U.S. patent application number 09/842005 was filed with the patent office on 2001-12-13 for novel ester compounds having alicyclic structure and method for preparing same.
This patent application is currently assigned to Shin-Etsu Chemical Co., Ltd.. Invention is credited to Hasegawa, Koji, Hatakeyama, Jun, Kinsho, Takeshi, Nakashima, Mutsuo, Nishi, Tsunehiro, Tachibana, Seiichiro, Watanabe, Takeru.
Application Number | 20010051741 09/842005 |
Document ID | / |
Family ID | 18640124 |
Filed Date | 2001-12-13 |
United States Patent
Application |
20010051741 |
Kind Code |
A1 |
Watanabe, Takeru ; et
al. |
December 13, 2001 |
Novel ester compounds having alicyclic structure and method for
preparing same
Abstract
Ester compounds of formula (1) are useful as monomers to form
base resins for use in chemically amplified resist compositions
adapted for micropatterning lithography. 1 R.sup.1 is H or
C.sub.1-6 alkyl, R.sup.2 is an acid labile group, k is 0 or 1, and
m is an integer from 0 to 5.
Inventors: |
Watanabe, Takeru;
(Niigata-ken, JP) ; Hasegawa, Koji; (Niigata-ken,
JP) ; Kinsho, Takeshi; (Niigata-ken, JP) ;
Nakashima, Mutsuo; (Niigata-ken, JP) ; Tachibana,
Seiichiro; (Niigata-ken, JP) ; Nishi, Tsunehiro;
(Niigata-ken, JP) ; Hatakeyama, Jun; (Niigata-ken,
JP) |
Correspondence
Address: |
MILLEN, WHITE, ZELANO & BRANIGAN, P.C.
2200 CLARENDON BLVD.
SUITE 1400
ARLINGTON
VA
22201
US
|
Assignee: |
Shin-Etsu Chemical Co.,
Ltd.
Tokyo
JP
|
Family ID: |
18640124 |
Appl. No.: |
09/842005 |
Filed: |
April 26, 2001 |
Current U.S.
Class: |
560/116 ;
560/120; 560/126; 560/128 |
Current CPC
Class: |
G03F 7/0397 20130101;
C07C 2603/74 20170501; C07C 2602/42 20170501; C07C 2603/68
20170501; G03F 7/0395 20130101; C07C 2601/14 20170501; C07C 2603/86
20170501; C07C 2601/08 20170501; C07C 69/732 20130101 |
Class at
Publication: |
560/116 ;
560/120; 560/126; 560/128 |
International
Class: |
C07C 069/74 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 28, 2000 |
JP |
2000-131177 |
Claims
1. An ester compound of the following general formula (1):
11wherein R.sup.1 is hydrogen or a straight, branched or cyclic
alkyl group of 1 to 6 carbon atoms, R.sup.2 is an acid labile
group, k is 0 or 1, and m is an integer from 0 to 5.
2. The ester compound of claim 1 having the following general
formula (2) or (3): 12wherein m is as defined above, R.sup.3 is
hydrogen or methyl, R.sup.4 to R.sup.7 are independently selected
from straight, branched or cyclic alkyl groups of 1 to 15 carbon
atoms, the sum of carbon atoms in R.sup.4, R.sup.5 and R.sup.6 is
at least 4, and Z is a divalent hydrocarbon group of 4 to 15 carbon
atoms which forms a ring with the carbon atom to which it is
connected at opposite ends.
3. A method for preparing the ester compound of claim 1 or 2,
comprising the step of effecting addition reaction of a metal
enolate of acetate of the following formula (5) to a carbonyl
compound of the following formula (4), 13wherein k, m, R.sup.1 and
R.sup.2 are as defined above, M is Li, Na, K, MgY or ZnY, and Y is
a halogen atom.
Description
[0001] This invention relates to novel ester compounds useful as
monomers to form base resins for use in chemically amplified resist
compositions adapted for micropatterning lithography, and a method
for preparing the same.
BACKGROUND OF THE INVENTION
[0002] While a number of recent efforts are being made to achieve a
finer pattern rule in the drive for higher integration and
operating speeds in LSI devices, deep-ultraviolet lithography is
thought to hold particular promise as the next generation in
microfabrication technology. In particular, photolithography using
a KrF or ArF excimer laser as the light source is strongly desired
to reach the practical level as the micropatterning technique
capable of achieving a feature size of 0.3 .mu.m or less.
[0003] The resist materials for use in photolithography using light
of an excimer laser, especially ArF excimer laser having a
wavelength of 193 nm, are, of course, required to have a high
transmittance to light of that wavelength. In addition, they are
required to have an etching resistance sufficient to allow for film
thickness reduction, a high sensitivity sufficient to eliminate any
extra burden on the expensive optical material, and especially, a
high resolution sufficient to form a precise micropattern. To meet
these requirements, it is crucial to develop a base resin having a
high transparency, rigidity and reactivity. None of the currently
available polymers satisfy all of these requirements. Practically
acceptable resist materials are not yet available.
[0004] Known high transparency resins include copolymers of acrylic
or methacrylic acid derivatives and polymers containing in the
backbone an alicyclic compound derived from a norbornene
derivative. All these resins are unsatisfactory. For example,
copolymers of acrylic or methacrylic acid derivatives are
relatively easy to increase reactivity in that highly reactive
monomers can be introduced and acid labile units can be increased
as desired, but difficult to increase rigidity because of their
backbone structure. On the other hand, the polymers containing an
alicyclic compound in the backbone have rigidity within the
acceptable range, but are less reactive with acid than
poly(meth)acrylate because of their backbone structure, and
difficult to increase reactivity because of the low freedom of
polymerization. Additionally, since the backbone is highly
hydrophobic, these polymers are less adherent when applied to
substrates. Therefore, some resist compositions which are
formulated using these polymers as the base resin fail to withstand
etching although they have satisfactory sensitivity and resolution.
Some other resist compositions are highly resistant to etching, but
have low sensitivity and low resolution below the practically
acceptable level.
SUMMARY OF THE INVENTION
[0005] An object of the invention is to provide a novel ester
compound useful as a monomer to form a polymer for use in the
formulation of a photoresist composition which exhibits a high
reactivity and substrate affinity when processed by
photolithography using light with a wavelength of less than 300 nm,
especially ArF excimer laser light as the light source. Another
object is to provide a method for preparing the ester compound.
[0006] The inventor has found that an ester compound of formula (1)
can be prepared in high yields by a simple method and that a resist
composition comprising a polymer obtained from this ester compound
as a base resin is improved in sensitivity, resolution and
substrate adhesion.
[0007] The invention provides an ester compound of the following
general formula (1). 2
[0008] Herein R.sup.1 is hydrogen or a straight, branched or cyclic
alkyl group of 1 to 6 carbon atoms, R.sup.2 is an acid labile
group, k is 0 or 1, and m is an integer from 0 to 5.
[0009] Preferably the ester compound has the following general
formula (2) or (3). 3
[0010] Herein m is as defined above, R.sup.3 is hydrogen or methyl,
R.sup.4 to R.sup.7 are independently selected from straight,
branched or cyclic alkyl groups of 1 to 15 carbon atoms, the sum of
carbon atoms in R.sup.4, R.sup.5 and R.sup.6 is at least 4, and Z
is a divalent hydrocarbon group of 4 to 15 carbon atoms which forms
a ring with the carbon atom to which it is connected at both
ends.
[0011] A method for preparing the ester compound forms another
aspect of the invention, which involves the step of effecting
addition reaction of a metal enolate of acetate of the following
formula (5) to a carbonyl compound of the following formula (4).
4
[0012] Herein k, m, R.sup.1 and R.sup.2 are as defined above, M is
Li, Na, K, MgY or ZnY, and Y is a halogen atom.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0013] The ester compounds of the invention are of the following
general formula (1). 5
[0014] Herein R.sup.1 is hydrogen or a straight, branched or cyclic
alkyl group of 1 to 6 carbon atoms. Exemplary alkyl groups include
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
tert-butyl, tert-amyl, pentyl, hexyl, cyclopentyl, and cyclohexyl.
R.sup.2 is an acid labile group. The letter k is 0 or 1, and m is
an integer from 0 to 5 (i.e., 0.ltoreq.m.ltoreq.5), and preferably
from 0 to 3.
[0015] The preferred acid labile group represented by R.sup.2 are
those of the following formulas. 6
[0016] R.sup.4 to R.sup.7 and Z are as defined below.
[0017] Preferred among the ester compounds of formula (1) are ester
compounds of the following general formula (2) or (3). 7
[0018] Herein m is as defined above. R.sup.3 is hydrogen or methyl.
R.sup.4 to R.sup.7 are independently selected from straight,
branched or cyclic alkyl groups of 1 to 15 carbon atoms. The total
number of carbon atoms in R.sup.4, R.sup.5 and R.sup.6 is at least
4. Examples of the straight, branched or cyclic alkyl groups of 1
to 15 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl, tert-butyl, tert-amyl, pentyl, hexyl,
cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl,
cyclohexylmethyl, cyclohexylethyl, bicyclo[2.2.1]heptyl,
bicyclo[2.2.2]octyl, bicyclo[3.3.1]nonyl, bicyclo[4.4.0]decanyl,
tricyclo[5.2.1.0.sup.2,6]decanyl,
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-dodecanyl, and adamantyl. Z
stands for divalent hydrocarbon groups of 4 to 15 carbon atoms,
such as alkylene and alkenylene groups, which forms a ring with the
carbon atom to which it is connected at both ends. Examples of the
rings that Z forms include cyclopentane, cyclopentene, cyclohexane,
cyclohexene, bicyclo[2.2.1]heptane, bicyclo[4.4.0]decane,
tricyclo[5.2.1.0.sup.2,6]dec- ane,
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecane, and adamantane.
[0019] Illustrative, non-limiting, examples of the ester compounds
of formula (1) and formulas (2) and (3) are given below. 8
[0020] As seen from the reaction scheme shown below, the ester
compound of formula (1) can be prepared by the step of causing a
base to act on a corresponding acetate of formula (6) (where X is
hydrogen) or a corresponding haloacetate of formula (6) (where X is
halogen) to form a metal enolate of formula (5) and effecting
nucleophilic addition reaction of the metal enolate to a carbonyl
compound of formula (4). 9
[0021] Herein, k, m, R.sup.1 and R.sup.2 are as defined above. X is
hydrogen or halogen. M is Li, Na, K, MgY or ZnY, and Y is
halogen.
[0022] The bases used for forming the metal enolate include metal
amides such as sodium amide, potassium amide, lithium
diisopropylamide, potassium diisopropylamide, lithium
dicyclohexylamide, potassium dicyclohexylamide, lithium
2,2,6,6-tetramethylpiperidine, lithium bistrimethylsilylamide,
sodium bistrimethylsilylamide, potassium bistrimethylsilylamide,
lithium isopropyl-cyclohexylamide, and bromomagnesium
diisopropylamide; alkoxides such as sodium methoxide, sodium
ethoxide, lithium methoxide, lithium ethoxide, lithium
tert-butoxide, and potassium tert-butoxide; inorganic hydroxides
such as sodium hydroxide, lithium hydroxide, potassium hydroxide,
barium hydroxide, and tetra-n-butylammonium hydroxide; inorganic
carbonates such as sodium carbonate, sodium hydrogen carbonate,
lithium carbonate and potassium carbonate; metal hydrides such as
boranes, alkylboranes, sodium hydride, lithium hydride, potassium
hydride, and calcium hydride; alkyl metal compounds such as trityl
lithium, trityl sodium, trityl potassium, methyl lithium, phenyl
lithium, sec-butyl lithium, tert-butyl lithium, and ethyl magnesium
bromide; and metals such as lithium, sodium, potassium, magnesium,
and zinc, but are not limited thereto. It is noted that reaction
using haloacetate and zinc is known as Reformatsky reaction.
[0023] In the addition reaction of the carbonyl compound of formula
(4) with the metal enolate of formula (5), 0.8 to 1.5 mol of the
metal enolate is preferably used per mol of the carbonyl compound.
Useful solvents are ethers such as tetrahydrofuran, diethyl ether,
di-n-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, and
ethylene glycol diethyl ether and hydrocarbons such as hexane,
heptane, benzene, toluene, xylene and cumene, alone or in admixture
thereof. The reaction temperature and time vary with particular
starting reactants used. In one example where an acetate of formula
(6) wherein X is hydrogen and a strong base such as lithium
diisopropylamide or lithium bistrimethylsilylamide are used, the
preferred reaction conditions include a reaction temperature in the
low range of -80.degree. C. to -30.degree. C. and a reaction time
of about 1/2 to 3 hours because the metal enolate is thermally
unstable. In another example where a haloacetate of formula (6)
wherein X is halogen and a metal such as zinc or magnesium are
used, it is generally preferred to keep the reaction temperature in
the range of 20 to 80.degree. C. and the reaction time in the range
of about 1 to 20 hours. The reaction conditions are not limited to
these ranges.
[0024] A polymer is prepared using the inventive ester compound as
a monomer. The method is generally by mixing the monomer with a
solvent, adding a catalyst or polymerization initiator, and
effecting polymerization reaction while heating or cooling the
system if necessary. This polymerization reaction can be effected
in a conventional way.
[0025] A resist composition is formulated using as a base resin the
polymer resulting from polymerization of the ester compound.
Usually, the resist composition is formulated by adding an organic
solvent and a photoacid generator to the polymer and if necessary,
further adding a crosslinker, a basic compound, a dissolution
inhibitor and other additives. Preparation of the resist
composition can be effected in a conventional way.
[0026] The resist composition formulated using the polymer
resulting from polymerization of the inventive ester compound lends
itself to micropatterning with electron beams or deep-UV rays since
it is sensitive to high-energy radiation and has excellent adhesion
to substrates, sensitivity, resolution, and etching resistance.
Especially because of the minimized absorption at the exposure
wavelength of an ArF or KrF excimer laser, a finely defined pattern
having sidewalls perpendicular to the substrate can easily be
formed. The resist composition is thus suitable as micropatterning
material for VLSI fabrication.
EXAMPLE
[0027] Synthesis Examples and Reference Examples are given below
for further illustrating the invention. It is not construed that
the invention be limited to these examples.
[0028] Synthesis Examples are first described. Ester compounds
within the scope of the invention were synthesized in accordance
with the following procedure.
Synthesis Example 1
[0029] Synthesis of 1-ethylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl)propi- onate (Monomer 1)
[0030] First, in a nitrogen atmosphere, 184 g of lithium
bis(trimethylsilyl)amide and 172 g of 1-ethylcyclopentyl acetate
were reacted in 1 kg of dry tetrahydrofuran at -60.degree. C. to
form lithium enolate. Then 122 g of 5-norbornene-2-carbaldehyde was
slowly added, following which the temperature was raised to
-20.degree. C. over one hour, at which reaction was effected. Then
1 kg of a saturated ammonium chloride aqueous solution was added to
stop the reaction, whereupon hexane was added for extraction. The
organic layer was washed with water, dried over anhydrous sodium
sulfate, filtered, concentrated in vacuo, and purified by silica
gel column chromatography, obtaining 264 g (yield 96%) of
1-ethylcyclopentyl 3-hydroxy-3-(5-norbornen-2-yl)propionate,
designated Monomer 1.
[0031] IR (thin film): v=3502 (br.), 3057, 2966, 2870, 1713, 1709,
1335, 1284, 1254, 1167, 1072 cm.sup.-1 1H-NMR of main diastereomer
(270 MHz in CDCl.sub.3): .delta.=0.44 (1H, m), 0.84 (3H, t, J=4.9
Hz), 1.21 (1H, m), 1.41 (1H, m), 1.50-1.80 (7H, m), 1.80-2.20 (5H,
m), 2.26 (1H, dd, J=16.6, 9.2 Hz), 2.44 (1H, dd, J=16.6, 2.4 Hz),
2.78 (1H, m), 3.08 (1H, m), 3.27 (1H, m), 3.50 (1H, m), 6.03 (1H,
m), 6.13 (1H, m).
Synthesis Example 2
[0032] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-3-(5-norbornen-2-yl)- propionate (Monomer 2)
[0033] By following the procedure of Synthesis Example 1 except
that 2-ethyl-2-exo-norbornyl acetate was used instead of
1-ethylcyclopentyl acetate, there was obtained
2-ethyl-2-exo-norbornyl 3-hydroxy-3-(5-norbornen-2-yl)propionate.
Yield 95%.
[0034] IR (thin film): v=3502 (br.), 3057, 2966, 2872, 1722, 1711,
1330, 1193, 1173, 1132, 1074, 1032 cm.sup.-1 1H-NMR of main
diastereomer (270 MHz in CDCl.sub.3): .delta.=0.45 (1H, m), 0.80
(3H, t, J=7.0 Hz), 1.03 (1H, m), 1.10-2.30 {(14H, m) including 2.23
(1H, dd, J=17.0, 7.8 Hz)}, 2.44 (1H, dd, J=17.0, 2.4 Hz), 2.53 (2H,
m), 2.78 (1H, m), 3.08 (1H, m), 3.14 (1H, m), 3.26 (1H, m), 6.03
(1H, m), 6.13 (1H, m).
Synthesis Example 3
[0035] Synthesis of 1-cyclohexylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl)- propionate (Monomer 3)
[0036] By following the procedure of Synthesis Example 1 except
that 1-cyclohexylcyclopentyl acetate was used instead of
1-ethylcyclopentyl acetate, there was obtained
1-cyclohexylcyclopentyl 3-hydroxy-3-(5-norbornen-2-yl)-propionate.
Yield 94%.
[0037] IR (thin film): v=3496 (br.), 3057, 2931, 2854, 1711, 1448,
1335, 1186, 1155, 1072, 1034 cm.sup.-1 1H-NMR of main diastereomer
(270 MHz in CDCl.sub.3): .delta.=0.45 (1H, m), 0.80-2.15 (23H, m),
2.25 (1H, dd, J=16.5, 9.0 Hz), 2.33 (1H, m), 2.42 (1H, dd, J=16.5,
2.4 Hz), 2.78 (1H, m), 3.07 (1H, m), 3.26 (1H, m), 6.04 (1H, m),
6.13 (1H, m).
Synthesis Example 4
[0038] Synthesis of 1-ethylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl)butyr- ate (Monomer 4)
[0039] By following the procedure of Synthesis Example 1 except
that 5-acetyl-2-norbornene was used instead of
5-norbornene-2-carbaldehyde, there was obtained 1-ethylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl)butyr- ate. Yield 95%.
[0040] IR (thin film): v=3502 (br.), 3057, 2968, 2873, 1722, 1705,
1459, 1373, 1336, 1211, 1171 cm.sup.-1 1H-NMR of main diastereomer
(270 MHz in CDCl.sub.3): .delta.=0.86 (3H, t, J=7.3 Hz), 1.05 (1H,
m), 1.21 (1H, s), 1.37 (1H, m), 1.39 (1H, m), 1.45-2.15 (13H, m),
2.28 (1H, d, J=14.7 Hz), 2.30 (1H, m), 2.37 (1H, d, J=14.7 Hz),
2.70-2.85 (2H, m), 2.91 (1H, m), 6.01 (1H, m), 6.17 (1H, m).
Synthesis Example 5
[0041] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-3-(5-norbornen-2-yl)- butyrate (Monomer 5)
[0042] By following the procedure of Synthesis Example 4 except
that 2-ethyl-2-exo-norbornyl acetate was used instead of
1-ethylcyclopentyl acetate, there was obtained
2-ethyl-2-exo-norbornyl 3-hydroxy-3-(5-norbornen-2-yl)butyrate.
Yield 94%.
[0043] IR (thin film): v=3502 (br.), 3057, 2966, 2873, 1704, 1702,
1457, 1373, 1331, 1203, 1173, 1132, 1105 cm.sup.-1 1H-NMR of main
diastereomer (270 MHz in CDCl.sub.3): .delta.=0.82 (3H, t, J=7.6
Hz), 1.00-1.10 (2H, m), 1.15-1.30 {(5H, m) including 1.21 (3H, s)},
1.30-1.60 (5H, m), 1.65 (1H, m), 1.70-1.90 (2H, m), 1.98 (1H, m),
2.15-2.35 {(4H, m) including 2.28 (1H, d, J=14.6 Hz)}, 2.37 (1H, d,
J=14.6 Hz), 2.58 (1H, m), 2.75-2.90 (2H, m), 2.92 (1H, m), 6.01
(1H, m), 6.17 (1H, m).
Synthesis Example 6
[0044] Synthesis of 1-cyclohexylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl)- butyrate (Monomer 6)
[0045] By following the procedure of Synthesis Example 4 except
that 1-cyclohexylcyclopentyl acetate was used instead of
1-ethylcyclopentyl acetate, there was obtained
1-cyclohexylcyclopentyl 3-hydroxy-3-(5-norbornen-2-yl)-butyrate.
Yield 95%.
[0046] IR (thin film): v=3502 (br.), 3057, 2933, 2854, 1701, 1699,
1450, 1371, 1336, 1209, 1186, 1157 cm.sup.-1 1H-NMR of main
diastereomer (270 MHz in CDCl.sub.3): .delta.=0.90-2.05 {(25H, m)
including 1.19 (3H, s)}, 2.20-2.40 {(4H, m) including 2.27 (1H, d,
J=14.6 Hz), 2.37 (1H, d, J=14.6 Hz)}, 2.79 (1H, m), 2.91 (1H, m),
3.11 (1H, m), 6.00 (1H, m), 6.16 (1H, m).
Synthesis Example 7
[0047] Synthesis of 1-(2-norbornyl)cyclopentyl
3-hydroxy-3-(5-norbornen-2-- yl)butyrate (Monomer 7)
[0048] By following the procedure of Synthesis Example 4 except
that 1-(2-norbornyl)cyclopentyl acetate was used instead of
1-ethylcyclopentyl acetate, there was obtained
1-(2-norbornyl)cyclopentyl 3-hydroxy-3-(5-norbornen-2-yl)-butyrate.
Yield 92%.
[0049] IR (thin film): v=3502 (br.), 3057, 2954, 2870, 1713, 1454,
1373, 1338, 1207, 1157, 1080 cm.sup.-1 1H-NMR (270 MHz in
CDCl.sub.3): .delta.=0.90-3.05 (32H, m), 5.80-6.35 (2H, m).
Synthesis Example 8
[0050] Synthesis of tert-butyl
3-hydroxy-3-(8-tetracyclo-[4.4.0.1.sup.2,5.-
1.sup.7,10]dodecen-3-yl)propionate (Monomer 8)
[0051] The procedure of Synthesis Example 1 was repeated except
that tert-butyl acetate was used instead of 1-ethylcyclopentyl
acetate, and
8-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-dodecene-3-carbaldehyde
was used instead of 5-norbornene-2-carbaldehyde. There was obtained
tert-butyl
3-hydroxy-3-(8-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecen-3-yl)propion-
ate. Yield 93%.
[0052] IR (KBr): v=3434 (br.), 3049, 2958, 1716, 1394, 1367, 1340,
1313, 1250, 1217, 1151, 1037 cm.sup.-1 1H-NMR of main diastereomer
(270 MHz in CDCl.sub.3): .delta.=0.50-0.70 (2H, m), 0.85 (1H, m),
1.10-2.60 {(19H, m) including 1.44 (9H, s)}, 2.75-3.20 (3H, m),
3.52 (1H, m), 5.85-6.00 (2H, m).
Synthesis Example 9
[0053] Synthesis of 1-ethylcyclopentyl
3-hydroxy-3-(8-tetracyclo-[4.4.0.1.-
sup.2,5.1.sup.7,10]dodecen-3-yl)propionate (Monomer 9)
[0054] The procedure of Synthesis Example 8 was repeated except
that 1-ethylcyclopentyl acetate was used instead of tert-butyl
acetate. There was obtained 1-ethylcyclopentyl
3-hydroxy-3-(8-tetracyclo[4.4.0.1.sup.2,5- .
1.sup.7,10]dodecen-3-yl)-propionate. Yield 92%.
[0055] IR (thin film): v=3502 (br.), 3049, 2958, 2879, 1722, 1713,
1460, 1452, 1356, 1313, 1281, 1165, 1080, 1036, 955 cm.sup.-1
1H-NMR of main diastereomer (270 MHz in CDCl.sub.3):
.delta.=0.50-0.70 (2H, m), 0.80-0.95 (4H, m), 1.10-1.30 (3H, m),
1.30-2.65 (17H, m), 2.75-3.20 (3H, m), 3.52 (1H, m), 5.85-6.00 (2H,
m).
Synthesis Example 10
[0056] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-3-(8-tetracyclo[4.4.-
0.1.sup.2,5.1.sup.7,10]dodecen-3-yl)propionate (Monomer 10)
[0057] The procedure of Synthesis Example 8 was repeated except
that 2-ethyl-2-exo-norbornyl acetate was used instead of tert-butyl
acetate. There was obtained 2-ethyl-2-exo-norbornyl
3-hydroxy-3-(8-tetracyclo[4.4.-
0.1.sup.2,5.1.sup.7,10]dodecen-3-yl)propionate. Yield 90%.
[0058] IR (KBr): v=3483, 3049, 2962, 2879, 1711, 1466, 1456, 1358,
1313, 1170, 1132, 1038, 972, 953 cm.sup.-1 1H-NMR of main
diastereomer (270 MHz in CDCl.sub.3): .delta.=0.50-0.70 (2H, m),
0.75-0.95 (4H, m), 1.00-2.65 (22H, m), 2.70-2.90 (2H, m), 3.01 (1H,
m), 3.52 (1H, m), 5.85-5.95 (2H, m).
Synthesis Example 11
[0059] Synthesis of 1-ethylcyclopentyl
3-hydroxy-3-(8-tetracyclo-[4.4.0.1.-
sup.2,5.1.sup.7,10]dodecen-3-yl)butyrate (Monomer 11)
[0060] The procedure of Synthesis Example 9 was repeated except
that 8-acetyl-3-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecene was
used instead of
8-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecene-3-carbaldehyd- e.
There was obtained 1-ethylcyclopentyl
3-hydroxy-3-(8-tetracyclo[4.4.0.1- .sup.2,5.
1.sup.7,10]dodecen-3-yl)butyrate. Yield 92%.
[0061] IR (thin film): v=3502 (br.), 3049, 2958, 2877, 1705, 1713,
1460, 1373, 1354, 1336, 1205, 1169, 958 cm.sup.-1 1H-NMR of main
diastereomer (270 MHz in CDCl.sub.3): .delta.=0.79 (1H, m), 0.87
(3H, t, J=7.3 Hz), 1.10-1.50 {(8H, m) including 1.17 (3H, s)},
1.50-1.80 (6H, m), 1.85-2.25 (9H, m), 2.26 (1H, d, J=15.1 Hz), 2.41
(1H, d, J=15.1 Hz), 2.75-2.85 (2H, m), 3.66 (1H, m), 5.90-5.95 (2H,
m).
Synthesis Example 12
[0062] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-3-(8-tetracyclo[4.4.-
0.1.sup.2,5.1.sup.7,10]dodecen-3-yl)butyrate (Monomer 12)
[0063] The procedure of Synthesis Example 11 was repeated except
that 2-ethyl-2-exo-norbornyl acetate was used instead of
1-ethylcyclopentyl acetate. There was obtained
2-ethyl-2-exo-norbornyl
3-hydroxy-3-(8-tetracyclo-[4.4.0.1.sup.2,5.1.sup.7,10]dodecen-3-yl)butyra-
te. Yield 90%. IR (thin film): v=3500 (br.), 3049, 2962, 2873,
1705, 1458, 1373, 1354, 1331, 1248, 1201, 1173, 1132, 1107, 951
cm.sup.-1 1H-NMR of main diastereomer (270 MHz in CDCl.sub.3):
.delta.=0.80 (1H, m), 0.82 (3H, t, J=7.3 Hz), 1.00-2.30 {(25H, m)
including 1.18 (3H, s), 2.26 (1H, d, J=15.1 Hz}, 2.41 (1H, d,
J=15.1 Hz), 2.53 (1H, m), 2.75-2.85 (2H, m), 3.73 (1H, m),
5.85-5.95 (2H, m).
Synthesis Example 13
[0064] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-4-(5-norbornen-2-yl)- butyrate (Monomer 13)
[0065] By following the procedure of Synthesis Example 2 except
that 2-(5-norbornen-2-yl)acetaldehyde was used instead of
5-norbornene-2-carbaldehyde, there was obtained
2-ethyl-2-exo-norbornyl 3-hydroxy-4-(5-norbornen-2-yl)-butyrate.
Yield 94%.
[0066] IR (thin film): v=3467 (br.), 3057, 2964, 2870, 1724, 1457,
1441, 1333, 1265, 1190, 1171, 1132, 1107, 955 cm.sup.-1 1H-NMR of
main diastereomer (270 MHz in CDCl.sub.3): .delta.=0.53 (1H, m),
0.82 (3H, t, J=7.3 Hz), 1.00-2.05 (14H, m), 2.15-2.50 (5H, m), 2.53
(1H, m), 2.70-2.85 (2H, m), 3.04 (1H, m), 3.95 (1H, m), 5.91 (1H,
m), 6.11 (1H, m).
Synthesis Example 14
[0067] Synthesis of 2-ethyl-2-exo-norbornyl
3-hydroxy-3-methyl-5-(5-norbor- nen-2-yl)valerate (Monomer 14)
[0068] By following the procedure of Synthesis Example 2 except
that 4-(5-norbornen-2-yl)butanone was used instead of
5-norbornene-2-carbaldeh- yde, there was obtained
2-ethyl-2-exo-norbornyl 3-hydroxy-3-methyl-5-(5-no-
rbornen-2-yl)valerate. Yield 92%.
[0069] IR (thin film): v=3502 (br.), 3057, 2966, 2937, 2870, 1705,
1458, 1441, 1348, 1331, 1200, 1173, 1132, 1107, 951 cm.sup.-1
1H-NMR of main diastereomer (300 MHz in CDCl.sub.3): .delta.=0.48
(1H, m), 0.82 (3H, t, J=7.6 Hz), 1.00-2.05 {(20H, m) including 1.17
(3H, s)}, 2.15-2.30 (2H, m), 2.32 (1H, d, J=14.9 Hz), 2.39 (1H, d,
J=14.9 Hz), 2.53 (1H, m), 2.70-2.80 (2H, m), 3.80 (1H, t, J=10.8
Hz), 5.90 (1H, m), 6.10 (1H, m).
Synthesis Example 15
[0070] Synthesis of 1-ethylcyclohexyl
3-hydroxy-3-methyl-4-(5-norbornen-2-- yl)butyrate (Monomer 15)
[0071] The procedure of Synthesis Example 1 was repeated except
that 1-ethylcyclohexyl acetate was used instead of
1-ethylcyclopentyl acetate, and 3-(5-norbornen-2-yl)acetone was
used instead of 5-norbornene-2-carbaldehyde. There was obtained
1-ethylcyclohexyl 3-hydroxy-3-methyl-4-(5-norbornen-2-yl)butyrate.
Yield 92%.
Synthesis Example 16
[0072] Synthesis of 8-ethyl-8-exo-tricyclo[5.2.1.0.sup.2,6]decanyl
3-hydroxy-5-(5-norbornen-2-yl)valerate (Monomer 16)
[0073] The procedure of Synthesis Example 1 was repeated except
that 8-ethyl-8-exo-tricyclo[5.2.1.0.sup.2,6]decanyl acetate was
used instead of 1-ethylcyclopentyl acetate, and
3-(5-norbornen-2-yl)propionaldehyde was used instead of
5-norbornene-2-carbaldehyde. There was obtained
8-ethyl-8-exo-tricyclo[5.2.1.0.sup.2,6]decanyl
3-hydroxy-5-(5-norbornen-2- -yl)valerate. Yield 93%.
Synthesis Example 17
[0074] Synthesis of 2-ethyl-2-adamantyl
3-hydroxy-5-(5-norbornen-2-yl)vale- rate (Monomer 17)
[0075] The procedure of Synthesis Example 16 was repeated except
that 2-ethyl-2-adamantyl acetate was used instead of
8-ethyl-8-exo-tricyclo[5.- 2.1.0.sup.2,6]decanyl acetate. There was
obtained 2-ethyl-2-adamantyl
3-hydroxy-5-(5-norbornen-2-yl)valerate. Yield 92%.
Synthesis Example 18
[0076] Synthesis of 2-(1-adamantyl)-2-propyl
3-hydroxy-6-(5-norbornen-2-yl- )hexanoate (Monomer 18)
[0077] The procedure of Synthesis Example 1 was repeated except
that 2-(1-adamantyl)-2-propyl acetate was used instead of
1-ethylcyclopentyl acetate, and 4-(5-norbornen-2-yl)butyrylaldehyde
was used instead of 5-norbornene-2-carbaldehyde. There was obtained
2-(1-adamantyl)-2-propyl 3-hydroxy-6-(5-norbornen-2-yl)hexanoate.
Yield 93%.
Synthesis Example 19
[0078] Synthesis of 2-(2-norbornyl)-2-propyl
3-hydroxy-6-(5-norbornen-2-yl- )hexanoate (Monomer 19)
[0079] The procedure of Synthesis Example 18 was repeated except
that 2-(2-norbornyl)-2-propyl acetate was used instead of
1-ethylcyclopentyl acetate. There was obtained
2-(2-norbornyl)-2-propyl 3-hydroxy-6-(5-norbornen-2-yl)-hexanoate.
Yield 92%.
Synthesis Example 20
[0080] Synthesis of 3-ethyl-3-pentyl
3-hydroxy-3-methyl-6-(5-norbornen-2-y- l)hexanoate (Monomer 20)
[0081] The procedure of Synthesis Example 1 was repeated except
that 3-ethyl-3-pentyl acetate was used instead of
1-ethylcyclopentyl acetate, and 5-(5-norbornen-2-yl)-2-pentanone
was used instead of 5-norbornene-2-carbaldehyde. There was obtained
3-ethyl-3-pentyl 3-hydroxy-3-methyl-6-(5-norbornen-2-yl)hexanoate.
Yield 91%.
[0082] The structural formulas of Monomers 1 to 20 are shown below.
10
Reference Example
[0083] Polymers were synthesized using the ester compounds obtained
in the above Synthesis Examples. Using the polymers as a base
resin, resist compositions were prepared, which were examined for
reactivity.
[0084] Polymerization reaction was effected between Monomer 1 and
maleic anhydride using the initiator V65 (by Wako Junyaku K.K.),
yielding an alternating copolymer of 1-ethylcyclopentyl
3-hydroxy-3-(5-norbornen-2-yl- )-propionate/maleic anhydride.
[0085] A resist composition was prepared by blending 80 parts by
weight of the above copolymer as a base resin, 1.0 part by weight
of triphenylsulfonium trifluoromethanesulfonate as a photoacid
generator, 480 parts by weight of propylene glycol monomethyl ether
acetate as a solvent, and 0.08 part by weight of tributylamine. The
composition was spin coated on a silicon wafer and heat treated at
110.degree. C. for 90 seconds, forming a resist film of 500 nm
thick. The resist film was exposed to ArF excimer laser light, heat
treated at 110.degree. C. for 90 seconds, and developed by
immersing in a 2.35% tetramethylammonium hydroxide aqueous solution
for 60 seconds. The dose of exposure (Eth) which allowed the resist
film to be fully dissolved was determined to be 8.0
mJ/cm.sup.2.
Comparative Reference Example
[0086] For comparison purposes, a similar resist composition was
prepared using an alternating copolymer of tert-butyl
5-norbornene-2-carboxylate/m- aleic anhydride. The composition was
examined by the same exposure test, finding a dose Eth of 12.5
mJ/cm.sup.2.
[0087] It was confirmed that polymers resulting from the inventive
ester compounds have very high reactivity as compared with prior
art polymers.
[0088] Japanese Patent Application No. 2000-131177 is incorporated
herein by reference.
[0089] Although some preferred embodiments have been described,
many modifications and variations may be made thereto in light of
the above teachings. It is therefore to be understood that the
invention may be practiced otherwise than as specifically described
without departing from the scope of the appended claims.
* * * * *