WO2004042476A1 - Chemically amplified polymer having pendant group with camphoryl and resist composition comprising the same - Google Patents

Chemically amplified polymer having pendant group with camphoryl and resist composition comprising the same Download PDF

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WO2004042476A1
WO2004042476A1 PCT/KR2002/002156 KR0202156W WO2004042476A1 WO 2004042476 A1 WO2004042476 A1 WO 2004042476A1 KR 0202156 W KR0202156 W KR 0202156W WO 2004042476 A1 WO2004042476 A1 WO 2004042476A1
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group
methyl
hydrogen
camphoryl
alkyl
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PCT/KR2002/002156
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French (fr)
Inventor
Yong-Joon Choi
Eun-Kyung Son
Deog-Bae Kim
Jae-Hyun Kim
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Dongjin Semichem Co., Ltd.
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Priority to AU2002368318A priority Critical patent/AU2002368318A1/en
Publication of WO2004042476A1 publication Critical patent/WO2004042476A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a chemically amplified polymer having a pendent group with camphoryl bonded thereto, a process for the preparation thereof and a resist composition comprising it, and more particularly, to a novel (meth)acrylic or norbornene carboxylate compound with camphoryl bonded thereto, a process for the preparation thereof, a chemically amplified polymer synthesized therewith, and a positive photoresist composition for ArF comprising said polymer with high resolution and excellent etching resistance.

Description

CHEMICALLY AMPLIFIED POLYMER HAVING PENDANT GROUP WITH
CAMPHORYL AND RESIST COMPOSITION COMPRISING THE SAME
BACKGROUND OF THE INVENTION (a) Field of the Invention!
The present invention relates to a novel (meth)acrylic or norbornene carboxylate compound having a pendent group with camphoryl bonded thereto, a process for the preparation thereof, a chemically amplified polymer synthesized therewith, and a photoresist composition for ArF comprising said polymer with high resolution and excellent etching resistance. (b) Description of the Related Art
As semiconductor devices become highly integrated, ultra-fine patterns having sub-quarter micron dimensions are needed. For this, the wavelengths of light sources used in patterning have become shortened according to Rayleigh's rule, such as from 436 nm (g-line) and 365 nm (1-line) to 193 nm (ArF), 157 nm (VUV), and 248 nm (KrF). In prior arts, however, in order to obtain a pattern size for devices having capacities exceeding 1 Gbit, general resist materials had to be used at 248 nm. Therefore, new resists capable of functioning at a shorter wavelength of 193-nm have been continuously developed to satisfy the requirements of fine resolution.
As is widely known, polymers for use as an ArF-resist material are classified according to their structure into three forms, polyacrylate, cycloolefin-maleic anhydride copolymer, and polynorbomene. Of them, the cycloolefin-maleic anhydride copolymer (COMA)-type resists are useful in view of more or less lithographic performances (pattern collapse, line edge roughness, SEM beam contraction, etching resistance, etc.) However, said COMA-based photoresists cause unsatisfactory results in resolution, especially in terms of line density and space pattern, due to the hydrolysis of maleic anhydride (MA). Also, photoresists comprising conventional COMA do not exhibit sufficient resistance and consequently a dry etching process is still difficult.
SUMMARY OF THE INVENTION
Therefore, it is an object of the present invention to provide a
(meth)acrylic carboxylate compound or norbornene carboxylate having a bulky aliphatic ring substituent capable of increasing high resolution and etching resistance and a process for the preparation thereof, in order to solve the problems of the prior arts as described above.
It is an another object of the invention to provide a photosensitive copolymer and terpolymer suitable to be used for a chemically amplified resist, comprising a pendent group having a cyclic structure and aliphatic ring compound capable of obtaining sufficient resolution for the high integration of semiconductors and exhibiting sufficiently strong resistance to dry etching.
It is still another object of the invention is to provide a chemically amplified positive photoresist composition for ArF comprising said photosensitive copolymer, terpolymer and a mixture thereof.
To achieve the aforementioned objects, the present invention provides 2-alkyl-2-camphoryl (meth)acrylate represented by the following formula 1 :
Figure imgf000004_0001
wherein R is a methyl or ethyl group, and R* is a hydrogen or a methyl group. Also, the invention provides a process for preparing 2-alkyl-2-camphoryl
(meth)acrylate of said formula 1 comprising the steps of a) preparing 2-alkyl-2-camphoryl alcohol by the reaction of camphor and an alkyl grinard reagent or alkyl lithium reagent; and b) reacting the 2-alkyl-2-camphoryl alcohol prepared above with (meth)acryloyl chloride.
Further, the invention provides
2-alkyl-2-camphoryl-5-norbornene-2-carboxylate represented by the following formula 2:
Figure imgf000004_0002
wherein R is a methyl or ethyl group, and R* is a hydrogen or a methyl group. Further, the invention provides a process for preparing 2-alkyl-2-camphoryl-5-norbornene-2-carboxylate of said formula 2 by the Diels-Alder reaction of 2-alkyl-2-camphoryl (meth)acrylate of formula 1 and cyclopentadiene.
Still further, the invention provides a photosensitive copolymer represented by the following formula 3:
Figure imgf000005_0001
wherein R is a methyl or ethyl, R* is a hydrogen or a methyl, and n is an integer of 25 to 30.
Still further, the invention provides a process for preparing the photosensitive copolymer of said formula 3 comprising the step of polymerizing the compound of said formula 2 with a maleic anhydride.
Also, the invention provides a photosensitive terpolymer represented by the following formula 4:
Figure imgf000005_0002
wherein R is a methyl or ethyl group; R* is a hydrogen or a methyl group; R' is a hydrogen, an alkyl group or a hydroxyalkyi group; R" is a hydrogen or a methyl group; and m and n each satisfy the conditions, m+n=1 , 0.1 <m<0.9 and 0.1 <n<0.9.
Also, the invention provides a process for preparing the photosensitive terpolymer of said formula 4 comprising the step of polymerizing the compound of formula 1 with a maleic anhydride and a norbomene compound of the following formula 6:
Figure imgf000006_0001
wherein R' is a hydrogen, an alkyl group or a hydroxyalkyi group, and R" is a hydrogen or a methyl group.
Further, the invention provides a photosensitive terpolymer represented by the following formula 5:
Figure imgf000006_0002
wherein R is a methyl or ethyl group; R* is a hydrogen or a methyl group; R' is a hydrogen, an alkyl group or a hydroxyalkyi group; R" is a hydrogen or a methyl group; and m and n each satisfy the conditions, m+n=1 , 0.1 <m<0.9 and
0.1 <n<0.9.
Further, the invention provides a process for preparing the photosensitive
terpolymer of said formula 5 comprising the step of polymerizing the compound of
formula 2 with a maleic anhydride and an acrylate compound of the following
formula 7:
C=0
OR1 7
wherein R' is a hydrogen, an alkyl group or a hydroxyalkyi group, and R"
is a hydrogen or a methyl group.
Furthermore, the invention provides a chemically amplified positive photoresist composition for ArF comprising one or more polymers selected from
the group consisting of the photosensitive copolymer of formula 3, the
photosensitive terpolymer of formula 4, and the photosensitive terpolymer of
formula 5.
More particularly, it is preferred in the formulae defined above that R' is
an alkyl group having an aliphatic hydrocarbon of C C10 or a hydroxyalkyi group
having an aliphatic hydrocarbon of CrC10.
Also, the invention provides a semiconductor device prepared comprising the
above positive photoresist composition.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a resist pattern in Example 7 according to the present
invention. FIG. 2 illustrates a pattern result of a prior COMA type resist. FIG. 3 illustrates etching resistance results against oxide of Examples 5 to 7 according to the present invention.
FIG. 4 illustrates etching resistance results against poly of prior COMA type resists.
DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS The present invention is hereinafter described in detail. The invention provides preparation of a photosensitive copolymer and terpolymer using a (meth)acrylic carboxylate compound or norbornene carboxylate compound having a bulky aliphatic ring substituent, and a chemically amplified positive photoresist composition using said copolymer and terpolymer, which has high resolution and is excellent in etching resistance.
2-Alkyl-2-camphoryl (meth)acrylate of formula 1 of the present invention can be prepared by reacting 2-alkyl-2-camphoryl alcohol and (meth)acryloyl chloride.
The preparation of said 2-alkyl-2-camphoryl alcohol follows the following Scheme 1 :
[Scheme 1]
Figure imgf000008_0001
wherein R is a methyl or ethyl, and X is Cl or Br.
As shown in Scheme 1 above, 2-alkyl-2-camphoryl alcohol can be prepared by reacting camphor with an alkyl grinard reagent or alkyl lithium reagent and thereby inducing an alkyl group on position 2 of camphor. The above grinard reagent includes an alkyl magnesium bromide, alkyl magnesium chloride, etc., and more preferably, methyl magnesium bromide or methyl magnesium chloride is used.
Thereafter, according to the invention, 2-alkyl-2-camphoryl (meth)acrylate
can be prepared by reacting 2-alkyl-2-camphoryl alcohol and (meth)acryloyl
chloride, as shown in the following Scheme 2:
[Scheme 2]
Figure imgf000009_0001
wherein R is a methyl or ethyl, and R* is a hydrogen or a methyl.
Also, according to the invention, the norbornene compound of formula 2 can be prepared using the compound of formula 1.
According to the invention,
2-alkyl-2-camphoryI-5-norbornene-2-carboxylate of formula 2 having the norbornene substituent can be prepared by the Diels-Alder reaction of the compound of formula 1 and cyclopentadiene, as shown in the following Scheme
3: [Scheme 3]
Figure imgf000010_0001
wherein R is a methyl or ethyl, and R* is a hydrogen or a methyl.
Also, according to the invention, the photosensitive copolymer of formula 3 and the photosensitive terpolymers of formulae 4 and 5 can be prepared using the compounds of formula 1 and formula 2.
First, the preparation of the photosensitive copolymer of formula 3 is as follows:
[Scheme 4]
Figure imgf000010_0002
wherein R, R* and n are as defined above.
As shown in Scheme 4 above, the photosensitive copolymer of formula 3 can be obtained by polymerizing the norbornene compound of formula 2 with a maleic anhydride. The polymerization reaction may comprise an initiator and for example, azobis(isobutyronitrile) (AIBN) can be employed. Preferably, the photosensitive copolymer of formula 3 thus obtained has a weight average molecular weight of 3,000 to 100,000 and a dispersity of 1.0 to 5.0. Also, the preparation of the photosensitive terpolymers represented by formulae 4 and 5 according to the invention follows the following Schemes 5 and 6, respectively:
[Scheme 5]
Figure imgf000011_0001
[Scheme 6]
Figure imgf000011_0002
wherein R, R*, R' and R" are as defined above.
As shown in Scheme 5 above, the photosensitive terpolymer of formula 4 of the invention can be obtained by polymerizing the compound of formula 1 and the norbornene compound of formula 6 together with a maleic anhydride.
Also, as shown in Scheme 6 above, the photosensitive terpolymer of formula 5 of the invention can be obtained by polymerizing the compound of formula 2 and the acrylate compound of formula 7 together with a maleic anhydride.
All of the above polymerization reactions for the photosensitive terpolymers of formulae 4 and 5 may comprise an initiator and for example, azobis(isobutyronitrile) (AIBN) can be employed. Preferably, all of the photosensitive terpolymers of formulae 4 and 5 thus obtained have a weight average molecular weight of 3,000 to 100,000 and a dispersity of 1.0 to 5.0.
Also, the invention provides a chemically amplified positive photoresist composition for ArF comprising one or more polymers selected from the group consisting of the photosensitive copolymer of formula 3, the photosensitive terpolymer of formula 4, and the photosensitive terpolymer of formula 5.
In the positive photoresist composition of the invention, the content of one or more polymers selected from the group consisting of the photosensitive copolymer of formula 3, the photosensitive terpolymer of formula 4, and the photosensitive terpolymer of formula 5 is preferably 1 to 30 % by weight and more preferably 5 to 8 % by weight, based on the total composition.
Further, the photoresist composition of the invention comprises a photoacid generator and solvent, if necessary, it may be prepared in combination with various additives, and preferably, it is prepared such that solid concentration becomes 20 to 50 % by weight based on 100 parts by weight of the total resist composition. Thereafter, it is filtered with 0.2 μ filter and then used.
The content of the photoacid generator is preferably 0.5 to 10 % by weight based on the total polymer. As the photoacid generator, there can be used onium salts, organic sulfonic acids, or a mixture thereof.
The solvent used in the invention includes ethyleneglycolmonomethylethyl, ethyleneglycolmonoethylether, ethyleneglycolmonomethylether, diethyleneglycolmonoethylether, propyleneglycol monomethyl ether acetate (PGMEA), toluene, xylene, methylethylketone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy 2-methyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy 3-methyl butanoate, methyl 3-methoxy 2-methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methyl propionate, ethyl acetate, butyl acetate, etc.
Furthermore, the resist composition of the invention may further comprise an organic base, which may be comprised in an amount of 0.01 to 2.00 % by weight. As the organic base, there can be used triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanolamine or a mixture thereof. Also, the invention can provide a semiconductor device having an excellent pattern by coating the above resist composition on a silicon wafer or aluminum substrate using a spin coater to form a resist film and by performing exposure to light, development and baking processes. As the developing solution, there can be employed aqueous alkali solution where alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate and tetramethylammoniumhydroxide (TMAH) are dissolved at a concentration of 0.1 to 10%. Further, a water-soluble, organic solvent such as methanol and ethanol and a surfactant may be added in a suitable amount to the above developing solution. After development with the developing solution, the film is rinsed with ultra-pure water.
Now, the present invention is described in detail with reference to the following examples. The invention, however, should not be construed to be limited to these examples. EXAMPLES
Example 1-1 : Synthesis of 2-Methyl-2-Camphoryl (Meth)acrylate (R=Methyl) (Compound 1) a) Preparation of 2-Methyl-2-Camphoryl Alcohol 210 Ml (0.64 mol) of diethyl ether solution (3.0 M) of methyl magnesium bromide was diluted with 200 ml of anhydrous THF. The solution was then charged into a M flask and the temperature was maintained at 0°C . Camphor (48.7 g, 0.32 mol) was slowly dropped into the above solution via a dropping funnel and then reaction was performed at room temperature for about 2 hours. After the reaction was complete, excess THF was removed using a rotary evaporator, and the reaction product was neutralized with a diluted sulfuric acid, extracted using diethyl ether, and dried over magnesium sulfate anhydride. The obtained product was purified by column chromatography to give the title compound, 2-methyl-2-camphoryl alcohol (yield: 90%). b) Synthesis of 2-Methyl-2-Camphoryl Acrylate
2-Methyl-2-camphoryl alcohol (45.4 g, 0.27 mol) prepared in above a) and thethylamine (44.48 mL, 0.32 mol) were dissolved in 250 ml of THF, and then acryloyl chloride (26 mL, 0.32 mol) was slowly dropped thereinto via a dropping funnel. Then, reaction was performed at room temperature for 2 hours. After the reaction was complete, excess THF was removed using a rotary evaporator and the product was poured into water. Thereafter, the resulting product was neutralized with a diluted hydrochloric acid, extracted using diethyl ether, and dried over magnesium sulfate anhydride. The obtained product was purified by column chromatography (n-hexane:ethyl acetate=4:1) to give the title compound, 2-methyl-2-camphoryl acrylate (yield: 70%). c) Synthesis of 2-Methyl-2-Camphoryl Methacrylate
The procedures were performed in the same manner as in above b), except that methacryloyl chloride was used instead of acryloyl chloride, to prepare 2-methyl-2-camphoryl methacrylate.
Example 1-2: Synthesis of 2-Methyl-2-Camphoryl-5 -Norbomene-2-Carboxylate (R=Methyl) (Compound 2)
2-Methyl-2-camphorylacrylate prepared in above Example 1-1 , b) (35.6 g, 0.16 mol) was dissolved in 250 ml of THF, cyclopentadiene (31.68 g, 0.48 mol) was slowly added thereto at 0°C , and then the reaction temperature was raised to room temperature. Thereafter, the reaction was performed while stirring at room temperature for 24 hours. After the reaction was complete, excess THF was removed using a rotary evaporator and the reaction product was subjected to vacuum distillation to give the title compound, 2-rnethyl-2-camphoryl-5-norbomene-2-carboxylate in the state of viscous colorless liquid (yield: 70%).
Example 1-3: Synthesis of 2-Ethyl-2-Camphoryl (Meth)acrylate (R=Ethyl) (Compound 1)
The procedures were performed in the same manner as in above Example 1-1 , a), except that 1.0 M diethyl ether solution of ethyl magnesium chloride was used instead of 3.0 M diethyl ether of methyl magnesium chloride, to prepare 2-ethyl-2-camphoryl acrylate and 2-ethyl-2-camphoryl methacrylate, respectively. Example 1-4: Synthesis of 2-Ethyl-2-Camphoryl-5-norbornene- 2-Carboxylate (R=Ethyl) (Compound 2)
The procedures were performed in the same manner as in above Example 1-2 except that 2-ethyl-2-camphoryl acrylate prepared in Example 1-3 was used instead of 2-methyl-2-camphoryl acrylate prepared in Example 1-1 , b). Example 2-1 : Synthesis of Copolymer (Compound 3) Using 2-Methyl-2-Camphoryl-5-Norbomene-2-Carboxylate
39.4 g (0.102 mol) of 2-methyl-2-camphoryl-5-norbornene-2-carboxylate prepared in Example 1-2, 10.0 g (0.102 mol) of maleic anhydride and 0.7 g of azobis(isobutyronitrile) (AIBN) were dissolved in 25 g of anhydrous THF, and the reactants were degassed using an ampoule by a freezing method. The reactants were then polymerized at 68 °C for 24 hours. After the polymerization was complete, the reactants were slowly dropped into excess diethyl ether to precipitate, dissolved again in THF and reprecipitated in diethyl ether to obtain a copolymer (yield: 40%).
The weight average molecular weight and polydispersity of the obtained copolymer were 8,000 and 1.80, respectively.
Example 2-2: Synthesis of Copolymer (Compound 3) using 2-Ethyl-2-Camphoryl-5-Norbornene-2-Carboxylate
The polymerization was conducted in the same manner as in Example 2-1 except that 2-ethyl-2-camphoryl-5-norbornene-2-carboxylate prepared in Example 1-4 was used to prepare a copolymer.
The weight average molecular weight and polydispersity of the obtained copolymer were 7,000 and 1.85, respectively.
Example 3-1 : Synthesis of Terpolymer (R=Methyl) (Compound 4)
Except that 2-methyl-2-camphoryl acrylate and 2-methyl-2-camphoryl methacrylate were used respectively, a terpolymer consisting of 2-methyl-2-camphoryl acrylate or 2-methyl-2-camphoryl methacrylate was prepared in the following manner. a) Synthesis of Terpolymer (R=Methyl, R3=Hydrogen)
45.4 g (0.204 mol) of 2-methyl-2-camphoryl acrylate prepared in Example 1-1 , 14.1 g (0.102 mol) of 5-norbornene-2-carboxylic acid, 10.0 g (0.102 mol) of maleic anhydride and 0.7 g of azobis(isobutyronit le) (AIBN) were dissolved in 50 g of anhydrous THF, and the reactants were degassed using an ampoule by a freezing method. The reactants were then polymerized at 68 °C for 24 hours. After the polymerization was complete, the reactants were slowly dropped into excess diethyl ether to precipitate, dissolved again in THF and reprecipitated in diethyl ether to obtain a terpolymer (yield: 40%).
The weight average molecular weight and polydispersity of the obtained terpolymer were 7,000 and 1.8, respectively. b) Synthesis of Terpolymer (R=Methyl, R3=Hydroxy ethyl)
The polymerization was conducted in the same manner as in Example 3-1 , a) except that 2-hydroxyethyl-5-norbornene-2-carboxylate was used instead of 5-norbornene-2-carboxylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively. c) Synthesis of Terpolymer (R=Methyl, R3=Methyl) The polymerization was conducted in the same manner as in Example 3-1 , a) except that methyl-5-norbornene-2-carboxylate was used instead of 5-norbornene-2-carboxylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively.
Example 3-2: Synthesis of Terpolymer (R=Ethyl) (Compound 4)
Except that 2-ethyl-2-camphoryl acrylate and 2-ethyl-2-camphoryl methacrylate were used respectively, a terpolymer consisting of 2-ethyl-2-camphoryl acrylate or 2-ethyl-2-camphoryl methacrylate was prepared in the following manner. a) Synthesis of Terpolymer (R=Ethyl, R3=Hydrogen)
The polymerization was conducted in the same manner as in Example 3-1 , a) except that 2-ethyl-2-camphoryl methacrylate prepared in Example 1-3 was used instead of 2-methyl-2-camphoryl methacrylate to prepare a terpolymer. The weight average molecular weight and polydispersity of the obtained terpolymer were 6,500 and 1.8, respectively. b) Synthesis of Terpolymer (R=Ethyl, R3=Hydroxyethyl)
The polymerization was conducted in the same manner as in Example 3-2, a) except that 2-hydroxyethyl-5-norbornene-2-carboxylate was used instead of 5-norbomene-2-carboxylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively. c) Synthesis of Terpolymer (R=Ethyl, R =Methyl)
The polymerization was conducted in the same manner as in Example 3-2, a) except that methyl-5-norbornene-2-carboxylate was used instead of 5-norbornene-2-carboxylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively. Example 4-1 : Synthesis of Terpolymer (Compound 5) a) Synthesis of Terpolymer (R=Methyl, R =Hydrogen)
29.4 g (0.102 mol) of 2-methyl-2-camphoryl-5-norbornene-2-carboxylate prepared in Example 1-2, 0.44 g (0.005 mol) of methacrylic acid, 10.0 g (0.102 mol) of maleic anhydride and 0.7 g of azobis(isobutyronitrile) (AIBN) were dissolved in 25 g of anhydrous THF, and the reactants were degassed using ampoule by a freezing method. The reactants were then polymerized at 68 °C for 24 hours. After the polymerization was complete, the reactants were slowly dropped into excess diethyl ether to precipitate, dissolved again in THF and reprecipitated in diethyl ether to obtain a terpolymer (yield: 40%). The weight average molecular weight and polydispersity of the obtained terpolymer were 8,500 and 1.8, respectively. b) Synthesis of Terpolymer (R=Methyl, R3=Hydroxyethyl)
The polymerization was conducted in the same manner as in Example 4-1 , a) except that 2-hydroxyethyl methacrylate was used instead of methacrylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively. c) Synthesis of Terpolymer (R=Methyl, R3=Methyl)
The polymerization was conducted in the same manner as in Example 4-1 , a) except that methyl methacylate was used instead of methacrylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,000 and 1.8, respectively. Example 4-2: Synthesis of Terpolymer (Compound 5) a) Synthesis of Terpolymer (R=Ethyl, R3=Hydrogen)
The polymerization was conducted in the same manner as in Example 4-1 , a) except that 2-ethyl-2-camphoryl-5 -norbornene-2-carboxylate prepared in Example 1-4 was used instead of 2-methyl-2-camphoryl-5-norbornene-2-carboxylate to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,500 and 1.8, respectively. b) Synthesis of Terpolymer (R=Ethyl, R3=Hydroxy ethyl)
The polymerization was conducted in the same manner as in Example 4-2, a) except that 2-hydroxyethyl methacrylate was used instead of methacrylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,500 and 1.8, respectively. c) Synthesis of Terpolymer (R=Ethyl, R3=Methyl) The polymerization was conducted in the same manner as in Example
4-2, a) except that methyl methacrylate was used instead of methacrylic acid to prepare a terpolymer.
The weight average molecular weight and polydispersity of the obtained terpolymer were 8,500 and 1.8, respectively. Example 5: Preparation of Resist Composition
2.0 g of copolymer prepared in Example 2-1 and 0.02 g of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 g of propyleneglycol monomethyl ether acetate (PGMEA). The solution was then filtered with a disc filter of 0.2 μm to give a resist composition. Then, the resist solution was coated on the silicon wafer which was treated with hexamethyldisilazane (HMDS), to a thickness of about 0.30 μm.
The silicon wafer having the resist composition coated thereon was pre-baked at 110°C for 90 seconds and exposed to light using an ArF excimer laser having a numerical aperture of 0.60. Then, post exposure baking (PEB) was performed at 130°C for 90 seconds.
Thereafter, the resultant was developed using 2.38 % by weight of tetramethylammonium hydroxide (TMAH) solution for 30 seconds. As a result, when exposure doses were about 20 mJ/cπf, it was observed that 0.13 μm equal line and space patterns of a rectangular shape were obtained. The copolymer of the present invention reduced the etching rate against polysilicon by 20%, thereby exhibiting excellent etching resistance as compared with conventional COMA. Example 6: Preparation of Resist Composition
2.0 g of terpolymer prepared in Example 3-1 and 0.02 g of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 g of propyleneglycol monomethyl ether acetate (PGMEA). The subsequent procedures were performed in the same manner as in Example 5 to form a resist pattern from the solution. The resist pattern exhibited 0.12 μm equal line and space patterns of a rectangular shape. Example 7: Preparation of Resist Composition
2.0 g of terpolymer prepared in Example 4-1 and 0.02 g of triphenyl sulfonium triflate (TPS-105) were completely dissolved in 17 g of propyleneglycol monomethyl ether acetate (PGMEA). The subsequent procedures were performed in the same manner as in Example 5 to form a resist pattern from the solution. The resist pattern exhibited 0.12 m equal line and space patterns of a rectangular shape.
The sensitivities, resolutions and pattern shapes of above Examples 5 to 7 and the previously-used COMA type resists are shown in Table 1 below. In addition, Example 7 and the prior COMA resist patterns are shown in Fig. 1 and Fig. 2, respectively. Also, Fig. 3 and Fig. 4 illustrate etching resistance results against oxide and poly, respectively, of Examples 5 to 7 of the present invention and the previously-used COMA type resists. Table 1
Figure imgf000022_0001
From Table 1 and Fig. 1 to Fig. 4, it can be seen that the resists according to the present invention are excellent in that their pattern shapes are rectangular and they are also excellent in etching resistance against oxide and etching resistance against poly, as compared with the prior COMA.
As described in the above, the invention can provide a copolymer and terpolymer using a novel (meth)acrylic compound or norbornene carboxylate compound having a pendent group with camphoryl bonded thereto, and it can also provide a chemically amplified positive photoresist composition for ArF which exhibits high resolution and excellent etching resistance by using said polymer and can thus obtain excellent resist pattern.

Claims

WHAT IS CLAIMED IS:
1. 2-Alkyl-2-camphoryl (meth)acrylate represented by the following formula 1 :
Figure imgf000024_0001
wherein R is a methyl or ethyl group, and R* is a hydrogen or a methyl group.
2. A process for the preparation of 2-alkyl-2-camphoryl (meth)acrylate of formula 1 as described in claim 1 comprising the steps of: a) preparing 2-alkyl-2-camphoryl alcohol by the reaction of camphor and an alkyl grinard reagent or alkyl lithium reagent; and b) reacting the 2-alkyl-2-camphoryl alcohol prepared above with (meth)acryloyl chloride.
3. 2-Alkyl-2-camphoryl-5-norbornene-2-carboxylate represented by the following formula 2:
Figure imgf000024_0002
wherein R is a methyl or ethyl group, and R* is a hydrogen or a methyl group.
4. A process for the preparation of 2-alkyl-2-camphoryl-5-norbornene-2-carboxylate of formula 2 as described in claim 3 by the Diels-Alder reaction of 2-alkyl-2-camphoryl (meth)acrylate of formula 1 as described in claim 1 and cyclopentadiene.
5. A photosensitive copolymer represented by the following formula 3:
Figure imgf000025_0001
3 wherein R is a methyl or ethyl, R* is a hydrogen or a methyl, and n is an integer of 25 to 30.
6. A process for the preparation of the photosensitive copolymer of formula 3 as described in claim 5 comprising the step of polymerizing the compound of formula 2 as described in claim 3 with a maleic anhydride.
7. A photosensitive terpolymer represented by the following formula 4:
Figure imgf000025_0002
wherein R is a methyl or ethyl group; R* is a hydrogen or a methyl group; R' is a hydrogen, an alkyl group or a hydroxyalkyi group; R" is a hydrogen or a methyl group; and m and n each satisfy the conditions, m+n=1 , 0.1<m<0.9 and 0.1<n<0.9.
8. A process for the preparation of the photosensitive terpolymer of formula 4 as described in claim 7 comprising the step of polymerizing the compound of formula 1 as described in claim 1 with a maleic anhydride and a norbornene compound of the following formula 6:
Figure imgf000026_0001
wherein R' is a hydrogen, an alkyl group or a hydroxyalkyi group, and R" is a hydrogen or a methyl group. 9. A photosensitive terpolymer represented by the following formula 5:
Figure imgf000026_0002
wherein R is a methyl or ethyl group; R* is a hydrogen or a methyl group; R' is a hydrogen, an alkyl group or a hydroxyalkyi group; R" is a hydrogen or a methyl group; and m and n each satisfy the conditions, m+n=1 , 0.1<m<0.9 and
0.1<n<0.
9.
10. A process for the preparation of the photosensitive terpolymer of formula 5 as
described in claim 9 comprising the step of polymerizing the compound of formula
2 as described in claim 3 with a maleic anhydride and an acrylate compound of
the following formula 7:
.R"
■"•',' -f
C=0
OR' 7
wherein R' is a hydrogen, an alkyl group or a hydroxyalkyi group, and R"
is a hydrogen or a methyl group.
11. A chemically amplified positive photoresist composition for ArF comprising one
or more polymers selected from the group consisting of the photosensitive
copolymer of the following formula 3, the photosensitive terpolymer of the
following formula 4, and the photosensitive terpolymer of the following formula 5:
Figure imgf000027_0001
Figure imgf000028_0001
4
Figure imgf000028_0002
5 wherein R is a methyl or ethyl group; R* is a hydrogen or a methyl group;
R' is a hydrogen, an alkyl group or a hydroxyalkyi group; R" is a hydrogen or a methyl group; and m and n each satisfy the conditions, m+n=1 , 0.1<m<0.9 and 0.1<n<0.9.
12. The positive photoresist composition according to claim 11 characterized in that the content of said polymers is 1 to 30% by weight based on the total composition.
13. The positive photoresist composition according to claim 11 characterized in that said photoresist composition further comprises a photoacid generator in an amount of 0.5 to 10 % by weight of the total polymer.
14. The positive photoresist composition according to claim 13 characterized in that said photoacid generator is selected from the group consisting of onium salts, organic sulfonic acids, and a mixture thereof.
15. The positive photoresist composition according to claim 11 characterized in that said photoresist composition further comprises an organic base selected from the group of triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanolamine and a mixture thereof, in an amount of 0.01 to 2.00 % by weight of the total polymer.
16. A semiconductor device prepared comprising the positive photoresist composition for ArF as described in claim 11.
PCT/KR2002/002156 2002-11-04 2002-11-19 Chemically amplified polymer having pendant group with camphoryl and resist composition comprising the same WO2004042476A1 (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
US5851727A (en) * 1996-08-05 1998-12-22 Samsung Electronics Co., Ltd. Photosensitive polymers and photoresist compositions containing the same
JPH1184663A (en) * 1996-12-24 1999-03-26 Toshiba Corp Photosensitive composition, pattern forming method using the same and production of electronic parts
US5962184A (en) * 1996-12-13 1999-10-05 International Business Machines Corporation Photoresist composition comprising a copolymer of a hydroxystyrene and a (meth)acrylate substituted with an alicyclic ester substituent
US5968713A (en) * 1995-06-28 1999-10-19 Fujitsu Limited Chemically amplified resist compositions and process for the formation of resist patterns

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US4166109A (en) * 1973-06-26 1979-08-28 L'oreal Anti-solar polymers, method of making the same and cosmetic compositions containing the same
US5607985A (en) * 1992-12-21 1997-03-04 Adell Co., Ltd. Photopolymerization initiator for visible light-polymerizing adhesive
DE19528472A1 (en) * 1995-08-03 1997-02-06 Boehringer Ingelheim Kg New process for the production of norbenzomorphan of an intermediate stage in the production of pharmaceutically valuable benzomorphan derivatives, in particular of (-) - (1R, 5S, S "R) -3'-hydroxy-2- (2-methoxypropyl -) - 5.9.9 -trimethyl-6.7 benzomorphan

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968713A (en) * 1995-06-28 1999-10-19 Fujitsu Limited Chemically amplified resist compositions and process for the formation of resist patterns
US5851727A (en) * 1996-08-05 1998-12-22 Samsung Electronics Co., Ltd. Photosensitive polymers and photoresist compositions containing the same
US5962184A (en) * 1996-12-13 1999-10-05 International Business Machines Corporation Photoresist composition comprising a copolymer of a hydroxystyrene and a (meth)acrylate substituted with an alicyclic ester substituent
JPH1184663A (en) * 1996-12-24 1999-03-26 Toshiba Corp Photosensitive composition, pattern forming method using the same and production of electronic parts

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