WO2011027882A1 - Photocurable composition for pattern formation, and method for measuring film thickness using same - Google Patents

Photocurable composition for pattern formation, and method for measuring film thickness using same Download PDF

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Publication number
WO2011027882A1
WO2011027882A1 PCT/JP2010/065220 JP2010065220W WO2011027882A1 WO 2011027882 A1 WO2011027882 A1 WO 2011027882A1 JP 2010065220 W JP2010065220 W JP 2010065220W WO 2011027882 A1 WO2011027882 A1 WO 2011027882A1
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Prior art keywords
photocurable composition
fluorescence
pattern
absorption
fluorescent material
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PCT/JP2010/065220
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French (fr)
Japanese (ja)
Inventor
信支 坂井
玉乃 平澤
敬 小林
勝 中川
Original Assignee
東洋合成工業株式会社
国立大学法人東北大学
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Priority to JP2011529966A priority Critical patent/JPWO2011027882A1/en
Publication of WO2011027882A1 publication Critical patent/WO2011027882A1/en

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    • 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
    • H01L21/0274—Photolithographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00—Measuring arrangements characterised by the use of optical techniques
    • G01B11/02—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0625—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating with measurement of absorption or reflection
    • G01B11/0633—Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating with measurement of absorption or reflection using one or more discrete wavelengths
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
    • H01L22/10—Measuring as part of the manufacturing process
    • H01L22/12—Measuring as part of the manufacturing process for structural parameters, e.g. thickness, line width, refractive index, temperature, warp, bond strength, defects, optical inspection, electrical measurement of structural dimensions, metallurgic measurement of diffusions

Definitions

  • the present invention relates to a photocurable composition for pattern formation used when forming a photocured product having a pattern by photoimprint lithography, and a method for measuring the film thickness of a photocured product having a pattern formed using the same. is there.
  • Optical nanoimprint lithography is a process in which a mold having a fine concavo-convex pattern is pressed against a transfer material such as a resist provided on a substrate to fill the transfer material into the mold pattern, and then the mold is released from the transfer material. By doing so, a pattern in which the concave / convex pattern of the mold is transferred to the transfer material is formed (see, for example, Patent Document 1).
  • the present invention provides a photocurable composition for pattern formation that can easily and easily measure the film thickness of a photocured product having a concavo-convex pattern in a non-destructive and non-contact manner, and It is an object to provide a film thickness measurement method using this.
  • a transfer material layer is sandwiched between a substrate and a mold having a concavo-convex pattern, the concavo-convex pattern of the mold is filled with the transfer material layer, and is exposed and cured.
  • a photocurable composition that can be used as the transfer material layer for forming a pattern after the mold is released, and has an absorption wavelength region that emits fluorescence within a range from an ultraviolet region to a visible light region.
  • the photocurable composition for pattern formation is characterized in that it is substantially absent in part and substantially absent in at least a part of the wavelength region of fluorescence emitted by the fluorescent substance.
  • the product of the molar extinction coefficient at the maximum value of the absorption wavelength at which the fluorescent substance emits fluorescence and the fluorescent quantum yield of the fluorescent substance is 1 ⁇ 10 4 or more.
  • the absorption of the photocured material other than the phosphor in the photocured composition obtained by exposing the photocurable composition to a wavelength in an absorption wavelength region in which the phosphor emits fluorescence substantially
  • the maximum value of the fluorescence intensity emitted before exposing the transfer material layer is A1
  • the maximum value of the fluorescence intensity emitted after being exposed and cured is A2
  • the value of A2 / A1 is 0.6 or more.
  • the photocured material having a concavo-convex pattern produced using the photocurable composition for formation is irradiated with light having a wavelength within an absorption wavelength region where the fluorescent material emits fluorescence, and from the intensity of the emitted fluorescence,
  • a thickness measurement method is characterized in that the thickness of at least one of a convex portion or a concave portion of a photocured product having an uneven pattern is obtained.
  • the film thickness measuring method according to the fourth aspect, wherein the thickness of each of the convex portions and concave portions of the photocured product having the concavo-convex pattern is in the range of 1 nm to 20 ⁇ m. It is in.
  • a sixth aspect of the present invention is the film according to the fourth or fifth aspect, wherein the width of at least one of the convex part or concave part of the photocured product having the concave / convex pattern is in the range of 10 nm to 100 ⁇ m. It is in the thickness measurement method.
  • the film thickness of the photocured product having a concavo-convex pattern to be formed can be measured in a short time and non-destructively. can do.
  • the photocurable composition for pattern formation of the present invention is formed into a concavo-convex pattern of a mold by sandwiching a transfer material layer made of a photocurable composition, that is, a photocurable composition, between a substrate and a mold having a concavo-convex pattern.
  • the material to be transferred is filled, exposed and cured to form, and then the mold is released to obtain a photocured product having an uneven pattern.
  • Those not in substantially the department. it comprises a predetermined photocurable component, a fluorescent material, and an additive that is added as necessary.
  • the photocurable component refers to a component that reacts and cures upon exposure. Specifically, if it is a photodimerization-type photocurable composition, it may be a photocrosslinkable photocurable composition such as a resin having a photodimer group such as a cinnamic acid ester resin or a cyclized rubber-bisazide.
  • a photopolymerizable photocurable composition such as a photocrosslinking agent and a polymer such as a cyclized rubber, an ene / thiol type, a radical, or a cation is a compound having a photopolymerizable group and a photopolymerization initiator.
  • the photo-curing component is most preferable as the photo-curable component.
  • the compound having a photopolymerizable group refers to a compound having a radical polymerizable group or a cationic polymerizable group.
  • the radical polymerizable group include acryloyl group, methacryloyl group, vinyl group and allyl group.
  • the cationic polymerizable group include an epoxy group, a vinyloxy group, and an oxetanyl group.
  • Examples of the compound having a radical polymerizable group include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) ) Acrylates, (meth) acrylates such as t-butyl (meth) acrylate, (meth) acrylamides such as morpholine (meth) acrylamide, monofunctional radical polymerizable compounds such as N-vinylpyrrolidone, N-vinylcaprolactone and styrene Trimethylolpropane tri (meth) acrylate, alkylene oxide modified trimethylolpropane tri (meth) acrylate, alkylene glycol di (meth) acrylate, dialkylene glycol (meth) Chryrate, trialkylene glycol (meth) acrylate, tetraalkylene
  • Typical examples of the compound having a cationic polymerizable group include aromatic ethers, alicyclic or aliphatic epoxy compounds, cyclic ether compounds such as oxetane compounds, and vinyl ether compounds.
  • aromatic epoxy compound include di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and a novolac-type epoxy resin.
  • Examples of the alicyclic epoxy compound include a cyclohexene oxide-containing compound or a cyclopentene oxide-containing compound obtained by epoxidizing at least one cyclohexene ring or cyclopentene ring-containing compound with an oxidizing agent.
  • Examples of the aliphatic epoxy compound include alkyl glycidyl ether, alkylene glycol diglycidyl ether, polyhydric alcohol polyglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.
  • oxetane compounds include bisphenol A type oxetane compounds, bisphenol oxetane compounds, bisphenol S type oxetane compounds, xylylene type oxetane compounds, phenol novolac type oxetane compounds, cresol novolac type oxetane compounds, alkylphenol novolak type oxetane compounds, biphenol type oxetane compounds, Examples thereof include xylenol type oxetane compounds, naphthalene type oxetane compounds, dicyclopentadiene type oxetane compounds, oxetaneates of condensation products of phenols and aromatic aldehydes having a phenolic hydroxyl group.
  • vinyl ether compound examples include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol.
  • Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.
  • the compound having a photopolymerizable group may be used alone or in combination of two or more kinds, and a compound having a radical polymerizable group and a compound having a cationic polymerizable group may be used in combination.
  • the photopolymerization initiator refers to a compound that generates an active species such as a radical or a cation capable of initiating polymerization of the compound having the photopolymerizable group upon irradiation with light.
  • Photopolymerization initiators can be classified into radical polymerization initiators and cationic polymerization initiators.
  • radical polymerization initiators include benzophenone, benzyldimethyl ketal, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, titanocenes and oxime esters, trihalomethyltriazines, and other trihalomethyls And a compound having a group.
  • Examples of the cationic polymerization initiator include aromatic sulfonium salts and aromatic iodonium salts.
  • the polymerization initiators may be used alone or in combination of two or more, and a radical polymerization initiator and a cationic polymerization initiator may be used in combination. Furthermore, you may use a sensitizer with a photoinitiator.
  • the content of the compound having a photopolymerizable group in the photocurable composition for pattern formation is preferably 50 to 99.99 parts by mass with respect to 100 parts by mass of the total amount of the photocurable composition.
  • the amount is less than 50 parts by mass, the amount of the photopolymerizable group is small.
  • the amount exceeds 99.99 parts by mass, the ratio of the photopolymerization initiator to the compound having the photopolymerizable group is decreased. This is because of a decrease.
  • the compound having a photopolymerizable group having two or more photopolymerizable groups in one molecule is contained in an amount of 5 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the photocurable composition.
  • the content of the photopolymerization initiator in the photocurable composition is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the compound having a photopolymerizable group. If it is less than 0.01 mass part, the ratio of the photoinitiator with respect to the compound which has a photopolymerizable group will become low, and photocurability will fall. Moreover, when it exceeds 20 mass parts, it is because the solubility of the photoinitiator with respect to a photocurable composition falls and it is not practical.
  • Additives added to the photocurable composition for pattern formation of the present invention as needed include non-photocurable oligomers, non-photocurable polymers, adhesion-imparting agents (for example, silane coupling agents), organic Examples include solvents, leveling agents, plasticizers, fillers, antifoaming agents, flame retardants, stabilizers, antioxidants, fragrances, thermal crosslinking agents, colorants, and polymerization inhibitors.
  • an ionic liquid may be added in order to improve mold releasability. Examples of the ionic liquid include those having a melting point of 40 ° C. or lower.
  • an ionic liquid having a polymerizable group is preferable because it is a photocurable component and does not cause a problem such as oozing out on the surface of the photocured product after exposure.
  • the photocurable composition for pattern formation of the present invention contains a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region.
  • fluorescence refers to light emitted when absorbing high-energy light (light rays) or radiation, and when the fluorescent material absorbs energy, electrons are excited and emitted when it returns to the ground state. Extra energy.
  • a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region is used.
  • the ultraviolet region is a region having a wavelength of 10 nm to less than 400 nm
  • the visible light region is a region having a wavelength of 400 nm to 900 nm.
  • the fluorescent material used in the present invention emits the fluorescence of the fluorescent material other than the fluorescent material in the photocured product obtained by exposing the photocurable composition for pattern formation of the present invention containing the fluorescent material. In other words, it satisfies the condition that it is substantially absent in at least a part of the absorption wavelength region and at least a part of the wavelength region of the fluorescence emitted by the fluorescent substance.
  • FIG. 1 is a diagram showing an absorption spectrum and a fluorescence spectrum of a fluorescent substance and the like contained in the photocurable composition for pattern formation of the present invention.
  • FIG. 1 shows (I) the absorption spectrum of a photocured material other than the fluorescent material obtained by exposing the photocurable composition for pattern formation of the present invention containing a fluorescent material in the vicinity of a wavelength of 250 to 600 nm.
  • the absorption spectrum of the substance is represented by (II)
  • the fluorescence spectrum emitted from the fluorescent substance is represented by (III).
  • the absorption spectrum (II) of the fluorescent substance has two peaks in FIG.
  • the absorption wavelength region that emits fluorescence particularly efficiently is a region on the long wavelength side (indicated by ⁇ in FIG. 1). Therefore, the ⁇ absorption wavelength region in FIG. 1 will be described as “an absorption wavelength region in which the fluorescent substance emits fluorescence”.
  • absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is substantially absent in at least a part of the absorption wavelength region that emits the fluorescence possessed by the fluorescent material. It is necessary. That is, a fluorescent material having absorption that emits fluorescence is used in a region where there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing at least the photocurable composition for pattern formation.
  • the absorption wavelength region ⁇ that emits fluorescence in the absorption spectrum (II) of the fluorescent material is the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation. It is necessary to have a region that does not substantially overlap. This is because, in (II), when the absorption wavelength region ⁇ that emits fluorescence does not have a region that does not substantially overlap with (I), excitation of the fluorescent material is inhibited. In FIG.
  • the absorption wavelength region ⁇ that emits fluorescence is In the wavelength region ⁇ , the absorption spectrum (I) does not substantially overlap.
  • absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is substantially absent in at least a part of the fluorescence wavelength region where the fluorescent material emits light. is required. That is, a fluorescent material that emits fluorescence is used at least in a region where there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation.
  • the fluorescence spectrum (III) indicating the wavelength region of the fluorescence emitted by the fluorescent material is substantially the same as the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation. It is necessary to have areas that do not overlap. This is because, when (III) does not have a region that does not substantially overlap with (I), the emitted fluorescence (III) is absorbed by absorption (I) and fluorescence emission cannot be detected.
  • the fluorescence spectrum (III) since the wavelength region ⁇ has substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation, the fluorescence spectrum (III) has the wavelength region ⁇ . Then, it does not substantially overlap with the absorption spectrum (I).
  • the photocured product obtained by exposing the photocurable composition for pattern formation is a molded product obtained by exposing and curing a photocurable component, a fluorescent material, an additive added as necessary, and the like.
  • the absorption of the photocured component and the additive added as necessary is "absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation" It is.
  • This "absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation” refers to components other than the fluorescent substance of the photocurable composition, that is, the photocurable component and, if necessary, It can be determined by measuring the absorption of the molded product obtained by exposing the additive to be added.
  • the absorbance per 1 ⁇ m of film thickness of absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation is 0.1 or less, preferably 0.05 or less, absorption is achieved. There is virtually no.
  • absorption other than the fluorescent substance of the photocured material obtained by exposing the photocurable composition for pattern formation to the maximum wavelength of absorption at which the fluorescent substance emits fluorescence or the maximum wavelength of emitted fluorescence is substantially reduced. Preferably no.
  • the absorption wavelength region ⁇ emitting fluorescence in the absorption spectrum (II) of the fluorescent substance exposes the photocurable composition for pattern formation.
  • the photocured material produced using the photocurable composition for pattern formation light having a wavelength in the wavelength region ⁇ that does not substantially overlap with the absorption spectrum (I) other than the fluorescent material of the photocured material obtained in this way Irradiation, excitation of the fluorescent material, the fluorescence spectrum (III) emitted by the fluorescent material is substantially the same as the absorption spectrum (I) of the photocured product other than the fluorescent material obtained by exposing the photocurable composition for pattern formation.
  • the thickness of the photocured product can be easily determined in a short time in a non-destructive and non-contact manner.
  • the intensity of the fluorescence in the wavelength region ⁇ that does not overlap there is a correlation between the intensity of emitted fluorescence and the film thickness of the photocured material. Therefore, by separately obtaining the relationship between the fluorescence intensity and the thickness of the photocured material, measurement is performed. The thickness of the photocured product can be obtained from the obtained fluorescence intensity.
  • the photocured material other than the fluorescent material is substantially absorbed in the entire absorption wavelength region that emits fluorescence, the light irradiated to emit the fluorescent light does not pass through the photocured material and excites the fluorescent material. Cannot be emitted.
  • the photocured material other than a fluorescent material in the entire wavelength region of the emitted fluorescence, it becomes difficult to detect the emitted fluorescence, and there is a correlation between the fluorescence intensity and the film thickness of the photocured product. The thickness of the photocured product cannot be determined from the fluorescence intensity.
  • a fluorescent material is a thing with little absorption near the wavelength of the light which hardens the photocurable composition for pattern formation. This is because the fluorescent material does not inhibit photocuring when the photocurable composition for pattern formation is exposed and cured.
  • the product ⁇ ⁇ ⁇ f of the molar extinction coefficient ⁇ at the maximum absorption wavelength at which the fluorescent material emits fluorescence and the fluorescent quantum yield ⁇ f of the fluorescent material is preferably 1 ⁇ 10 4 or more.
  • the fluorescent material emits light having a wavelength near the maximum value of the absorption wavelength region where the fluorescent material emits fluorescence, and the molar absorption coefficient of the absorption wavelength of the fluorescent material is This is because the larger the value, the higher the detection sensitivity, and the thickness of the photocured product can be accurately measured even when a small amount is added.
  • the molar extinction coefficient can be calculated from the following Lambert-Beer equation.
  • the fluorescent substance has a fluorescence quantum yield close to 1. This is because the detection sensitivity becomes high, and the thickness of the photocured product can be accurately measured even when a small amount is added.
  • the fluorescent material needs to be capable of being uniformly dispersed or dissolved in the photocurable component.
  • the fluorescent material has less quenching or dimming when the photocurable composition for pattern formation is exposed and cured. This is because the detection sensitivity and quantitativeness are lowered.
  • the wavelength region of the absorption wavelength region in which the fluorescent material emits fluorescence, and a wavelength region in which there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition (FIG. 1).
  • the maximum value of the fluorescence intensity emitted before exposing the transfer material layer is A1
  • the light is emitted after the transfer material layer is exposed and cured.
  • the maximum value of the fluorescence intensity is A2
  • the value of A2 / A1 is 0.6 or more, preferably 0.8 or more.
  • the fluorescent substance examples include fluorescent luminescent dyes such as fluorescent dyes and fluorescent pigments, and organic or inorganic fluorescent substances.
  • fluorescent luminescent dyes such as fluorescent dyes and fluorescent pigments
  • organic or inorganic fluorescent substances examples include organic fluorescent light-emitting dye.
  • an organic fluorescent light-emitting dye is preferable because it is easily dissolved in the photocurable composition and has a high fluorescence quantum yield. Since the photocurable composition of the present invention is used for optical nanoimprint lithography, an organic fluorescent dye that does not contain metal ions and can be finally removed by reactive ion etching or the like is more preferable.
  • organic fluorescent light-emitting dyes examples include xanthene dyes such as rhodamine (rhodamine 6G (the counter anion is Cl ⁇ or BF 4 ⁇ ), rhodamine B, etc.), coumarin dyes, oxazine dyes, stilbene dyes, aryls, and the like.
  • xanthene dyes such as rhodamine (rhodamine 6G (the counter anion is Cl ⁇ or BF 4 ⁇ ), rhodamine B, etc.
  • coumarin dyes examples include dimethylidene dyes, cyanine dyes, pyridine dyes, and quinacridone derivatives.
  • the amount of the fluorescent substance added depends on the molar extinction coefficient of the fluorescent substance, the fluorescence quantum yield, and the thickness of the concave and convex portions of the concavo-convex pattern of the photocured product.
  • the amount is 0001 to 10 parts by mass, preferably 0.0005 to 5 parts by mass, and more preferably 0.001 to 1 part by mass.
  • the addition amount is less than 0.0001 parts by mass, the detection sensitivity decreases.
  • the addition amount exceeds 10 parts by mass, the solubility in the photocurable component becomes insufficient, or self-absorption of the fluorescent substance occurs, and the film thickness This is because the correlation may not be obtained.
  • the pattern-forming photocurable composition should be used in a liquid state at room temperature or near room temperature under an atmospheric pressure environment.
  • the photocurable composition for pattern formation has fluidity enough to fill the uneven pattern of the mold.
  • the viscosity may be 10 Pa ⁇ s or less at 25 ° C., preferably 100 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or less, and most preferably 25 mPa ⁇ s or less.
  • the viscosity measuring method include a method of measuring using a B-type viscometer manufactured by TOKIMEC.
  • the thickness of the concave portion or convex portion of the photocured product having the concave / convex pattern to be formed is non-destructive / non-destructive Measurement can be easily performed in a short time by contact.
  • FIG. 2 is sectional drawing which shows the outline of the method of forming the photocured material which has an uneven
  • the pattern-forming photocurable composition of the present invention is applied onto the substrate 1, and the transfer material layer made of the pattern-forming photocurable composition on the substrate 1. 2 is provided.
  • the pattern-forming photocurable composition is applied on the substrate 1, but the pattern-forming photocurable composition may be applied to the mold 3.
  • the mold 3 may have a desired uneven pattern on the surface.
  • the material of the mold 3 include transparent materials such as quartz glass and synthetic resin, as well as materials that do not transmit light such as metals such as silicon, silicon carbide, silicon oxide, and nickel, and metal oxides.
  • the appearance of the mold 3 may be the same as that of the mold 3 used in normal optical imprint lithography. For example, the appearance may be a rectangular parallelepiped shape or a roll shape.
  • the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold 3 used in normal optical imprint lithography, but is not limited thereto. It is not what is done. For example, it is good also as the mold 3 which formed the recessed part by forming the hollow in the surface of the material of a mold, and the part which protruded relatively to the surface side becomes a convex part in this case. Moreover, it is good also as the mold 3 which formed the convex part by providing a permite
  • each concave portion of the concave / convex pattern may be square, rectangular, half-moon shape, or a shape similar to those shapes.
  • Each concave portion has a depth of about 1 nm to 100 ⁇ m and an opening width of 1 nm, for example. It may be about 100 ⁇ m.
  • the surface of the mold 3 may be subjected to a mold release treatment.
  • a known release treatment agent exemplified by a perfluoro- or hydrocarbon-based polymer compound, an alkoxysilane compound or a trichlorosilane compound, diamond-like carbon, or the like is used by a gas phase method or a liquid phase method. Can be done.
  • the method for forming the transfer material layer 2 made of the pattern-forming photocurable composition on the substrate 1 or the like is not particularly limited.
  • application of the pattern-forming photocurable composition diluted with a solvent or the like as necessary Dropping specifically, spin coating, roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, dispenser coating, and the like.
  • the transfer material layer 2 may be provided so as to cover the entire surface of the mold 3 and the substrate 1, or may be provided so as to cover only a part thereof.
  • the thickness of the transfer material layer 2 is set in consideration of the amount of the transfer material layer 2 filled in the recesses of the uneven pattern formed on the mold 3, for example, the depth of the recesses of the uneven pattern. do it.
  • the transfer material layer 2 is sandwiched between the substrate 1 and the mold 3.
  • the substrate 1 may be pressed against the mold 3, the mold 3 may be pressed against the substrate 1, or both the substrate 1 and the mold 3 may be pressed.
  • the force for pressing the substrate 1 and the mold 3 can be set to about 0.01 to 100 MPa, for example. Further, pressing by the weight of the mold 3 or the substrate 1 may be performed without applying force. In this way, by pressing the mold 3 against the substrate 1, the transferred material layer 2 is filled in the uneven pattern of the mold 3 as shown in FIG.
  • the transfer material layer 2 and the mold 3 are both kept horizontal, the transfer material layer 2 and the mold 3 are brought into contact with each other, and the uneven pattern of the mold 3 is filled with the transfer material layer 2. As long as there is no hindrance, it is not necessary to limit to keeping it horizontal.
  • a conventional apparatus for optical imprint lithography can be used.
  • the light source used for exposure may be any light source that can irradiate light having a wavelength at which the photocurable composition for pattern formation is cured.
  • Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc, mercury xenon lamps, excimer lasers such as XeCl, KrF and ArF, ultraviolet or visible light lasers, and ultraviolet light. Or visible light LED etc. are mentioned.
  • the light irradiation amount may be an amount that can cure the transfer material layer 2. When it implements industrially, it is usually preferable to select an irradiation dose within a range of 10 J / cm 2 or less.
  • light is irradiated to the to-be-transferred material layer 2 from the member side which is substantially transparent with respect to the light irradiated among the board
  • the photocurable composition for pattern formation contains a component that is cured by light or a component that is cured by heat, it is photocured by light or heat after the mold release step in order to improve the strength of the photocured product 4. You may further have the process of hardening the thing 4 further.
  • the photocured material 4 having a concavo-convex pattern formed using the photocurable composition for pattern formation of the present invention easily measures the thickness of the concave portions and convex portions in a short time without breaking. be able to.
  • the fluorescent material contained in the pattern forming photocurable composition has an absorption wavelength at which fluorescence is emitted,
  • Light having a wavelength in the wavelength region ⁇ that does not substantially overlap with the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is irradiated.
  • the fluorescence spectrum (III) in which the fluorescent substance is excited by the light irradiation to emit light is substantially equal to the absorption spectrum (I) other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation.
  • the intensity of fluorescence in the wavelength region ⁇ that does not overlap is measured.
  • the fluorescence intensity can be measured with, for example, a fluorescence spectrophotometer or a fluorescence microscope. Since the predetermined fluorescent material is used, there is a correlation between the intensity of the emitted fluorescence and the film thickness of the photocured material 4, so that the relationship between the fluorescence intensity and the thickness of the photocured material is obtained separately. Thereby, the thickness of the recessed part and convex part of the photocured material 4 can be calculated
  • the surface roughness meter which is a general method for measuring unevenness cannot measure the thickness of the recess (residual film) in a non-destructive state, but in the present invention, the thickness of the recess can also be measured non-destructively. it can.
  • the fluorescent X-ray analysis has a problem that the apparatus becomes large and the measurement becomes complicated. The thickness of the unevenness cannot be easily measured.
  • the thickness of the convex portion and the thickness of the concave portion could not be detected at the same time in a non-destructive state, but according to the present invention, the thickness of the convex portion and the thickness of the concave portion can be detected simultaneously and non-destructively. ⁇ It can be measured easily in a short time without contact.
  • the thickness of the light-cured product 4 having a convex or concave portion of 1 nm to 20 ⁇ m was so thin that the thickness could not be accurately determined by a non-destructive / non-contact measuring method.
  • the detection sensitivity is high, so that the thickness can be measured accurately and easily in a short time.
  • the width of the convex part or concave part of the pattern of the photocured product 4 is 10 nm to 100 ⁇ m, the measurement area becomes narrow, so the thickness could not be obtained accurately by the non-destructive / non-contact measuring method.
  • the thickness can be detected by simultaneously detecting the fluorescence intensity and the horizontal pattern shape. Can be measured accurately and easily.
  • the method for forming a photocured product having a concavo-convex pattern by photoimprint lithography and the method for measuring the film thickness of a photocured product having a concavo-convex pattern obtained by the method are used for pattern formation of the present invention.
  • a photocurable composition for pattern formation of this invention
  • the fluorescent material which has the absorption wavelength range which light-emits fluorescence in the range of an ultraviolet region from a visible light region Can be applied as long as it is 0.0001 to 10 parts by mass of the photocurable component.
  • Example 1 Preparation of photocurable composition for pattern formation>
  • a photopolymerizable compound 30 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate, 45 parts by mass of diacrylate KAYARAD R-604 (manufactured by Nippon Kayaku Co., Ltd.), and 20 parts by mass of trimethylolpropane triacrylate
  • a photopolymerization initiator 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone was stirred and mixed at room temperature to obtain a liquid composition a comprising a photocurable component.
  • composition A is added 0.005 parts by mass of a fluorescent substance rhodamine 6G (counter anion; BF 4 ⁇ ) having an absorption wavelength region for emitting fluorescence in the visible light region, and the mixture is stirred and mixed at room temperature to be photocured.
  • a liquid pattern-forming photocurable composition A comprising an organic component a and a fluorescent substance rhodamine 6G (counter anion; BF 4 ⁇ ) was obtained.
  • Table 1 shows the composition of the photocurable composition A for pattern formation.
  • the absorption maximum wavelength ⁇ ex that emits fluorescence the maximum wavelength ⁇ em of emission fluorescence
  • the molar absorption coefficient ⁇ at the absorption maximum wavelength ⁇ ex that emits fluorescence fluorescence Table 2 shows the quantum yield ⁇ f and the product of ⁇ and ⁇ f.
  • the absorbance per 1 ⁇ m of the film thickness of the photocured product of the composition a composed of the photocurable component is the absorption maximum wavelength 530 nm at which rhodamine 6G (counter anion; BF 4 ⁇ ) emits fluorescence. And at the maximum wavelength of 560 nm of the emitted fluorescence, they were 7.7 ⁇ 10 ⁇ 3 and 7.3 ⁇ 10 ⁇ 3 , respectively, and it was confirmed that there was substantially no absorption.
  • the absorption wavelength and absorption intensity were measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: MultiIspec-1500), and the emitted fluorescence wavelength and fluorescence intensity were measured with a fluorescence spectrophotometer (manufactured by Hitachi High-Technologies Corporation). Model No .: F-7000).
  • the prepared photocurable composition A for pattern formation was spin-coated on a silicon substrate so as to have a film thickness of 120 nm.
  • A1 was 9.7.
  • the coating film was cured by irradiating ultraviolet rays having a wavelength of 365 nm with an exposure amount of 1 J / cm 2 .
  • A2 was 10.6.
  • the value of A2 / A1 was 1.1, and it was confirmed that sufficient intensity of fluorescence could be detected even after the photocurable composition A for pattern formation was photocured.
  • the photocurable composition A for pattern formation of Example 1 was spin-coated on a silicon substrate, and ultraviolet light having a wavelength of 365 nm was photocured in an inert gas at an exposure amount of 1 J / cm 2 to form a photocurable composition for pattern formation.
  • Five types of photocured films of the product A were produced by changing the film thickness.
  • the photocured film was irradiated with light having a wavelength of 530 nm, and the emitted fluorescence intensity was measured, and was found to be 76, 91, 112, 127, 148.
  • the photocured film was scratched, and the film thickness was measured with a stylus type surface shape measuring instrument (product name: DEKTAK150, manufactured by ULVAC-ES Co., Ltd.).
  • the film thickness was 62 nm, 68 nm, 75 nm, 85 nm, and It was 98 nm.
  • FIG. 3 a proportional relationship was observed between the fluorescence intensity and the film thickness.
  • the pattern-forming photocurable composition A of Example 1 was spin-coated on a silicon substrate so as to have a film thickness of 100 nm to form a transfer material layer made of the pattern-forming photocurable composition A.
  • the transfer material layer is sandwiched between the silicon substrate and the release-treated quartz mold, and an imprint apparatus (trade name; NM-801, manufactured by Myeongchang Kiko Co., Ltd.) is used at a pressure of 0.3 MPa. It pressed and filled the pattern concavo-convex pattern with pattern forming photocurable composition A.
  • a microscope was used as an emission pattern image acquisition device.
  • a light emission pattern image was acquired with an ISO value of 200 and an acquisition time of 7 seconds as image acquisition conditions, and the light emission intensity was measured.
  • the thickness of the recess was determined from the fluorescence intensity 19 of the recess of the photocured product having the above pattern.
  • the concave portion of the photocured product was 31.4 nm.
  • the recess was 32.0 nm, and the film thickness could be accurately measured by the method of the present invention. I confirmed that.
  • the calibration curve in FIG. 3 does not pass through the origin, but the film thickness could be accurately measured using this calibration curve as described above. In the example, the thickness of the recess having a narrow measurement region and a small thickness could be easily measured by a non-destructive and non-contact method.
  • Example 2 A composition a comprising a photocurable component and a photocurable composition for pattern formation were prepared in the same manner as in Example 1 except that 0.005 parts by mass of rhodamine 6G (counter anion; Cl ⁇ ) was used as the fluorescent substance. B was prepared.
  • the composition of the photocurable composition B for pattern formation is shown in Table 1, and the properties of rhodamine 6G (counter anion; Cl ⁇ ) are shown in Table 2.
  • the absorbance per 1 ⁇ m of the film thickness of the photocured product of the composition a comprising the photocurable component, as shown in Table 3, is the absorption maximum wavelength 530 nm at which rhodamine 6G (counter anion; Cl ⁇ ) emits fluorescence, In addition, it was confirmed that the emission was 7.7 ⁇ 10 ⁇ 3 and 7.3 ⁇ 10 ⁇ 3 at the maximum wavelength of 560 nm of the emitted light, and there was substantially no absorption.
  • the absorption wavelength and absorption intensity, and the emitted fluorescence wavelength and fluorescence intensity were measured in the same manner as in Example 1.
  • the prepared photocurable composition B for pattern formation was spin-coated on a silicon substrate so as to have a film thickness of 120 nm.
  • A1 was 8.7.
  • the coating film was cured by irradiating ultraviolet rays having a wavelength of 365 nm with an exposure amount of 1 J / cm 2 .
  • this photocured product was irradiated with light having a wavelength of 530 nm and the maximum value A2 of the emitted fluorescence intensity was measured, A2 was 9.1. Therefore, the value of A2 / A1 is 1.0, and fluorescence with sufficient intensity can be detected even after the photocurable composition B for pattern formation is photocured, and the film thickness is precisely as in Example 1. It was confirmed that measurement was possible.
  • Example 3 A composition a composed of a photocurable component and a photocurable composition C for pattern formation were prepared in the same manner as in Example 1 except that Coumarin 540A was used as the fluorescent material.
  • Table 1 shows the composition of the photocurable composition C for pattern formation
  • Table 2 shows the properties of Coumarin 540A.
  • the fluorescence intensity ratio A2 / A1 of the coating film before and after photocuring was determined in the same manner as in Example 1. The results are shown in Table 3.
  • the wavelength of the light irradiated in order to make fluorescence light-emit is 410 nm.
  • A1 was 1.0
  • A2 was 0.53,
  • A2 / A1 value was 0.53, and the fluorescence intensity was lower than those in Examples 1 and 2, but these values were sufficiently detectable.
  • Example 4 A composition a comprising a photocurable component and a photocurable composition D for pattern formation were prepared in the same manner as in Example 1 except that pyromethene 597 was used as the fluorescent material.
  • the composition of the photocurable composition D for pattern formation is shown in Table 1, and the properties of pyromethene 597 are shown in Table 2.
  • the fluorescence intensity ratio A2 / A1 of the coating film before and after photocuring was determined in the same manner as in Example 1. The results are shown in Table 3. Note that the wavelength of light irradiated to emit fluorescence is 520 nm. A1 was 1.5, A2 was 0.36, and A2 / A1 value was 0.24. The fluorescence intensity was lower than those in Examples 1 to 3, but these values were sufficiently detectable. Similarly, it was confirmed that the film thickness could be measured accurately.
  • Composition b was prepared in the same manner as in Example 1 except that 1.5 parts by mass of UV Red 101 (Mitsui Chemicals, Inc.) was added as an additive. To this composition b, 0.005 parts by mass of rhodamine 6G (counter anion; Cl ⁇ ) is added, and stirred and mixed at room temperature to comprise composition b and the fluorescent substance rhodamine 6G (counter anion; Cl ⁇ ). A liquid photocurable composition E for pattern formation was obtained.
  • UV Red 101 Mitsubishi Chemicals, Inc.
  • the absorbance per 1 ⁇ m film thickness of the photocured product of composition b is the absorption maximum wavelength 530 nm for causing rhodamine 6G (counter anion; Cl ⁇ ) to emit light, and the maximum wavelength of the emitted fluorescence. Since the photocured material of the composition b inhibits excitation and light emission of the fluorescent material at 560 nm, the fluorescence of the photocured material of the pattern forming photocurable composition E can be detected. could not.
  • composition c was prepared in the same manner as in Example 1 except that 1.5 parts by mass of UV Yellow 1549 (manufactured by Mitsui Chemicals, Inc.) was added as an additive. To this composition c, 0.005 part by mass of coumarin 540A was added and stirred and mixed at room temperature to obtain a liquid pattern-forming photocurable composition F comprising the composition c and the fluorescent substance coumarin 540A. .
  • the absorbance per 1 ⁇ m of the film thickness of the photocured product of the composition c exceeds 0.1 at the absorption maximum wavelength 410 nm for causing the coumarin 540A to emit light, and the photocured product of the composition c Inhibits excitation of the fluorescent substance, and thus the fluorescence of the photocured product of the photocurable composition F for pattern formation could not be detected.

Abstract

Disclosed is a photocurable composition which can be a transfer-receiving material layer that is used in a pattern formation wherein the transfer-receiving material layer is sandwiched between a substrate and a mold, which is provided with a recessed and projected pattern, so that the recessed and projected pattern is filled with the transfer-receiving material layer, and the mold is released therefrom after molding the transfer-receiving material layer by exposure and curing. The photocurable composition contains, per 100 parts by mass of a photocurable component, 0.0001-10 parts by mass of a fluorescent substance that has an absorption wavelength range, at which the fluorescent substance emits fluorescent light, within the range from the ultraviolet range to the visible light range, and there is substantially no absorption by the materials other than the fluorescent substance in the photocured product obtained by light exposure in at least a part of the absorption wavelength range of the fluorescent substance nor in at least a part of the wavelength range of the fluorescent light emitted by the fluorescent substance.

Description

パターン形成用光硬化性組成物及びこれを用いた膜厚測定方法Photocurable composition for pattern formation and film thickness measuring method using the same
　本発明はパターンを有する光硬化物を光インプリントリソグラフィにより形成する際に用いるパターン形成用光硬化性組成物及びそれを用いて形成されたパターンを有する光硬化物の膜厚測定方法に関するものである。 The present invention relates to a photocurable composition for pattern formation used when forming a photocured product having a pattern by photoimprint lithography, and a method for measuring the film thickness of a photocured product having a pattern formed using the same. is there.
　半導体集積回路の高密度化、高速化に伴い、集積回路のパターン線幅が縮小されているため微細なパターンを製造できる技術が求められている。微細なパターンの形成方法として、光ナノインプリントリソグラフィが注目されている。光ナノインプリントリソグラフィとは、微細な凹凸パターンを有するモールドを基板上に設けられたレジスト等の被転写材に押し付けることによって被転写材をモールドのパターンに充填した後、モールドを被転写材から離型することにより、被転写材にモールドの凹凸パターンが転写されたパターンを形成するものである（例えば特許文献１参照）。 With the increase in density and speed of semiconductor integrated circuits, since the pattern line width of integrated circuits is reduced, a technology capable of manufacturing fine patterns is required. As a method for forming a fine pattern, optical nanoimprint lithography has attracted attention. Optical nanoimprint lithography is a process in which a mold having a fine concavo-convex pattern is pressed against a transfer material such as a resist provided on a substrate to fill the transfer material into the mold pattern, and then the mold is released from the transfer material. By doing so, a pattern in which the concave / convex pattern of the mold is transferred to the transfer material is formed (see, for example, Patent Document 1).
　このような光ナノインプリントリソグラフィにより形成された凹凸パターンを有する光硬化物の厚さを測定する方法として、光硬化物の断面を走査型電子顕微鏡で観察する方法があるが、光硬化物の破壊が必要であるという問題や、測定に長時間を要するという問題がある。また、エリプソメーター等の反射分光膜厚計を用いる方法は、非破壊且つ非接触の方法であるが、測定に長時間を要し、また、直径約５μｍの測定領域で膜厚が光学的に平滑である必要があり、膜厚斑や凹凸構造があると膜厚の解析が難しいため、容易に膜厚を測定し難いという問題がある。 As a method of measuring the thickness of a photocured product having a concavo-convex pattern formed by such optical nanoimprint lithography, there is a method of observing a cross section of the photocured product with a scanning electron microscope. There is a problem that it is necessary and a problem that it takes a long time for measurement. In addition, a method using a reflection spectral film thickness meter such as an ellipsometer is a non-destructive and non-contact method. However, it takes a long time to measure, and the film thickness is optically measured in a measurement region having a diameter of about 5 μm. There is a problem that it is difficult to measure the film thickness easily because it is necessary to be smooth, and it is difficult to analyze the film thickness if there is a film thickness unevenness or uneven structure.
米国特許第６３３４９６０号明細書US Pat. No. 6,334,960
　本発明は、このような事情に鑑み、形成される凹凸パターンを有する光硬化物の膜厚を非破壊・非接触で短時間且つ容易に測定することができるパターン形成用光硬化性組成物及びこれを用いた膜厚測定方法を提供することを課題とする。 In view of such circumstances, the present invention provides a photocurable composition for pattern formation that can easily and easily measure the film thickness of a photocured product having a concavo-convex pattern in a non-destructive and non-contact manner, and It is an object to provide a film thickness measurement method using this.
　本発明者等は、上記課題を解決するという目的のために種々検討した結果、蛍光物質を含有する特定の光硬化性組成物が上記目的に合致することを見出し、本発明に到達した。 As a result of various studies for the purpose of solving the above-mentioned problems, the present inventors have found that a specific photocurable composition containing a fluorescent substance meets the above-mentioned purpose, and have reached the present invention.
　かかる本発明の第１の態様は、基板と凹凸パターンが形成されたモールドとで被転写材層を挟み込んで前記モールドの凹凸パターンに前記被転写材層を充填し、露光して硬化させることにより成形した後、前記モールドを離型するパターン形成に用いられる前記被転写材層となりうる光硬化性組成物であって、蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有し、露光して得られる光硬化物の前記蛍光物質以外の吸収が、前記蛍光物質が有する前記吸収波長領域の少なくとも一部に実質的に無く、且つ、前記蛍光物質が発光する蛍光の波長領域の少なくとも一部に実質的に無いことを特徴とするパターン形成用光硬化性組成物にある。 According to the first aspect of the present invention, a transfer material layer is sandwiched between a substrate and a mold having a concavo-convex pattern, the concavo-convex pattern of the mold is filled with the transfer material layer, and is exposed and cured. A photocurable composition that can be used as the transfer material layer for forming a pattern after the mold is released, and has an absorption wavelength region that emits fluorescence within a range from an ultraviolet region to a visible light region. 0.0001 to 10 parts by mass of the fluorescent substance with respect to 100 parts by mass of the photocurable component, and the absorption of the photocured product obtained by exposure other than the fluorescent substance is at least in the absorption wavelength region of the fluorescent substance The photocurable composition for pattern formation is characterized in that it is substantially absent in part and substantially absent in at least a part of the wavelength region of fluorescence emitted by the fluorescent substance.
　本発明の第２の態様は、前記蛍光物質が蛍光を発光する吸収波長の極大値におけるモル吸光係数と、前記蛍光物質の蛍光量子収率との積が１×１０４以上であることを特徴とする第１の態様に記載のパターン形成用光硬化性組成物にある。 In a second aspect of the present invention, the product of the molar extinction coefficient at the maximum value of the absorption wavelength at which the fluorescent substance emits fluorescence and the fluorescent quantum yield of the fluorescent substance is 1 × 10 4 or more. In the photocurable composition for pattern formation as described in 1st aspect.
　本発明の第３の態様は、前記蛍光物質が蛍光を発光する吸収波長領域の波長であって前記光硬化性組成物を露光して得られる光硬化物の前記蛍光物質以外の吸収が実質的に無い波長の光を照射して蛍光を発光させる場合において、前記被転写材層を露光する前に発光した蛍光強度の極大値をＡ１、露光して硬化させた後に発光した蛍光強度の極大値をＡ２としたとき、Ａ２／Ａ１の値が０．６以上であることを特徴とする第１又は２の態様に記載のパターン形成用光硬化性組成物にある。 According to a third aspect of the present invention, the absorption of the photocured material other than the phosphor in the photocured composition obtained by exposing the photocurable composition to a wavelength in an absorption wavelength region in which the phosphor emits fluorescence substantially In the case where fluorescent light is emitted by irradiating light with a wavelength not included in the above, the maximum value of the fluorescence intensity emitted before exposing the transfer material layer is A1, the maximum value of the fluorescence intensity emitted after being exposed and cured When A2 is A2, the value of A2 / A1 is 0.6 or more. The photocurable composition for pattern formation according to the first or second aspect is characterized in that.
　本発明の第４の態様は、蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有するパターン形成用光硬化性組成物を用いて製造された凹凸パターンを有する光硬化物に、前記蛍光物質が蛍光を発光する吸収波長領域内の波長の光を照射し、発光した蛍光の強度から、前記凹凸パターンを有する光硬化物の凸部又は凹部の少なくとも一方の厚さを求めることを特徴とする膜厚測定方法にある。 According to a fourth aspect of the present invention, there is provided a pattern containing 0.0001 to 10 parts by mass of a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region with respect to 100 parts by mass of the photocurable component. The photocured material having a concavo-convex pattern produced using the photocurable composition for formation is irradiated with light having a wavelength within an absorption wavelength region where the fluorescent material emits fluorescence, and from the intensity of the emitted fluorescence, A thickness measurement method is characterized in that the thickness of at least one of a convex portion or a concave portion of a photocured product having an uneven pattern is obtained.
　本発明の第５の態様は、前記凹凸パターンを有する光硬化物の凸部及び凹部の各厚さが１ｎｍ～２０μｍの範囲であることを特徴とする第４の態様に記載の膜厚測定方法にある。 According to a fifth aspect of the present invention, there is provided the film thickness measuring method according to the fourth aspect, wherein the thickness of each of the convex portions and concave portions of the photocured product having the concavo-convex pattern is in the range of 1 nm to 20 μm. It is in.
　本発明の第６の態様は、前記凹凸パターンを有する光硬化物の凸部又は凹部の少なくとも一方の幅が１０ｎｍ～１００μｍの範囲であることを特徴とする第４又は５の態様に記載の膜厚測定方法にある。 A sixth aspect of the present invention is the film according to the fourth or fifth aspect, wherein the width of at least one of the convex part or concave part of the photocured product having the concave / convex pattern is in the range of 10 nm to 100 μm. It is in the thickness measurement method.
　本発明によれば、蛍光物質を含有する上記特定の光硬化性組成物を用いることにより、形成される凹凸パターンを有する光硬化物の膜厚を非破壊・非接触で短時間且つ容易に測定することができる。 According to the present invention, by using the above-mentioned specific photocurable composition containing a fluorescent material, the film thickness of the photocured product having a concavo-convex pattern to be formed can be measured in a short time and non-destructively. can do.
本発明の組成物に含まれる蛍光物質等の吸収スペクトル及び発光スペクトルの一例を示す図である。It is a figure which shows an example of the absorption spectrum and emission spectrum, such as a fluorescent substance contained in the composition of this invention. 本発明の組成物を用いたパターン形成方法の概略を示す断面図である。It is sectional drawing which shows the outline of the pattern formation method using the composition of this invention. 実施例１の光硬化物の検量線を示す図である。It is a figure which shows the calibration curve of the photocured material of Example 1. 実施例１の光硬化物の蛍光顕微鏡写真である。2 is a fluorescence micrograph of the photocured product of Example 1. FIG.
　以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
　本発明のパターン形成用光硬化性組成物は、光インプリントリソグラフィ、すなわち、光硬化性組成物からなる被転写材層を基板と凹凸パターンが形成されたモールドとで挟み込んでモールドの凹凸パターンに被転写材層を充填し、露光して硬化させることにより成形した後、モールドを離型することにより凹凸のパターンを有する光硬化物を得るパターン形成に用いられるものであり、蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有し、露光して得られる光硬化物の蛍光物質以外の吸収が、蛍光物質が有する蛍光を発光させる吸収波長領域の少なくとも一部に実質的に無く、且つ、蛍光物質が発光する蛍光の波長領域の少なくとも一部に実質的に無いものである。具体的には、所定の光硬化性成分と、蛍光物質と、必要に応じて添加する添加剤等からなる。 The photocurable composition for pattern formation of the present invention is formed into a concavo-convex pattern of a mold by sandwiching a transfer material layer made of a photocurable composition, that is, a photocurable composition, between a substrate and a mold having a concavo-convex pattern. The material to be transferred is filled, exposed and cured to form, and then the mold is released to obtain a photocured product having an uneven pattern. Absorption that emits fluorescence 0.0001 to 10 parts by mass of a fluorescent material having a wavelength region in the range from the ultraviolet region to the visible light region with respect to 100 parts by mass of the photocurable component, and absorption of the photocured product obtained by exposure other than the fluorescent material Is substantially absent in at least a part of the absorption wavelength region that emits the fluorescence of the fluorescent material, and at least in the wavelength region of the fluorescence that the fluorescent material emits. Those not in substantially the department. Specifically, it comprises a predetermined photocurable component, a fluorescent material, and an additive that is added as necessary.
　光硬化性成分とは、露光により反応して硬化する成分をいう。具体的には、光二量化型の光硬化性組成物であれば桂皮酸エステル系樹脂等の光二量性基を有する樹脂、環化ゴム－ビスアジド等の光架橋型の光硬化性組成物であれば光架橋剤及び環化ゴム等の高分子、エン/チオール型、ラジカル、カチオン等の光重合型の光硬化性組成物であれば光重合性基を有する化合物及び光重合開始剤である。なお、汎用性等の面から、光硬化性成分としては光重合型が最も好ましい。 The photocurable component refers to a component that reacts and cures upon exposure. Specifically, if it is a photodimerization-type photocurable composition, it may be a photocrosslinkable photocurable composition such as a resin having a photodimer group such as a cinnamic acid ester resin or a cyclized rubber-bisazide. For example, a photopolymerizable photocurable composition such as a photocrosslinking agent and a polymer such as a cyclized rubber, an ene / thiol type, a radical, or a cation is a compound having a photopolymerizable group and a photopolymerization initiator. In view of versatility, the photo-curing component is most preferable as the photo-curable component.
　光重合性基を有する化合物とは、ラジカル重合性基又はカチオン重合性基を有する化合物をいう。ラジカル重合性基の例としては、アクリロイル基、メタアクリロイル基、ビニル基、アリル基等が挙げられる。カチオン重合性基の例としては、エポキシ基、ビニロキシ基、オキセタニル基等が挙げられる。 The compound having a photopolymerizable group refers to a compound having a radical polymerizable group or a cationic polymerizable group. Examples of the radical polymerizable group include acryloyl group, methacryloyl group, vinyl group and allyl group. Examples of the cationic polymerizable group include an epoxy group, a vinyloxy group, and an oxetanyl group.
　ラジカル重合性基を有する化合物としては、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、（ポリ）プロピレングリコールモノ（メタ）アクリレート、ｔ－ブチル（メタ）アクリレートなどの（メタ）アクリレート類、モルホリン（メタ）アクリルアミドなどの（メタ）アクリルアミド類、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクトン、スチレンなどの単官能ラジカル重合性化合物や、トリメチロールプロパントリ（メタ）アクリレート、アルキレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、アルキレングリコールジ（メタ）アクリレート、ジアルキレングリコール（メタ）アクリレート、トリアルキレングリコール（メタ）アクリレート、テトラアルキレングリコールジ（メタ）アクリレート、ポリアルキレングリコール（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンテニルジ（メタ）アクリレート、ジアリルフタレート、ジアリルフマレート、アルキレンオキサイド変性ビスフェノールＡジ（メタ）アクリレートなどの多官能ラジカル重合性化合物、及び単官能又は多官能のエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等が挙げられる。 Examples of the compound having a radical polymerizable group include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (poly) propylene glycol mono (meth) ) Acrylates, (meth) acrylates such as t-butyl (meth) acrylate, (meth) acrylamides such as morpholine (meth) acrylamide, monofunctional radical polymerizable compounds such as N-vinylpyrrolidone, N-vinylcaprolactone and styrene Trimethylolpropane tri (meth) acrylate, alkylene oxide modified trimethylolpropane tri (meth) acrylate, alkylene glycol di (meth) acrylate, dialkylene glycol (meth) Chryrate, trialkylene glycol (meth) acrylate, tetraalkylene glycol di (meth) acrylate, polyalkylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Polyfunctional radical polymerizable compounds such as neopentyl glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, diallyl phthalate, diallyl fumarate, alkylene oxide modified bisphenol A di (meth) acrylate, and monofunctional or polyfunctional Functional epoxy (meth) acrylate, urethane (meth) acrylate, etc. are mentioned.
　カチオン重合性基を有する化合物としては、芳香族、脂環式又は脂肪族エポキシ化合物、オキセタン化合物などの環状エーテル化合物やビニルエーテル化合物などが代表的である。芳香族エポキシ化合物としては、ビスフェノールＡ或いはそのアルキレンオキサイド付加体のジ又はポリグリシジルエーテル、水素添加ビスフェノールＡ或いはそのアルキレンオキサイド付加体のジ又はポリグリシジルエーテル、並びにノボラック型エポキシ樹脂等が挙げられる。脂環式エポキシ化合物としては、例えば少なくとも１個のシクロヘキセン環あるいはシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキシド含有化合物あるいはシクロペンテンオキシド含有化合物等が挙げられる。脂肪族エポキシ化合物としては、アルキルグリシジルエーテル、アルキレングリコールのジグリシジルエーテル、多価アルコールのポリグリシジルエーテル、ポリアルキレングリコールのジグリシジルエーテル等が挙げられる。オキセタン化合物としては、ビスフェノールＡ型オキセタン化合物、ビスフェノールオキセタン化合物、ビスフェノールＳ型オキセタン化合物、キシリレン型オキセタン化合物、フェノールノボラック型オキセタン化合物、クレゾールノボラック型オキセタン化合物、アルキルフェノールノボラック型オキセタン化合物、ビフェノール型オキセタン化合物、ビキシレノール型オキセタン化合物、ナフタレン型オキセタン化合物、ジシクロペンタジエン型オキセタン化合物、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のオキセタン化物等が挙げられる。ビニルエーテル化合物としては、例えばエチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物、エチルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、ドデシルビニルエーテル、ジエチレングリコールモノビニルエーテル、オクタデシルビニルエーテル等のモノビニルエーテル化合物等が挙げられる。 Typical examples of the compound having a cationic polymerizable group include aromatic ethers, alicyclic or aliphatic epoxy compounds, cyclic ether compounds such as oxetane compounds, and vinyl ether compounds. Examples of the aromatic epoxy compound include di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and a novolac-type epoxy resin. Examples of the alicyclic epoxy compound include a cyclohexene oxide-containing compound or a cyclopentene oxide-containing compound obtained by epoxidizing at least one cyclohexene ring or cyclopentene ring-containing compound with an oxidizing agent. Examples of the aliphatic epoxy compound include alkyl glycidyl ether, alkylene glycol diglycidyl ether, polyhydric alcohol polyglycidyl ether, polyalkylene glycol diglycidyl ether, and the like. Examples of oxetane compounds include bisphenol A type oxetane compounds, bisphenol oxetane compounds, bisphenol S type oxetane compounds, xylylene type oxetane compounds, phenol novolac type oxetane compounds, cresol novolac type oxetane compounds, alkylphenol novolak type oxetane compounds, biphenol type oxetane compounds, Examples thereof include xylenol type oxetane compounds, naphthalene type oxetane compounds, dicyclopentadiene type oxetane compounds, oxetaneates of condensation products of phenols and aromatic aldehydes having a phenolic hydroxyl group. Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylol. Di- or trivinyl ether compounds such as propane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-pro Vinyl ether, isopropyl vinyl ether, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.
　光重合性基を有する化合物は単独で用いても２種以上を組み合わせて用いてもよく、また、ラジカル重合性基を有する化合物とカチオン重合性基を有する化合物とを併用してもよい。 The compound having a photopolymerizable group may be used alone or in combination of two or more kinds, and a compound having a radical polymerizable group and a compound having a cationic polymerizable group may be used in combination.
　光重合開始剤とは、光の照射により、上記光重合性基を有する化合物の重合を開始させることができるラジカル、カチオン等の活性種を発生する化合物をいう。光重合開始剤は、ラジカル重合開始剤とカチオン重合開始剤とに分類できる。ラジカル重合開始剤の例としては、ベンゾフェノン、ベンジルジメチルケタール、α－ヒドロキシアルキルフェノン類、α－アミノアルキルフェノン類、アシルフォスフィンオキサイド類、チタノセン類及びオキシムエステル類、トリハロメチルトリアジン類、その他トリハロメチル基を有する化合物等が挙げられる。カチオン重合開始剤の例としては、芳香族スルホニウム塩及び芳香族ヨードニウム塩等が挙げられる。重合開始剤は単独で用いても２種以上を組み合わせて用いてもよく、また、ラジカル重合開始剤とカチオン重合開始剤とを併用してもよい。さらに、光重合開始剤と共に増感剤を用いてもよい。 The photopolymerization initiator refers to a compound that generates an active species such as a radical or a cation capable of initiating polymerization of the compound having the photopolymerizable group upon irradiation with light. Photopolymerization initiators can be classified into radical polymerization initiators and cationic polymerization initiators. Examples of radical polymerization initiators include benzophenone, benzyldimethyl ketal, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, titanocenes and oxime esters, trihalomethyltriazines, and other trihalomethyls And a compound having a group. Examples of the cationic polymerization initiator include aromatic sulfonium salts and aromatic iodonium salts. The polymerization initiators may be used alone or in combination of two or more, and a radical polymerization initiator and a cationic polymerization initiator may be used in combination. Furthermore, you may use a sensitizer with a photoinitiator.
　パターン形成用光硬化性組成物における光重合性基を有する化合物の含有率は、光硬化性組成物の総量１００質量部に対して、５０～９９．９９質量部が好ましい。５０質量部未満では光重合性基の量が少ないことにより、９９．９９質量部を超えると、光重合性基を有する化合物に対する光重合開始剤の割合が低くなることにより、いずれも光硬化性が低下するためである。さらに、光重合性基を１分子中に２つ以上有する光重合性基を有する化合物を、光硬化性組成物の総量１００質量部に対して５質量部以上、好ましくは２０質量部以上含有するのが望ましい。光架橋により光硬化物の機械的強度を向上させるためである。また、光硬化性組成物における光重合開始剤の含有率は、光重合性基を有する化合物１００質量部に対して、０．０１～２０質量部が好ましい。０．０１質量部未満では光重合性基を有する化合物に対する光重合開始剤の割合が低くなり、光硬化性が低下する。また２０質量部を超えると、光硬化性組成物に対する光重合開始剤の溶解性が低下し、実用的でないためである。 The content of the compound having a photopolymerizable group in the photocurable composition for pattern formation is preferably 50 to 99.99 parts by mass with respect to 100 parts by mass of the total amount of the photocurable composition. When the amount is less than 50 parts by mass, the amount of the photopolymerizable group is small. When the amount exceeds 99.99 parts by mass, the ratio of the photopolymerization initiator to the compound having the photopolymerizable group is decreased. This is because of a decrease. Further, the compound having a photopolymerizable group having two or more photopolymerizable groups in one molecule is contained in an amount of 5 parts by mass or more, preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the photocurable composition. Is desirable. This is to improve the mechanical strength of the photocured product by photocrosslinking. The content of the photopolymerization initiator in the photocurable composition is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the compound having a photopolymerizable group. If it is less than 0.01 mass part, the ratio of the photoinitiator with respect to the compound which has a photopolymerizable group will become low, and photocurability will fall. Moreover, when it exceeds 20 mass parts, it is because the solubility of the photoinitiator with respect to a photocurable composition falls and it is not practical.
　本発明のパターン形成用光硬化性組成物に必要に応じて添加する添加剤としては、非光硬化性オリゴマーや非光硬化性ポリマー、密着性付与剤（例えば、シランカップリング剤等）、有機溶剤、レベリング剤、可塑剤、充填剤、消泡剤、難燃剤、安定剤、酸化防止剤、香料、熱架橋剤、着色剤、及び重合禁止剤等が挙げられる。また、モールドの離型性を向上させるために、イオン液体を添加してもよい。イオン液体として、例えば、融点が４０℃以下のものが挙げられる。種々あるイオン液体の中でも重合性基を持つイオン液体は、光硬化性成分であり、露光後の光硬化物の表面に染み出す等の問題が生じないため、好ましい。 Additives added to the photocurable composition for pattern formation of the present invention as needed include non-photocurable oligomers, non-photocurable polymers, adhesion-imparting agents (for example, silane coupling agents), organic Examples include solvents, leveling agents, plasticizers, fillers, antifoaming agents, flame retardants, stabilizers, antioxidants, fragrances, thermal crosslinking agents, colorants, and polymerization inhibitors. Further, an ionic liquid may be added in order to improve mold releasability. Examples of the ionic liquid include those having a melting point of 40 ° C. or lower. Among various ionic liquids, an ionic liquid having a polymerizable group is preferable because it is a photocurable component and does not cause a problem such as oozing out on the surface of the photocured product after exposure.
　本発明のパターン形成用光硬化性組成物は、蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を含有する。ここで、蛍光とは、高エネルギーの光（光線）又は放射線を吸収した時に発する光をいい、蛍光物質がエネルギーを吸収することにより電子が励起し、それが基底状態に戻る際に放出される余分なエネルギーである。本発明においては、蛍光を発光する吸収波長領域を、紫外線領域から可視光線領域の範囲内に有する蛍光物質を用いる。なお、本明細書において、紫外線領域とは波長が１０ｎｍ以上４００ｎｍ未満の領域であり、また、可視光線領域とは波長が４００ｎｍ以上９００ｎｍ以下の領域である。 The photocurable composition for pattern formation of the present invention contains a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region. Here, fluorescence refers to light emitted when absorbing high-energy light (light rays) or radiation, and when the fluorescent material absorbs energy, electrons are excited and emitted when it returns to the ground state. Extra energy. In the present invention, a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region is used. In this specification, the ultraviolet region is a region having a wavelength of 10 nm to less than 400 nm, and the visible light region is a region having a wavelength of 400 nm to 900 nm.
　さらに、本発明で用いる蛍光物質は、蛍光物質を含有する本発明のパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が、蛍光物質が有する蛍光を発光する吸収波長領域の少なくとも一部、及び、蛍光物質が発光する蛍光の波長領域の少なくとも一部に、実質的に無いという条件を満たすものである。 Furthermore, the fluorescent material used in the present invention emits the fluorescence of the fluorescent material other than the fluorescent material in the photocured product obtained by exposing the photocurable composition for pattern formation of the present invention containing the fluorescent material. In other words, it satisfies the condition that it is substantially absent in at least a part of the absorption wavelength region and at least a part of the wavelength region of the fluorescence emitted by the fluorescent substance.
　本発明のパターン形成用光硬化性組成物に含まれる蛍光物質等の吸収スペクトルや蛍光スペクトルを示す図である図１を用いて具体的に説明する。図１は、波長２５０～６００ｎｍ付近における蛍光物質を含有する本発明のパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトルを（I）で表し、蛍光物質の吸収スペクトルを（II）で表し、蛍光物質が発光する蛍光スペクトルを（III）で表す。なお、蛍光物質の吸収スペクトル（II）は図１においては二つのピークを有するが、特に効率良く蛍光を発光する吸収波長領域は、長波長側の領域（図１においてαで示す。）であるので、図１のαの吸収波長領域を「蛍光物質が蛍光を発光する吸収波長領域」として説明する。まず、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が、蛍光物質が有する蛍光を発光する吸収波長領域の少なくとも一部に実質的に無いものであることが必要である。すなわち、少なくともパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が実質的に無い領域に、蛍光を発光する吸収がある蛍光物質を用いる。換言すると、蛍光物質の吸収スペクトル（II）のうち蛍光を発光する吸収波長領域αは、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない領域を有することが必要である。（II）のうち蛍光を発光する吸収波長領域αが、（I）と実質的に重ならない領域を有しない場合、蛍光物質の励起が阻害されるためである。図１においては、波長領域βは、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が実質的に無いため、蛍光を発光する吸収波長領域αは、波長領域βでは吸収スペクトル（I）と実質的に重なっていない。同様に、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が、蛍光物質が発光する蛍光の波長領域の少なくとも一部に実質的に無いものであることが必要である。すなわち、少なくともパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が実質的に無い領域で、蛍光を発光する蛍光物質を用いる。換言すると、蛍光物質が発光する蛍光の波長領域を示す蛍光スペクトル（III）は、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない領域を有することが必要である。（III）が（I）と実質的に重ならない領域を有しない場合、発光した蛍光（III）が吸収（I）に吸収されて蛍光発光を検出できなくなるためである。図１においては、波長領域γは、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が実質的に無いため、蛍光スペクトル（III）は、波長領域γでは、吸収スペクトル（I）と実質的に重なっていない。 Specific description will be given with reference to FIG. 1, which is a diagram showing an absorption spectrum and a fluorescence spectrum of a fluorescent substance and the like contained in the photocurable composition for pattern formation of the present invention. FIG. 1 shows (I) the absorption spectrum of a photocured material other than the fluorescent material obtained by exposing the photocurable composition for pattern formation of the present invention containing a fluorescent material in the vicinity of a wavelength of 250 to 600 nm. The absorption spectrum of the substance is represented by (II), and the fluorescence spectrum emitted from the fluorescent substance is represented by (III). The absorption spectrum (II) of the fluorescent substance has two peaks in FIG. 1, but the absorption wavelength region that emits fluorescence particularly efficiently is a region on the long wavelength side (indicated by α in FIG. 1). Therefore, the α absorption wavelength region in FIG. 1 will be described as “an absorption wavelength region in which the fluorescent substance emits fluorescence”. First, absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is substantially absent in at least a part of the absorption wavelength region that emits the fluorescence possessed by the fluorescent material. It is necessary. That is, a fluorescent material having absorption that emits fluorescence is used in a region where there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing at least the photocurable composition for pattern formation. In other words, the absorption wavelength region α that emits fluorescence in the absorption spectrum (II) of the fluorescent material is the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation. It is necessary to have a region that does not substantially overlap. This is because, in (II), when the absorption wavelength region α that emits fluorescence does not have a region that does not substantially overlap with (I), excitation of the fluorescent material is inhibited. In FIG. 1, since the wavelength region β has substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation, the absorption wavelength region α that emits fluorescence is In the wavelength region β, the absorption spectrum (I) does not substantially overlap. Similarly, absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is substantially absent in at least a part of the fluorescence wavelength region where the fluorescent material emits light. is required. That is, a fluorescent material that emits fluorescence is used at least in a region where there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation. In other words, the fluorescence spectrum (III) indicating the wavelength region of the fluorescence emitted by the fluorescent material is substantially the same as the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation. It is necessary to have areas that do not overlap. This is because, when (III) does not have a region that does not substantially overlap with (I), the emitted fluorescence (III) is absorbed by absorption (I) and fluorescence emission cannot be detected. In FIG. 1, since the wavelength region γ has substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation, the fluorescence spectrum (III) has the wavelength region γ. Then, it does not substantially overlap with the absorption spectrum (I).
　なお、パターン形成用光硬化性組成物を露光して得られる光硬化物は、光硬化性成分と蛍光物質と必要に応じて添加する添加剤等とを露光して硬化した成型体であるが、そのうち、光硬化性成分と、必要に応じて添加する添加剤等とを露光したものの吸収が「パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収」である。この「パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収」は、光硬化性組成物の蛍光物質以外の成分、すなわち、光硬化性成分及び必要に応じて添加する添加剤等を露光して得られた成型体の吸収を測定することにより求めることができる。 The photocured product obtained by exposing the photocurable composition for pattern formation is a molded product obtained by exposing and curing a photocurable component, a fluorescent material, an additive added as necessary, and the like. Among them, the absorption of the photocured component and the additive added as necessary is "absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation" It is. This "absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation" refers to components other than the fluorescent substance of the photocurable composition, that is, the photocurable component and, if necessary, It can be determined by measuring the absorption of the molded product obtained by exposing the additive to be added.
　また、図１においては、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が零の領域を、吸収が実質的に無い領域として説明したが、吸収が実質的に無いとは、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が、蛍光物質の励起や蛍光発光を妨げない程度であればよい。したがって、吸収が零の領域と零ではないが実質的無い領域とが混在していてもよく、また、吸収が零ではないが実質的に無い領域のみでもよい。例えば、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収の膜厚１μｍあたりの吸光度が０．１以下、好ましくは０．０５以下であれば、吸収が実質的に無い。なお、蛍光物質が蛍光を発光する吸収の極大波長や発光した蛍光の極大波長において、パターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収が、実質的に無いことが好ましい。 Moreover, in FIG. 1, although the area | region where absorption other than the fluorescent substance of the photocured material obtained by exposing the photocurable composition for pattern formation was demonstrated as an area | region which has substantially no absorption, absorption was demonstrated. The phrase “substantially absent” is sufficient if absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation does not interfere with excitation of the fluorescent material or fluorescence emission. Therefore, a region where absorption is zero and a region which is not zero but substantially absent may be mixed, or only a region where absorption is not zero but substantially absent may be present. For example, if the absorbance per 1 μm of film thickness of absorption other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation is 0.1 or less, preferably 0.05 or less, absorption is achieved. There is virtually no. In addition, absorption other than the fluorescent substance of the photocured material obtained by exposing the photocurable composition for pattern formation to the maximum wavelength of absorption at which the fluorescent substance emits fluorescence or the maximum wavelength of emitted fluorescence is substantially reduced. Preferably no.
　このような蛍光物質をパターン形成用光硬化性組成物に含有させることにより、蛍光物質の吸収スペクトル（II）のうち蛍光を発光する吸収波長領域αがパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない波長領域β内の波長の光を、パターン形成用光硬化性組成物を用いて製造された光硬化物に照射し、蛍光物質を励起させて、蛍光物質が発光する蛍光スペクトル（III）がパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない波長領域γ内の蛍光の強度を測定することにより、光硬化物の厚さを非破壊・非接触で短時間且つ容易に求めることができる。なお、上記蛍光物質であれば、発光される蛍光の強度と光硬化物の膜厚とに相関関係があるため、蛍光強度と光硬化物の厚さとの関係を別途求めておくことにより、測定された蛍光強度から光硬化物の厚さを求めることができる。ここで、蛍光を発光する吸収波長領域全てにおいて蛍光物質以外の光硬化物に吸収が実質的にあると、蛍光を発光させるために照射した光が光硬化物を透過せず、蛍光物質を励起して発光させることができない。また、発光される蛍光の波長領域全てにおいて蛍光物質以外の光硬化物の吸収が実質的にあると、発光された蛍光を検出し難くなり、蛍光強度と光硬化物の膜厚とに相関関係がなくなり、蛍光強度から光硬化物の厚さを求めることができない。 By including such a fluorescent substance in the photocurable composition for pattern formation, the absorption wavelength region α emitting fluorescence in the absorption spectrum (II) of the fluorescent substance exposes the photocurable composition for pattern formation. In the photocured material produced using the photocurable composition for pattern formation, light having a wavelength in the wavelength region β that does not substantially overlap with the absorption spectrum (I) other than the fluorescent material of the photocured material obtained in this way Irradiation, excitation of the fluorescent material, the fluorescence spectrum (III) emitted by the fluorescent material is substantially the same as the absorption spectrum (I) of the photocured product other than the fluorescent material obtained by exposing the photocurable composition for pattern formation. By measuring the intensity of the fluorescence in the wavelength region γ that does not overlap, the thickness of the photocured product can be easily determined in a short time in a non-destructive and non-contact manner. In addition, in the case of the above-mentioned fluorescent substance, there is a correlation between the intensity of emitted fluorescence and the film thickness of the photocured material. Therefore, by separately obtaining the relationship between the fluorescence intensity and the thickness of the photocured material, measurement is performed. The thickness of the photocured product can be obtained from the obtained fluorescence intensity. Here, if the photocured material other than the fluorescent material is substantially absorbed in the entire absorption wavelength region that emits fluorescence, the light irradiated to emit the fluorescent light does not pass through the photocured material and excites the fluorescent material. Cannot be emitted. In addition, if there is substantially absorption of a photocured material other than a fluorescent material in the entire wavelength region of the emitted fluorescence, it becomes difficult to detect the emitted fluorescence, and there is a correlation between the fluorescence intensity and the film thickness of the photocured product. The thickness of the photocured product cannot be determined from the fluorescence intensity.
　なお、蛍光物質は、パターン形成用光硬化性組成物を硬化させる光の波長付近の吸収が少ないものであることが好ましい。パターン形成用光硬化性組成物を露光して硬化させる際に、蛍光物質が光硬化を阻害しないようにするためである。 In addition, it is preferable that a fluorescent material is a thing with little absorption near the wavelength of the light which hardens the photocurable composition for pattern formation. This is because the fluorescent material does not inhibit photocuring when the photocurable composition for pattern formation is exposed and cured.
　また、蛍光物質が蛍光を発光する吸収波長の極大値におけるモル吸光係数εと、蛍光物質の蛍光量子収率φｆとの積ε・φｆが１×１０４以上であることが望ましい。蛍光を発光させるためには、蛍光物質が蛍光を発光する吸収波長領域の極大値付近の波長の光を照射するのが検出感度の点から望ましく、且つ蛍光物質の該吸収波長のモル吸光係数が大きい方が検出感度は高くなり、少量の添加でも正確に光硬化物の厚さを測定できるためである。モル吸光係数は以下のランベルト＝ベールの式から算出できる。 Further, the product ε · φf of the molar extinction coefficient ε at the maximum absorption wavelength at which the fluorescent material emits fluorescence and the fluorescent quantum yield φf of the fluorescent material is preferably 1 × 10 4 or more. In order to emit fluorescence, it is desirable from the point of detection sensitivity that the fluorescent material emits light having a wavelength near the maximum value of the absorption wavelength region where the fluorescent material emits fluorescence, and the molar absorption coefficient of the absorption wavelength of the fluorescent material is This is because the larger the value, the higher the detection sensitivity, and the thickness of the photocured product can be accurately measured even when a small amount is added. The molar extinction coefficient can be calculated from the following Lambert-Beer equation.
ｌｏｇ１０（I０／I）＝ε・ｌ・ｃ
　I０：入射光の強度
　I：透過光の強度
　ｌｏｇ１０(I０／I)：吸光度（Ａｂｓ）
　ε：モル吸光係数
　ｌ：光路長(ｃｍ)
　ｃ：濃度（ｍｏｌ／ｄｍ３） log 10 (I 0 / I) = ε · l · c
I 0 : intensity of incident light I: intensity of transmitted light log 10 (I 0 / I): absorbance (Abs)
ε: molar extinction coefficient l: optical path length (cm)
c: Concentration (mol / dm 3 )
　また、蛍光物質は、蛍光量子収率が１に近い方が望ましい。検出感度が高くなり、少量の添加でも正確に光硬化物の厚さを測定できるためである。 Also, it is desirable that the fluorescent substance has a fluorescence quantum yield close to 1. This is because the detection sensitivity becomes high, and the thickness of the photocured product can be accurately measured even when a small amount is added.
　なお、蛍光物質は、光硬化性成分中に均一に分散又は溶解させることができるものである必要がある。 Note that the fluorescent material needs to be capable of being uniformly dispersed or dissolved in the photocurable component.
　また、蛍光物質は、パターン形成用光硬化性組成物を露光して硬化させる際に消光や減光等が少ないものである方が望ましい。検出感度や定量性が低下するためである。具体的には、蛍光物質が蛍光を発光する吸収波長領域の波長であって光硬化性組成物に露光して得られる光硬化物の蛍光物質以外の吸収が実質的に無い波長領域（図１においては、β）の光を照射して蛍光を発光させる場合において、被転写材層を露光する前に発光した蛍光強度の極大値をＡ１、被転写材層を露光して硬化した後に発光した蛍光強度の極大値をＡ２としたとき、Ａ２／Ａ１の値が０．６以上、望ましくは０．８以上である。 Further, it is desirable that the fluorescent material has less quenching or dimming when the photocurable composition for pattern formation is exposed and cured. This is because the detection sensitivity and quantitativeness are lowered. Specifically, the wavelength region of the absorption wavelength region in which the fluorescent material emits fluorescence, and a wavelength region in which there is substantially no absorption other than the fluorescent material of the photocured product obtained by exposing the photocurable composition (FIG. 1). In the case of emitting fluorescence by irradiating the light of β), the maximum value of the fluorescence intensity emitted before exposing the transfer material layer is A1, and the light is emitted after the transfer material layer is exposed and cured. When the maximum value of the fluorescence intensity is A2, the value of A2 / A1 is 0.6 or more, preferably 0.8 or more.
　上記蛍光物質としては、例えば蛍光染料や蛍光顔料などの蛍光発光性色素、有機又は無機蛍光体等が挙げられる。特に、光硬化性組成物に溶解しやすく蛍光量子収率が高い点から、有機蛍光発光性色素が好ましい。本発明の光硬化性組成物は光ナノインプリントリソグラフィに用いられるため、リアクティブイオンエッチング等で最終的に除去できる、金属イオンを含まない有機蛍光発光性色素がより好ましい。有機蛍光発光性色素としては、例えば、ローダミン（ローダミン６Ｇ（対アニオンが、Ｃｌ－やＢＦ４ －）、ローダミンＢなど）等のキサンテン系色素や、クマリン色素、オキサジン系色素、スチルベン系色素、アリールジメチリデン系色素、シアニン系色素、ピリジン系色素、及びキナクリドン誘導体等がある。 Examples of the fluorescent substance include fluorescent luminescent dyes such as fluorescent dyes and fluorescent pigments, and organic or inorganic fluorescent substances. In particular, an organic fluorescent light-emitting dye is preferable because it is easily dissolved in the photocurable composition and has a high fluorescence quantum yield. Since the photocurable composition of the present invention is used for optical nanoimprint lithography, an organic fluorescent dye that does not contain metal ions and can be finally removed by reactive ion etching or the like is more preferable. Examples of organic fluorescent light-emitting dyes include xanthene dyes such as rhodamine (rhodamine 6G (the counter anion is Cl − or BF 4 − ), rhodamine B, etc.), coumarin dyes, oxazine dyes, stilbene dyes, aryls, and the like. Examples include dimethylidene dyes, cyanine dyes, pyridine dyes, and quinacridone derivatives.
　蛍光物質の添加量は、蛍光物質のモル吸光係数や蛍光量子収率、光硬化物の凹凸パターンの凹部や凸部の厚さにもよるが、光硬化性成分１００質量部に対して０．０００１～１０質量部、好ましくは０．０００５～５質量部、さらに好ましくは０．００１～１質量部である。添加量が０．０００１質量部未満では検出感度が低下し、１０質量部を超えると光硬化性成分への溶解性が不十分になる場合や、蛍光物質の自己吸収が起こり、膜厚との相関関係が取れなくなる場合があるからである。 The amount of the fluorescent substance added depends on the molar extinction coefficient of the fluorescent substance, the fluorescence quantum yield, and the thickness of the concave and convex portions of the concavo-convex pattern of the photocured product. The amount is 0001 to 10 parts by mass, preferably 0.0005 to 5 parts by mass, and more preferably 0.001 to 1 part by mass. When the addition amount is less than 0.0001 parts by mass, the detection sensitivity decreases. When the addition amount exceeds 10 parts by mass, the solubility in the photocurable component becomes insufficient, or self-absorption of the fluorescent substance occurs, and the film thickness This is because the correlation may not be obtained.
　なお、パターン形成用光硬化性組成物は基板やモールドへの塗膜形成性を良好にする上では、大気圧環境下、室温ないし室温近辺の温度にて液状を呈しているものを用いることが好ましい。具体的には、パターン形成用光硬化性組成物がモールドの凹凸パターンに充填できる程度の流動性を有することが好ましい。例えば、粘度が２５℃で１０Ｐａ・ｓ以下であればよいが、１００ｍＰａ・ｓ以下が好ましく、５０ｍＰａ・ｓ以下がさらに好ましく、２５ｍＰａ・ｓ以下が最も好ましい。粘度の測定方法としては、例えば、ＴＯＫIＭＥＣ社製のＢ型粘度計を用いて測定する方法が挙げられる。 In order to improve the film-forming property on the substrate or mold, the pattern-forming photocurable composition should be used in a liquid state at room temperature or near room temperature under an atmospheric pressure environment. preferable. Specifically, it is preferable that the photocurable composition for pattern formation has fluidity enough to fill the uneven pattern of the mold. For example, the viscosity may be 10 Pa · s or less at 25 ° C., preferably 100 mPa · s or less, more preferably 50 mPa · s or less, and most preferably 25 mPa · s or less. Examples of the viscosity measuring method include a method of measuring using a B-type viscometer manufactured by TOKIMEC.
　詳しくは後述するが、このような所定の蛍光物質等の成分からなる光硬化性組成物を用いれば、形成される凹凸パターンを有する光硬化物の凹部や凸部の厚さを非破壊・非接触で短時間且つ容易に測定することができる。 As will be described in detail later, if such a photocurable composition comprising a component such as a fluorescent substance is used, the thickness of the concave portion or convex portion of the photocured product having the concave / convex pattern to be formed is non-destructive / non-destructive Measurement can be easily performed in a short time by contact.
　次に、上記本発明のパターン形成用光硬化性組成物を用いて光インプリントリソグラフィにより凹凸パターンを有する光硬化物を形成する方法の一例を、図２を用いて説明する。なお、図２は、本発明のパターン形成用光硬化性組成物を用いて凹凸パターンを有する光硬化物を形成する方法の概略を示す断面図である。 Next, an example of a method for forming a photocured product having an uneven pattern by photoimprint lithography using the photocurable composition for pattern formation of the present invention will be described with reference to FIG. In addition, FIG. 2 is sectional drawing which shows the outline of the method of forming the photocured material which has an uneven | corrugated pattern using the photocurable composition for pattern formation of this invention.
　まず、図２（ａ）に示すように、基板１上に本発明のパターン形成用光硬化性組成物を塗布して、基板１上にパターン形成用光硬化性組成物からなる被転写材層２を設ける。なお、図２では基板１上にパターン形成用光硬化性組成物を塗布したが、モールド３にパターン形成用光硬化性組成物を塗布してもよい。 First, as shown in FIG. 2 (a), the pattern-forming photocurable composition of the present invention is applied onto the substrate 1, and the transfer material layer made of the pattern-forming photocurable composition on the substrate 1. 2 is provided. In FIG. 2, the pattern-forming photocurable composition is applied on the substrate 1, but the pattern-forming photocurable composition may be applied to the mold 3.
　モールド３は、表面に所望の凹凸のパターンが形成されていればよい。モールド３の材質の例としては、石英ガラス、合成樹脂等の透明なものの他、シリコン、シリコンカーバイド、酸化シリコン、ニッケル等の金属や金属酸化物等の光を透過しないものも挙げられる。モールド３の外観は、通常の光インプリントリソグラフィにおいて用いられているモールド３の外観と同様のものでよく、例えば外観が直方体状又はロール状であってよい。 The mold 3 may have a desired uneven pattern on the surface. Examples of the material of the mold 3 include transparent materials such as quartz glass and synthetic resin, as well as materials that do not transmit light such as metals such as silicon, silicon carbide, silicon oxide, and nickel, and metal oxides. The appearance of the mold 3 may be the same as that of the mold 3 used in normal optical imprint lithography. For example, the appearance may be a rectangular parallelepiped shape or a roll shape.
　また、モールド３表面に形成されている凹凸のパターンは、通常の光インプリントリソグラフィにおいて用いられているモールド３の表面に形成されている凹凸のパターンと同様のものであってよいが、それに限定されるものでない。例えば、モールドの材料の表面に窪みを形成することにより凹部を形成したモールド３としてもよく、この場合、相対的に表面側に突出した部分が凸部となる。また、モールド３の材料の表面に突起を設けることにより凸部を形成したモールド３としてもよく、この場合、相対的に内側に窪んだ部分が凹部となる。さらに、原盤の材料の表面に窪みまたは突起を設けることにより形成した凹凸パターンを有する原盤を用い、この原盤を鋳型として形成したモールド３としてもよい。凹凸のパターンの各凹部の断面の形状は、正方形、長方形、半月形、またはそれら形状に類似した形状等でもよく、各凹部は、例えば、深さが１ｎｍ～１００μｍ程度、開口部の幅が１ｎｍ～１００μｍ程度のものであってよい。 Further, the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold 3 used in normal optical imprint lithography, but is not limited thereto. It is not what is done. For example, it is good also as the mold 3 which formed the recessed part by forming the hollow in the surface of the material of a mold, and the part which protruded relatively to the surface side becomes a convex part in this case. Moreover, it is good also as the mold 3 which formed the convex part by providing a processus | protrusion on the surface of the material of the mold 3, In this case, the recessed part relatively inside becomes a recessed part. Furthermore, it is good also as the mold 3 which used the original disk which has the uneven | corrugated pattern formed by providing the hollow or protrusion on the surface of the original material, and formed this original disk as a casting_mold | template. The cross-sectional shape of each concave portion of the concave / convex pattern may be square, rectangular, half-moon shape, or a shape similar to those shapes. Each concave portion has a depth of about 1 nm to 100 μm and an opening width of 1 nm, for example. It may be about 100 μm.
　また、後段の離型工程でモールド３と被転写材層２が硬化した光硬化物４との離型性を良好にするために、モールド３の表面に、離型処理が施されていてもよい。離型処理は気相法や液相法等により、パーフルオロ系又は炭化水素系の高分子化合物、アルコキシシラン化合物又はトリクロロシラン化合物、ダイヤモンドライクカーボン等に例示される公知の離型処理剤を用いて行うことができる。 Further, in order to improve the mold releasability between the mold 3 and the photocured material 4 obtained by curing the transfer material layer 2 in the subsequent mold release step, the surface of the mold 3 may be subjected to a mold release treatment. Good. For the release treatment, a known release treatment agent exemplified by a perfluoro- or hydrocarbon-based polymer compound, an alkoxysilane compound or a trichlorosilane compound, diamond-like carbon, or the like is used by a gas phase method or a liquid phase method. Can be done.
　基板１等にパターン形成用光硬化性組成物からなる被転写材層２を形成する方法は特に限定されず、例えば、必要に応じ溶剤等で希釈したパターン形成用光硬化性組成物の塗布や滴下、具体的には、スピンコート、ロールコート、ディップコート、グラビアコート、ダイコート、カーテンコート、インクジェット塗布及びディスペンサー塗布等が挙げられる。 The method for forming the transfer material layer 2 made of the pattern-forming photocurable composition on the substrate 1 or the like is not particularly limited. For example, application of the pattern-forming photocurable composition diluted with a solvent or the like as necessary Dropping, specifically, spin coating, roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, dispenser coating, and the like.
　モールド３や基板１の全面を覆うように被転写材層２を設けてもよく、一部のみを覆うように設けてもよい。また、被転写材層２の厚さは、モールド３に形成された凹凸のパターンの凹部に充填される被転写材層２の量、例えば凹凸のパターンの凹部の深さなどを考慮して設定すればよい。 The transfer material layer 2 may be provided so as to cover the entire surface of the mold 3 and the substrate 1, or may be provided so as to cover only a part thereof. The thickness of the transfer material layer 2 is set in consideration of the amount of the transfer material layer 2 filled in the recesses of the uneven pattern formed on the mold 3, for example, the depth of the recesses of the uneven pattern. do it.
　次に、基板１とモールド３とで被転写材層２を挟みこむ。基板１をモールド３に押圧しても、モールド３を基板１に押圧してもよく、基板１及びモールド３の両方を押圧してもよい。基板１やモールド３を押圧する力は、例えば、０．０１～１００ＭＰａ程度とすることができる。また、力をかけず、モールド３や基板１の自重による押圧でもよい。このように、基板１に対してモールド３を押圧することにより、図２（ｂ）に示すように、モールド３の凹凸パターンに被転写材層２が充填される。 Next, the transfer material layer 2 is sandwiched between the substrate 1 and the mold 3. The substrate 1 may be pressed against the mold 3, the mold 3 may be pressed against the substrate 1, or both the substrate 1 and the mold 3 may be pressed. The force for pressing the substrate 1 and the mold 3 can be set to about 0.01 to 100 MPa, for example. Further, pressing by the weight of the mold 3 or the substrate 1 may be performed without applying force. In this way, by pressing the mold 3 against the substrate 1, the transferred material layer 2 is filled in the uneven pattern of the mold 3 as shown in FIG.
　被転写材層２とモールド３とを共に水平に保って被転写材層２とモールド３とを接触させてモールド３の凹凸パターンに被転写材層２を充填させることが好ましいが、得られるパターンに支障が生じなければ、水平に保つことに限定する必要はない。なお、従来の光インプリントリソグラフィにおける装置を用いることができる。 It is preferable that the transfer material layer 2 and the mold 3 are both kept horizontal, the transfer material layer 2 and the mold 3 are brought into contact with each other, and the uneven pattern of the mold 3 is filled with the transfer material layer 2. As long as there is no hindrance, it is not necessary to limit to keeping it horizontal. A conventional apparatus for optical imprint lithography can be used.
　次いで、図２（ｃ）に示すように、モールド３の凹凸パターンに被転写材層２を充填した状態で被転写材層２を露光し、硬化させて光硬化物４とする（光硬化工程）。露光に用いる光源は、パターン形成用光硬化性組成物が硬化する波長の光を照射できるものであればよい。光源の例としては、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、キセノンランプ、カーボンアーク、水銀キセノンランプ、ＸｅＣｌ、ＫｒＦやＡｒＦ等のエキシマーレーザー、紫外あるいは可視光レーザー、及び紫外あるいは可視光ＬＥＤ等が挙げられる。光の照射量は、被転写材層２を硬化させることができる量であればよい。工業的に実施する際には、通常、１０Ｊ／ｃｍ２以下の範囲内で照射量を選定するとよい。なお、基板１及びモールド３のうち、照射する光に対して実質的に透明である部材の側から被転写材層２に光を照射する。 Next, as shown in FIG. 2C, the transferred material layer 2 is exposed in a state where the uneven pattern of the mold 3 is filled with the transferred material layer 2 and cured to obtain a photocured product 4 (photocuring step). ). The light source used for exposure may be any light source that can irradiate light having a wavelength at which the photocurable composition for pattern formation is cured. Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc, mercury xenon lamps, excimer lasers such as XeCl, KrF and ArF, ultraviolet or visible light lasers, and ultraviolet light. Or visible light LED etc. are mentioned. The light irradiation amount may be an amount that can cure the transfer material layer 2. When it implements industrially, it is usually preferable to select an irradiation dose within a range of 10 J / cm 2 or less. In addition, light is irradiated to the to-be-transferred material layer 2 from the member side which is substantially transparent with respect to the light irradiated among the board | substrate 1 and the mold 3. FIG.
　その後、図２（ｄ）に示すように、光硬化物４からモールド３を離型することにより、モールド３の凹凸パターンが転写されたパターンを表面に有する光硬化物４を形成することができる（離型工程）。なお、離型する際には、基板とモールドとを共に水平に保って離型することが好ましいが、水平に保つことに限定する必要はない。 Thereafter, as shown in FIG. 2 (d), by releasing the mold 3 from the photocured product 4, it is possible to form the photocured product 4 having a pattern on which the concave and convex pattern of the mold 3 is transferred. (Release process). When releasing, it is preferable to release the substrate and the mold while keeping them both horizontal, but it is not necessary to be limited to keeping them horizontal.
　パターン形成用光硬化性組成物が光により硬化する成分や熱により硬化する成分を含有する場合は、光硬化物４の強度を向上させるために、離型工程の後に、光または熱により光硬化物４をさらに硬化する工程をさらに有していてもよい。 When the photocurable composition for pattern formation contains a component that is cured by light or a component that is cured by heat, it is photocured by light or heat after the mold release step in order to improve the strength of the photocured product 4. You may further have the process of hardening the thing 4 further.
　このように本発明のパターン形成用光硬化性組成物を用いて形成された凹凸パターンを有する光硬化物４は、破壊することなく、短時間で容易に凹部や凸部の厚さを測定することができる。 Thus, the photocured material 4 having a concavo-convex pattern formed using the photocurable composition for pattern formation of the present invention easily measures the thickness of the concave portions and convex portions in a short time without breaking. be able to.
　具体的には、まず、凹凸パターンを有する光硬化物４の厚さを測定したい領域に、パターン形成用光硬化性組成物に含有させた上記蛍光物質が蛍光を発光する吸収波長であって、光硬化物４の蛍光物質以外の吸収が実質的に無い波長の光、すなわち、蛍光物質が有する蛍光を発光する吸収波長領域を示す吸収スペクトル（II）のうち蛍光を発光する吸収波長領域αがパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない波長領域β内の波長の光を照射する。そして、該光の照射により蛍光物質が励起して発光する蛍光スペクトル（III）がパターン形成用光硬化性組成物を露光して得られる光硬化物の蛍光物質以外の吸収スペクトル（I）と実質的に重ならない波長領域γ内の蛍光の強度を測定する。なお、蛍光強度は、例えば、蛍光分光光度計や蛍光顕微鏡等により測定することができる。そして、上記所定の蛍光物質を用いているので発光される蛍光の強度と光硬化物４の膜厚とは相関関係があるため、蛍光強度と光硬化物の厚さとの関係を別途求めておくことにより、測定された蛍光強度から、光硬化物４の凹部や凸部の厚さを求めることができる。 Specifically, first, in the region where the thickness of the photocured product 4 having a concavo-convex pattern is desired to be measured, the fluorescent material contained in the pattern forming photocurable composition has an absorption wavelength at which fluorescence is emitted, The absorption wavelength region α that emits fluorescence out of the absorption spectrum (II) indicating the absorption wavelength region that emits fluorescence of the fluorescent material, that is, light having substantially no absorption other than the fluorescent material of the photocured product 4 Light having a wavelength in the wavelength region β that does not substantially overlap with the absorption spectrum (I) other than the fluorescent material of the photocured product obtained by exposing the photocurable composition for pattern formation is irradiated. Then, the fluorescence spectrum (III) in which the fluorescent substance is excited by the light irradiation to emit light is substantially equal to the absorption spectrum (I) other than the fluorescent substance of the photocured product obtained by exposing the photocurable composition for pattern formation. The intensity of fluorescence in the wavelength region γ that does not overlap is measured. The fluorescence intensity can be measured with, for example, a fluorescence spectrophotometer or a fluorescence microscope. Since the predetermined fluorescent material is used, there is a correlation between the intensity of the emitted fluorescence and the film thickness of the photocured material 4, so that the relationship between the fluorescence intensity and the thickness of the photocured material is obtained separately. Thereby, the thickness of the recessed part and convex part of the photocured material 4 can be calculated | required from the measured fluorescence intensity.
　ここで、凹凸を測定する一般的な方法である表面粗さ計では非破壊の状態で凹部（残膜）の厚さは測定できないが、本発明では凹部の厚さも非破壊で測定することができる。また、Ｘ線で蛍光を発光する蛍光物質を用いて蛍光Ｘ線分析により厚さを測定することも考えられるが、蛍光Ｘ線分析は装置が大掛かりになり、測定が複雑になる等の問題があり容易に凹凸の厚さを測定することはできない。さらに、従来は非破壊の状態で凸部の厚さと凹部の厚さとを同時に検出することはできなかったが、本発明によれば、凸部の厚さと凹部の厚さとを同時に、しかも非破壊・非接触で短時間且つ容易に測定することができる。また、光硬化物４の凸部や凹部の厚さが１ｎｍ～２０μｍのものは厚さが薄いため非破壊・非接触の測定方法で正確に厚さを求めることはできなかったが、このような微細なパターンを有する光硬化物であっても、本発明のパターン形成用光硬化性組成物を用いれば、検出感度が高いので、厚さを正確且つ短時間で容易に測定することができる。また、光硬化物４のパターンの凸部や凹部の幅が１０ｎｍ～１００μｍのものは測定領域が狭くなるため非破壊・非接触の測定方法で正確に厚さを求めることはできなかったが、このような微細なパターンを有する光硬化物であっても、本発明のパターン形成用光硬化性組成物を用いれば、蛍光強度の検出と水平方向のパターン形状の検出を同時に行うことにより厚さを正確且つ容易に測定することができる。 Here, the surface roughness meter which is a general method for measuring unevenness cannot measure the thickness of the recess (residual film) in a non-destructive state, but in the present invention, the thickness of the recess can also be measured non-destructively. it can. In addition, it is conceivable to measure the thickness by fluorescent X-ray analysis using a fluorescent substance that emits fluorescence by X-rays. However, the fluorescent X-ray analysis has a problem that the apparatus becomes large and the measurement becomes complicated. The thickness of the unevenness cannot be easily measured. Furthermore, conventionally, the thickness of the convex portion and the thickness of the concave portion could not be detected at the same time in a non-destructive state, but according to the present invention, the thickness of the convex portion and the thickness of the concave portion can be detected simultaneously and non-destructively.・ It can be measured easily in a short time without contact. In addition, the thickness of the light-cured product 4 having a convex or concave portion of 1 nm to 20 μm was so thin that the thickness could not be accurately determined by a non-destructive / non-contact measuring method. Even if it is a photocured material having a fine pattern, if the photocurable composition for pattern formation of the present invention is used, the detection sensitivity is high, so that the thickness can be measured accurately and easily in a short time. . Further, when the width of the convex part or concave part of the pattern of the photocured product 4 is 10 nm to 100 μm, the measurement area becomes narrow, so the thickness could not be obtained accurately by the non-destructive / non-contact measuring method. Even if it is a photocured material having such a fine pattern, if the photocurable composition for pattern formation of the present invention is used, the thickness can be detected by simultaneously detecting the fluorescence intensity and the horizontal pattern shape. Can be measured accurately and easily.
　なお、上記では、光インプリントリソグラフィにより凹凸パターンを有する光硬化物を形成する方法、及び、該方法によって得られた凹凸パターンを有する光硬化物の膜厚測定方法を、本発明のパターン形成用光硬化性組成物を用いた場合について説明したが、本発明のパターン形成用光硬化性組成物に限らず、蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有するパターン形成用光硬化性組成物であれば、適用することができる。 In the above, the method for forming a photocured product having a concavo-convex pattern by photoimprint lithography and the method for measuring the film thickness of a photocured product having a concavo-convex pattern obtained by the method are used for pattern formation of the present invention. Although the case where a photocurable composition was used was demonstrated, it is not restricted to the photocurable composition for pattern formation of this invention, The fluorescent material which has the absorption wavelength range which light-emits fluorescence in the range of an ultraviolet region from a visible light region Can be applied as long as it is 0.0001 to 10 parts by mass of the photocurable component.
　以下、実施例を示し、本発明をさらに具体的に説明する。なお、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.
　（実施例１）
　＜パターン形成用光硬化性組成物の調製＞
　光重合性化合物として２－ヒドロキシ－３－フェノキシプロピルアクリレート３０質量部、ジアクリレートであるＫＡＹＡＲＡＤ　Ｒ－６０４（日本化薬（株）製）４５質量部、及びトリメチロールプロパントリアクリレート２０質量部と、光重合開始剤として１－ヒドロキシシクロヘキシルフェニルケトン５質量部とを室温で撹拌・混合して、光硬化性成分からなる液状の組成物ａを得た。 Example 1
<Preparation of photocurable composition for pattern formation>
As a photopolymerizable compound, 30 parts by mass of 2-hydroxy-3-phenoxypropyl acrylate, 45 parts by mass of diacrylate KAYARAD R-604 (manufactured by Nippon Kayaku Co., Ltd.), and 20 parts by mass of trimethylolpropane triacrylate, As a photopolymerization initiator, 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone was stirred and mixed at room temperature to obtain a liquid composition a comprising a photocurable component.
　この組成物ａに、蛍光を発光する吸収波長領域を可視光線領域に有する蛍光物質ローダミン６Ｇ（対アニオン；ＢＦ４ -)を０．００５質量部添加し、室温で撹拌・混合して、光硬化性成分ａと蛍光物質ローダミン６Ｇ（対アニオン；ＢＦ４ -)からなる液状のパターン形成用光硬化性組成物Ａを得た。表１にパターン形成用光硬化性組成物Ａの組成を示す。また、蛍光物質ローダミン６Ｇ（対アニオン；ＢＦ４ -)における、蛍光を発光する吸収の極大波長λｅｘ、発光する蛍光の極大波長λｅｍ、蛍光を発光する吸収の極大波長λｅｘにおけるモル吸光係数ε、蛍光量子収率φｆ、及びεとφｆとの積の値を表２に示す。 To this composition a is added 0.005 parts by mass of a fluorescent substance rhodamine 6G (counter anion; BF 4 − ) having an absorption wavelength region for emitting fluorescence in the visible light region, and the mixture is stirred and mixed at room temperature to be photocured. A liquid pattern-forming photocurable composition A comprising an organic component a and a fluorescent substance rhodamine 6G (counter anion; BF 4 − ) was obtained. Table 1 shows the composition of the photocurable composition A for pattern formation. Further, in the fluorescent substance rhodamine 6G (counter anion; BF 4 − ), the absorption maximum wavelength λex that emits fluorescence, the maximum wavelength λem of emission fluorescence, the molar absorption coefficient ε at the absorption maximum wavelength λex that emits fluorescence, fluorescence Table 2 shows the quantum yield φf and the product of ε and φf.
　また、光硬化性成分からなる組成物ａの光硬化物の膜厚１μｍあたりの吸光度は、表３に示すように、ローダミン６Ｇ（対アニオン；ＢＦ４ -)が蛍光を発光する吸収極大波長５３０ｎｍ、及び、発光する蛍光の極大波長５６０ｎｍにおいて、それぞれ７．７×１０－３、７．３×１０－３であり実質的に吸収がないことを確認した。なお、吸収波長及び吸収強度は紫外－可視分光光度計（島津製作所（株）製、型番：ＭｕｌｔIｓｐｅｃ-１５００）、発光した蛍光波長及び蛍光強度は蛍光分光光度計（（株）日立ハイテクノロジーズ製、型番：Ｆ－７０００）により測定した。 Further, as shown in Table 3, the absorbance per 1 μm of the film thickness of the photocured product of the composition a composed of the photocurable component is the absorption maximum wavelength 530 nm at which rhodamine 6G (counter anion; BF 4 − ) emits fluorescence. And at the maximum wavelength of 560 nm of the emitted fluorescence, they were 7.7 × 10 −3 and 7.3 × 10 −3 , respectively, and it was confirmed that there was substantially no absorption. The absorption wavelength and absorption intensity were measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model number: MultiIspec-1500), and the emitted fluorescence wavelength and fluorescence intensity were measured with a fluorescence spectrophotometer (manufactured by Hitachi High-Technologies Corporation). Model No .: F-7000).
　＜パターン形成用光硬化性組成物の蛍光発光性評価＞
　調製した上記パターン形成用光硬化性組成物Ａを、シリコン基板上に膜厚１２０ｎｍになるようにスピンコートした。この光硬化前の塗布膜に波長５３０ｎｍの光を照射し、発光した蛍光強度の極大値Ａ１を測定したところ、Ａ１は９．７であった。次に上記塗布膜に波長３６５ｎｍの紫外線を露光量１Ｊ／ｃｍ２で照射し硬化させた。この光硬化物に波長５３０ｎｍの光を照射し、発光した蛍光強度の極大値Ａ２を測定したところ、Ａ２は１０．６であった。この結果、Ａ２／Ａ１の値は１．１であり、パターン形成用光硬化性組成物Ａを光硬化させた後も十分な強度の蛍光を検出できることが確認された。 <Fluorescence emission evaluation of photocurable composition for pattern formation>
The prepared photocurable composition A for pattern formation was spin-coated on a silicon substrate so as to have a film thickness of 120 nm. When the coating film before photocuring was irradiated with light having a wavelength of 530 nm and the maximum value A1 of the emitted fluorescence intensity was measured, A1 was 9.7. Next, the coating film was cured by irradiating ultraviolet rays having a wavelength of 365 nm with an exposure amount of 1 J / cm 2 . When the photocured product was irradiated with light having a wavelength of 530 nm and the maximum value A2 of the emitted fluorescence intensity was measured, A2 was 10.6. As a result, the value of A2 / A1 was 1.1, and it was confirmed that sufficient intensity of fluorescence could be detected even after the photocurable composition A for pattern formation was photocured.
　（モールドの離型処理）
　高さ３５０ｎｍ、幅１０μｍでラインアンドスペースが１：５のラインパターンを有する１インチ角の石英モールドを純水で洗浄後、ＵＶオゾンクリーナーで３０分間処理した。これを１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロデシルトリメトキシシランの１質量％ハイドロフルオロエーテル（Ｃ４Ｆ９ＯＣＨ３）溶液に浸漬し、引き上げた後、室温、常圧で一昼夜放置し乾燥させた。これをハイドロフルオロエーテルに浸漬して余分な１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロデシルトリメトキシシランを除き、表面に離型処理を施した石英モールドを得た。 (Mold release process)
A 1-inch square quartz mold having a line pattern with a height of 350 nm and a width of 10 μm and a line-and-space ratio of 1: 5 was washed with pure water and then treated with a UV ozone cleaner for 30 minutes. This was immersed in a 1% by mass hydrofluoroether (C 4 F 9 OCH 3 ) solution of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, pulled up, allowed to stand overnight at room temperature and atmospheric pressure, and dried. It was. This was immersed in hydrofluoroether to remove excess 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, and a quartz mold having a release treatment on the surface was obtained.
　（検量線の作成）
　実施例１のパターン形成用光硬化性組成物Ａをシリコン基板上にスピンコートし、不活性ガス中で波長３６５ｎｍの紫外線を露光量１Ｊ／ｃｍ２で光硬化させ、パターン形成用光硬化性組成物Ａの光硬化膜を、膜厚を変えて５種類作製した。この光硬化膜に波長５３０ｎｍの光を照射し、発光した蛍光強度を測定したところ、７６、９１、１１２、１２７、１４８であった。またこの光硬化膜に傷をつけ、触針式表面形状測定器（製品名：ＤＥＫＴＡＫ１５０、アルバック　イーエス（株）製）で膜厚を測定したところ、それぞれ膜厚６２ｎｍ、６８ｎｍ、７５ｎｍ、８５ｎｍ、及び９８ｎｍであった。結果を図３に示す。図３に示すように、蛍光強度と膜厚には比例関係が見られた。 (Create a calibration curve)
The photocurable composition A for pattern formation of Example 1 was spin-coated on a silicon substrate, and ultraviolet light having a wavelength of 365 nm was photocured in an inert gas at an exposure amount of 1 J / cm 2 to form a photocurable composition for pattern formation. Five types of photocured films of the product A were produced by changing the film thickness. The photocured film was irradiated with light having a wavelength of 530 nm, and the emitted fluorescence intensity was measured, and was found to be 76, 91, 112, 127, 148. Further, the photocured film was scratched, and the film thickness was measured with a stylus type surface shape measuring instrument (product name: DEKTAK150, manufactured by ULVAC-ES Co., Ltd.). The film thickness was 62 nm, 68 nm, 75 nm, 85 nm, and It was 98 nm. The results are shown in FIG. As shown in FIG. 3, a proportional relationship was observed between the fluorescence intensity and the film thickness.
　（パターンを有する光硬化物の形成及び膜厚測定）
　実施例１のパターン形成用光硬化性組成物Ａを、シリコン基板上に膜厚１００ｎｍになるようにスピンコートしてパターン形成用光硬化性組成物Ａからなる被転写材層を形成した。この被転写材層を上記のシリコン基板と上記の離型処理済石英モールドとで挟み込み、インプリント装置（商品名；ＮＭ－８０１、明昌機工（株）製）を用いて０．３ＭＰａの圧力で押圧して、モールドの凹凸パターンにパターン形成用光硬化性組成物Ａを充填した。その後、超高圧水銀ランプを用いて波長３６５ｎｍの紫外線を１Ｊ／ｃｍ２露光して光硬化性組成物Ａを硬化させることにより成形した後、モールドを離型し、モールドの凹凸形状が転写されたパターンを有する光硬化物を得た。この光硬化物に波長５３０ｎｍの光を照射し、蛍光顕微鏡を使用してパターンを有する光硬化物の凹部及び凸部から発光した蛍光強度を測定した。蛍光顕微鏡写真を図４に示す。なおオリンパス製ＢＸ６０光学顕微鏡に、光源１００Ｗハロゲンランプ、オリンパス製蛍光キューブＵ－ＭＷIＧ（励起波長５３０～５５０ｎｍ、検出波長５７０ｎｍ以上）、オリンパス製ＣＣＤカメラＦＤ７０、三谷商事製解析ソフトウエアＷIｎＲＯＯＦを装着した蛍光顕微鏡を発光パターン画像取得装置として用いた。画像取得条件をIＳＯ値２００および取得時間７秒で発光パターン画像の取得を行い、発光強度を測定した。 (Formation of photocured product having pattern and measurement of film thickness)
The pattern-forming photocurable composition A of Example 1 was spin-coated on a silicon substrate so as to have a film thickness of 100 nm to form a transfer material layer made of the pattern-forming photocurable composition A. The transfer material layer is sandwiched between the silicon substrate and the release-treated quartz mold, and an imprint apparatus (trade name; NM-801, manufactured by Myeongchang Kiko Co., Ltd.) is used at a pressure of 0.3 MPa. It pressed and filled the pattern concavo-convex pattern with pattern forming photocurable composition A. Then, after molding by curing the photocurable composition A by exposing ultraviolet rays having a wavelength of 365 nm to 1 J / cm 2 using an ultra-high pressure mercury lamp, the mold was released, and the uneven shape of the mold was transferred. A photocured product having a pattern was obtained. The photocured product was irradiated with light having a wavelength of 530 nm, and the fluorescence intensity emitted from the concave and convex portions of the photocured product having a pattern was measured using a fluorescence microscope. A fluorescence micrograph is shown in FIG. A fluorescent lamp equipped with a light source 100W halogen lamp, Olympus fluorescent cube U-MWIG (excitation wavelength 530 to 550 nm, detection wavelength 570 nm or more), Olympus CCD camera FD70, Mitani Corporation analysis software WInROOF to Olympus BX60 optical microscope A microscope was used as an emission pattern image acquisition device. A light emission pattern image was acquired with an ISO value of 200 and an acquisition time of 7 seconds as image acquisition conditions, and the light emission intensity was measured.
　そして、上記検量線をもとに、上記のパターンを有する光硬化物の凹部の蛍光強度１９から凹部の厚さを求めた。この結果、光硬化物の凹部は３１．４ｎｍであった。一方、この光硬化物に傷をナイフで付け、触針式表面粗さ計で凹部の厚さを計測したところ、凹部は３２．０ｎｍであり、本発明の方法で正確に膜厚が測定できたことを確認した。なお、図３の検量線は、原点を通らないものであるが、上記のようにこの検量線を用いて正確に膜厚が測定できていた。実施例では、測定領域が狭く厚さが薄い凹部の厚さを非破壊且つ非接触の方法で容易に測定することができた。 Then, based on the calibration curve, the thickness of the recess was determined from the fluorescence intensity 19 of the recess of the photocured product having the above pattern. As a result, the concave portion of the photocured product was 31.4 nm. On the other hand, when this photocured product was scratched with a knife and the thickness of the recess was measured with a stylus type surface roughness meter, the recess was 32.0 nm, and the film thickness could be accurately measured by the method of the present invention. I confirmed that. The calibration curve in FIG. 3 does not pass through the origin, but the film thickness could be accurately measured using this calibration curve as described above. In the example, the thickness of the recess having a narrow measurement region and a small thickness could be easily measured by a non-destructive and non-contact method.
　（実施例２）
　蛍光物質としてローダミン６Ｇ（対アニオン；Ｃｌ-)０．００５質量部を用いたこと以外は実施例１と同様の方法で、光硬化性成分からなる組成物ａ及びパターン形成用光硬化性組成物Ｂを調製した。パターン形成用光硬化性組成物Ｂの組成を表１、ローダミン６Ｇ（対アニオン；Ｃｌ-)の性質を表２に示す。 (Example 2)
A composition a comprising a photocurable component and a photocurable composition for pattern formation were prepared in the same manner as in Example 1 except that 0.005 parts by mass of rhodamine 6G (counter anion; Cl − ) was used as the fluorescent substance. B was prepared. The composition of the photocurable composition B for pattern formation is shown in Table 1, and the properties of rhodamine 6G (counter anion; Cl − ) are shown in Table 2.
　また、光硬化性成分からなる組成物ａの光硬化物の膜厚１μｍあたりの吸光度は、表３に示すように、ローダミン６Ｇ（対アニオン；Ｃｌ-)が蛍光を発光する吸収極大波長５３０ｎｍ、及び、発光する蛍光の極大波長５６０ｎｍにおいて、それぞれ７．７×１０－３、７．３×１０－３であり実質的に吸収がないことを確認した。なお、吸収波長及び吸収強度、発光した蛍光波長及び蛍光強度は、実施例１と同様にして測定した。 Further, the absorbance per 1 μm of the film thickness of the photocured product of the composition a comprising the photocurable component, as shown in Table 3, is the absorption maximum wavelength 530 nm at which rhodamine 6G (counter anion; Cl − ) emits fluorescence, In addition, it was confirmed that the emission was 7.7 × 10 −3 and 7.3 × 10 −3 at the maximum wavelength of 560 nm of the emitted light, and there was substantially no absorption. The absorption wavelength and absorption intensity, and the emitted fluorescence wavelength and fluorescence intensity were measured in the same manner as in Example 1.
　調製した上記パターン形成用光硬化性組成物Ｂを、シリコン基板上に膜厚１２０ｎｍになるようにスピンコートした。この光硬化前の塗布膜に波長５３０ｎｍの光を照射し、発光した蛍光強度の極大値Ａ１を測定したところ、Ａ１は８．７であった。次に上記塗布膜に波長３６５ｎｍの紫外線を露光量１Ｊ／ｃｍ２で照射し硬化させた。この光硬化物に波長５３０ｎｍの光を照射し、発光した蛍光強度の極大値Ａ２を測定したところ、Ａ２は９．１であった。したがって、Ａ２／Ａ１の値は１．０であり、パターン形成用光硬化性組成物Ｂを光硬化させた後も十分な強度の蛍光を検出でき、実施例１と同様に正確に膜厚が測定できることを確認した。 The prepared photocurable composition B for pattern formation was spin-coated on a silicon substrate so as to have a film thickness of 120 nm. When the coating film before photocuring was irradiated with light having a wavelength of 530 nm and the maximum value A1 of the emitted fluorescence intensity was measured, A1 was 8.7. Next, the coating film was cured by irradiating ultraviolet rays having a wavelength of 365 nm with an exposure amount of 1 J / cm 2 . When this photocured product was irradiated with light having a wavelength of 530 nm and the maximum value A2 of the emitted fluorescence intensity was measured, A2 was 9.1. Therefore, the value of A2 / A1 is 1.0, and fluorescence with sufficient intensity can be detected even after the photocurable composition B for pattern formation is photocured, and the film thickness is precisely as in Example 1. It was confirmed that measurement was possible.
　（実施例３）
　蛍光物質としてクマリン５４０Ａを用いたこと以外は実施例１と同様の方法で光硬化性成分からなる組成物ａ及びパターン形成用光硬化性組成物Ｃを調製した。パターン形成用光硬化性組成物Ｃの組成を表１、クマリン５４０Ａの性質を表２に示す。また実施例１と同様の方法で光硬化前後の塗布膜の蛍光強度比Ａ２／Ａ１を求めた。結果を表３に示す。なお、蛍光を発光させるために照射した光の波長は４１０ｎｍである。Ａ１は１．０、Ａ２は０．５３、Ａ２／Ａ１値は０．５３であり、蛍光強度は実施例１及び２と比較して低下したが、十分検出できる値であり、実施例１と同様に正確に膜厚が測定できることを確認した。 (Example 3)
A composition a composed of a photocurable component and a photocurable composition C for pattern formation were prepared in the same manner as in Example 1 except that Coumarin 540A was used as the fluorescent material. Table 1 shows the composition of the photocurable composition C for pattern formation, and Table 2 shows the properties of Coumarin 540A. Further, the fluorescence intensity ratio A2 / A1 of the coating film before and after photocuring was determined in the same manner as in Example 1. The results are shown in Table 3. In addition, the wavelength of the light irradiated in order to make fluorescence light-emit is 410 nm. A1 was 1.0, A2 was 0.53, A2 / A1 value was 0.53, and the fluorescence intensity was lower than those in Examples 1 and 2, but these values were sufficiently detectable. Similarly, it was confirmed that the film thickness could be measured accurately.
　（実施例４）
　蛍光物質としてピロメテン５９７を用いたこと以外は実施例１と同様の方法で光硬化性成分からなる組成物ａ及びパターン形成用光硬化性組成物Ｄを調製した。パターン形成用光硬化性組成物Ｄの組成を表１に、ピロメテン５９７の性質を表２に示す。また実施例１と同様の方法で光硬化前後の塗布膜の蛍光強度比Ａ２／Ａ１を求めた。結果を表３に示す。なお、蛍光を発光させるために照射した光の波長は５２０ｎｍである。Ａ１は１．５、Ａ２は０．３６、Ａ２／Ａ１値は０．２４であり、蛍光強度は実施例１～３と比較して低下したが、十分検出できる値であり、実施例１と同様に正確に膜厚が測定できることを確認した。 Example 4
A composition a comprising a photocurable component and a photocurable composition D for pattern formation were prepared in the same manner as in Example 1 except that pyromethene 597 was used as the fluorescent material. The composition of the photocurable composition D for pattern formation is shown in Table 1, and the properties of pyromethene 597 are shown in Table 2. Further, the fluorescence intensity ratio A2 / A1 of the coating film before and after photocuring was determined in the same manner as in Example 1. The results are shown in Table 3. Note that the wavelength of light irradiated to emit fluorescence is 520 nm. A1 was 1.5, A2 was 0.36, and A2 / A1 value was 0.24. The fluorescence intensity was lower than those in Examples 1 to 3, but these values were sufficiently detectable. Similarly, it was confirmed that the film thickness could be measured accurately.
　（比較例１）
　添加剤等としてＵＶ Ｒｅｄ １０１（三井化学（株）製）を１．５質量部添加したこと以外は実施例１と同様の方法で組成物ｂを調製した。この組成物ｂに、ローダミン６Ｇ（対アニオン；Ｃｌ-)を０．００５質量部添加し、室温で撹拌・混合して、組成物ｂと蛍光物質ローダミン６Ｇ（対アニオン；Ｃｌ-)とからなる液状のパターン形成用光硬化性組成物Ｅを得た。 (Comparative Example 1)
Composition b was prepared in the same manner as in Example 1 except that 1.5 parts by mass of UV Red 101 (Mitsui Chemicals, Inc.) was added as an additive. To this composition b, 0.005 parts by mass of rhodamine 6G (counter anion; Cl − ) is added, and stirred and mixed at room temperature to comprise composition b and the fluorescent substance rhodamine 6G (counter anion; Cl − ). A liquid photocurable composition E for pattern formation was obtained.
　表３に示すように、組成物ｂの光硬化物の膜厚１μｍあたりの吸光度は、ローダミン６Ｇ（対アニオン；Ｃｌ-)を発光させるための吸収極大波長５３０ｎｍ、及び、発光した蛍光の極大波長５６０ｎｍにおいてそれぞれ０．１を超えており、組成物ｂの光硬化物が蛍光物質の励起及び発光を阻害するため、パターン形成用光硬化性組成物Ｅの光硬化物の蛍光を検出することができなかった。 As shown in Table 3, the absorbance per 1 μm film thickness of the photocured product of composition b is the absorption maximum wavelength 530 nm for causing rhodamine 6G (counter anion; Cl − ) to emit light, and the maximum wavelength of the emitted fluorescence. Since the photocured material of the composition b inhibits excitation and light emission of the fluorescent material at 560 nm, the fluorescence of the photocured material of the pattern forming photocurable composition E can be detected. could not.
　（比較例２）
　添加剤等としてＵＶ Ｙｅｌｌｏｗ　１５４９（三井化学（株）製）を１．５質量部添加したこと以外は実施例１と同様の方法で組成物ｃを調製した。この組成物ｃに、クマリン５４０Ａを０．００５質量部添加し、室温で撹拌・混合して、組成物ｃと蛍光物質クマリン５４０Ａとからなる液状のパターン形成用光硬化性組成物Ｆを得た。 (Comparative Example 2)
A composition c was prepared in the same manner as in Example 1 except that 1.5 parts by mass of UV Yellow 1549 (manufactured by Mitsui Chemicals, Inc.) was added as an additive. To this composition c, 0.005 part by mass of coumarin 540A was added and stirred and mixed at room temperature to obtain a liquid pattern-forming photocurable composition F comprising the composition c and the fluorescent substance coumarin 540A. .
　表３に示すように、組成物ｃの光硬化物の膜厚１μｍあたりの吸光度は、クマリン５４０Ａを発光させるための吸収極大波長４１０ｎｍにおいて０．１を超えており、組成物ｃの光硬化物が蛍光物質の励起を阻害するため、パターン形成用光硬化性組成物Ｆの光硬化物の蛍光を検出することができなかった。 As shown in Table 3, the absorbance per 1 μm of the film thickness of the photocured product of the composition c exceeds 0.1 at the absorption maximum wavelength 410 nm for causing the coumarin 540A to emit light, and the photocured product of the composition c Inhibits excitation of the fluorescent substance, and thus the fluorescence of the photocured product of the photocurable composition F for pattern formation could not be detected.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　　１　基板
　　２　被転写材層
　　３　モールド
　　４　光硬化物 1 Substrate 2 Transferred material layer 3 Mold 4 Photocured material

Claims (6)

  1. 基板と凹凸パターンが形成されたモールドとで被転写材層を挟み込んで前記モールドの凹凸パターンに前記被転写材層を充填し、露光して硬化させることにより成形した後、前記モールドを離型するパターン形成に用いられる前記被転写材層となりうる光硬化性組成物であって、
    蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有し、
    露光して得られる光硬化物の前記蛍光物質以外の吸収が、前記蛍光物質が有する前記吸収波長領域の少なくとも一部に実質的に無く、且つ、前記蛍光物質が発光する蛍光の波長領域の少なくとも一部に実質的に無いことを特徴とするパターン形成用光硬化性組成物。     The transfer material layer is sandwiched between a substrate and a mold having a concavo-convex pattern, the concavo-convex pattern of the mold is filled with the transfer material layer, and is molded by exposure and curing, and then the mold is released. A photocurable composition that can be the transfer material layer used for pattern formation,
    0.0001 to 10 parts by mass of a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region with respect to 100 parts by mass of the photocurable component,
    Absorption other than the fluorescent material of the photocured product obtained by exposure is substantially absent in at least a part of the absorption wavelength region of the fluorescent material, and at least in the wavelength region of fluorescence emitted by the fluorescent material. A photocurable composition for pattern formation, which is substantially absent in part.
  2. 前記蛍光物質が蛍光を発光する吸収波長の極大値におけるモル吸光係数と、前記蛍光物質の蛍光量子収率との積が１×１０４以上であることを特徴とする請求項１に記載のパターン形成用光硬化性組成物。 2. The pattern according to claim 1, wherein a product of a molar extinction coefficient at a maximum value of an absorption wavelength at which the fluorescent material emits fluorescence and a fluorescent quantum yield of the fluorescent material is 1 × 10 4 or more. A photocurable composition for forming.
  3. 前記蛍光物質が蛍光を発光する吸収波長領域の波長であって前記光硬化性組成物を露光して得られる光硬化物の前記蛍光物質以外の吸収が実質的に無い波長の光を照射して蛍光を発光させる場合において、前記被転写材層を露光する前に発光した蛍光強度の極大値をＡ１、露光して硬化させた後に発光した蛍光強度の極大値をＡ２としたとき、Ａ２／Ａ１の値が０．６以上であることを特徴とする請求項１又は２に記載のパターン形成用光硬化性組成物。 Irradiating light having a wavelength in an absorption wavelength region in which the fluorescent material emits fluorescence and having substantially no absorption other than the fluorescent material in a photocured product obtained by exposing the photocurable composition. In the case of emitting fluorescence, when the maximum value of fluorescence intensity emitted before exposure of the transfer material layer is A1, and the maximum value of fluorescence intensity emitted after exposure and curing is A2, A2 / A1 3 is a photocurable composition for pattern formation according to claim 1 or 2, wherein the value is 0.6 or more.
  4. 蛍光を発光する吸収波長領域を紫外線領域から可視光線領域の範囲内に有する蛍光物質を光硬化性成分１００質量部に対し０．０００１～１０質量部含有するパターン形成用光硬化性組成物を用いて製造された凹凸パターンを有する光硬化物に、前記蛍光物質が蛍光を発光する吸収波長領域内の波長の光を照射し、発光した蛍光の強度から、前記凹凸パターンを有する光硬化物の凸部又は凹部の少なくとも一方の厚さを求めることを特徴とする膜厚測定方法。 A pattern-forming photocurable composition containing 0.0001 to 10 parts by mass of a fluorescent material having an absorption wavelength region for emitting fluorescence in the range from the ultraviolet region to the visible light region with respect to 100 parts by mass of the photocurable component The photocured material having a concavo-convex pattern is irradiated with light having a wavelength in the absorption wavelength region where the fluorescent material emits fluorescence. From the intensity of the emitted fluorescence, the photocured product having the concavo-convex pattern is projected. A method for measuring a film thickness, characterized in that the thickness of at least one of a portion or a recess is obtained.
  5. 前記凹凸パターンを有する光硬化物の凸部及び凹部の各厚さが１ｎｍ～２０μｍの範囲であることを特徴とする請求項４に記載の膜厚測定方法。 5. The film thickness measuring method according to claim 4, wherein the thickness of each of the convex portions and concave portions of the photocured product having the concave / convex pattern is in the range of 1 nm to 20 μm.
  6. 前記凹凸パターンを有する光硬化物の凸部又は凹部の少なくとも一方の幅が１０ｎｍ～１００μｍの範囲であることを特徴とする請求項４又は５に記載の膜厚測定方法。 6. The film thickness measuring method according to claim 4, wherein the width of at least one of the convex portion or concave portion of the photocured product having the concave / convex pattern is in the range of 10 nm to 100 μm.
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