane-1-carboxylate-3-sulfonate,
bis(4-t-butylphenyl diphenyl sulfonium)
perfluorobutane-1-carboxylate-4-sulfonate, bis(4-t-butylphenyl
iodonium) methane disulfonate, bis(triphenyl sulfonium) methane
disulfonate, bis(4-t-butylphenyl iodonium) perfluoromethane
disulfonate, bis(triphenyl sulfonium) perfluoromethane disulfonate,
bis(benzoyltetramethylenesulfonium) perfluoromethane disulfonate,
bis(benzoyl-tetramethylenesulfonium) methane disulfonate,
bis(tris(4-t-butyl phenyl) sulfonium) perfluoromethane disulfonate,
bis(tris(4-t-butyl phenyl) sulfonium) methane disulfonate,
bis(4-t-butylphenyl diphenylsulfonium) perfluoromethane
disulfonate, bis(4-t-butylphenyl diphenylsulfonium) methane
disulfonate, bis(4-octyloxyphenyl) iodonium
perfluorobutane-1,4-disulfonate, bis(4-octyloxyphenyl) iodonium
ethane disulfonate, bis(4-octyloxyphenyl) iodonium perfluoroethane
disulfonate, bis(4-octyloxyphenyl) iodonium
perfluoropropane-1,3-disulfonate, bis(4-octyloxyphenyl) iodonium
perfluoropropane-1-carboxylate-3-sulfonate, bis(4-octyloxyphenyl)
iodonium perfluorobutane-1-carboxylate-4-sulfonate,
bis(4-octyloxyphenyl) iodonium methane disulfonate,
bis(4-octyloxyphenyl) iodonium perfluoromethane disulfonate,
bis(4-octyloxyphenyl) phenyl sulfonium
perfluorobutane-1,4-disulfonate, bis(4-octyloxyphenyl) phenyl
sulfonium ethane disulfonate, bis(4-octyloxyphenyl) phenyl
sulfonium perfluoroethane disulfonate, bis(4-octyloxyphenyl) phenyl
sulfonium perfluoropropane-1,3-disulfonate, bis(4-octyloxyphenyl)
phenyl sulfonium perfluoropropane-1-carboxylate-3-sulfonate,
bis(4-octyloxyphenyl) phenyl sulfonium
perfluorobutane-1-carboxylate-4-sulfonate, bis(4-octyloxyphenyl)
phenyl sulfonium methane disulfonate, bis(4-octyloxyphenyl) phenyl
sulfonium perfluoromethane disulfonate,
bis[bis[4-pentafluorobenzenesulfonyloxy-phenyl]phenylsulfonium]perfluorob-
utane-1,4-disulfonate,
bis[bis[4-pentafluoro-benzene-sulfonyloxyphenyl]phenylsulfonium]ethane
disulfonate,
bis[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenyl-sulfonium]perfluoroe-
thane disulfonate,
bis[bis[4-pentafluorobenzene-sulfonyloxyphenyl]phenylsulfonium]perfluorop-
ropane-1,3-disulfon ate,
bis[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]perfluoropr-
opane-1-carboxylate-3-sulfonate,
bis[bis[4-pentafluorobenzenesulfonyloxy-phenyl]phenylsulfonium]perfluorob-
utane-1-carboxylate-4-sulfonate,
bis[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]methane
disulfonate,
bis[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]perfluorome-
thane disulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfon-
ium]perfluorobutane-1,4-disulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)-benzenesulfonyloxy)phenyl]phenylsulfon-
ium]ethane disulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)phenyl]phenylsulfoni-
um]perfluoroethane disulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)phenyl]phenylsulfoni-
um]perfluoropropane-1,3-disulfonate,
bis[bis[4-(3,5-di(trifluoro-methyl)-benzenesulfonyloxy)phenyl]phenylsulfo-
nium]perfluoropropane-1-carboxylate-3-sulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfon-
ium]perfluorobutane-1-carboxylate-4-sulfonate,
bis[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)phenyl]phenylsulfoni-
um]methane disulfonate, bis(4-t-butylphenyl iodonium) ethane
disulfonate, bis(4-t-butylphenyl iodonium) perfluoroethane
disulfonate, bis(triphenyl sulfonium) ethane disulfonate,
bis(triphenyl sulfonium) perfluoroethane disulfonate,
bis(benzoyltetramethylene-sulfonium) perfluoroethane disulfonate,
bis(benzoyltetramethylenesulfonium) ethane disulfonate,
bis(tris(4-t-butyl phenyl) sulfonium) perfluoroethane disulfonate,
bis(tris(4-t-butyl phenyl) sulfonium) ethane disulfonate,
bis(4-t-butylphenyl diphenyl-sulfonium) perfluoroethane
disulfonate, bis(4-t-butylphenyl diphenylsulfonium) ethane
disulfonate,
bis[bis[2-methyladamantylacetyloxymethoxyphenyl]phenyl-sulfonium]perfluor-
obutane-1,4-disulfonate,
bis[bis[2-methyladamantylacetyl-oxymethoxyphenyl]phenylsulfonium]ethane
disulfonate,
bis[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]perfluor-
oethane disulfonate,
bis[bis[2-methyladamantylacetyloxymethoxyphenyl]phenylsulfonium]perfluoro-
-propane-1,3-disulfonate,
bis[bis[2-methyladamantylacetyloxymethoxyphenyl]phenylsulfonium]perfluoro-
propane-1-carboxylate-3-sulfonate,
bis[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]perfluor-
obutane-1-carboxylate-4-sulfonate,
bis[bis[2-methyladamantylacetyloxymethoxyphenyl]phenylsulfonium]methane
disulfonate,
bis[bis[2-methyladamantylacetyloxy-methoxyphenyl]phenylsulfonium]perfluor-
omethane disulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmeth-
oxyphenyl]phenyl sulfonium]perfluorobutane-1,4-disulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo-[4.2.1.0.sup.2,5]-nonylmet-
hoxy-phenyl]phenyl sulfonium]ethane disulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmeth-
oxyphenyl]phenyl sulfonium]-perfluoroethane disulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmeth-
oxy-phenyl]phenyl sulfonium]perfluoropropane-1,3-disulfonate,
bis[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmet-
hoxyphenyl]phenyl
sulfonium]-perfluoropropane-1-carboxylate-3-sulfonate,
bis[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]_nonylmet-
hoxyphenyl]phenyl
sulfonium]perfluoro-butane-1-carboxylate-4-sulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo-[4.2.1.0.sup.2,5]-nonylmet-
hoxyphenyl]phenyl sulfonium]methane disulfonate,
bis[bis[4,4-bis(trifluoromethyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmeth-
oxyphenyl]phenyl sulfonium]perfluoromethane disulfonate,
bis(4-t-butylphenyl) iodonium bis-perfluoroethane sulfonimide,
diphenyliodonium trifluoromethane sulfonate, diphenyliodonium
nonafluorobutane sulfonate, triphenylsulfonium trifluromethane
sulfonate, triphenylsulfonium nonafluorobutane sulfonate,
4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluorobutanesulfonyl)imide,
4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-perfluorobutanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-(perfluoroethanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluorobutanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
toluenediphenylsulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide, tris-(tert-butylphenyl)sulfonium
bis-(perfluorobutanesulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-bis-(trifluoromethanesulfonyl)imide,
and mixtures thereof.
16. The composition of claim 11, wherein b) the compound of claim 1
is selected from the group bis [di(4-t-butyl phenyl)
iodonium]di-(tetrafluoroethyl sulfonate) ether, bis
[di(4-octyloxyphenyl) iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis [(4-octyloxyphenyl) phenyl iodonium]di-(tetrafluoroethyl
sulfonate) ether, bis [(4-methylphenyl) phenyl
iodonium]di-(tetrafluoroethyl sulfonate) ether, bis
[(4-t-butylphenyl) phenyl iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis [(4-methoxyphenyl) phenyl iodonium]di-(tetrafluoroethyl
sulfonate) ether, bis(4-methoxyphenyl) iodonium
di-(tetrafluoroethyl sulfonate) ether, bis(4-octyloxyphenyl) phenyl
sulfonium di-(tetrafluoroethyl sulfonate) ether,
bis(4-t-butylphenyl diphenyl sulfonium) di-(tetrafluoroethyl
sulfonate) ether, bis(4-t-butylphenyl iodonium)
di-(tetrafluoroethyl sulfonate) ether, bis(4-t-butylphenyl
iodonium) triphenyl sulfonium di-(tetrafluoroethyl sulfonate)
ether, bis(benzoyltetramethylenesulfonium) di-(tetrafluoroethyl
sulfonate) ether, bis(triphenyl sulfonium) di-(tetrafluoroethyl
sulfonate) ether, bis(tris(4-t-butyl phenyl) sulfonium)
di-(tetrafluoroethyl sulfonate) ether, bis
[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]di-(tetrafl-
uoroethyl sulfonate) ether, bis
[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfonium-
]di-(tetrafluoroethyl sulfonate) ether, bis
[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmethox-
yphenyl]phenyl sulfonium]di-(tetrafluoroethyl sulfonate) ether, and
bis
[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]di-(tetrafluor-
oethyl sulfonate) ether, and mixtures thereof.
17. The composition of claim 11, wherein the ratio of b) to c)
ranges from about 1:1 to about 1:4.
18. The composition of claim 11, wherein the ratio of b) to c)
ranges from about 1:1.25 to about 1:3.5.
19. A process for imaging a photoresist comprising the steps of:
include a) applying a coating layer a substrate with the
composition of claim 11; b) baking the substrate to substantially
remove the solvent; c) image-wise exposing the photoresist coating;
d) optionally, postexposure baking the photoresist coating; and e)
developing the photoresist coating with an aqueous alkaline
solution.
20. A coated substrate comprising a substrate with a photoresist
coating film, wherein the photoresist coating film is formed from
the photoresist composition of claim 11.
Description
FIELD OF INVENTION
[0001] The present invention relates to novel photoactive compounds
useful in photoresist compositions in the field of
microlithography, and especially useful for imaging negative and
positive patterns in the production of semiconductor devices, as
well as photoresist compositions and processes for imaging
photoresists.
BACKGROUND OF THE INVENTION
[0002] Photoresist compositions are used in microlithography
processes for making miniaturized electronic components such as in
the fabrication of computer chips and integrated circuits.
Generally, in these processes, a thin coating of film of a
photoresist composition is first applied to a substrate material,
such as silicon wafers used for making integrated circuits. The
coated substrate is then baked to evaporate any solvent in the
photoresist composition and to fix the coating onto the substrate.
The photoresist coated on the substrate is next subjected to an
image-wise exposure to radiation.
[0003] The radiation exposure causes a chemical transformation in
the exposed areas of the coated surface. Visible light, ultraviolet
(UV) light, electron beam and X-ray radiant energy are radiation
types commonly used today in microlithographic processes. After
this image-wise exposure, the coated substrate is treated with a
developer solution to dissolve and remove either the radiation
exposed or the unexposed areas of the photoresist. The trend toward
the miniaturization of semiconductor devices has led to the use of
new photoresists that are sensitive at lower and lower wavelengths
of radiation and has also led to the use of sophisticated
multilevel systems to overcome difficulties associated with such
miniaturization.
[0004] There are two types of photoresist compositions:
negative-working and positive-working. The type of photoresist used
at a particular point in lithographic processing is determined by
the design of the semiconductor device. When negative-working
photoresist compositions are exposed image-wise to radiation, the
areas of the photoresist composition exposed to the radiation
become less soluble to a developer solution (e.g. a cross-linking
reaction occurs) while the unexposed areas of the photoresist
coating remain relatively soluble to such a solution. Thus,
treatment of an exposed negative-working resist with a developer
causes removal of the non-exposed areas of the photoresist coating
and the creation of a negative image in the coating, thereby
uncovering a desired portion of the underlying substrate surface on
which the photoresist composition was deposited.
[0005] On the other hand, when positive-working photoresist
compositions are exposed image-wise to radiation, those areas of
the photoresist composition exposed to the radiation become more
soluble to the developer solution (e.g. a rearrangement reaction
occurs) while those areas not exposed remain relatively insoluble
to the developer solution. Thus, treatment of an exposed
positive-working photoresist with the developer causes removal of
the exposed areas of the coating and the creation of a positive
image in the photoresist coating. Again, a desired portion of the
underlying surface is uncovered.
[0006] Photoresist resolution is defined as the smallest feature,
which the resist composition can transfer from the photomask to the
substrate with a high degree of image edge acuity after exposure
and development. In many leading edge manufacturing applications
today, photoresist resolution on the order of less than one-half
micron are necessary. In addition, it is almost always desirable
that the developed photoresist wall profiles be near vertical
relative to the substrate. Such demarcations between developed and
undeveloped areas of the resist coating translate into accurate
pattern transfer of the mask image onto the substrate. This becomes
even more critical as the push toward miniaturization reduces the
critical dimensions on the devices. In cases where the photoresist
dimensions have been reduced to below 150 nm, the roughness of the
photoresist patterns has become a critical issue. Edge roughness,
commonly known as line edge roughness, is typically observed for
line and space patterns as roughness along the photoresist line,
and for contact holes as side wall roughness. Edge roughness can
have adverse effects on the lithographic performance of the
photoresist, especially in reducing the critical dimension latitude
and also in transferring the line edge roughness of the photoresist
to the substrate. Hence, photoresists that minimize edge roughness
are highly desirable.
[0007] Photoresists sensitive to short wavelengths, between about
100 nm and about 300 nm are often used where subhalfmicron
geometries are required. Particularly preferred are photoresists
comprising non-aromatic polymers, a photoacid generator, optionally
a dissolution inhibitor, and solvent.
[0008] High resolution, chemically amplified, deep ultraviolet
(100-300 nm) positive and negative tone photoresists are available
for patterning images with less than quarter micron geometries. To
date, there are three major deep ultraviolet (UV) exposure
technologies that have provided significant advancement in
miniaturization, and these use lasers that emit radiation at 248
nm, 193 nm and 157 nm. Photoresists used in the deep UV typically
comprise a polymer which has an acid labile group and which can
deprotect in the presence of an acid, a photoactive component which
generates an acid upon absorption of light, and a solvent.
[0009] Photoresists for 248 nm have typically been based on
substituted polyhydroxystyrene and its copolymers, such as those
described in U.S. Pat. No. 4,491,628 and U.S. Pat. No. 5,350,660.
On the other hand, photoresists for 193 nm exposure require
non-aromatic polymers, since aromatics are opaque at this
wavelength. U.S. Pat. No. 5,843,624 and GB 2,320,718 disclose
photoresists useful for 193 nm exposure. Generally, polymers
containing alicyclic hydrocarbons are used for photoresists for
exposure below 200 nm. Alicyclic hydrocarbons are incorporated into
the polymer for many reasons, primarily since they have relatively
high carbon:hydrogen ratios which improve etch resistance, they
also provide transparency at low wavelengths and they have
relatively high glass transition temperatures. Photoresists
sensitive at 157 nm have been based on fluorinated polymers, which
are known to be substantially transparent at that wavelength.
Photoresists derived from polymers containing fluorinated groups
are described in WO 00/67072 and WO 00/17712.
[0010] The polymers used in a photoresist are designed to be
transparent to the imaging wavelength, but on the other hand, the
photoactive component has been typically designed to be absorbing
at the imaging wavelength to maximize photosensitivity. The
photosensitivity of the photoresist is dependent on the absorption
characteristics of the photoactive component, the higher the
absorption, the less the energy required to generate the acid, and
the more photosensitive is the photoresist.
SUMMARY OF THE INVENTION
[0011] The present invention relates to a compound of the
formula
Ai Xi Bi,
[0012] where Ai and Bi are each individually an organic onium
cation; and
Xi is anion of the formula
.sup.-O.sub.3S--CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--SO.sub.3.sup.-,
[0013] where each of Ai and Bi are selected from
##STR00001##
and
Y--Ar
[0014] where Ar is selected from
##STR00002##
naphthyl, or anthryl;
Y is selected from
##STR00003##
[0015]--I.sup.+-naphtyl, --I.sup.+-anthryl
[0016] where R.sub.1, R.sub.2, R.sub.3, R.sub.1A, R.sub.1B,
R.sub.2A, R.sub.2B, R.sub.3A, R.sub.3B, R.sub.4A, R.sub.4B,
R.sub.5A, and R.sub.5B are each independently selected from Z,
hydrogen, OSO.sub.2R.sub.9, OR.sub.20, straight or branched alkyl
chain optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
arylcarbonylmethyl group, alkoxyalkyl, alkoxycarbonylalkyl,
alkylcarbonyl, monocycloalkyl- or polycycloalkyloxycarbonylalkyl
with the cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, straight or branched
perfluoroalkyl, monocycloperfluoroalkyl or polycycloperfluoroalkyl,
straight or branched alkoxy chain, nitro, cyano, halogen, carboxyl,
hydroxyl, sulfate, tresyl, or hydroxyl; R.sub.6 and R.sub.7 are
each independently selected from straight or branched alkyl chain
optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
straight or branched perfluoroalkyl, monocycloperfluoroalkyl or
polycycloperfluoroalkyl, arylcarbonylmethyl group, nitro, cyano, or
hydroxyl or R.sub.6 and R.sub.7 together with the S atom to which
they are attached form a 5-, 6-, or 7-membered saturated or
unsaturated ring optionally containing one or more O atoms; R.sub.9
is selected from alkyl, fluoroalkyl, perfluoroalkyl, aryl,
fluoroaryl, perfluoroaryl, monocycloalkyl or polycycloalkyl group
with the cycloalkyl ring optionally containing one or more O atoms,
monocyclofluoroalkyl or polycyclofluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms, or
monocycloperfluoralkyl or polycycloperfluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms; R.sub.20
is alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyl, monocycloalkyl-
or polycycloalkyloxycarbonylalkyl with the cycloalkyl ring
optionally containing one or more O atoms, or monocycloalkyl- or
polycycloalkyloxyalkyl with the cycloalkyl ring optionally
containing one or more O atoms;
T is a direct bond, a divalent straight or branched alkyl group
optionally containing one or more O atoms, divalent aryl group,
divalent aralkyl group, or divalent monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms;
[0017] Z is
--(V).sub.j--(C(X11)(X12)).sub.n--O--C(.dbd.O)--R.sub.8, where
either (i) one of X11 or X12 is straight or branched alkyl chain
containing at least one fluorine atom and the other is hydrogen,
halogen, or straight or branched alkyl chain or (ii) both of X11
and X12 are straight or branched alkyl chain containing at least
one fluorine atom; V is a linkage group selected from a direct
bond, a divalent straight or branched alkyl group optionally
containing one or more O atoms, divalent aryl group, divalent
aralkyl group, or divalent monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms;
X2 is hydrogen, halogen, or straight or branched alkyl chain
optionally containing one or more O atoms;
R.sub.8 is a straight or branched alkyl chain optionally containing
one or more O atoms, a monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms, or aryl;
X3 is hydrogen, straight or branched alkyl chain, halogen, cyano,
or --C(.dbd.O)--R.sub.50 where R.sub.50 is selected from straight
or branched alkyl chain optionally containing one or more O atoms
or --O--R.sub.51 where R.sub.51 is hydrogen or straight or branched
alkyl chain;
[0018] each of i and k are independently 0 or a positive integer; j
is 0 to 10; m is 0 to 10; and n is 0 to 10, the straight or
branched alkyl chain optionally containing one or more O atoms,
straight or branched alkyl chain, straight or branched alkoxy
chain, monocycloalkyl or polycycloalkyl group optionally containing
one or more O atoms, monocycloalkyl- or polycycloalkylcarbonyl
group, alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyl,
monocycloalkyl- or polycycloalkyloxycarbonylalkyl with the
cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, aralkyl, aryl, naphthyl,
anthryl, 5-, 6-, or 7-membered saturated or unsaturated ring
optionally containing one or more O atoms, or arylcarbonylmethyl
group being unsubstituted or substituted by one or more groups
selected from the group consisting of Z, halogen, alkyl, C.sub.1-8
perfluoroalkyl, monocycloalkyl or polycycloalkyl, OR.sub.20,
alkoxy, C.sub.3-20 cyclic alkoxy, dialkylamino, dicyclic
dialkylamino, hydroxyl, cyano, nitro, tresyl, oxo, aryl, aralkyl,
oxygen atom, CF.sub.3SO.sub.3, aryloxy, arylthio, and groups of
formulae (II) to (VI):
##STR00004##
wherein R.sub.10 and R.sub.11 each independently represent a
hydrogen atom, a straight or branched alkyl chain optionally
containing one or more O atoms, or a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms, or
R.sub.10 and R.sub.11 together can represent an alkylene group to
form a five- or six-membered ring; R.sub.12 represents a straight
or branched alkyl chain optionally containing one or more O atoms,
a monocycloalkyl or polycycloalkyl group optionally containing one
or more O atoms, or aralkyl, or R.sub.10 and R.sub.12 together
represent an alkylene group which forms a five- or six-membered
ring together with the interposing --C--O-- group, the carbon atom
in the ring being optionally substituted by an oxygen atom;
R.sub.13 represents a straight or branched alkyl chain optionally
containing one or more O atoms or a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms;
R.sub.14 and R.sub.15 each independently represent a hydrogen atom,
a straight or branched alkyl chain optionally containing one or
more O atoms or a monocycloalkyl or polycycloalkyl group optionally
containing one or more O atoms;
R.sub.16 represents a straight or branched alkyl chain optionally
containing one or more O atoms, a monocycloalkyl or polycycloalkyl
group optionally containing one or more O atoms, aryl, or aralkyl;
and
[0019] R.sub.17 represents straight or branched alkyl chain
optionally containing one or more O atoms, a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
aryl, aralkyl, the group --Si(R.sub.16).sub.2R.sub.17, or the group
--O--Si(R.sub.16).sub.2R.sub.17, the straight or branched alkyl
chain optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
aryl, and aralkyl being unsubstituted or substituted as above.
[0020] The present invention also relates to a photoresist
composition comprising a polymer containing an acid labile group
and a compound as described above together with one or more
additional photoacid generators selected from (a) a compound having
the formula Ai Xi1 Bi, where Ai and Bi are as defined above and Xi1
is an anion of the formula Q-R.sub.500--SO.sub.3.sup.-, where Q is
selected from O.sub.3S and .sup.-O.sub.2C; and R.sub.500 is a group
selected from linear or branched alkyl, cycloalkyl, aryl, or
combinations thereof, optionally containing a catenary S or N,
where the alkyl, cycloalkyl, and aryl groups are unsubstituted or
substituted by one or more groups selected from the group
consisting of halogen, unsubstituted or substituted alkyl,
unsubstituted or substituted C.sub.1-8 perfluoroalkyl, hydroxyl,
cyano, sulfate, and nitro; and (b) a compound having the formula Ai
Xi2, where Ai is an organic onium cation as previously defined and
Xi2 is an anion; and mixtures of (a) and (b) thereof. Examples of
the Xi2 anion include CF.sub.3SO.sub.3.sup.-,
CHF.sub.2SO.sub.3.sup.-, CH.sub.3SO.sub.3.sup.-,
CCl.sub.3SO.sub.3.sup.-, C.sub.2F.sub.5SO.sub.3.sup.-,
C.sub.2HF.sub.4SO.sub.3, C.sub.4F.sub.9SO.sub.3.sup.-, camphor
sulfonate, perfluorooctane sulfonate, benzene sulfonate,
pentafluorobenzene sulfonate, toluene sulfonate, perfluorotoluene
sulfonate, (Rf1SO.sub.2).sub.3C.sup.- and (Rf1
SO.sub.2).sub.2N.sup.-, wherein each Rf1 is independently selected
from the group consisting of highly fluorinated or perfluorinated
alkyl or fluorinated aryl radicals and may be cyclic, when a
combination of any two Rf1 groups are linked to form a bridge,
further, the Rf1 alkyl chains contain from 1-20 carbon atoms and
may be straight, branched, or cyclic, such that divalent oxygen,
trivalent nitrogen or hexavalent sulfur may interrupt the skeletal
chain, further when Rf1 contains a cyclic structure, such structure
has 5 or 6 ring members, optionally, 1 or 2 of which are
heteroatoms, and Rg-O--Rf2--SO.sub.3--, where Rf2 is selected from
the group consisting of linear or branched (CF.sub.2).sub.j where j
is an integer from 4 to 10 and C.sub.1-C.sub.12 cycloperfluoroalkyl
divalent radical which is optionally perfluoroC.sub.1-10alkyl
substituted, Rg is selected from the group consisting of
C.sub.1-C.sub.20 linear, branched, monocycloalkyl or
polycycloalkyl, C.sub.1-C.sub.20 linear, branched, monocycloalkenyl
or polycycloalkenyl, aryl, and aralkyl, the alkyl, alkenyl, aralkyl
and aryl groups being unsubstituted, substituted, optionally
containing one or more catenary oxygen atoms, partially fluorinated
or perfluorinated. Examples of such an ions Xi1 include
(C.sub.2F.sub.5SO.sub.2).sub.2N.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.2N.sup.-,
(C.sub.8F.sub.17SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.3C.sup.-, (CF.sub.3SO.sub.2).sub.2N.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.4F.sub.9SO.sub.2)C.sup.-,
(C.sub.2F.sub.5SO.sub.2).sub.3C.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.2F.sub.5SO.sub.2)C.sup.-,
(C.sub.4F.sub.9SO.sub.2)(C.sub.2F.sub.5SO.sub.2).sub.2C.sup.-,
(CF.sub.3SO.sub.2)(C.sub.4F.sub.9SO.sub.2)N.sup.-,
[(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2].sub.2N.sup.-,
(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2C.sup.-(SO.sub.2CF.sub.3).sub.2,
(3,5-bis(CF.sub.3)C.sub.6H.sub.3)SO.sub.2N.sup.-SO.sub.2CF.sub.3,
C.sub.6F.sub.5SO.sub.2C.sup.-(SO.sub.2CF.sub.3).sub.2,
C.sub.6F.sub.5SO.sub.2N.sup.-SO.sub.2CF.sub.3,
##STR00005##
CF.sub.3CHFO(CF.sub.2).sub.4SO.sub.3.sup.-,
CF.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3O(CF.sub.2).sub.4SO.sub.3,
C.sub.2H.sub.5O(CF.sub.2).sub.4SO.sub.3,
C.sub.4H.sub.9O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.6H.sub.5CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.2H.sub.5OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
CH.sub.2.dbd.CHCH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.4H.sub.9OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.8H.sub.17O(CF.sub.2).sub.2SO.sub.3.sup.-, and
C.sub.4H.sub.9O(CF.sub.2).sub.2SO.sub.3.sup.-. Other examples of
suitable anions can be found in U.S. Pat. No. 6,841,333 and U.S.
Pat. No. 5,874,616.
[0021] Examples of Ai Xi2 include bis(4-t-butylphenyl) iodonium
bis-perfluoroethane sulfonimide, diphenyliodonium trifluoromethane
sulfonate, diphenyliodonium nonafluorobutane sulfonate,
triphenylsulfonium trifluromethane sulfonate, triphenylsulfonium
nonafluorobutane sulfonate, 4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluorobutanesulfonyl)imide,
4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-perfluorobutanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-(perfluoroethanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluorobutanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
toluenediphenylsulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide, tris-(tert-butylphenyl)sulfonium
bis-(perfluorobutanesulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-bis-(trifluoromethanesulfonyl)imide,
and the like as well as other photoacid generators known to those
skilled in the art.
[0022] The ratio of the inventive photoacid generators of the
present application to the additional photoacid generators Ai
Xi1Bi, Ai Xi2, and mixtures thereof can range from about 1:1 to
about 1:4, and further from about 1:1.25 to about 1:3.5.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention relates to a compound of the formula
Ai Xi Bi,
where Ai and Bi are each individually an organic onium cation;
and
Xi is anion of the formula
.sup.-O.sub.3S--CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--SO.sub.3.sup.-,
[0024] where each of Ai and Bi are selected from
##STR00006##
and
Y--Ar
[0025] where Ar is selected from
##STR00007##
naphthyl, or anthryl;
Y is selected from
##STR00008##
[0026]--I.sup.+-naphtyl, --I.sup.+-anthryl
[0027] where R.sub.1, R.sub.2, R.sub.3, R.sub.1A, R.sub.1B,
R.sub.2A, R.sub.2B, R.sub.3A, R.sub.3B, R.sub.4A, R.sub.4B,
R.sub.5A, and R.sub.5B are each independently selected from Z,
hydrogen, OSO.sub.2R.sub.9, OR.sub.20, straight or branched alkyl
chain optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
arylcarbonylmethyl group, alkoxyalkyl, alkoxycarbonylalkyl,
alkylcarbonyl, monocycloalkyl- or polycycloalkyloxycarbonylalkyl
with the cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, straight or branched
perfluoroalkyl, monocycloperfluoroalkyl or polycycloperfluoroalkyl,
straight or branched alkoxy chain, nitro, cyano, halogen, carboxyl,
hydroxyl, sulfate, tresyl, or hydroxyl; R.sub.6 and R.sub.7 are
each independently selected from straight or branched alkyl chain
optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkylcarbonyl group, aryl, aralkyl,
straight or branched perfluoroalkyl, monocycloperfluoroalkyl or
polycycloperfluoroalkyl, arylcarbonylmethyl group, nitro, cyano, or
hydroxyl or R.sub.6 and R.sub.7 together with the S atom to which
they are attached form a 5-, 6-, or 7-membered saturated or
unsaturated ring optionally containing one or more O atoms;
[0028] Rg is selected from alkyl, fluoroalkyl, perfluoroalkyl,
aryl, fluoroaryl, perfluoroaryl, monocycloalkyl or polycycloalkyl
group with the cycloalkyl ring optionally containing one or more O
atoms, monocyclofluoroalkyl or polycyclofluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms, or
monocycloperfluoralkyl or polycycloperfluoroalkyl group with the
cycloalkyl ring optionally containing one or more O atoms;
R.sub.20 is alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyl,
monocycloalkyl- or polycycloalkyloxycarbonylalkyl with the
cycloalkyl ring optionally containing one or more O atoms, or
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms;
T is a direct bond, a divalent straight or branched alkyl group
optionally containing one or more O atoms, divalent aryl group,
divalent aralkyl group, or divalent monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms;
[0029] Z is --(V).sub.j--(C(X11)(X12)).sub.n-O--C(.dbd.O)--R.sub.8,
where either (i) one of X11 or X12 is straight or branched alkyl
chain containing at least one fluorine atom and the other is
hydrogen, halogen, or straight or branched alkyl chain or (ii) both
of X11 and X12 are straight or branched alkyl chain containing at
least one fluorine atom; V is a linkage group selected from a
direct bond, a divalent straight or branched alkyl group optionally
containing one or more O atoms, divalent aryl group, divalent
aralkyl group, or divalent monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms;
X2 is hydrogen, halogen, or straight or branched alkyl chain
optionally containing one or more O atoms;
R.sub.8 is a straight or branched alkyl chain optionally containing
one or more O atoms, a monocycloalkyl or polycycloalkyl group
optionally containing one or more O atoms, or aryl;
X3 is hydrogen, straight or branched alkyl chain, halogen, cyano,
or --C(.dbd.O)--R.sub.50 where R.sub.50 is selected from straight
or branched alkyl chain optionally containing one or more O atoms
or --O--R.sub.51 where R.sub.51 is hydrogen or straight or branched
alkyl chain;
[0030] each of i and k are independently 0 or a positive integer; j
is 0 to 10; m is 0 to 10; and n is 0 to 10, the straight or
branched alkyl chain optionally containing one or more O atoms,
straight or branched alkyl chain, straight or branched alkoxy
chain, monocycloalkyl or polycycloalkyl group optionally containing
one or more O atoms, monocycloalkyl- or polycycloalkylcarbonyl
group, alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyl,
monocycloalkyl- or polycycloalkyloxycarbonylalkyl with the
cycloalkyl ring optionally containing one or more O atoms,
monocycloalkyl- or polycycloalkyloxyalkyl with the cycloalkyl ring
optionally containing one or more O atoms, aralkyl, aryl, naphthyl,
anthryl, 5-, 6-, or 7-membered saturated or unsaturated ring
optionally containing one or more O atoms, or arylcarbonylmethyl
group being unsubstituted or substituted by one or more groups
selected from the group consisting of Z, halogen, alkyl, C.sub.1-8
perfluoroalkyl, monocycloalkyl or polycycloalkyl, OR.sub.20,
alkoxy, C.sub.3-20 cyclic alkoxy, dialkylamino, dicyclic
dialkylamino, hydroxyl, cyano, nitro, tresyl, oxo, aryl, aralkyl,
oxygen atom, CF.sub.3SO.sub.3, aryloxy, arylthio, and groups of
formulae (II) to (VI):
##STR00009##
wherein R.sub.10 and R.sub.11 each independently represent a
hydrogen atom, a straight or branched alkyl chain optionally
containing one or more O atoms, or a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms, or
R.sub.10 and R.sub.11 together can represent an alkylene group to
form a five- or six-membered ring; R.sub.12 represents a straight
or branched alkyl chain optionally containing one or more O atoms,
a monocycloalkyl or polycycloalkyl group optionally containing one
or more O atoms, or aralkyl, or R.sub.10 and R.sub.12 together
represent an alkylene group which forms a five- or six-membered
ring together with the interposing --C--O-- group, the carbon atom
in the ring being optionally substituted by an oxygen atom;
R.sub.13 represents a straight or branched alkyl chain optionally
containing one or more O atoms or a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms;
R.sub.14 and R.sub.15 each independently represent a hydrogen atom,
a straight or branched alkyl chain optionally containing one or
more O atoms or a monocycloalkyl or polycycloalkyl group optionally
containing one or more O atoms;
R.sub.16 represents a straight or branched alkyl chain optionally
containing one or more O atoms, a monocycloalkyl or polycycloalkyl
group optionally containing one or more O atoms, aryl, or aralkyl;
and
[0031] R.sub.17 represents straight or branched alkyl chain
optionally containing one or more O atoms, a monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
aryl, aralkyl, the group --Si(R.sub.16).sub.2R.sub.17, or the group
--O--Si(R.sub.16).sub.2R.sub.17, the straight or branched alkyl
chain optionally containing one or more O atoms, monocycloalkyl or
polycycloalkyl group optionally containing one or more O atoms,
aryl, and aralkyl being unsubstituted or substituted as above.
[0032] The present invention also relates to a photoresist
composition comprising a polymer containing an acid labile group
and a compound as described above together with one or more
additional photoacid generators selected from (a) a compound having
the formula Ai Xi1 Bi, where Ai and Bi are as defined above and Xi1
is an anion of the formula Q-R.sub.500--SO.sub.3.sup.-, where Q is
selected from O.sub.3S and .sup.-O.sub.2C; and R.sub.500 is a group
selected from linear or branched alkyl, cycloalkyl, aryl, or
combinations thereof, optionally containing a catenary S or N,
where the alkyl, cycloalkyl, and aryl groups are unsubstituted or
substituted by one or more groups selected from the group
consisting of halogen, unsubstituted or substituted alkyl,
unsubstituted or substituted C.sub.1-8 perfluoroalkyl, hydroxyl,
cyano, sulfate, and nitro; and (b) a compound having the formula Ai
Xi2, where Ai is an organic onium cation as previously defined and
Xi2 is an anion; and mixtures of (a) and (b) thereof. Examples of
the Xi2 anion include CF.sub.3SO.sub.3.sup.-,
CHF.sub.2SO.sub.3.sup.-, CH.sub.3SO.sub.3.sup.-,
CCl.sub.3SO.sub.3.sup.-, C.sub.2F.sub.5SO.sub.3.sup.-,
C.sub.2HF.sub.4SO.sub.3, C.sub.4F.sub.9SO.sub.3, camphor sulfonate,
perfluorooctane sulfonate, benzene sulfonate, pentafluorobenzene
sulfonate, toluene sulfonate, perfluorotoluene sulfonate,
(Rf1SO.sub.2).sub.3C.sup.- and (Rf1SO.sub.2).sub.2N.sup.-, wherein
each Rf1 is independently selected from the group consisting of
highly fluorinated or perfluorinated alkyl or fluorinated aryl
radicals and may be cyclic, when a combination of any two Rf1
groups are linked to form a bridge, further, the Rf1 alkyl chains
contain from 1-20 carbon atoms and may be straight, branched, or
cyclic, such that divalent oxygen, trivalent nitrogen or hexavalent
sulfur may interrupt the skeletal chain, further when Rf1 contains
a cyclic structure, such structure has 5 or 6 ring members,
optionally, 1 or 2 of which are heteroatoms, and
Rg-O--Rf2--SO.sub.3.sup.-, where Rf2 is selected from the group
consisting of linear or branched (CF.sub.2).sub.j where j is an
integer from 4 to 10 and C.sub.1-C.sub.12 cycloperfluoroalkyl
divalent radical which is optionally perfluoroC.sub.1-10alkyl
substituted, Rg is selected from the group consisting of
C.sub.1-C.sub.20 linear, branched, monocycloalkyl or
polycycloalkyl, C.sub.1-C.sub.20 linear, branched, monocycloalkenyl
or polycycloalkenyl, aryl, and aralkyl, the alkyl, alkenyl, aralkyl
and aryl groups being unsubstituted, substituted, optionally
containing one or more catenary oxygen atoms, partially fluorinated
or perfluorinated. Examples of such anions Xi1 include
(C.sub.2F.sub.5SO.sub.2).sub.2N.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.2N.sup.-,
(C.sub.8F.sub.17SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.3C.sup.-, (CF.sub.3SO.sub.2).sub.2N.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.4F.sub.9SO.sub.2)C.sup.-,
(C.sub.2F.sub.5SO.sub.2).sub.3C.sup.-,
(C.sub.4F.sub.9SO.sub.2).sub.3C.sup.-,
(CF.sub.3SO.sub.2).sub.2(C.sub.2F.sub.5SO.sub.2)C.sup.-,
(C.sub.4F.sub.9SO.sub.2)(C.sub.2F.sub.5SO.sub.2).sub.2C.sup.-,
(CF.sub.3SO.sub.2)(C.sub.4F.sub.9SO.sub.2)N.sup.-,
[(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2].sub.2N.sup.-,
(CF.sub.3).sub.2NC.sub.2F.sub.4SO.sub.2C.sup.-
(SO.sub.2CF.sub.3).sub.2,
(3,5-bis(CF.sub.3)C.sub.6H.sub.3)SO.sub.2N.sup.-SO.sub.2CF.sub.3,
C.sub.6F.sub.5SO.sub.2C.sup.-(SO.sub.2CF.sub.3).sub.2,
C.sub.6F.sub.5SO.sub.2N.sup.-SO.sub.2CF.sub.3,
##STR00010##
CF.sub.3CHFO(CF.sub.2).sub.4SO.sub.3.sup.-,
CF.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3CH.sub.2CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3O(CF.sub.2).sub.4SO.sub.3,
C.sub.2H.sub.5O(CF.sub.2).sub.4SO.sub.3,
C.sub.4H.sub.9O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.6H.sub.5CH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
C.sub.2H.sub.5OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
CH.sub.2.dbd.CHCH.sub.2O(CF.sub.2).sub.4SO.sub.3.sup.-,
CH.sub.3OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.4H.sub.9OCF.sub.2CF(CF.sub.3)SO.sub.3.sup.-,
C.sub.8H.sub.17O(CF.sub.2).sub.2SO.sub.3.sup.-, and
C.sub.4H.sub.9O(CF.sub.2).sub.2SO.sub.3.sup.-. Other examples of
suitable anions can be found in U.S. Pat. No. 6,841,333 and U.S.
Pat. No. 5,874,616.
[0033] Examples of Ai Xi2 include bis(4-t-butylphenyl) iodonium
bis-perfluoroethane sulfonimide, diphenyliodonium trifluoromethane
sulfonate, diphenyliodonium nonafluorobutane sulfonate,
triphenylsulfonium trifluromethane sulfonate, triphenylsulfonium
nonafluorobutane sulfonate, 4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluorobutanesulfonyl)imide,
4-(1-butoxyphenyl)diphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-perfluorobutanesulfonyl)imide,
2,4,6-trimethylphenyldiphenylsulfonium
bis-(perfluoroethanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluorobutanesulfonyl)imide, toluenediphenylsulfonium
bis-(perfluoroethanesulfonyl)imide,
toluenediphenylsulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-(trifluoromethyl
perfluorobutylsulfonyl)imide, tris-(tert-butylphenyl)sulfonium
bis-(perfluorobutanesulfonyl)imide,
tris-(tert-butylphenyl)sulfonium-bis-(trifluoromethanesulfonyl)imide,
and the like as well as other photoacid generators known to those
skilled in the art.
[0034] The term alkyl as used herein means a straight or branched
chain hydrocarbon. Representative examples of alkyl include, but
are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl,
sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl,
n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl,
n-heptyl, n-octyl, n-nonyl, and n-decyl.
[0035] Alkylene refers to divalent alkyl radicals, which can be
linear or branched, such as, for example, methylene, ethylene,
propylene, butylene or the like.
[0036] By the term aryl is meant a radical derived from an aromatic
hydrocarbon by the elimination of one atom of hydrogen and can be
substituted or unsubstituted. The aromatic hydrocarbon can be
mononuclear or polynuclear. Examples of aryl of the mononuclear
type include phenyl, tolyl, xylyl, mesityl, cumenyl, and the like.
Examples of aryl of the polynuclear type include naphthyl, anthryl,
phenanthryl, and the like. The aryl group can be unsubstituted or
substituted as provided for hereinabove.
[0037] The term alkoxy refers to a group of alkyl-O--, where alkyl
is defined herein. Representative examples of alkoxy include, but
are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy,
tert-butoxy, pentyloxy, and hexyloxy.
[0038] The term aryloxy refers to a group of aryl-O--, where aryl
is defined herein.
[0039] By the term aralkyl is meant an alkyl group containing an
aryl group. It is a hydrocarbon group having both aromatic and
aliphatic structures, that is, a hydrocarbon group in which a lower
alkyl hydrogen atom is substituted by a mononuclear or polynuclear
aryl group. Examples of aralkyl groups include, without limitation,
benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl,
5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl,
4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, naphthylmethyl,
and the like.
[0040] The term monocycloalkyl as used herein, refers to an
optionally substituted, saturated or partially unsaturated
monocycloalkyl ring system, where if the ring is partially
unsaturated, it is then a monocycloalkenyl group. The term
polycycloalkyl as used herein refers to an optionally substituted,
saturated or partially unsaturated polycycloalkyl ring system
containing two or more rings, where if the ring is partially
unsaturated, it is then a polycycloalkenyl group. Examples of
monocycloalkyl or polycycloalkyl groups optionally containing one
or more O atoms are well know to those skilled in the art and
include, for example, cyclopropyl, cyclobutyl, cyclopentyl,
cycloheptyl, cyclohexyl, 2-methyl-2-norbornyl, 2-ethyl-2-norbornyl,
2-methyl-2-isobornyl, 2-ethyl-2-isobornyl, 2-methyl-2-adamantyl,
2-ethyl-2-adamantyl, 1-adamantyl-1-methylethyl, adamantyl,
tricyclodecyl, 3-oxatricyclo[4.2.1.0.sup.2,5]nonyl,
tetracyclododecanyl, tetracyclo[5.2.2.0.0]undecanyl, bornyl,
isobornyl norbornyl lactone, adamantyl lactone and the like.
[0041] The term alkoxycarbonylalkyl embraces alkyl radicals
substituted with an alkoxycarbonyl radical as defined herein.
Examples of alkoxycarbonylalkyl radicals include methoxycarbonyl
methyl [CH.sub.3O--C(.dbd.O)--CH.sub.2--], ethoxycarbonyl methyl
[CH.sub.3CH.sub.2O--C(.dbd.O)--CH.sub.2--], methoxycarbonylethyl
[CH.sub.3O--C(.dbd.O)--CH.sub.2CH.sub.2--], and ethoxycarbonylethyl
[CH.sub.3CH.sub.2O--C(.dbd.O)--CH.sub.2CH.sub.2--].
[0042] The term alkylcarbonyl as used herein means an alkyl group,
as defined herein, appended to the parent molecular moiety through
a carbonyl group, as defined herein, which can be generically
represented as alkyl-C(O)--. Representative examples of
alkylcarbonyl include, but are not limited to acetyl (methyl
carbonyl), butyryl(propylcarbonyl), octanoyl(heptylcarbonyl),
dodecanoyl (undecylcarbonyl), and the like.
[0043] Alkoxycarbonyl means alkyl-O--C(O)--, wherein alkyl is as
previously described. Non-limiting examples include methoxycarbonyl
[CH.sub.3O--C(O)--] and the ethoxycarbonyl
[CH.sub.3CH.sub.2O--C(O)--], benzyloxycarbonyl
[C.sub.6H.sub.5CH.sub.2O--C(O)--] and the like.
[0044] Alkoxyalkyl means that a terminal alkyl group is linked
through an ether oxygen atom to an alkyl moiety, which can be
generically represented as alkyl-O-alkyl wherein the alkyl groups
can be linear or branched. Examples of alkoxyalkyl include, but are
not limited to, methoxypropyl, methoxybutyl, ethoxypropyl,
methoxymethyl
[0045] Monocycloalkyl- or polycycloalkyloxycarbonylalkyl means that
a terminal monocycloalkyl or polycycloalkyl group is linked through
--O--C(.dbd.O)-- to an alkyl moiety, generically represented as
monocycloalkyl- or polycycloalkyl-O--C(.dbd.O)-alkyl.
[0046] Monocycloalkyl- or polycycloalkyloxyalkyl means that a
terminal monocycloalkyl or polycycloalkyl group is linked through
an ether oxygen atom to an alkyl moiety, which can be generically
represented as monocycloalkyl- or polycycloalkyl-O-alkyl.
[0047] Monocyclofluoroalkyl- or polycyclofluoroalkyl means a
monocyclalkyl- or polycycloalkyl group substituted with one or more
fluorine atoms.
[0048] Polymers useful in the photoresist compositions include
those that have acid labile groups that make the polymer insoluble
in aqueous alkaline solution, but such a polymer in the presence of
an acid catalytically deprotects the polymer, wherein the polymer
then becomes soluble in an aqueous alkaline solution. The polymers
preferably are transparent below 200 nm, and are essentially
non-aromatic, and preferably are acrylates and/or cycloolefin
polymers. Such polymers are, for example, but not limited to, those
described in U.S. Pat. No. 5,843,624, U.S. Pat. No. 5,879,857, WO
97/33,198, EP 789,278 and GB 2,332,679. Nonaromatic polymers that
are preferred for irradiation below 200 nm are substituted
acrylates, cycloolefins, substituted polyethylenes, etc. Aromatic
polymers based on polyhydroxystyrene and its copolymers may also be
used, especially for 248 nm exposure.
[0049] Polymers based on acrylates are generally based on
poly(meth)acrylates with at least one unit containing pendant
alicyclic groups, and with the acid labile group being pendant from
the polymer backbone and/or from the alicyclic group. Examples of
pendant alicyclic groups, may be adamantyl, tricyclodecyl,
isobornyl, menthyl and their derivatives. Other pendant groups may
also be incorporated into the polymer, such as mevalonic lactone,
gamma butyrolactone, alkyloxyalkyl, etc. Examples of structures for
the alicyclic group include:
##STR00011##
[0050] The type of monomers and their ratios incorporated into the
polymer are optimized to give the best lithographic performance.
Such polymers are described in R. R. Dammel et al., Advances in
Resist Technology and Processing, SPIE, Vol. 3333, p144, (1998).
Examples of these polymers include poly(2-methyl-2-adamantyl
methacrylate-co-mevalonic lactone methacrylate),
poly(carboxy-tetracyclododecyl
methacrylate-co-tetrahydropyranylcarboxytetracyclododecyl
methacrylate),
poly(tricyclodecylacrylate-co-tetrahydropyranylmethacrylate-co-methacryli-
cacid), poly(3-oxocyclohexyl
methacrylate-co-adamantylmethacrylate).
[0051] Polymers synthesized from cycloolefins, with norbornene and
tetracyclododecene derivatives, may be polymerized by ring-opening
metathesis, free-radical polymerization or using metal organic
catalysts. Cycloolefin derivatives may also be copolymerized with
cyclic anhydrides or with maleimide or its derivatives. Examples of
cyclic anhydrides are maleic anhydride (MA) and itaconic anhydride.
The cycloolefin is incorporated into the backbone of the polymer
and may be any substituted or unsubstituted multicyclic hydrocarbon
containing an unsaturated bond. The monomer can have acid labile
groups attached. The polymer may be synthesized from one or more
cycloolefin monomers having an unsaturated bond. The cycloolefin
monomers may be substituted or unsubstituted norbornene, or
tetracyclododecane. The substituents on the cycloolefin may be
aliphatic or cycloaliphatic alkyls, esters, acids, hydroxyl,
nitrile or alkyl derivatives. Examples of cycloolefin monomers,
without limitation, include:
##STR00012##
[0052] Other cycloolefin monomers which may also be used in
synthesizing the polymer are:
##STR00013##
[0053] Such polymers are described in the following reference and
incorporated herein, M-D. Rahman et al, Advances in Resist
Technology and Processing, SPIE, Vol. 3678, p1193, (1999). Examples
of these polymers include
poly((t-butyl-5-norbornene-2-carboxylate-co-2-hydroxyethyl-5-norb-
ornene-2-carboxylate-co-5-norbornene-2-carboxylic acid-co-maleic
anhydride),
poly(t-butyl-5-norbornene-2-carboxylate-co-isobornyl-5-norbornene-2-carbo-
xylate-co-2-hydroxyethyl-5-norbornene-2-carboxylate-co-5-norbornene-2-carb-
oxylic acid-co-maleic an hydride),
poly(tetracyclododecene-5-carboxylate-co-maleic an hydride),
poly(t-butyl-5-norbornene-2-carboxylate-co-maleic
anhydride-co-2-methyladamantyl methacrylate-co-2-mevalonic lactone
methacrylate), poly(2-methyladamantyl methacrylate-co-2-mevalonic
lactone methacylate) and the like.
[0054] Polymers containing mixtures of (meth)acrylate monomers,
cycloolefinic monomers and cyclic anhydrides, where such monomers
are described above, may also be combined into a hybrid polymer.
Examples of cycloolefin monomers include those selected from
t-butyl norbornene carboxylate (BNC), hydroxyethyl norbornene
carboxylate (HNC), norbornene carboxylic acid (NC),
t-butyltetracyclo[4.4.0.1..sup.2,61..sup.7,10]dodec-8-ene-3-carboxylate,
and t-butoxy carbonylmethyl
tetracyclo[4.4.0.1.sup.2,61..sup.7,10]dodec-8-ene-3-carboxylate. In
some instances, preferred examples of cycloolefins include t-butyl
norbornene carboxylate (BNC), hydroxyethyl norbornene carboxylate
(HNC), and norbornene carboxylic acid (NC). Examples of
(meth)acrylate monomers include those selected from mevalonic
lactone methacrylate (MLMA), 2-methyl-2-adamantyl methacrylate
(MAdMA), 2-adamantyl methacrylate (AdMA), 2-methyl-2-adamantyl
acrylate (MAdA), 2-ethyl-2-adamantyl methacrylate (EAdMA),
3,5-dimethyl-7-hydroxy adamantyl methacrylate (DMHAdMA), adamantyl
methyloxy methyl methacrylate (AdOMMA), isoadamantyl methacrylate,
hydroxy-1-methacryloxyadamatane (HAdMA; for example, hydroxy at the
3-position), hydroxy-1-adamantyl acrylate (HADA; for example,
hydroxy at the 3-position), ethylcyclopentylacrylate (ECPA),
ethylcyclopentylmethacrylate (ECPMA),
tricyclo[5,2,1,0.sup.2,6]deca-8-yl methacrylate (TCDMA),
3,5-dihydroxy-1-methacryloxyadamantane (DHAdMA),
.beta.-methacryloxy-.gamma.-butyrolactone, .alpha.- or
.beta.-gamma-butyrolactone methacrylate (either .alpha.- or
.beta.-GBLMA), 5-methacryloyloxy-2,6-norbornanecarbolactone (MNBL),
5-acryloyloxy-2,6-norbornanecarbolactone (ANBL), isobutyl
methacrylate (IBMA), .alpha.-gamma-butyrolactone acrylate
(.alpha.-GBLA), spirolactone (meth)acrylate, oxytricyclodecane
(meth)acrylate, adamantane lactone (meth)acrylate, and
.alpha.-methacryloxy-.gamma.-butyrolactone, among others. Examples
of polymers formed with these monomers include
poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyr-
olactone methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate); poly(t-butyl norbornene
carboxylate-co-maleic anhydride-co-2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-methacryloyloxy norbornene methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.beta.-gamma-butyrolactone methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3,5-dihydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-b-
utyrolactone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3,5-dimethyl-7-hydroxy adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-methyl-2-adamantyl
acrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyrolac-
tone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-ethylcyclopentylacr-
ylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyr-
olactone methacrylate-co-2-ethyl-2-adamantyl methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane);
poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-.beta.-gamma-butyrolactone
methacrylate);
poly(ethylcyclopentylmethacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-isobutyl methacrylate-co-.alpha.-gamma-butyrolactone
acrylate); poly(2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-methyl-2-adamantyl methacrylate-co-.beta.
gamma-butyrolactone methacrylate-co-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-tricyclo[5,2,1,02,6]deca-8-yl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane-co-.alpha.-gamma-butyro-
lactone methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl
methacrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane-co-.alpha.-gamma-butyro-
lactone methacrylate-co-2-ethyl-2-adamantyl-co-methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-methyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-5-acryloyloxy-2,6-norbornanecarbolactone);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate-co-2-adamantyl
methacrylate); and poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl methacrylate).
[0055] Other examples of suitable polymers include those described
in U.S. Pat. Nos. 6,610,465, 6,120,977, 6,136,504, 6,013,416,
5,985,522, 5,843,624, 5,693,453, 4,491,628, WO 00/25178, WO
00/67072, JP 2000-275845, JP 2000-137327, and JP 09-73173 which are
incorporated herein by reference. Blends of one or more photoresist
resins may be used. Standard synthetic methods are typically
employed to make the various types of suitable polymers. Procedures
or references to suitable standard procedures (e.g., free radical
polymerization) can be found in the aforementioned documents.
[0056] The cycloolefin and the cyclic anhydride monomer are
believed to form an alternating polymeric structure, and the amount
of the (meth)acrylate monomer incorporated into the polymer can be
varied to give the optimal lithographic properties. The percentage
of the (meth)acrylate monomer relative to the cycloolefin/anhydride
monomers within the polymer ranges from about 95 mole % to about 5
mole %, further ranging from about 75 mole % to about 25 mole %,
and also further ranging from about 55 mole % to about 45 mole
%.
[0057] Fluorinated non-phenolic polymers, useful for 157 nm
exposure, also exhibit line edge roughness and can benefit from the
use of the novel mixture of photoactive compounds described in the
present invention. Such polymers are described in WO 00/17712 and
WO 00/67072 and incorporated herein by reference. Example of one
such polymer is
poly(tetrafluoroethylene-co-norbornene-co-5-hexafluoroisopropanol-substit-
uted 2-norbornene.
[0058] Polymers synthesized from cycloolefins and cyano containing
ethylenic monomers are described in the U.S. Pat. No. 6,686,429,
the contents of which are hereby incorporated herein by reference,
may also be used.
[0059] The molecular weight of the polymers is optimized based on
the type of chemistry used and on the lithographic performance
desired. Typically, the weight average molecular weight is in the
range of 3,000 to 30,000 and the polydispersity is in the range 1.1
to 5, preferably 1.5 to 2.5.
[0060] Other polymers of interest include those found and described
in U.S. patent application Ser. No. 10/371,262, filed Feb. 21,
2003, now filed as U.S. patent application Ser. No. 10/658,840,
filed Dec. 17, 2003 (and published now as US patent application
publication no. 2004/0166433, the contents of which are
incorporated herein by reference. Still other polymers, such as
those disclosed in U.S. patent application Ser. No. 10/440,452,
filed May 16, 2003 titled "Photoresist Composition for Deep UV and
Process Thereof", the contents of which are hereby incorporated
herein by reference, may also be used.
[0061] The solid components of the present invention are dissolved
in an organic solvent. The amount of solids in the solvent or
mixture of solvents ranges from about 1 weight % to about 50 weight
%. The polymer may be in the range of 5 weight % to 90 weight % of
the solids and the photoacid generator may be in the range of 1
weight % to about 50 weight % of the solids. Suitable solvents for
such photoresists may include for example ketones such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
isophorone, methyl isoamyl ketone, 2-heptanone 4-hydroxy, and
4-methyl 2-pentanone; C.sub.1 to C.sub.10 aliphatic alcohols such
as methanol, ethanol, and propanol; aromatic group
containing-alcohols such as benzyl alcohol; cyclic carbonates such
as ethylene carbonate and propylene carbonate; aliphatic or
aromatic hydrocarbons (for example, hexane, toluene, xylene, etc
and the like); cyclic ethers, such as dioxane and tetrahydrofuran;
ethylene glycol; propylene glycol; hexylene glycol; ethylene glycol
monoalkylethers such as ethylene glycol monomethylether, ethylene
glycol monoethylether; ethylene glycol alkylether acetates such as
methylcellosolve acetate and ethylcellosolve acetate; ethylene
glycol dialkylethers such as ethylene glycol dimethylether,
ethylene glycol diethylether, ethylene glycol methylethylether,
diethylene glycol monoalkylethers such as diethylene glycol
monomethylether, diethylene glycol monoethylether, and diethylene
glycol dimethylether; propylene glycol monoalkylethers such as
propylene glycol methylether, propylene glycol ethylether,
propylene glycol propylether, and propylene glycol butylether;
propylene glycol alkyletheracetates such as propylene glycol
methylether acetate, propylene glycol ethylether acetate, propylene
glycol propylether acetate, and propylene glycol butylether
acetate; propylene glycol alkyletherpropionates such as propylene
glycol methyletherpropionate, propylene glycol
ethyletherpropionate, propylene glycol propyletherpropionate, and
propylene glycol butyletherpropionate; 2-methoxyethyl ether
(diglyme); solvents that have both ether and hydroxy moieties such
as methoxy butanol, ethoxy butanol, methoxy propanol, and ethoxy
propanol; esters such as methyl acetate, ethyl acetate, propyl
acetate, and butyl acetate methyl-pyruvate, ethyl pyruvate; ethyl
2-hydroxy propionate, methyl 2-hydroxy 2-methyl propionate, ethyl
2-hydroxy 2-methyl propionate, methyl hydroxy acetate, ethyl
hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl
lactate, propyl lactate, butyl lactate, methyl 3-hydroxy
propionate, ethyl 3-hydroxy propionate, propyl 3-hydroxy
propionate, butyl 3-hydroxy propionate, methyl 2-hydroxy 3-methyl
butanoic acid, methyl methoxy acetate, ethyl methoxy acetate,
propyl methoxy acetate, butyl methoxy acetate, methyl ethoxy
acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy
acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl
propoxy acetate, butyl propoxy acetate, methyl butoxy acetate,
ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate,
methyl 2-methoxy propionate, ethyl 2-methoxy propionate, propyl
2-methoxy propionate, butyl 2-methoxy propionate, methyl
2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl
2-ethoxypropionate, butyl 2-ethoxypropionate, methyl
2-butoxypropionate, ethyl 2-butoxypropionate, propyl
2-butoxypropionate, butyl 2-butoxypropionate, methyl
3-methoxypropionate, ethyl 3-methoxypropionate, propyl
3-methoxypropionate, butyl 3-methoxypropionate, methyl
3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl
3-ethoxypropionate, butyl 3-ethoxypropionate, methyl
3-propoxypropionate, ethyl 3-propoxypropionate, propyl
3-propoxypropionate, butyl 3-propoxypropionate, methyl
3-butoxypropionate, ethyl 3-butoxypropionate, propyl
3-butoxypropionate, and butyl 3-butoxypropionate; oxyisobutyric
acid esters, for example, methyl-2-hydroxyisobutyrate, methyl
.alpha.-methoxyisobutyrate, ethyl methoxyisobutyrate, methyl
.alpha.-ethoxyisobutyrate, ethyl .alpha.-ethoxyisobutyrate, methyl
.beta.-methoxyisobutyrate, ethyl .beta.-methoxyisobutyrate, methyl
.beta.-ethoxyisobutyrate, ethyl .beta.-ethoxyisobutyrate, methyl
.beta.-isopropoxyisobutyrate, ethyl .beta.-isopropoxyisobutyrate,
isopropyl .beta.-isopropoxyisobutyrate, butyl
.beta.-isopropoxyisobutyrate, methyl .beta.-butoxyisobutyrate,
ethyl .beta.-butoxyisobutyrate, butyl .beta.-butoxyisobutyrate,
methyl .alpha.-hydroxyisobutyrate, ethyl
.alpha.-hydroxyisobutyrate, isopropyl .alpha.-hydroxyisobutyrate,
and butyl .alpha.-hydroxyisobutyrate; solvents that have both ether
and hydroxy moieties such as methoxy butanol, ethoxy butanol,
methoxy propanol, and ethoxy propanol; and other solvents such as
dibasic esters, and gamma-butyrolactone; a ketone ether derivative
such as diacetone alcohol methyl ether; a ketone alcohol derivative
such as acetol or diacetone alcohol; lactones such as
butyrolactone; an amide derivative such as dimethylacetamide or
dimethylformamide, anisole, and mixtures thereof.
[0062] Various other additives such as colorants, non-actinic dyes,
anti-striation agents, plasticizers, adhesion promoters,
dissolution inhibitors, coating aids, photospeed enhancers,
additional photoacid generators, and solubility enhancers (for
example, certain small levels of solvents not used as part of the
main solvent (examples of which include glycol ethers and glycol
ether acetates, valerolactone, ketones, lactones, and the like),
and surfactants may be added to the photoresist composition before
the solution is coated onto a substrate. Surfactants that improve
film thickness uniformity, such as fluorinated surfactants, can be
added to the photoresist solution. A sensitizer that transfers
energy from a particular range of wavelengths to a different
exposure wavelength may also be added to the photoresist
composition. Often bases are also added to the photoresist to
prevent t-tops or bridging at the surface of the photoresist image.
Examples of bases are amines, ammonium hydroxide, and
photosensitive bases. Particularly preferred bases are
trioctylamine, diethanolamine and tetrabutylammonium hydroxide.
[0063] The prepared photoresist composition solution can be applied
to a substrate by any conventional method used in the photoresist
art, including dipping, spraying, and spin coating. When spin
coating, for example, the photoresist solution can be adjusted with
respect to the percentage of solids content, in order to provide
coating of the desired thickness, given the type of spinning
equipment utilized and the amount of time allowed for the spinning
process. Suitable substrates include silicon, aluminum, polymeric
resins, silicon dioxide, doped silicon dioxide, silicon nitride,
tantalum, copper, polysilicon, ceramics, aluminum/copper mixtures;
gallium arsenide and other such Group III/V compounds. The
photoresist may also be coated over antireflective coatings.
[0064] The photoresist coatings produced by the described procedure
are particularly suitable for application to silicon/silicon
dioxide wafers, such as are utilized in the production of
microprocessors and other miniaturized integrated circuit
components. An aluminum/aluminum oxide wafer can also be used. The
substrate may also comprise various polymeric resins, especially
transparent polymers such as polyesters.
[0065] The photoresist composition solution is then coated onto the
substrate, and the substrate is treated (baked) at a temperature
from about 70.degree. C. to about 150.degree. C. for from about 30
seconds to about 180 seconds on a hot plate or for from about 15 to
about 90 minutes in a convection oven. This temperature treatment
is selected in order to reduce the concentration of residual
solvents in the photoresist, while not causing substantial thermal
degradation of the solid components. In general, one desires to
minimize the concentration of solvents and this first temperature.
Treatment (baking) is conducted until substantially all of the
solvents have evaporated and a thin coating of photoresist
composition, on the order of half a micron (micrometer) in
thickness, remains on the substrate. In a preferred embodiment the
temperature is from about 95.degree. C. to about 120.degree. C. The
treatment is conducted until the rate of change of solvent removal
becomes relatively insignificant. The film thickness, temperature
and time selection depends on the photoresist properties desired by
the user, as well as the equipment used and commercially desired
coating times. The coated substrate can then be imagewise exposed
to actinic radiation, e.g., ultraviolet radiation, at a wavelength
of from about 100 nm (nanometers) to about 300 nm, x-ray, electron
beam, ion beam or laser radiation, in any desired pattern, produced
by use of suitable masks, negatives, stencils, templates, etc.
[0066] The photoresist is then subjected to a post exposure second
baking or heat treatment before development. The heating
temperatures may range from about 90.degree. C. to about
150.degree. C., more preferably from about 100.degree. C. to about
130.degree. C. The heating may be conducted for from about 30
seconds to about 2 minutes, more preferably from about 60 seconds
to about 90 seconds on a hot plate or about 30 to about 45 minutes
by convection oven.
[0067] The exposed photoresist-coated substrates are developed to
remove the image-wise exposed areas by immersion in a developing
solution or developed by spray development process. The solution is
preferably agitated, for example, by nitrogen burst agitation. The
substrates are allowed to remain in the developer until all, or
substantially all, of the photoresist coating has dissolved from
the exposed areas. Developers include aqueous solutions of ammonium
or alkali metal hydroxides. One preferred developer is an aqueous
solution of tetramethyl ammonium hydroxide. After removal of the
coated wafers from the developing solution, one may conduct an
optional post-development heat treatment or bake to increase the
coating's adhesion and chemical resistance to etching conditions
and other substances. The post-development heat treatment can
comprise the oven baking of the coating and substrate below the
coating's softening point or UV hardening process. In industrial
applications, particularly in the manufacture of microcircuitry
units on silicon/silicon dioxide-type substrates, the developed
substrates may be treated with a buffered, hydrofluoric acid base
etching solution or dry etching. Prior to dry etching the
photoresist may be treated to electron beam curing in order to
increase the dry-etch resistance of the photoresist.
[0068] The invention further provides a method for producing a
semiconductor device by producing a photo-image on a substrate by
coating a suitable substrate with a photoresist composition. The
subject process comprises coating a suitable substrate with a
photoresist composition and heat treating the coated substrate
until substantially all of the photoresist solvent is removed;
image-wise exposing the composition and removing the image-wise
exposed areas of such composition with a suitable developer.
[0069] The following examples provide illustrations of the methods
of producing and utilizing the present invention. These examples
are not intended, however, to limit or restrict the scope of the
invention in any way and should not be construed as providing
conditions, parameters or values which must be utilized exclusively
in order to practice the present invention. Unless otherwise
specified, all parts and percents are by weight.
EXAMPLE 1
Synthesis of bis [di(4-t-butyl phenyl)iodonium]di-(tetrafluoroethyl
sulfonate) ether
##STR00014##
[0071] Bis[2-(fluorosulfonyl)tetrafluoroethyl]ether obtained from
Synquest (5 g) was taken in a flask in water and excess amount of
KOH was and heated under stirring at 80.degree. C. for six hours.
The solution was cooled to room temperature and di
t-butylphenylphenyl iodonium acetate (2 mol equivalent) in water
and THF was added on stirring. After six hours, chloroform was
added and stirred for 3 hours. The chloroform layer was washed
several times with water, dried over anhydrous sodium sulfate,
filtered and chloroform evaporated. Hexane was added to form
crystals, filtered and dried under vacuum, mp 101.degree. C. 6.5 g
was isolated.
EXAMPLE 2
Synthesis of bis [(triphenyl)sulfonium]di-(tetrafluoroethyl
sulfonate) ether
##STR00015##
[0073] Bis[2-(fluorosulfonyl)tetrafluoroethyl]ether obtained from
Synquest (5 g) was taken in a flask in water and excess amount of
KOH (2.93 g) was and heated under stirring at 80.degree. C. for six
hours. The solution was cooled to room temperature and trilphenyl
sulfonium bromide (2 mole equivalent) in water and THF was added on
stirring. After 3 hours, dichloromethane was added and stirred for
2 hours. The dichloromethane layer was washed several times with
water, dried over anhydrous sodium sulfate, filtered and
dichloromethane evaporated. Hexane was added to form crystals,
filtered and dried under vacuum, mp 86-87.degree. C. 8.0 g was
isolated.
EXAMPLE 3
Synthesis of bis [(4-octyloxyphenyl
phenyl)iodonium]di-(tetrafluoroethyl sulfonate) ether
##STR00016##
[0075] Bis[2-(fluorosulfonyl)tetrafluoroethyl]ether obtained from
Synquest (5 g) was taken in a flask in water and excess amount of
KOH (2.9 g) was and heated under stirring at 80.degree. C. for six
hours. The solution was cooled to room temperature and
4-octyloxyphenyl phenyl iodonium chloride (11.64 g) in water and
THF was added on stirring. After six hours, chloroform was added
and stirred for 3 hours. The chloroform layer was washed several
times with water, dried over anhydrous sodium sulfate, filtered and
chloroform evaporated. Hexane was added on stirring, separated as
oil layer, decanted and dried under vacuum. (14.5 g) was isolated
as oil.
EXAMPLE 4
Synthesis of bis [(diphenyl)iodonium]di-(tetrafluoroethyl
sulfonate) ether
##STR00017##
[0077] Bis[2-(fluorosulfonyl)tetrafluoroethyl]ether obtained from
Synquest (5 g) was taken in a flask in water and excess amount of
KOH (2.9 g) was and heated under stirring at 80.degree. C. for six
hours. The solution was cooled to room temperature and di phenyl
iodonium chloride 8.2 g) in water and THF was added on stirring.
After six hours, chloroform was added and stirred for 3 hours. The
chloroform layer was washed several times with water, dried over
anhydrous sodium sulfate, filtered and chloroform evaporated.
Hexane was added on stirring and white crystals were formed. The
solution was filtered and the white crystals were washed with
hexane. The crystals were dried under vacuum and isolated (6.5 g;
mp 210.degree. C.).
[0078] Following the procedure in Example 1, the following
compounds can be made from the corresponding iodonium acetate or
halide or sulfonium acetate or halide: bis
[di(4-octyloxyphenyl)iodonium]di-(tetrafluoroethyl sulfonate) ether
bis [(4-methylphenyl)phenyl iodonium]di-(tetrafluoroethyl
sulfonate) ether bis [(4-t-butylphenyl) phenyl
iodonium]di-(tetrafluoroethyl sulfonate) ether bis
[(4-methoxyphenyl) phenyl iodonium]di-(tetrafluoroethyl sulfonate)
ether bis(4-methoxyphenyl) iodonium di-(tetrafluoroethyl sulfonate)
ether bis(4-t-butylphenyl diphenyl sulfonium) di-(tetrafluoroethyl
sulfonate) ether bis(4-t-butylphenyl iodonium) di-(tetrafluoroethyl
sulfonate) ether bis(4-t-butylphenyl iodonium) triphenyl sulfonium
di-(tetrafluoroethyl sulfonate) ether
bis(benzoyltetramethylenesulfonium) di-(tetrafluoroethyl sulfonate)
ether bis(triphenyl sulfonium) di-(tetrafluoroethyl sulfonate)
ether bis(tris(4-t-butyl phenyl) sulfonium) di-(tetrafluoroethyl
sulfonate) ether bis
[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]di-(tetrafl-
uoroethyl sulfonate) ether bis
[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfonium-
]di-(tetrafluoroethyl sulfonate) ether bis
[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmethox-
yphenyl]phenyl sulfonium]di-(tetrafluoroethyl sulfonate) ether bis
[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]di-(tetrafluor-
oethyl sulfonate) ether
EXAMPLE 5
[0079] 0.5352 g of poly(EAdMA/AdOMMA/HAdA/.alpha.-GBLMA/AdMA;
20/10/20/40/10) polymer, 0.0124 g (30 .mu.mol/g) of
bis(4-t-butylphenyl) iodonium bis-perfluoroethane sulfonimide and
0.0142 g (30 .mu.mol/g) of bis(triphenyl sulfonium)
perfluorobutane-1,4-disulfonate, and 0.0292 g (47 .mu.mol/g) of bis
[di(4-t-butyl phenyl) iodonium]di-(tetrafluoroethyl sulfonate)
ether from Example 1, 0.3919 g of DIPA 1 weight % in PGMEA) and
0.0204 g of 10 weight % PGMEA solution of a surfactant
(fluoroaliphatic polymeric ester, supplied by 3M Corporation, St.
Paul Minn.) were dissolved in 13.122 g of MHIB and 3.224 g of PGME
to give a 17 g photoresist solution.
EXAMPLE 6
[0080] A silicon substrate coated with a bottom antireflective
coating (B.A.R.C.) was prepared by spin coating the bottom
anti-reflective coating solution (AZ.RTM. ArF-38, available from AZ
Electronic Materials Corporation, Somerville, N.J.) onto the
silicon substrate and baked at 225.degree. C. for 90 sec. The
B.A.R.C film thickness was 87 nm. The photoresist solution from
Example 5 was then coated on the B.A.R.C coated silicon substrate.
The spin speed was adjusted such that the photoresist film
thickness was 300 nm, soft baked at 100.degree. C./60 s, exposed
with Nikon 306D 0.78 NA & 4/5 Annular Illumination using a
binary mask; then the wafer was post exposure baked at 110.degree.
C./60 s, and developed using a 2.38 weight % aqueous solution of
tetramethyl ammonium hydroxide for 30 sec. The line and space
patterns were then observed on a scanning electron microscope. The
photoresist had a photosensitivity of 68.0 mJ/cm.sup.2 and had very
good exposure latitude (18.7%), good LER and profile shape.
EXAMPLE 7
[0081] 0.6443 g of poly(EAdMA/HAdA/.alpha.-GBLMA/AdMA; 30/20/40/10)
polymer, 0.0199 g (40 .mu.mol/g) of bis(4-t-butylphenyl) iodonium
bis-perfluoroethane sulfonimide and 0.0171 g (30 .mu.mol/g) of
bis(triphenyl sulfonium) perfluorobutane-1,4-disulfonate, and
0.0150 g (20 .mu.mol/g) of bis [di(4-t-butyl phenyl)
iodonium]di-(tetrafluoroethyl sulfonate) ether from Example 1,
0.3598 g of DIPA 1 weight % in PGMEA) and 0.0204 g of 10 weight %
PGMEA solution of a surfactant (fluoroaliphatic polymeric ester,
supplied by 3M Corporation, St. Paul Minn.) were dissolved in
13.122 g of MHIB and 3.7914 g of PGME to give a 20 g photoresist
solution.
EXAMPLE 8
[0082] A silicon substrate coated with a bottom antireflective
coating (B.A.R.C.) was prepared by spin coating the bottom
anti-reflective coating solution (AZ.RTM. ArF-38, available from AZ
Electronic Materials Corporation, Somerville, N.J.) onto the
silicon substrate and baking at 225.degree. C. for 90 sec. The
B.A.R.C film thickness was 87 nm. The photoresist solution from
Example 7 was then coated on the B.A.R.C coated silicon substrate.
The spin speed was adjusted such that the photoresist film
thickness was 300 nm, soft baked at 100.degree. C./60 s, exposed
with Nikon 306D 0.78 NA & 4/5 Annular Illumination using a
binary mask; then the wafer was post exposure baked at 110.degree.
C./60 s, and developed using a 2.38 weight % aqueous solution of
tetramethyl ammonium hydroxide for 30 sec. The line and space
patterns were then observed on a scanning electron microscope. The
photoresist had a photosensitivity of 68.0 mJ/cm.sup.2 and had very
good exposure latitude (18.7%), good LER and profile shape.
EXAMPLE 9
[0083] 0.5352 g of poly(ECPMA/HAdA/.alpha.-GBLMA; 30/30/40)
polymer, 0.0124 g (30 .mu.mol/g) of bis(4-t-butylphenyl) iodonium
bis-perfluoroethane sulfonimide and 0.0142 g (30 .mu.mol/g) of
bis(triphenyl sulfonium) perfluorobutane-1,4-disulfonate, and
0.0292 g (47 .mu.mol/g) of bis [di(4-t-butyl phenyl)
iodonium]di-(tetrafluoroethyl sulfonate) ether from Example 1,
0.3919 g of DIPA 1 weight % in PGMEA) and 0.0204 g of 10 weight %
PGMEA solution of a surfactant (fluoroaliphatic polymeric ester,
supplied by 3M Corporation, St. Paul Minn.) were dissolved in
13.122 g of MHIB and 3.224 g of PGME to give a 17 g photoresist
solution.
EXAMPLE 10
[0084] A silicon substrate coated with a bottom antireflective
coating (B.A.R.C.) was prepared by spin coating the bottom
anti-reflective coating solution (AZ.RTM. ArF-38, available from AZ
Electronic Materials Corporation, Somerville, N.J.) onto the
silicon substrate and baking at 225.degree. C. for 90 sec. The
B.A.R.C film thickness was 87 nm. The photoresist solution from
Example 9 was then coated on the B.A.R.C coated silicon substrate.
The spin speed was adjusted such that the photoresist film
thickness was thickness 300 nm, soft baked at 100.degree. C./60 s,
exposed with Nikon 306D 0.78 NA & 4/5 Annular Illumination
using a binary mask; then the wafer was post exposure baked at
110.degree. C./60 s, and developed using a 2.38 weight % aqueous
solution of tetramethyl ammonium hydroxide for 30 sec. The line and
space patterns were then observed on a scanning electron
microscope. The photoresist had a photosensitivity of 68.0
mJ/cm.sup.2 and had very good exposure latitude (18.7%), good LER
and profile shape.
EXAMPLE 11
[0085] 0.5352 g of poly(EAdMA/ECPMA/HAdA/.alpha.-GBLMA;
15/15/30/40) polymer, 0.0124 g (30 .mu.mol/g) of
bis(4-t-butylphenyl) iodonium bis-perfluoroethane sulfonimide and
0.0142 g (30 .mu.mol/g) of bis(triphenyl sulfonium)
perfluorobutane-1,4-disulfonate, and 0.0292 g (47 .mu.mol/g) of
bis[di(4-t-butyl phenyl) iodonium]di-(tetrafluoroethyl sulfonate)
ether from Example 1, 0.3919 g of DIPA 1 weight % in PGMEA) and
0.0204 g of 10 weight % PGMEA solution of a surfactant
(fluoroaliphatic polymeric ester, supplied by 3M Corporation, St.
Paul Minn.) were dissolved in 13.122 g of MHIB and 3.224 g of PGME
to give a 17 g photoresist solution.
EXAMPLE 12
[0086] A silicon substrate coated with a bottom antireflective
coating (B.A.R.C.) was prepared by spin coating the bottom
anti-reflective coating solution (AZ.RTM. ArF-38, available from AZ
Electronic Materials Corporation, Somerville, N.J.) onto the
silicon substrate and baking at 225.degree. C. for 90 sec. The
B.A.R.C film thickness was 87 nm. The photoresist solution from
Example 11 was then coated on the B.A.R.C coated silicon substrate.
The spin speed was adjusted such that the photoresist film
thickness was 300 nm, soft baked at 100.degree. C./60 s, exposed
with Nikon 306D 0.78 NA & 4/5 Annular Illumination using a
binary mask; then the wafer was post exposure baked at 110.degree.
C./60 s, and developed using a 2.38 weight % aqueous solution of
tetramethyl ammonium hydroxide for 30 sec. The line and space
patterns were then observed on a scanning electron microscope. The
photoresist had a photosensitivity of 68.0 mJ/cm.sup.2 and had very
good exposure latitude (18.7%), good LER and profile shape.
EXAMPLE 13
[0087] 0.6291 g of poly(EAdMA/ECPMA/AdOMMA/HAdA/.alpha.-GBLMA;
5/15/10/30/40) polymer, 0.0146 g (30 .mu.mol/g) of
bis(4-t-butylphenyl) iodonium bis-perfluoroethane sulfonimide and
0.0142 g (30 .mu.mol/g) of bis(triphenyl sulfonium)
perfluorobutane-1,4-disulfonate, and 0.0170 g (47 .mu.mol/g) of
bis[di(triphenyl) sulfonium]di-(tetrafluoroethyl sulfonate) ether
from Example 2, 0.5336 g of DIPA 1 weight % Q9 (DBA in MHIB) and
0.0204 g of 10 weight % PGMEA solution of a surfactant
(fluoroaliphatic polymeric ester, supplied by 3M Corporation, St.
Paul Minn.) were dissolved in 11.3994 g of MHIB and 3.7918 g of
PGME to give a 20 g photoresist solution.
EXAMPLE 14
[0088] A silicon substrate coated with a bottom antireflective
coating (B.A.R.C.) was prepared by spin coating the bottom
anti-reflective coating solution (AZ.RTM. ArF-38, available from AZ
Electronic Materials Corporation, Somerville, N.J.) onto the
silicon substrate and baking at 225.degree. C. for 90 sec. The
B.A.R.C film thickness was 87 nm. The photoresist solution from
Example 13 was then coated on the B.A.R.C coated silicon substrate.
The spin speed was adjusted such that the photoresist film
thickness was 300 nm, soft baked at 100.degree. C./60 s, exposed
with Nikon 306D 0.78 NA & 4/5 Annular Illumination using a
binary mask; then the wafer was post exposure baked at 110.degree.
C./60 s, and developed using a 2.38 weight % aqueous solution of
tetramethyl ammonium hydroxide for 30 sec. The line and space
patterns were then observed on a scanning electron microscope. The
photoresist had a photosensitivity of 37.5 mJ/cm.sup.2 and had very
good exposure latitude (8.52%), good LER and profile shape.
EXAMPLE 15
[0089] Examples 5, 7, 9, 11, and 13 can be repeated by substituting
the polymer therein with one of the following polymers:
[0090] poly(2-methyl-2-adamantyl
methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyr-
olactone methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate);
[0091] poly(t-butyl norbornene carboxylate-co-maleic
anhydride-co-2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-methacryloyloxy norbornene methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.beta.-gamma-butyrolactone methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3,5-dihydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-b-
utyrolactone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3,5-dimethyl-7-hydroxy adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-methyl-2-adamantyl
acrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyrolac-
tone methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-ethylcyclopentylacr-
ylate); poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.alpha.-gamma-butyr-
olactone methacrylate-co-2-ethyl-2-adamantyl methacrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamantane-co-.beta.-gamma-butyro-
lactone methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl
methacrylate); poly(2-methyl-2-adamantyl
methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane);
poly(2-methyl-2-adamantyl methacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-methacryloxyadamantane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-.beta.-gamma-butyrolactone
methacrylate);
poly(ethylcyclopentylmethacrylate-co-2-ethyl-2-adamantyl
methacrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-isobutyl methacrylate-co-.alpha.-gamma-butyrolactone
acrylate); poly(2-methyl-2-adamantyl
methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-methyl-2-adamantyl methacrylate-co-.beta.
gamma-butyrolactone methacrylate-co-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-.beta.-gamma-butyrolactone
methacrylate-co-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane);
poly(2-methyl-2-adamantyl methacrylate-co-methacryloyloxy
norbornene methacrylate-co-tricyclo[5,2,1,02,6]deca-8-yl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane-co-.alpha.-gamma-butyro-
lactone methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl
methacrylate-co-.alpha.-gamma-butyrolactone methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone acrylate);
poly(2-methyl-2-adamantyl
methacrylate-co-3-hydroxy-1-methacryloxyadamatane-co-.alpha.-gamma-butyro-
lactone methacrylate-co-2-ethyl-2-adamantyl-co-methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
methacrylate-co-tricyclo[5,2,1,0.sup.2,6]deca-8-yl methacrylate);
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate-co-2-adamantyl
methacrylate); poly(2-ethyl-2-adamantyl
methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone methacrylate); and
poly(2-ethyl-2-adamantyl methacrylate-co-3-hydroxy-1-adamantyl
acrylate-co-.alpha.-gamma-butyrolactone
acrylate-co-tricyclo[5,2,1,02,6]deca-8-yl methacrylate) to form a
photoresist solution. The photoresist solutions formed therefrom
are expected to give similar results as to those found in Examples
4, 6, 8, and 10.
EXAMPLE 16
[0092] Example 15 can be repeated by replacing bis [di(4-t-butyl
phenyl) iodonium]di-(tetrafluoroethyl sulfonate) ether from Example
1 with one of the following: bis [di(4-octyloxyphenyl)
iodonium]di-(tetrafluoroethyl sulfonate) ether, bis
[(4-octyloxyphenyl) phenyl iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis [(4-methylphenyl) phenyl iodonium]di-(tetrafluoroethyl
sulfonate) ether, bis [(4-t-butylphenyl) phenyl
iodonium]di-(tetrafluoroethyl sulfonate) ether, bis
[(4-methoxyphenyl) phenyl iodonium]di-(tetrafluoroethyl sulfonate)
ether, bis(4-methoxyphenyl) iodonium di-(tetrafluoroethyl
sulfonate) ether, bis(4-octyloxyphenyl) phenyl sulfonium
di-(tetrafluoroethyl sulfonate) ether, bis(4-t-butylphenyl diphenyl
sulfonium) di-(tetrafluoroethyl sulfonate) ether,
bis(4-t-butylphenyl iodonium) di-(tetrafluoroethyl sulfonate)
ether, bis(4-t-butylphenyl iodonium) triphenyl sulfonium
di-(tetrafluoroethyl sulfonate) ether,
bis(benzoyltetramethylenesulfonium) di-(tetrafluoroethyl sulfonate)
ether, bis(tris(4-t-butyl phenyl) sulfonium) di-(tetrafluoroethyl
sulfonate) ether, bis
[bis[2-methyl-adamantylacetyloxymethoxyphenyl]phenylsulfonium]di-(tetrafl-
uoroethyl sulfonate) ether, bis
[bis[4-(3,5-di(trifluoromethyl)benzenesulfonyloxy)-phenyl]phenylsulfonium-
]di-(tetrafluoroethyl sulfonate) ether, bis
[bis[4,4-bis(trifluoro-methyl)-3-oxatricyclo[4.2.1.0.sup.2,5]-nonylmethox-
yphenyl]phenyl sulfonium]di-(tetrafluoroethyl sulfonate) ether, or
bis
[bis[4-pentafluorobenzenesulfonyloxyphenyl]phenylsulfonium]di-(tetrafluor-
oethyl sulfonate) ether. The photoresist solutions formed therefrom
are expected to give similar results as to those found in Examples
6, 8,10,12, and 14.
[0093] The additional photoacid generators of formula Ai Xi1 Bi can
be made in accordance with the procedures set forth in U.S. patent
application Ser. Nos. 11/179,886, filed Jul. 12, 2005, and Ser. No.
11/355,762, filed Feb. 16, 2006, the contents of which are hereby
incorporated herein by reference. Other examples are found in U.S.
patent application Ser. No. 11/355,400, filed Feb. 16, 2006, United
States Published Patent Application 2004-0229155, and United States
Published Patent Application 2005-0271974, U.S. Pat. No. 5,837,420,
U.S. Pat. No. 6,111,143, and U.S. Pat. No. 6,358,665, the contents
of which are hereby incorporated herein by reference. Those
additional photoacid generators of formula Ai Xi2 are well known to
those skilled in the art, for example, those known from United
States Patent Application No. 20030235782 and United States Patent
Application No. 20050271974, the contents of which are hereby
incorporated herein by reference.
[0094] The foregoing description of the invention illustrates and
describes the present invention. Additionally, the disclosure shows
and describes only certain embodiments of the invention but, as
mentioned above, it is to be understood that the invention is
capable of use in various other combinations, modifications, and
environments and is capable of changes or modifications within the
scope of the inventive concept as expressed herein, commensurate
with the above teachings and/or the skill or knowledge of the
relevant art. The embodiments described hereinabove are further
intended to explain best modes known of practicing the invention
and to enable others skilled in the art to utilize the invention in
such, or other, embodiments and with the various modifications
required by the particular applications or uses of the invention.
Accordingly, the description is not intended to limit the invention
to the form disclosed herein. Also, it is intended that the
appended claims be construed to include alternative
embodiments.
* * * * *