WO2008004735A1 - Micropattern-forming resin compositon and method for forming micropattern using the same - Google Patents

Micropattern-forming resin compositon and method for forming micropattern using the same Download PDF

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Publication number
WO2008004735A1
WO2008004735A1 PCT/KR2006/005917 KR2006005917W WO2008004735A1 WO 2008004735 A1 WO2008004735 A1 WO 2008004735A1 KR 2006005917 W KR2006005917 W KR 2006005917W WO 2008004735 A1 WO2008004735 A1 WO 2008004735A1
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WO
WIPO (PCT)
Prior art keywords
water
micropattern
soluble polymer
composition according
photoresist pattern
Prior art date
Application number
PCT/KR2006/005917
Other languages
French (fr)
Inventor
Dong Sun Uh
Yong Sik Yoo
Hee Jae Kim
Chang Soo Woo
Sang Geun Yun
Original Assignee
Cheil Industries Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cheil Industries Inc. filed Critical Cheil Industries Inc.
Publication of WO2008004735A1 publication Critical patent/WO2008004735A1/en

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Classifications

    • 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
    • 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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/08—Homopolymers or copolymers of vinyl-pyridine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/08—Homopolymers or copolymers of vinyl-pyridine
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0338—Process specially adapted to improve the resolution of the mask

Definitions

  • the present invention relates to a micropattern-forming resin composition that can be used to reduce the area or width of recessed portions in a semiconductor lithographic process.
  • Typical lithographic processes involve formation of a patterned resist layer by patternwise exposing a radiation- sensitive resist to an imaging radiation.
  • the image is subsequently developed by contacting the exposed resist layer with a material (typically an aqueous alkaline developer) to selectively remove portions of the resist layer to reveal the desired pattern.
  • the pattern is subsequently transferred to an underlying material by etching the material in openings of the patterned resist layer. After completion of the transfer, the remaining resist layer is removed.
  • Japanese Patent No. 3,071,401 suggests a micropattern-forming material which uses a water-soluble resin causing a crosslinking reaction with a resist in the presence of an acid to form a crosslinked film at the interface between a resist pattern and the micropattern-forming material by the acid supplied from the resist pattern and to strip the uncrosslinked portions.
  • the present invention has been made in view of the problems of the prior art, and it is an object of the present invention to provide a micropattern-forming material with a new type of mechanism that overcomes the limitation of wavelength in the miniaturization of a pattern, such as an isolation pattern or a hole pattern.
  • the present inventors have earnestly and intensively conducted research to achieve the object. As a result, the present inventors have found that an aqueous alcoholic or alkaline solution is used to induce swelling of a photoresist pattern layer and a water- soluble polymer is used to induce entanglement between the swollen photoresist pattern layer and the water-soluble polymer so that the width of recessed portions of the photoresist pattern layer can be reduced.
  • the present invention has been achieved based on this finding.
  • a micropattern-forming resin composition comprising a water-soluble polymer and a solvent wherein a micropattern is formed by coating the resin composition on a photoresist pattern layer, inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and removing portions of the water-soluble polymer other than the entangled portions using a developing solution.
  • the solvent may be an aqueous alcoholic or alkaline solution.
  • the water-soluble polymer may be a homopolymer composed of a hydrophilic monomer unit or a copolymer composed of two or more hydrophilic monomer units.
  • the water-soluble polymer may be a copolymer composed of at least one hydrophilic monomer unit and at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotri- imidazole, vinyltriimidazole and vinyltetraimidazole.
  • the water-soluble polymer may be a copolymer composed of at least one hydrophilic monomer unit and at least one (meth)acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups.
  • the hydrophilic monomer unit of the water-soluble polymer may have at least one functional group selected from the group consisting of hydroxyl, carboxylic acid, amide, amine, heterocyclic, ether, ester, acetal and sulfonic acid groups.
  • the hydrophilic monomer unit of the water-soluble polymer may be selected from the group consisting of vinyl alcohol, vinyl carbohydrate, acrylic acid, methacrylic acid, ethylene oxide, vinylhydroxyethyl methacrylate, benzoacrylic acid, vinylpyrrolidone, vinylamine, allylamine, vinylimidazole, vinyloxazoline, and combinations thereof.
  • the ratio of the number of the hydrophilic monomer unit to the number of the at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinyl- benzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinyltetraimidazole may be between 1 : 0.01 and 1 : 0.5.
  • the ratio of the number of the hydrophilic monomer unit to the number of the (meth) acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups may be between 1 : 0.01 and 1 : 0.5.
  • the water-soluble polymer may have a weight- average molecular weight (M ) of 5,000 to 1,000,000.
  • the alcohol may be selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, hydrobenzoin, and mixtures thereof.
  • the alkali may be an organic amine or an ammonium hydroxide salt.
  • the alkali may be selected from the group consisting of 2-(2-aminoethylamino)ethanol, l,l,3,3-tetrakis(methoxymethyl)urea, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and mixtures thereof.
  • the micropattern-forming resin composition may comprise 50 to 99% by weight of the aqueous alcoholic or alkaline solution and 1 to 50% by weight of the water-soluble polymer.
  • the aqueous solution may contain 0.1 to 5 parts by weight of the alcohol or alkali, based on 100 parts by weight of water.
  • a method for forming a micropattern comprising the steps of a) forming a photoresist resin layer on a substrate, b) light-exposing and developing the photoresist resin layer to form a photoresist pattern layer, c) applying the micropattern-forming resin composition to the surface of the photoresist pattern layer, d) inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, e) inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and f) removing portions of the water-soluble polymer other than the entangled portions using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent.
  • FIG. 1 shows conceptual diagrams illustrating respective steps of a method for forming a micropattern by applying a micropattern-forming resin composition of the present invention to the surface of a resist pattern layer.
  • the present invention is directed to a micropattern-forming resin composition that is coated on a photoresist pattern.
  • the micropattern-forming resin composition of the present invention comprises an aqueous alcoholic or alkaline solution and a water- soluble polymer.
  • the aqueous alcoholic or alkaline solution serves to induce a swelling phenomenon of the surface of a photoresist pattern layer, and the water-soluble polymer in contact with the surface of the photoresist pattern layer serves to induce entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition to form an insoluble film. Portions of the micropattern-forming resin composition in which no entanglement is reduced are removed by water, an aqueous alkaline solution or an aqueous solution containing an organic solvent as a developing solution.
  • the water-soluble polymer is a homopolymer composed of a hydrophilic monomer unit or a copolymer composed of two or more hydrophilic monomer units.
  • the hydrophilic monomer unit of the water-soluble polymer preferably has at least one functional group selected from the group consisting of hydroxyl, carboxylic acid, amide, amine, heterocyclic, ether, ester, acetal and sulfonic acid groups.
  • vinyl alcohol, vinyl carbohydrate, vinylhydroxyethyl methacrylate or the like may be used as the monomer having a hydroxyl group; acrylic acid, methacrylic acid, benzoacrylic acid or the like may be used as the monomer having a carboxylic acid group; vinylamine, allylamine or the like may used as the monomer having an amine group; and vinylpyrrolidone, vinyloxazoline, vinylimidazole or the like may be used as the monomer having a heterocyclic group.
  • Ethylene oxide may also be used as the hydrophilic monomer unit.
  • water-soluble polymer there can be used a homopolymer composed of one of the hydrophilic monomer units and a copolymer composed of two or more kinds of the hydrophilic monomer units.
  • the water-soluble polymer there can be used a copolymer composed of at least one hydrophilic monomer unit and a monomer unit having an affinity for a resin constituting the photoresist pattern.
  • the monomer unit having an affinity for a resin constituting the photoresist pattern may be selected depending on the kind of the photoresist pattern layer.
  • a monomer unit having an affinity for the resin constituting the photoresist pattern may be selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinyl- methylimidazole, vinyldiaminotriimidazole, vinyltriimidazole, vinyltetraimidazole, and mixtures thereof.
  • a monomer unit having an affinity for the resin constituting the photoresist pattern may be at least one (meth)acrylic monomer having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups.
  • the hydrophilic monomer unit may be copolymerized with the monomer unit having an affinity for a resin constituting the photoresist pattern by various processes, for example, random copolymerization, block copolymerization and graft copoly- merization, so long as the water solubility of the water-soluble polymer is not impaired. Random copolymerization is preferred.
  • the ratio of the number of the hydrophilic monomer unit to the number of the monomer unit having an affinity for a resin constituting the photoresist pattern is preferably between 1 : 0.01 and 1 : 0.5. If the monomer unit having an affinity for a resin constituting the photoresist pattern is used in a relatively small amount, entanglement between the soluble polymer and the photoresist resin is not readily induced.
  • the molecular weight of the water-soluble polymer may be optionally determined.
  • the weight- average molecular weight (M ) of the water-soluble polymer is preferably adjusted to the range of 5,000 to 1,000,000 and more preferably to the range of 30,000 to 100,000.
  • the water-soluble polymer has a weight-average molecular weight (M ) lower than 5,000, entanglement between the water- soluble polymer and the swollen photoresist resin is not sufficient. Meanwhile, when the water-soluble polymer has a weight-average molecular weight (M ) higher than 1,000,000, the water solubility of the water-soluble polymer is poor and aggregation of the water-soluble polymer occurs when being applied, resulting in a non-uniform coating.
  • M weight-average molecular weight
  • any photosensitive resin that can constitute the resist pattern may be used in the present invention.
  • a photosensitive resin that can constitute the resist pattern
  • hydroxyl groups of the polyhydroxystyrene are partially substituted with ethyl vinyl ether groups as acid- labile protecting groups.
  • an ArF photoresist comprising an alicyclic compound
  • the alicyclic compound is substituted with acid-labile protecting groups.
  • the KrF photoresist and the ArF photoresist are water-insoluble organic polymers.
  • the polymers may be soluble in a high- concentration aqueous alcoholic or alkaline solution.
  • the surface of the photoresist pattern layer can be swollen without being completely dissolved by controlling the alcohol or alkali content of the aqueous alcoholic or alkaline solution.
  • the molecular weight of the water-soluble polymer can be controlled to vary the degree of insolubility of the water- soluble polymer arising from the entanglement, and as a result, the degree of reduction of the distance between patterned portions or the size of hole openings can be controlled.
  • a water-soluble polymer having a weight-average molecular weight of about 7OK was used to reduce the width of recessed portions of a photoresist pattern layer having a width of about 40 nm in the Example section that follows.
  • the water-soluble resin composition of the present invention comprises an aqueous alcoholic or alkaline solution.
  • the aqueous alcoholic or alkaline solution penetrates the surface of a resin constituting a photoresist pattern layer to swell the resin. Accordingly, the kind of the aqueous alcoholic or alkaline solution is not particularly restricted so long as the alcohol or alkali is soluble in water.
  • a water-soluble alcohol such as an alkyl or allyl alcohol
  • the alcohol is preferably selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, hydrobenzoin, and mixtures thereof.
  • an organic amine e.g., an alkylamine, a benzoamine or a diamine, or an ammonium hydroxide salt
  • the alkali is preferably selected from the group consisting of 2-(2-aminoethylamino)ethanol of Formula 1, l,l,3,3-tetrakis(methoxymethyl) urea of Formula 2, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and mixtures thereof.
  • the micropattern-forming resin composition of the present invention preferably comprises 50 to 99% by weight of the aqueous alcoholic or alkaline solution and 10 to 50% by weight of the water-soluble polymer.
  • the water-soluble polymer is present in an amount of less than 1% by weight, it is insufficiently entangled with a photoresist resin.
  • the water-soluble polymer is present in an amount of more than 50% by weight, there is a problem in that the micropattern-forming resin composition cannot be readily coated on the surface of a photoresist pattern layer.
  • the aqueous solution preferably contains 0.1 to 5 parts by weight and more preferably 0.5 to 1 part by weight of the alcohol or alkali, based on 100 parts by weight of water.
  • the use of the alcohol or alkali in an amount of less than 0.1 parts by weight causes unsatisfactory swelling of a resin constituting a photoresist pattern layer. Meanwhile, the use of the alcohol or alkali in an amount of more than 5 parts by weight may cause dissolution of a resin constituting a photoresist pattern layer, leading to a collapse of the pattern.
  • the present invention is directed to a method for forming a micropattern, the method comprising the steps of a) forming a photoresist resin layer on a substrate, b) light-exposing and developing the photoresist resin layer to form a photoresist pattern layer, c) applying the micropattern-forming resin composition to the surface of the photoresist pattern layer, d) inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, e) inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and f) removing portions of the water-soluble polymer other than the entangled portions using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent.
  • FIG. 1 illustrating the formation of a micropattern using a KrF resist.
  • FIG. 1 shows conceptual diagrams illustrating respective steps (a) to (f) of a method for forming a micropattern by applying the micropattern-forming resin composition of the present invention to the surface of a KrF resist pattern layer to induce swelling of a resin constituting the resist pattern layer and entanglement between the soluble polymer and the swollen photoresist resin layer.
  • the KrF resist resin layer 2 is formed on a substrate 1, such as a semiconductor substrate (step a). Then, the photoresist resin layer 2 is irradiated with a KrF eximer laser as a light source using a photomask (not shown), exposed and developed to form a resist pattern layer 3 (step b).
  • the micropattern-forming resin composition of the present invention is applied to the resist pattern layer 3 to form a coating layer 4 (step c).
  • the aqueous alcoholic or alkaline solution contained in the coating layer 4 induces a swelling phenomenon of the surface of the resist pattern layer 3 to form a swollen resist pattern layer 5 (step d).
  • step e entanglement between chains of the water-soluble polymer of the micropattern-forming resin composition and the coating layer is induced to form an entangled layer 6 at the interface between the coating layer 4 and the swollen photoresist pattern layer 5 (step e).
  • portions of the coating layer 4 in which no entanglement is induced are removed using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent to form a micropattern in which the width (CD ) of a recessed portion of the photoresist pattern layer is reduced (step f).
  • a micropattern formed by the method can be used to fabricate a semiconductor integrated circuit device. Specifically, after a micropattern is formed on a substrate, such as a silicon wafer, by the method, patterning is performed using the micropattern as a mask pattern to form a pattern on the substrate. Etching may be employed for the patterning.
  • the present invention provides a semiconductor integrated circuit device comprising a pattern formed using the micropattern.
  • the weight-average molecular weight of the polymer was measured to be 7OK.
  • an organic ARC was coated on a silicon wafer.
  • a KrF photoresist was coated on the silicon wafer, exposed using exposure system (ASML800, NA 0.93), and developed to obtain a patterned substrate on which an L/S pattern having a CD of a minimum of 179 nm and a maximum of 183 nm was formed.
  • each of the micropattern-forming resin compositions prepared in Examples 1 to 12 was coated on the patterned substrate, followed by drying. [99] Thereafter, development was performed by dipping the coated substrate in distilled water. The critical dimension (CD) of the pattern was measured using a FE-SEM and the value was represented as CD (CD is the CD value of the patterned substrate before coating with each of the micropattern-forming resin compositions). The obtained results are shown in Table 3.
  • the resin compositions of the present invention for example, the resin compositions prepared in Examples 23 and 24, comprise no unit causing crosslinking
  • the reduction in the width of recessed portions of the micropatterns was due to a new type of mechanism different from known chemical crosslinking mechanisms. That is, this phenomenon was attributed to physical bonding between chains of the water-soluble polymers on a molecular level.
  • the foregoing examples clearly support that variation in CD A values arising from the control over the molecular weight of the water-soluble polymers having the same composition was associated with a physical mechanism due to a swelling phenomenon of the photoresist resin and an entanglement phenomenon between the photoresist resin and the water-soluble polymers, rather than a chemical crosslinking mechanism.
  • Example 19 The procedure of Example 19 was repeated, except that each of the micropattern- forming resin compositions prepared in Comparative Examples 1 and 2 was coated on a substrate instead of the micropattern-forming resin composition prepared in Example 7.
  • the micropattern-forming resin composition of the present invention is used for a lithographic process, the aqueous alcoholic or alkaline solution serves to induce a swelling phenomenon of a photoresist pattern layer and the water-soluble polymer serves to induce an entanglement phenomenon between the swollen photoresist pattern layer and the water-soluble polymer, resulting in a reduction in the width of recessed portions of the photoresist pattern layer. Therefore, the use of the micropattern-forming resin composition according to the present invention enables the formation of a mi- cropattern that overcomes the limitation of wavelength.

Abstract

Disclosed is a micropattern-forming resin composition that can be used to reduce the area or width of recessed portions in a semiconductor lithographic process. The resin composition is coated on a photoresist pattern layer and comprises an aqueous alcoholic or alkaline solution and a water-soluble polymer. The resin composition can be used reduce the width of recessed portions of the photoresist pattern layer. Therefore, the use of the resin composition enables the formation of a micropattern that overcomes the limitation of wavelength.

Description

Description
MICROPATTERN-FORMING RESIN COMPOSITION AND METHOD FOR FORMING MICROPATTERN USING THE
SAME
Technical Field
[1] The present invention relates to a micropattern-forming resin composition that can be used to reduce the area or width of recessed portions in a semiconductor lithographic process. Background Art
[2] In recent years, high integration of semiconductor devices has resulted in a considerable reduction in the line width of lines necessary for the fabrication of the semiconductor devices and the distance between the lines. General processes required to develop semiconductor devices are largely classified into lithography, etching, cleaning, ion implantation, thin film formation, metal line formation, and other processes. Of these, patterning techniques are the most important in lithographic processes and provide the motive power for ultra-large scale integration of semiconductor devices.
[3] Typical lithographic processes involve formation of a patterned resist layer by patternwise exposing a radiation- sensitive resist to an imaging radiation. The image is subsequently developed by contacting the exposed resist layer with a material (typically an aqueous alkaline developer) to selectively remove portions of the resist layer to reveal the desired pattern. The pattern is subsequently transferred to an underlying material by etching the material in openings of the patterned resist layer. After completion of the transfer, the remaining resist layer is removed.
[4] Lithographic techniques require irradiation with light of shorter wavelength and development of high-resolution resist materials depending on the characteristics of the light. However, improvements of exposure systems are needed to shorten the wavelength of light, thus incurring considerable costs. In addition, it is not easy to develop resist materials in response to short-wavelength light for exposure.
[5] In particular, conventional lithographic techniques have limitations in improving the degree of integration through micropatterning due to limited wavelength of light for exposure. Some attempts to overcome these limitations have been proposed. For example, Japanese Patent No. 3,071,401 suggests a micropattern-forming material which uses a water-soluble resin causing a crosslinking reaction with a resist in the presence of an acid to form a crosslinked film at the interface between a resist pattern and the micropattern-forming material by the acid supplied from the resist pattern and to strip the uncrosslinked portions.
[6] However, when the material is used to form a pattern, the resist pattern may be deformed by the action of an internal stress resulting from volume shrinkage of the resin during the crosslinking reaction. There is thus a demand for a micropattern- forming material with a new type of mechanism that is capable of overcoming the limitations of conventional materials. Disclosure of Invention Technical Problem
[7] The present invention has been made in view of the problems of the prior art, and it is an object of the present invention to provide a micropattern-forming material with a new type of mechanism that overcomes the limitation of wavelength in the miniaturization of a pattern, such as an isolation pattern or a hole pattern. Technical Solution
[8] The present inventors have earnestly and intensively conducted research to achieve the object. As a result, the present inventors have found that an aqueous alcoholic or alkaline solution is used to induce swelling of a photoresist pattern layer and a water- soluble polymer is used to induce entanglement between the swollen photoresist pattern layer and the water-soluble polymer so that the width of recessed portions of the photoresist pattern layer can be reduced. The present invention has been achieved based on this finding.
[9] According to the present invention, there is provided a micropattern-forming resin composition comprising a water-soluble polymer and a solvent wherein a micropattern is formed by coating the resin composition on a photoresist pattern layer, inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and removing portions of the water-soluble polymer other than the entangled portions using a developing solution.
[10] In an embodiment of the present invention, the solvent may be an aqueous alcoholic or alkaline solution.
[11] In a further embodiment of the present invention, the water-soluble polymer may be a homopolymer composed of a hydrophilic monomer unit or a copolymer composed of two or more hydrophilic monomer units.
[12] In another embodiment of the present invention, the water-soluble polymer may be a copolymer composed of at least one hydrophilic monomer unit and at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotri- imidazole, vinyltriimidazole and vinyltetraimidazole.
[13] In another embodiment of the present invention, the water-soluble polymer may be a copolymer composed of at least one hydrophilic monomer unit and at least one (meth)acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups.
[14] In another embodiment of the present invention, the hydrophilic monomer unit of the water-soluble polymer may have at least one functional group selected from the group consisting of hydroxyl, carboxylic acid, amide, amine, heterocyclic, ether, ester, acetal and sulfonic acid groups.
[15] In another embodiment of the present invention, the hydrophilic monomer unit of the water-soluble polymer may be selected from the group consisting of vinyl alcohol, vinyl carbohydrate, acrylic acid, methacrylic acid, ethylene oxide, vinylhydroxyethyl methacrylate, benzoacrylic acid, vinylpyrrolidone, vinylamine, allylamine, vinylimidazole, vinyloxazoline, and combinations thereof.
[16] In another embodiment of the present invention, the ratio of the number of the hydrophilic monomer unit to the number of the at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinyl- benzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinyltetraimidazole may be between 1 : 0.01 and 1 : 0.5.
[17] In another embodiment of the present invention, the ratio of the number of the hydrophilic monomer unit to the number of the (meth) acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups may be between 1 : 0.01 and 1 : 0.5.
[18] In another embodiment of the present invention, the water-soluble polymer may have a weight- average molecular weight (M ) of 5,000 to 1,000,000.
[19] In another embodiment of the present invention, the alcohol may be selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, hydrobenzoin, and mixtures thereof. [20] In another embodiment of the present invention, the alkali may be an organic amine or an ammonium hydroxide salt. [21] In another embodiment of the present invention, the alkali may be selected from the group consisting of 2-(2-aminoethylamino)ethanol, l,l,3,3-tetrakis(methoxymethyl)urea, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and mixtures thereof. [22] In another embodiment of the present invention, the micropattern-forming resin composition may comprise 50 to 99% by weight of the aqueous alcoholic or alkaline solution and 1 to 50% by weight of the water-soluble polymer. [23] In yet another embodiment of the present invention, the aqueous solution may contain 0.1 to 5 parts by weight of the alcohol or alkali, based on 100 parts by weight of water.
[24] According to the present invention, there is also provided a method for forming a micropattern, the method comprising the steps of a) forming a photoresist resin layer on a substrate, b) light-exposing and developing the photoresist resin layer to form a photoresist pattern layer, c) applying the micropattern-forming resin composition to the surface of the photoresist pattern layer, d) inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, e) inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and f) removing portions of the water-soluble polymer other than the entangled portions using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent.
[25] According to the present invention, there is also provided a micropattern formed by the method.
[26] According to the present invention, there is also provided a semiconductor integrated circuit device comprising a pattern formed using the micropattern. Brief Description of the Drawings
[27] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawing, in which:
[28] FIG. 1 shows conceptual diagrams illustrating respective steps of a method for forming a micropattern by applying a micropattern-forming resin composition of the present invention to the surface of a resist pattern layer. Best Mode for Carrying Out the Invention
[29] The present invention will now be described in greater detail.
[30] The present invention is directed to a micropattern-forming resin composition that is coated on a photoresist pattern. The micropattern-forming resin composition of the present invention comprises an aqueous alcoholic or alkaline solution and a water- soluble polymer.
[31] The aqueous alcoholic or alkaline solution serves to induce a swelling phenomenon of the surface of a photoresist pattern layer, and the water-soluble polymer in contact with the surface of the photoresist pattern layer serves to induce entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition to form an insoluble film. Portions of the micropattern-forming resin composition in which no entanglement is reduced are removed by water, an aqueous alkaline solution or an aqueous solution containing an organic solvent as a developing solution. [32] The water-soluble polymer is a homopolymer composed of a hydrophilic monomer unit or a copolymer composed of two or more hydrophilic monomer units.
[33] The hydrophilic monomer unit of the water-soluble polymer preferably has at least one functional group selected from the group consisting of hydroxyl, carboxylic acid, amide, amine, heterocyclic, ether, ester, acetal and sulfonic acid groups. More specifically, vinyl alcohol, vinyl carbohydrate, vinylhydroxyethyl methacrylate or the like may be used as the monomer having a hydroxyl group; acrylic acid, methacrylic acid, benzoacrylic acid or the like may be used as the monomer having a carboxylic acid group; vinylamine, allylamine or the like may used as the monomer having an amine group; and vinylpyrrolidone, vinyloxazoline, vinylimidazole or the like may be used as the monomer having a heterocyclic group. Ethylene oxide may also be used as the hydrophilic monomer unit.
[34] As the water-soluble polymer, there can be used a homopolymer composed of one of the hydrophilic monomer units and a copolymer composed of two or more kinds of the hydrophilic monomer units.
[35] As the water-soluble polymer, there can be used a copolymer composed of at least one hydrophilic monomer unit and a monomer unit having an affinity for a resin constituting the photoresist pattern. In this case, the monomer unit having an affinity for a resin constituting the photoresist pattern may be selected depending on the kind of the photoresist pattern layer.
[36] For example, in the case where the photoresist pattern layer is formed of a KrF photoresist comprising polyhydroxystyrene, a monomer unit having an affinity for the resin constituting the photoresist pattern may be selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinyl- methylimidazole, vinyldiaminotriimidazole, vinyltriimidazole, vinyltetraimidazole, and mixtures thereof.
[37] In the case where the photoresist pattern layer is formed of an ArF photoresist comprising an alicyclic compound, a monomer unit having an affinity for the resin constituting the photoresist pattern may be at least one (meth)acrylic monomer having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups.
[38] The hydrophilic monomer unit may be copolymerized with the monomer unit having an affinity for a resin constituting the photoresist pattern by various processes, for example, random copolymerization, block copolymerization and graft copoly- merization, so long as the water solubility of the water-soluble polymer is not impaired. Random copolymerization is preferred.
[39] In the case where the water-soluble polymer is a copolymer composed of the hydrophilic monomer unit and a monomer unit having an affinity for a resin constituting the photoresist pattern, the ratio of the number of the hydrophilic monomer unit to the number of the monomer unit having an affinity for a resin constituting the photoresist pattern is preferably between 1 : 0.01 and 1 : 0.5. If the monomer unit having an affinity for a resin constituting the photoresist pattern is used in a relatively small amount, entanglement between the soluble polymer and the photoresist resin is not readily induced. Meanwhile, if the monomer unit having an affinity for a resin constituting the photoresist pattern is used in a relatively large amount, there is the problem that the water solubility of the water-soluble polymer may be impaired. [40] So long as the effects of the present invention are not impaired, the molecular weight of the water-soluble polymer may be optionally determined. To maximize entanglement effects between the water-soluble polymer and the photoresist resin after being applied while ensuring effective water solubility and coatability of the water- soluble polymer, the weight- average molecular weight (M ) of the water-soluble polymer is preferably adjusted to the range of 5,000 to 1,000,000 and more preferably to the range of 30,000 to 100,000. When the water-soluble polymer has a weight- average molecular weight (M ) lower than 5,000, entanglement between the water- soluble polymer and the swollen photoresist resin is not sufficient. Meanwhile, when the water-soluble polymer has a weight-average molecular weight (M ) higher than 1,000,000, the water solubility of the water-soluble polymer is poor and aggregation of the water-soluble polymer occurs when being applied, resulting in a non-uniform coating.
[41] Any photosensitive resin that can constitute the resist pattern may be used in the present invention. For example, in the case of a KrF photoresist comprising polyhy- droxystyrene, hydroxyl groups of the polyhydroxystyrene are partially substituted with ethyl vinyl ether groups as acid- labile protecting groups. In the case of an ArF photoresist comprising an alicyclic compound, the alicyclic compound is substituted with acid-labile protecting groups. The KrF photoresist and the ArF photoresist are water-insoluble organic polymers.
[42] In both cases, since the water- insoluble organic polymers present on the surface of a patterned layer are partially deprotected, the polymers may be soluble in a high- concentration aqueous alcoholic or alkaline solution. However, as will be explained below, the surface of the photoresist pattern layer can be swollen without being completely dissolved by controlling the alcohol or alkali content of the aqueous alcoholic or alkaline solution.
[43] In addition to control over the alcohol or alkali content, the molecular weight of the water-soluble polymer can be controlled to vary the degree of insolubility of the water- soluble polymer arising from the entanglement, and as a result, the degree of reduction of the distance between patterned portions or the size of hole openings can be controlled. For example, a water-soluble polymer having a weight-average molecular weight of about 7OK was used to reduce the width of recessed portions of a photoresist pattern layer having a width of about 40 nm in the Example section that follows.
[44] The water-soluble resin composition of the present invention comprises an aqueous alcoholic or alkaline solution. The aqueous alcoholic or alkaline solution penetrates the surface of a resin constituting a photoresist pattern layer to swell the resin. Accordingly, the kind of the aqueous alcoholic or alkaline solution is not particularly restricted so long as the alcohol or alkali is soluble in water.
[45] As the alcohol contained in the aqueous solution, a water-soluble alcohol, such as an alkyl or allyl alcohol, may be used. Specifically, the alcohol is preferably selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, hydrobenzoin, and mixtures thereof.
[46] As the alkali contained in the aqueous solution, an organic amine, e.g., an alkylamine, a benzoamine or a diamine, or an ammonium hydroxide salt may be used. Specifically, the alkali is preferably selected from the group consisting of 2-(2-aminoethylamino)ethanol of Formula 1, l,l,3,3-tetrakis(methoxymethyl) urea of Formula 2, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and mixtures thereof.
[47]
HOx ^ ^. NH2 -^ NH ^^
(1) [48]
Figure imgf000009_0001
(2)
[49] The micropattern-forming resin composition of the present invention preferably comprises 50 to 99% by weight of the aqueous alcoholic or alkaline solution and 10 to 50% by weight of the water-soluble polymer. When the water-soluble polymer is present in an amount of less than 1% by weight, it is insufficiently entangled with a photoresist resin. Meanwhile, when the water-soluble polymer is present in an amount of more than 50% by weight, there is a problem in that the micropattern-forming resin composition cannot be readily coated on the surface of a photoresist pattern layer.
[50] The aqueous solution preferably contains 0.1 to 5 parts by weight and more preferably 0.5 to 1 part by weight of the alcohol or alkali, based on 100 parts by weight of water. The use of the alcohol or alkali in an amount of less than 0.1 parts by weight causes unsatisfactory swelling of a resin constituting a photoresist pattern layer. Meanwhile, the use of the alcohol or alkali in an amount of more than 5 parts by weight may cause dissolution of a resin constituting a photoresist pattern layer, leading to a collapse of the pattern.
[51] The present invention is directed to a method for forming a micropattern, the method comprising the steps of a) forming a photoresist resin layer on a substrate, b) light-exposing and developing the photoresist resin layer to form a photoresist pattern layer, c) applying the micropattern-forming resin composition to the surface of the photoresist pattern layer, d) inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, e) inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and f) removing portions of the water-soluble polymer other than the entangled portions using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent.
[52] Hereinafter, the method of the present invention will be specifically explained with reference to FIG. 1 illustrating the formation of a micropattern using a KrF resist.
[53] FIG. 1 shows conceptual diagrams illustrating respective steps (a) to (f) of a method for forming a micropattern by applying the micropattern-forming resin composition of the present invention to the surface of a KrF resist pattern layer to induce swelling of a resin constituting the resist pattern layer and entanglement between the soluble polymer and the swollen photoresist resin layer.
[54] As shown in FIG. 1, the KrF resist resin layer 2 is formed on a substrate 1, such as a semiconductor substrate (step a). Then, the photoresist resin layer 2 is irradiated with a KrF eximer laser as a light source using a photomask (not shown), exposed and developed to form a resist pattern layer 3 (step b). The micropattern-forming resin composition of the present invention is applied to the resist pattern layer 3 to form a coating layer 4 (step c). The aqueous alcoholic or alkaline solution contained in the coating layer 4 induces a swelling phenomenon of the surface of the resist pattern layer 3 to form a swollen resist pattern layer 5 (step d). At this time, entanglement between chains of the water-soluble polymer of the micropattern-forming resin composition and the coating layer is induced to form an entangled layer 6 at the interface between the coating layer 4 and the swollen photoresist pattern layer 5 (step e). Next, portions of the coating layer 4 in which no entanglement is induced are removed using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent to form a micropattern in which the width (CD ) of a recessed portion of the photoresist pattern layer is reduced (step f).
[55] A micropattern formed by the method can be used to fabricate a semiconductor integrated circuit device. Specifically, after a micropattern is formed on a substrate, such as a silicon wafer, by the method, patterning is performed using the micropattern as a mask pattern to form a pattern on the substrate. Etching may be employed for the patterning.
[56] The present invention provides a semiconductor integrated circuit device comprising a pattern formed using the micropattern. Mode for the Invention
[57] Hereinafter, the present invention will be explained in more detail with reference to the following examples. However, these examples are given for the purpose of illustration and are not intended to limit the present invention.
[58]
[59] EXAMPLES
[60] [Synthesis Example 1] (Synthesis of water-soluble polymer 1 (M = 5K))
[61] 300 ml of isopropyl alcohol was put into a 500 ml three-neck flask, stirred under a nitrogen atmosphere for one hour, and refluxed at 7O0C. 71.94g of N-vinylpyrrolidone, 13.60g of 4-vinylpyridine, 2.56g of dimethyl-2,2'-azobis-2-methylpropionate and 50 ml of isopropyl alcohol were added to the flask. The mixture was stirred for 4 hours. The reaction solution was cooled to room temperature and concentrated to a volume of less than a half of the initial volume by distillation in vacuo. 500 ml of diethyl ether was added to the concentrate to obtain a precipitate. The precipitate was filtered, washed and purified three times using diethyl ether, and dried in an oven, yielding 80.53g of poly(vinylpyrrolidone-co-vinylpyridine) of Formula 3.
[62]
Figure imgf000011_0001
(3) [63] The weight- average molecular weight of the copolymer was measured to be 5K
(m/n = 0.2). [64] [65] [Synthesis Example 2] (Synthesis of water-soluble polymer 2 (M = 10K))
[66] 80.53g of poly(vinylpyrrolidone-co-vinylpyridine) was synthesized in the same manner as in Synthesis Example 1, except that 1.5g of dimethyl- 2,2'-azobis-2-methylpropionate was used as an initiator. The weight-average molecular weight of the copolymer was measured to be 10K.
[67]
[68] [Synthesis Example 3] (Synthesis of water-soluble polymer 3 (M = 20K))
[69] 70.7Og of poly(vinylpyrrolidone-co-vinylpyridine) was synthesized in the same manner as in Synthesis Example 1, except that 0.7g of dimethyl- 2,2'-azobis-2-methylpropionate was used as an initiator. The weight-average molecular weight of the copolymer was measured to be 2OK.
[70]
[71] [Synthesis Example 4] (Synthesis of water-soluble polymer 4 (M = 70K))
[72] 78.43g of poly(vinylpyrrolidone-co-vinylpyridine) was synthesized in the same manner as in Synthesis Example 1, except that 0.2g of dimethyl- 2,2'-azobis-2-methylpropionate was used as an initiator. The weight-average molecular weight of the copolymer was measured to be 7OK.
[73]
[74] [Synthesis Example 5] (Synthesis of water-soluble polymer 5 (M = 150K))
[75] 80.33g of poly(vinylpyrrolidone-co-vinylpyridine) was synthesized in the same manner as in Synthesis Example 1, except that O.lg of dimethyl- 2,2'-azobis-2-methylpropionate was used as an initiator. The weight-average molecular weight of the copolymer was measured to be 150K.
[76]
[77] [Synthesis Example 6] (Synthesis of water-soluble polymer 6 (M = 70K))
[78] 110.5g of polyvinylimidazole (Formula 4) was synthesized in the same manner as in Synthesis Example 1, except that 0.7g of dimethyl-2,2'-azobis-2-methylpropionate as an initiator and 127.3g of vinylimidazole were used.
[79]
Figure imgf000012_0001
(4)
[80] The weight- average molecular weight of the polymer was measured to be 7OK.
[81] [82] [Synthesis Example 7] (Synthesis of water-soluble polymer 7 (M = 70K))
[83] 155.85g of polyhydroxyethyl methacrylate (Formula 5) was synthesized in the same manner as in Synthesis Example 1, except that 0.7g of dimethyl- 2,2'-azobis-2-methylpropionate as an initiator and 167.5g of hydroxy ethyl methacrylate were used.
[84]
Figure imgf000013_0001
(5)
[85] The weight- average molecular weight of the polymer was measured to be 7OK. [86] [87] [Examples 1 to 12] [88] In accordance with the compositions indicated in Table 1, the water-soluble polymers prepared in Synthesis Examples 1 to 7 were used to prepare micropattern- forming resin compositions.
[89] Table 1
Figure imgf000013_0002
[90] [91] [Comparative Examples 1 and 2] [92] As indicated in Table 2, 1Og of the water-soluble polymer prepared in Synthesis Example 4, lOOg of water and different amounts (0.05g and 1Og) of 2-(2-aminoethylamino)ethanol were used to prepare micropattern-forming resin compositions.
[93] Table 2
Figure imgf000014_0001
[94] [95] [Examples 13 to 24] [96] Lithographic experiments were conducted using the respective micropattern- forming resin compositions prepared in Examples 1 to 12 in accordance with the following procedure.
[97] First, an organic ARC was coated on a silicon wafer. A KrF photoresist was coated on the silicon wafer, exposed using exposure system (ASML800, NA 0.93), and developed to obtain a patterned substrate on which an L/S pattern having a CD of a minimum of 179 nm and a maximum of 183 nm was formed.
[98] Next, each of the micropattern-forming resin compositions prepared in Examples 1 to 12 was coated on the patterned substrate, followed by drying. [99] Thereafter, development was performed by dipping the coated substrate in distilled water. The critical dimension (CD) of the pattern was measured using a FE-SEM and the value was represented as CD (CD is the CD value of the patterned substrate before coating with each of the micropattern-forming resin compositions). The obtained results are shown in Table 3.
[100] Table 3
Figure imgf000014_0002
[101] [102] As can be seen from the results of Table 3, an increase in the molecular weight of the water-soluble polymers gave a greater contribution to the formation of mi- cropatterns. This is attributed to enhanced entanglement effects with increasing molecular weight of the water-soluble polymers.
[103] Since the resin compositions of the present invention, for example, the resin compositions prepared in Examples 23 and 24, comprise no unit causing crosslinking, the reduction in the width of recessed portions of the micropatterns was due to a new type of mechanism different from known chemical crosslinking mechanisms. That is, this phenomenon was attributed to physical bonding between chains of the water-soluble polymers on a molecular level. The foregoing examples clearly support that variation in CD A values arising from the control over the molecular weight of the water-soluble polymers having the same composition was associated with a physical mechanism due to a swelling phenomenon of the photoresist resin and an entanglement phenomenon between the photoresist resin and the water-soluble polymers, rather than a chemical crosslinking mechanism.
[104]
[105] [Comparative Examples 3 and 4]
[106] The procedure of Example 19 was repeated, except that each of the micropattern- forming resin compositions prepared in Comparative Examples 1 and 2 was coated on a substrate instead of the micropattern-forming resin composition prepared in Example 7.
[107] Table 4
Figure imgf000015_0001
[108]
[109] As evident from the results of Table 4, the pattern (Comparative Example 3) formed using the micropattern-forming resin composition prepared in Comparative Example 1 showed a slight decrease (2 nm) in CD and the pattern (Comparative Example 4) formed using the micropattern-forming resin composition prepared in Comparative Example 2 collapsed, making it impossible to measure the CD of the pattern.
[110] These results lead to the conclusion that the use of the alkali in an amount of less than 0.1 parts by weight with respect to 100 parts by weight of water had little influence on the formation of a micropattern and the use of the alkali in an amount of more than 5 parts by weight caused collapse of a pattern.
[I l l] Although the L/S patterns have been explained with reference to the foregoing examples, the present invention is not limited thereto and can be applied to the formation of various kinds of patterns, including hole patterns. Industrial Applicability
[112] The micropattern-forming resin composition of the present invention is used for a lithographic process, the aqueous alcoholic or alkaline solution serves to induce a swelling phenomenon of a photoresist pattern layer and the water-soluble polymer serves to induce an entanglement phenomenon between the swollen photoresist pattern layer and the water-soluble polymer, resulting in a reduction in the width of recessed portions of the photoresist pattern layer. Therefore, the use of the micropattern-forming resin composition according to the present invention enables the formation of a mi- cropattern that overcomes the limitation of wavelength.

Claims

Claims
[1] A micropattern-forming resin composition comprising a water-soluble polymer and a solvent wherein a micropattern is formed by coating the resin composition on a photoresist pattern layer, inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer, inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition, and removing portions of the water- soluble polymer other than the entangled portions using a developing solution.
[2] The composition according to claim 1, wherein the solvent is an aqueous alcoholic or alkaline solution.
[3] The composition according to claim 1, wherein the water-soluble polymer is a homopolymer composed of a hydrophilic monomer unit or a copolymer composed of two or more hydrophilic monomer units.
[4] The composition according to claim 1, wherein the water-soluble polymer is a copolymer composed of at least one hydrophilic monomer unit and at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinyl- methylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinylte- traimidazole.
[5] The composition according to claim 1, wherein the water-soluble polymer is a copolymer composed of at least one hydrophilic monomer unit and at least one (meth)acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl and isobornyl groups.
[6] The composition according to any one of claims 3 to 5, wherein the hydrophilic monomer unit of the water-soluble polymer has at least one functional group selected from the group consisting of hydroxyl, carboxylic acid, amide, amine, heterocyclic, ether, ester, acetal and sulfonic acid groups.
[7] The composition according to any one of claims 3 to 5, wherein the hydrophilic monomer unit of the water-soluble polymer is selected from the group consisting of vinyl alcohol, vinyl carbohydrate, acrylic acid, methacrylic acid, ethylene oxide, vinylhydroxyethyl methacrylate, benzoacrylic acid, vinylpyrrolidone, vinylamine, allylamine, vinylimidazole, vinyloxazoline, and combinations thereof.
[8] The composition according to claim 4, wherein the ratio of the number of the hydrophilic monomer unit to the number of the at least one monomer unit selected from the group consisting of vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinyltetraimidazole is between 1 : 0.01 and 1 : 0.5.
[9] The composition according to claim 5, wherein the ratio of the number of the hy- drophilic monomer unit to the number of the (me th) acrylic monomer unit is between 1 : 0.01 and 1 : 0.5.
[10] The composition according to claim 1, wherein the water-soluble polymer has a weight-average molecular weight (M ) of 5,000 to 1,000,000.
[11] The composition according to claim 2, wherein the alcohol is selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, hydrobenzoin, and mixtures thereof.
[12] The composition according to claim 2, wherein the alkali is an organic amine or an ammonium hydroxide salt.
[13] The composition according to claim 2, wherein the alkali is selected from the group consisting of 2-(2-aminoethylamino)ethanol,
1 , 1 ,3,3-tetrakis(methoxymethyl)urea, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and mixtures thereof.
[14] The composition according to claim 1, wherein the composition comprises 50 to
99% by weight of the solvent and 1 to 50% by weight of the water-soluble polymer.
[15] The composition according to claim 2, wherein the aqueous solution contains 0.1 to 5 parts by weight of an alcohol or alkali, based on 100 parts by weight of water.
[16] A method for forming a micropattern, the method comprising the steps of: a) forming a photoresist resin layer on a substrate; b) light-exposing and developing the photoresist resin layer to form a photoresist pattern layer; c) applying the micropattern-forming resin composition according to claim 1 to the surface of the photoresist pattern layer; d) inducing swelling of the surface of the photoresist pattern layer to form a swollen photoresist pattern layer; e) inducing entanglement at the interface between the swollen photoresist pattern layer and the micropattern-forming resin composition; and f) removing portions of the water-soluble polymer other than the entangled portions using water, an aqueous alkaline solution or an aqueous solution containing an organic solvent.
[17] A micropattern formed by the method according to claim 16.
[18] A semiconductor integrated circuit device comprising a pattern formed using the micropattern according to claim 17.
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CN112108348A (en) * 2020-09-23 2020-12-22 苏州太阳井新能源有限公司 Preparation method of graphical material
CN112108348B (en) * 2020-09-23 2022-03-04 苏州太阳井新能源有限公司 Preparation method of graphical material

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