WO2012046917A1 - Polymère à base de (méth)acrylate et composition de résine photosensible incluant ledit polymère - Google Patents

Polymère à base de (méth)acrylate et composition de résine photosensible incluant ledit polymère Download PDF

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WO2012046917A1
WO2012046917A1 PCT/KR2010/008804 KR2010008804W WO2012046917A1 WO 2012046917 A1 WO2012046917 A1 WO 2012046917A1 KR 2010008804 W KR2010008804 W KR 2010008804W WO 2012046917 A1 WO2012046917 A1 WO 2012046917A1
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formula
group
meth
acrylate
photosensitive resin
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PCT/KR2010/008804
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English (en)
Korean (ko)
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김태호
양영수
이준호
최승집
최상준
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제일모직 주식회사
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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
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • 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
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate

Definitions

  • the present disclosure relates to a (meth) acrylate polymer and a photosensitive resin composition comprising the same.
  • the resin of the chemically amplified resist using deep ultraviolet ray must be transparent to the light source used and the resin having a good protection reaction
  • a polyhydroxy styrene is used for the KrF (248 nm) resist
  • ArF An acrylate polymer is used for the (193 nm) resist
  • a polymer including a hydrocarbon ring compound such as adamantyl in the side chain portion of the ester group is used to compensate for the insufficient etch resistance compared to the KrF resist.
  • One aspect of the present invention is to provide a (meth) acrylate-based polymer that can produce a resin film that is excellent in adhesion to a substrate and excellent in implant resistance without generating scum even at a high film thickness. .
  • Another aspect of the present invention is to provide a photosensitive resin composition comprising the (meth) acrylate-based polymer.
  • One aspect of the present invention provides a (meth) acrylate-based polymer comprising a repeating unit represented by the following formula (1) to (3).
  • R 1 includes hydrogen or a methyl group
  • R 10 includes a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 heterocycloalkyl group
  • n is an integer from 0 to 3.
  • R 2 comprises hydrogen or a methyl group
  • R 20 comprises an ester group and comprises a substituted or unsubstituted C3 to C20 cycloalkyl group.
  • R 3 contains hydrogen or a methyl group
  • R 30 includes a t-butyl group, triethylcarbyl group, 1-methyl cyclohexyl group, 1-ethylcyclopentyl group, t-amyl group or acetal group.
  • the repeating unit represented by Formula 1 may include any one of the repeating units represented by the following Formulas 4 to 23.
  • the heterocycloalkyl group may include a hetero atom of oxygen (O) or nitrogen (N).
  • R 20 in Formula 2 is a gamma-butyrolactonyl group, a valerolactonyl group, a 1,3-cyclohexanecarbolactonyl group, 2,6 Norbornanecarbolacton-5-yl (2,6-norbornanecarbolacton-5-yl) or 7-oxa-2,6-norbornanecarbolactone-5-yl (7-oxa-2,6-norbornanecarbolacton -5-yl) group.
  • the (meth) acrylate-based polymer may have a weight average molecular weight of 3,000 to 20,000 g / mol, dispersion degree may be 1.3 to 2.5.
  • the (meth) acrylate-based polymer 10 to 40 mol% of repeating units represented by Formula 1; 20 to 60 mol% of repeating units represented by Formula 2; And it may include 20 to 50 mol% of the repeating unit represented by the formula (3).
  • the (meth) acrylate-based polymer comprises Photo acid generator (PAG); And it provides a photosensitive resin composition comprising a solvent.
  • PAG Photo acid generator
  • the (meth) acrylate-based polymer may be included in 5 to 15% by weight based on the total amount of the photosensitive resin composition.
  • the photoacid generator is triarylsulfonium perfluoroalkylsulfonate, triarylsulfonium triflate, diaryliodonium triflate, triarylsulfonium nonaplate, diaryliodonium nonaplate, succinimidyl tri It may include a plate, 2,6-dinitrobenzyl sulfonate or a combination thereof, the photoacid generator may be included in 1 to 15 parts by weight based on 100 parts by weight of the (meth) acrylate-based polymer.
  • the photosensitive resin composition may further include 0.1 to 5 parts by weight of an organic amine based on 100 parts by weight of the (meth) acrylate-based polymer, wherein the organic amine is triethylamine, triisobutylamine, trioctylamine, tri Isodecylamine, triethanolamine, hydroxypiperidine or combinations thereof.
  • the (meth) acrylate-based polymer is excellent in solubility in a developer, does not generate scum, and is excellent in implant resistance and dry etch resistance, and has good hydrophilic property, which is excellent in adhesion to a substrate. Less occurrence of lifting. Thereby, the resin film suitable for an ion implantation process can be provided.
  • FIG. 1A is a CD-SEM photograph of a 150 nm pattern (optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 1A is a CD-SEM photograph of a 150 nm pattern (optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 1B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 1B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 1C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 1C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1.
  • FIG. 2A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 2A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 2B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy E op ) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 2B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy E op ) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 2C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 2C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 1.
  • FIG. 3A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2.
  • FIG. 3A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2.
  • 3B is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2.
  • FIG. 1 is a CD-SEM photograph of a 150 nm pattern (2 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2.
  • 3C is a CD-SEM photograph of a 150 nm pattern (4 mJ / cm 2 less than the optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2.
  • E op optimal energy
  • FIG. 5 shows the exposure latitude (EL) margin of the 150 nm pattern (optimum energy (E op ): 36 mJ / cm 2 ) obtained using the photosensitive resin composition according to Example 1 with respect to the pattern center and edges.
  • heterocycloalkyl group each have at least one hetero atom of N, O, S or P in the ring compound. It means to be included.
  • the (meth) acrylate-based polymer includes a repeating unit represented by the following Chemical Formulas 1 to 3.
  • R 1 contains hydrogen or a methyl group
  • R 10 comprises a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 heterocycloalkyl group,
  • n is an integer of 0 to 3)
  • R 2 contains hydrogen or a methyl group
  • R 20 includes an ester group and includes a substituted or unsubstituted C3 to C20 cycloalkyl group.
  • R 3 contains hydrogen or a methyl group
  • R 30 includes t-butyl group, triethylcarbyl group, 1-methyl cyclohexyl group, 1-ethylcyclopentyl group, t-amyl group or acetal group.
  • the repeating unit represented by Formula 1 has a cyclic alkyl group, thereby improving the etch resistance of the (meth) acrylate-based polymer.
  • the cyclic alkyl group is a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C2 to C20 heterocycloalkyl group, wherein the substitution may specifically mean substituted with a C1 to C4 alkyl group, more Specifically, it may mean that a methyl group, an ethyl group, n-propyl group, iso-propyl group or the like is substituted.
  • heterocycloalkyl group may specifically include a hetero atom of oxygen (O) or nitrogen (N).
  • repeating unit represented by Formula 1 include any one of the repeating units represented by the following Formulas 4 to 23.
  • the repeating unit represented by Formula 1 may be included in 10 to 40 mol%, specifically, 20 to 30 mol% based on the total amount of the (meth) acrylate-based polymer.
  • the repeating unit represented by Chemical Formula 1 is included in the above range, the etch resistance and the lifting resistance are excellent.
  • the repeating unit represented by Formula 2 is a monocyclic or polycyclic (meth) acrylate repeating unit including an ester group, which may improve the hydrophilicity of the photosensitive resin composition and improve adhesion to the substrate.
  • R 20 in Formula 2 may be a lactone derivative.
  • lactone derivatives include gamma butyrolactonyl groups, valerolactonyl groups, 1,3-cyclohexanecarbolactonyl groups, and 2,6- Norbornane carbolactone-5-yl (2,6-norbornanecarbolacton-5-yl) group, 7-oxa-2,6-norbornanecarbolactone-5-yl (7-oxa-2,6-norbornanecarbolacton- 5-yl) group etc. are mentioned.
  • the repeating unit represented by Formula 2 may be included in 20 to 60 mol%, specifically 30 to 50 mol% based on the total amount of the (meth) acrylate-based polymer. When the repeating unit represented by Formula 2 is included in the above range, the adhesion to the substrate is excellent.
  • the repeating unit represented by Chemical Formula 3 is a (meth) acrylate repeating unit including an acid labile group in which decomposition occurs in the presence of a acidic catalyst, and is decomposed by an acid catalyst generated during exposure to (meth) acrylic acid.
  • the rate-based polymer may help to dissolve well in the alkaline developer.
  • Examples of the acid-decomposable group include t-butyl group, triethylcarbyl group, 1-methyl cyclohexyl group, 1-ethylcyclopentyl group, t-amyl group, acetal group, and the like, and among them, development speed T-butyl group may be used in the aspect.
  • the repeating unit represented by Formula 3 may be included in 20 to 50 mol%, specifically 30 to 40 mol% based on the total amount of the (meth) acrylate-based polymer.
  • the repeating unit represented by Formula 1 is included in the above range, the development speed is excellent.
  • the (meth) acrylate-based polymer comprising a repeating unit represented by Formula 1 to 3 may be a terpolymer, or may be a multipart copolymer further including the same type or different types of repeating units. , Random copolymers, block copolymers, alternating copolymers, branched copolymers, or the like can be used.
  • the (meth) acrylate-based polymer may have a weight average molecular weight of 3,000 to 20,000 g / mol, specifically 5,000 to 10,000 g / mol. When it has the said weight average molecular weight range, the surface edge roughness (LER) characteristic of the resin film obtained from the photosensitive resin composition is excellent.
  • LER surface edge roughness
  • Dispersion degree of the (meth) acrylate-based polymer may be 1.3 to 2.5, specifically, may be 1.5 to 2.0.
  • the dispersion degree is a value obtained by dividing the weight average molecular weight by the number average molecular weight.
  • the (meth) acrylate polymer is a general radical polymerization method using a repeating unit derivative monomer represented by Formula 1, a repeating unit derivative monomer represented by Formula 2, and a repeating unit derivative monomer represented by Formula 3 By polymerization.
  • Another embodiment includes a photosensitive resin composition including the (meth) acrylate-based polymer described above.
  • the photosensitive resin composition includes the (meth) acrylate-based polymer, a photo acid generator, and a solvent.
  • the (meth) acrylate-based polymer may be included in 5 to 15% by weight, specifically, 7 to 12% by weight based on the total amount of the photosensitive resin composition.
  • the (meth) acrylate-based polymer is included in the above range can be obtained excellent etch resistance and adhesion.
  • the photoacid generator may be an inorganic onium salt, organic triflate, organic sulfonate, or a combination thereof.
  • inorganic onium salt examples include triarylsulfonium salt, diaryl iodonium salt, and the like.
  • the photoacid generator include triarylsulfonium perfluoroalkylsulfonate, triarylsulfonium triflate, diaryliononium triflate, triarylsulfonium nonaplate, diaryliodonium nonaplate, Succinimidyl triflate, 2,6-dinitrobenzyl sulfonate or combinations thereof.
  • the photoacid generator may be included in an amount of 1 to 15 parts by weight, specifically 3 to 8 parts by weight, based on 100 parts by weight of the (meth) acrylate polymer.
  • an excellent exposure amount and transmittance of the photosensitive resin composition can be obtained.
  • propyleneglycol monomethylether acetate PGMEA
  • propyleneglycol monomethylether PGME
  • EL ethyl lactate
  • cyclohexanone 2-heptanone (2 -heptanone) etc.
  • the solvent may be included in the remainder with respect to 100 parts by weight of the (meth) acrylate-based polymer, specifically, may be included in 80 to 95 parts by weight.
  • the film thickness uniformity of the photosensitive resin composition may be excellent when applied to a wafer, and coating failure may be reduced.
  • the photosensitive resin composition may further include an organic amine as a quencher for the purpose of controlling the exposure dose and forming an excellent profile together with the constituent components.
  • the organic amine may be an amine compound, and examples thereof include triethylamine, triisobutylamine, trioctylamine, triisodecylamine, triethanolamine, hydroxypiperidine, or a mixture thereof.
  • the organic amine may be included in an amount of 0.1 to 5 parts by weight, and specifically 0.5 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylate-based polymer.
  • DOF depth of focus
  • EL energy latitude
  • a bare silicon wafer, or a silicon wafer having a silicon oxide film, a silicon nitride film, or a lower film quality of a silicon oxynitride film formed on a top surface thereof, is prepared, and the silicon wafer is hexamethyl disilazane (HMDS). Treatment or by forming a bottom anti-reflective coating (BARC). Thereafter, the photosensitive resin composition is coated on the silicon wafer to a thickness of about 3800 kPa to about 4000 kPa to form a photosensitive resin film.
  • HMDS hexamethyl disilazane
  • BARC bottom anti-reflective coating
  • the silicon wafer on which the photosensitive resin film was formed was soft-baked (SB, pre-baking) for about 60 seconds to about 90 seconds in a temperature range of about 90 ° C to about 120 ° C.
  • the solvent is removed and exposed using ArF or extreme UV (EUV), E-beam, and the like.
  • a post-exposure baking for about 60 seconds to about 90 seconds in a temperature range of about 90 ° C to about 120 ° C, in order to cause the exposed wafer to undergo a chemical reaction in the exposure region of the photosensitive resin film. PEB).
  • the photosensitive resin film is developed with an aqueous alkali solution which is a developer.
  • an aqueous alkali solution which is a developer.
  • the exposed portion exhibits a very large solubility characteristic with respect to the developer, so that it is well dissolved and removed during development.
  • Tetramethylammonium hydroxide (TMAH) aqueous solution may be used as the developer.
  • TMAH Tetramethylammonium hydroxide
  • L / S line and space pattern of about 80 nm to about 300 nm at a dose of about 20 mJ / cm 2 to about 50 mJ / cm 2 Can be formed.
  • the lower film quality such as a silicon oxide film is etched by using a photosensitive resin pattern thus obtained as a mask and using a plasma of a specific etching gas, for example, a halogen gas or a fluorocarbon gas. Subsequently, a stripper may be used to remove the photosensitive resin pattern remaining on the wafer to form a desired silicon oxide film pattern.
  • a specific etching gas for example, a halogen gas or a fluorocarbon gas.
  • reaction product was diluted with 250 ml of dichloromethane, washed once with 250 ml of brine and three times with 250 ml of deionized water (DIW). The organic layer was taken up, dried over Na 2 SO 4 , and the solvent was removed to obtain 13.14 g of tetrahydro-2H-pyran-2-yl methacrylate (THP2M). Yield 83%.
  • reaction product was quenched with NaHCO 3 , diluted with 100 ml of ethyl acetate, washed three times with 100 ml of saturated NaHCO 3 , once with 150 ml of brine, and twice with 150 ml of deionized water (DIW). It was.
  • Cyclohexyl methacrylate (CHMA) (TCI), ⁇ -butyrolactonyl methacrylate (GBLMA) (aldrich) and t-butyl methacrylate (tert-butylmethacrylate, t) -BMA) (TCI Co., Ltd.) were each mixed in a molar ratio of 3: 3: 4, and azobisisobutyronitrile (AIBN) (Cafe Gold Co., Ltd.) was used as an initiator. 5 mole% together of the total amount of CHMA, GBLMA 'and t-BMA).
  • MEK methyl ethyl ketone
  • a (meth) acrylate polymer was obtained in the same manner as in Example 1 except that CHMA, GBLMA ', and t-BMA were each used at a molar ratio of 3: 4: 3.
  • a (meth) acrylate polymer was obtained in the same manner as in Example 1, except that CHMA, GBLMA ', and t-BMA were used in a molar ratio of 2: 5: 3, respectively.
  • Example 1 Except for using CHMA in Example 1 except that tetrahydro-2H-pyran-2-yl methacrylate (THP2M) prepared in Synthesis Example 1 was used, A (meth) acrylate polymer was obtained in the same manner as in Example 1.
  • THP2M tetrahydro-2H-pyran-2-yl methacrylate
  • Example 1 Except for using CHMA in Example 1 except that tetrahydrofuran-2-yl methacrylate (tetrahydrofuran-2-yl methacrylate, THFM) prepared in the same manner as in Example 1 ( A meta) acrylate type polymer was obtained.
  • tetrahydrofuran-2-yl methacrylate tetrahydrofuran-2-yl methacrylate, THFM
  • a (meth) acrylate polymer was obtained in the same manner as in Example 1, except that tetrahydrofurfuryl methacrylate (THFFMA) (TCI, Inc.) was used in place of CHMA.
  • THFFMA tetrahydrofurfuryl methacrylate
  • a (meth) acrylate polymer was obtained in the same manner as in Example 1, except that hydroxyadamantyl methacrylate (HAMA) (TCI, Inc.) was used in place of CHMA.
  • HAMA hydroxyadamantyl methacrylate
  • Example 1 and 1 except that 2-methyladamantan-2-yl methacrylate (MAMA) (TCI, Inc.) was used in place of t-BMA in Comparative Example 1 In the same manner, a (meth) acrylate polymer was obtained.
  • MAMA 2-methyladamantan-2-yl methacrylate
  • (Meta) acrylate-based polymer was obtained in the same manner as in Example 1 except that HAMA, GBLMA ', and MAMA were used in a molar ratio of 3: 4: 3, respectively.
  • (Meta) acrylate-based polymer was obtained in the same manner as in Example 1 except that HAMA, GBLMA ', and EAMA were each used in a molar ratio of 3: 4: 3.
  • Example 1 and 2 except that 2-methyladamantan-2-yl methacrylate (MAMA) (TCI Co., Ltd.) was used in place of t-BMA. In the same manner, a (meth) acrylate polymer was obtained.
  • MAMA 2-methyladamantan-2-yl methacrylate
  • PGMEA propyleneglycol monomethylether acetate
  • a 8 "bare silicon wafer is baked at 150 ° C./60 s with hexamethyl disilazane (HMDS), and the photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 6, respectively, are baked. After spin coating to a thickness of 4,000 kPa, soft baking (SB) was performed at 110 ° C. for 60 seconds.
  • HMDS hexamethyl disilazane
  • Each of the photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 6 was spin coated to a thickness of 4,000 kPa on an 8 "bare silicon wafer, and then baked at 110 ° C for 60 seconds, which was then applied for about 1 minute.
  • the thickness of the wafer coated with the photosensitive resin composition was measured by using a thickness gauge (K-MAC Co., Ltd.)
  • the wafer coated with the photosensitive resin composition was then 2.38% by weight of tetramethylammonium hydroxide.
  • Each of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 5 was applied to an 8 "bare silicon wafer and baked at 110 ° C. for 60 seconds. The resultant was cooled to room temperature for about 1 minute again, respectively, 300 ⁇ and 500 ⁇ A wafer coated with a photosensitive resin composition having a thickness of 1,000 ⁇ , 2,000 ⁇ , 3,000 ⁇ and 4,000.
  • a photosensitive resin composition having a thickness of 1,000 ⁇ , 2,000 ⁇ , 3,000 ⁇ and 4,000.
  • BF boron monofluoride
  • 5 ⁇ 10 13 boron / cm 2 doses were implanted, and the remaining photosensitive resin composition was then O 2 ashed using PSK DAS2000 equipment and thoroughly cleaned with Hitachi NXWET.
  • boron (B) permeated to the wafer was carried out using secondary ion mass spectrometry (SIMS) using an IMS-6f Magnetic Sector device from CAMECA, O 2 + Gun, impact energy: 7.5 keV, 300nA Measured by current.
  • SIMS secondary ion mass spectrometry
  • the photosensitive resin composition had a high intensity of boron (B) measured in the wafer after the implant at a thickness lower than the high thickness, boron penetrated the wafer through the photosensitive resin film during the implant. Therefore, as the minimum thickness of the boron in the wafer after the ion implantation is not different, the implant resistance was evaluated as good.
  • the minimum thickness is shown in Table 1 below.
  • the 8 "bare silicon wafer was spin-coated each of the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-6 with the thickness of 5,000 kPa, and soft-baked at 110 degreeC for 60 second.
  • the coated wafer was subjected to a phase shift mask (PSM) using an NSR-S308F (LENS NA: 0.85, ILLUMINATION NA: 0.68, Conv. (Large), sigma: 0.80), an NIKON ArF scanner.
  • PSM phase shift mask
  • NSR-S308F LENS NA: 0.85, ILLUMINATION NA: 0.68, Conv. (Large), sigma: 0.80
  • PEM phase shift mask
  • NSR-S308F LENS NA: 0.85, ILLUMINATION NA: 0.68, Conv. (Large), sigma: 0.80
  • PEB post exposure baking
  • TMAH tetramethyl ammonium hydroxide
  • CD-SEM was used to observe the scum at the end of the trench pattern. The edge of the pattern was developed, but the scum performance was evaluated to the extent that no scum remained inside. That is, despite the evaluation of the thick film thickness, it was determined that less scum occurred as the inside of the fine trench pattern melted well.
  • FIG. 1A is a CD-SEM photograph of a 150 nm pattern (optimal energy (E op )) obtained using the photosensitive resin composition according to Example 1
  • FIG. 1B is 150 nm obtained using the photosensitive resin composition according to Example 1 CD-SEM photograph of the pattern (2 mJ / cm 2 less than the optimal energy (E op )
  • FIG. 1C is 4 nm than the 150 nm pattern (optimal energy (E op ) obtained using the photosensitive resin composition according to Example 1 mJ / cm 2 less) CD-SEM photo.
  • FIG. 2A is a CD-SEM photograph of a 150 nm pattern (optimal energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 1
  • FIG. 2B is 150 nm obtained using the photosensitive resin composition according to Comparative Example 1
  • Figure 2c is a 150 nm pattern obtained by using the photosensitive resin composition according to Comparative Example 1 (4 than the optimal energy (E op ) mJ / cm 2 less) CD-SEM photo.
  • FIG. 3A is a CD-SEM photograph of a 150 nm pattern (optimum energy (E op )) obtained using the photosensitive resin composition according to Comparative Example 2
  • FIG. 3B is 150 nm obtained using the photosensitive resin composition according to Comparative Example 2.
  • Figure 3c is 4 nm than the 150 nm pattern (optimal energy (E op ) obtained using the photosensitive resin composition according to Comparative Example 2 mJ / cm 2 less) CD-SEM photo.
  • the pattern of Example 1 using the (meth) acrylate-based polymer according to one embodiment, the phenomenon is clear to the inside, the pattern is formed in a straight line can be seen not only excellent scum performance but also patternability have.
  • Figures 2a and 3a it can be seen that the patterns of Comparative Examples 1 and 2 are not well formed due to scum.
  • Comparative Examples 1 and 2 have a maximum trench pattern width of 130 nm, but Example 1 has a depth of focus (DOF) margin and exposure latitude (EL) of up to 110 nm. Margin and the like can be excellently implemented.
  • DOF depth of focus
  • EL exposure latitude
  • the depth of focus margin refers to the allowable focus range of the resultant pattern even when the focus at the optimal energy E op is out of the best focus.
  • the acceptable focus range typically represents ⁇ 10% of the CD size.
  • the best condition is -0.05 um, and the depth of focus margin is 0.25 um (-0.15 um to 0.1 um).
  • both the center and the edge of the pattern are developed cleanly, so it can be confirmed that the scum surface is clean.
  • FIG. 5 shows the exposure latitude (EL) margin of the 150 nm pattern (optimum energy (E op ): 36 mJ / cm 2 ) obtained using the photosensitive resin composition according to Example 1 with respect to the pattern center and edges.
  • the exposure allowance margin indicates an allowable exposure range of the resultant pattern even when the exposure energy is out of the optimum energy E op at the best focus, and the allowable energy range is optimal energy. Divided by (E op ).
  • the acceptable exposure range typically represents ⁇ 10% of the CD size.
  • the exposure allowance margin is 22% (32 mJ to 8 mJ from 40 mJ).
  • the center and the edge of the pattern are developed cleanly from the under dose to the over dose, it can be confirmed that the scum surface is also clean.

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

Abstract

L'invention concerne un polymère à base de (méth)acrylate et une composition de résine photosensible incluant ledit polymère.
PCT/KR2010/008804 2010-10-07 2010-12-09 Polymère à base de (méth)acrylate et composition de résine photosensible incluant ledit polymère WO2012046917A1 (fr)

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KR1020100097834A KR101413079B1 (ko) 2010-10-07 2010-10-07 (메타)아크릴레이트계 고분자 및 이를 포함하는 감광성 수지 조성물

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KR20170042688A (ko) * 2014-09-30 2017-04-19 후지필름 가부시키가이샤 패턴 형성 방법, 레지스트 패턴, 및 전자 디바이스의 제조 방법
WO2022037909A1 (fr) * 2020-08-18 2022-02-24 Henkel IP & Holding GmbH Accélérateurs de durcissement pour compositions durcissables par voie anaérobie

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KR102680736B1 (ko) 2016-12-14 2024-07-03 삼성전자주식회사 기판 가공 방법 및 접착층 세정 조성물
KR102503675B1 (ko) * 2020-12-24 2023-02-23 최상준 감광성 고분자 및 포토레지스트 조성물
KR20230121331A (ko) 2022-02-11 2023-08-18 동우 화인켐 주식회사 착색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 표시장치
KR102689508B1 (ko) * 2023-09-26 2024-07-29 주식회사 씨지피머트리얼즈 나프탈렌 구조를 갖는 방향족 화합물, 이로 이루어지는 감광성 고분자, 및 이를 포함하는 레지스트 조성물

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US6080524A (en) * 1998-06-02 2000-06-27 Samsung Electronics Co., Ltd. Photosensitive polymer having cyclic backbone and resist composition comprising the same
JP2000119992A (ja) * 1998-10-14 2000-04-25 Nippon Kayaku Co Ltd 紙用活性エネルギー線硬化性樹脂組成物及びその硬化物
KR20050078320A (ko) * 2004-01-29 2005-08-05 주식회사 동진쎄미켐 감광성 고분자 수지 및 이를 포함하는 화학증폭형포토레지스트 조성물
KR20070018251A (ko) * 2005-08-09 2007-02-14 주식회사 동진쎄미켐 감광성 고분자 및 이를 포함하는 포토레지스트 조성물

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Publication number Priority date Publication date Assignee Title
KR20170042688A (ko) * 2014-09-30 2017-04-19 후지필름 가부시키가이샤 패턴 형성 방법, 레지스트 패턴, 및 전자 디바이스의 제조 방법
KR101982556B1 (ko) * 2014-09-30 2019-05-27 후지필름 가부시키가이샤 패턴 형성 방법, 레지스트 패턴, 및 전자 디바이스의 제조 방법
WO2022037909A1 (fr) * 2020-08-18 2022-02-24 Henkel IP & Holding GmbH Accélérateurs de durcissement pour compositions durcissables par voie anaérobie

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