WO2019159916A1 - キット、インプリント用下層膜形成組成物、パターン形成方法、半導体デバイスの製造方法 - Google Patents
キット、インプリント用下層膜形成組成物、パターン形成方法、半導体デバイスの製造方法 Download PDFInfo
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- WO2019159916A1 WO2019159916A1 PCT/JP2019/004931 JP2019004931W WO2019159916A1 WO 2019159916 A1 WO2019159916 A1 WO 2019159916A1 JP 2019004931 W JP2019004931 W JP 2019004931W WO 2019159916 A1 WO2019159916 A1 WO 2019159916A1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Images
Classifications
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
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- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- 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
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/161—Coating processes; Apparatus therefor using a previously coated surface, e.g. by stamping or by transfer lamination
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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
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3083—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/3086—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
Definitions
- the present invention relates to a kit, a composition for forming an underlayer film for imprinting, a pattern forming method, and a method for manufacturing a semiconductor device.
- the imprint method is to transfer a fine pattern by pressing a mold against a curable composition, curing the composition, and then peeling the mold. This method is being applied to precision processing fields such as fabrication of semiconductor integrated circuits.
- the imprint method eliminates the need for expensive microfabrication devices such as steppers and electron beams, simplifies the device structure, and significantly reduces the manufacturing cost. Since the manufacturing cost is reduced, the process is simple, and high resolution and high throughput can be realized, studies for mass production of devices in various fields are being actively pursued.
- the imprint method there is a technique in which a photosensitive resin composition is used as a material applied for patterning and processing is performed by combining a light-transmitting mold.
- a pattern is formed on the cured film of the photosensitive resin composition disposed on the substrate by irradiating light through a mold, and this is used as an insulating member or as a mask for further processing.
- What uses ultraviolet (UV) as light to irradiate may be called especially the UV nanoimprint method.
- the optical nanoimprinting method including the UV nanoimprinting method processing at room temperature is possible, unlike the thermal nanoimprinting method that requires heating using a thermosetting resin composition. Therefore, it can be widely applied as a technique for realizing high quality in the manufacture of semiconductor devices and the like that dissipate heat.
- Patent Document 1 discloses a method of forming a pretreatment coating on a substrate using a pretreatment composition containing a polymerizable component, and disposing a discontinuous portion of an imprint resist there. There, a composite polymerizable coating containing a mixture of a pretreatment composition and an imprint resist is formed on a substrate, and this is contacted and polymerized with a template to obtain a composite polymer layer on the substrate. Thereby, the throughput in the nanoimprint lithography process can be promoted.
- An object of the present invention is to provide a kit including both compositions that provide excellent adhesion to a cured product, a composition for forming an underlayer film for imprinting, a pattern forming method, and a method for manufacturing a semiconductor device.
- the present inventors examined the composition of the underlayer film forming composition for imprinting and investigated and analyzed the influence of various components on the physical properties and performance. As a result, it is important to clarify the chemical relationship with the components of the curable composition for imprints in addition to the design of the composition of the underlayer film forming composition for imprints, and to add it to the formulation design. I came to think. In particular, a compound to be combined with a polymer having a polymerizable functional group to be blended with the composition for forming an underlayer film for imprinting was accurately selected.
- a kit comprising a curable composition for imprints and a composition for forming a lower layer film for imprints
- the lower layer film-forming composition for imprints is a polymer having a polymerizable functional group, and the lower one of the boiling point and the thermal decomposition temperature is 480 ° C.
- ⁇ 2> The kit according to ⁇ 1>, wherein the compound contained in the composition for forming an underlayer film for imprinting has a plurality of polymerizable functional groups and polymerizable groups in the polymer in one molecule.
- ⁇ 3> The kit according to ⁇ 1> or ⁇ 2>, wherein at least one of the polymer and the compound contained in the composition for forming an underprint film for imprinting has a polar functional group.
- the polar functional group has at least one member selected from the group consisting of a sulfonyl group-containing group, a sulfonic acid group, a phosphoric acid group, and a hydroxyl group.
- ⁇ 5> The kit according to any one of ⁇ 1> to ⁇ 4>, wherein the polymerizable functional group of the polymer is a (meth) acryloyl group.
- ⁇ 6> The kit according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer is an acrylic resin.
- ⁇ 7> The kit according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer has a weight average molecular weight of 4,000 or more.
- ⁇ 8> The kit according to any one of ⁇ 1> to ⁇ 7>, wherein the compound contained in the composition for forming an underlayer for imprinting has a viscosity at 23 ° C. of 2,000 mPa ⁇ s or less.
- the compound contained in the composition for forming an underlayer film for imprinting has three polymerizable functional groups and polymerizable groups in the polymer in the molecule.
- the polymerizable functional group of the polymer is a (meth) acryloyl group.
- Kit. ⁇ 13> The kit according to any one of ⁇ 1> to ⁇ 12>, wherein the composition for forming an underprint film for imprinting further contains at least one of a thermal polymerization initiator and a photopolymerization initiator.
- ⁇ 14> Any one of ⁇ 1> to ⁇ 13>, wherein the underlayer film forming composition for imprints further contains a solvent, and the solvent occupies 99.0% by mass or more of the underlayer film forming composition for imprints Kit described in 1.
- the difference between the boiling point of the most compounded component in the curable composition for imprints and the boiling point of the compound contained in the composition for forming an underlayer film for imprints is 150 ° C. or higher, ⁇ 1> The kit according to any one of ⁇ 14>.
- the surface tension of the compound contained in the curable composition for imprints is greater than the surface tension of the component having the largest blending amount in the curable composition for imprints, ⁇ 1> to ⁇ 15>
- ⁇ D Dispersion of the Hansen solubility parameter vector component of the component with the highest content contained in the curable composition for imprints, and the dispersion of the Hansen solubility parameter vector of the compound contained in the underlayer film forming composition for imprints Difference from the term component;
- ⁇ P Polarity component of the Hansen solubility parameter vector of the component having the highest content contained in the curable composition for imprints, and the polarity of the Hansen solubility parameter vector of the compound contained in the above-mentioned underlayer film forming composition for imprints Difference in term component;
- ⁇ H the hydrogen bond term component of the Hansen solubility parameter vector of the component with the highest content contained in the curable composition for imprints, and the Hansen solub
- object. ⁇ 19> a step of applying an imprint lower layer film-forming composition contained in the kit according to any one of ⁇ 1> to ⁇ 16> to a substrate to form an imprint lower layer film; Applying the curable composition for imprints contained in the kit to the underlayer film for imprints,
- the pattern formation method including the process of exposing the said curable composition for imprints in the state which made the mold contact the said curable composition for imprints, and the process of peeling the said mold.
- ⁇ 20> The pattern forming method according to ⁇ 19>, wherein the step of forming the lower layer film for imprint includes a spin coating method.
- the wettability of the curable composition for imprints to the lower layer film formed from the lower layer film forming composition for imprints can be improved.
- (meth) acrylate represents acrylate and methacrylate.
- imprint preferably refers to pattern transfer having a size of 1 nm to 10 mm, more preferably pattern transfer (nanoimprint) having a size of approximately 10 nm to 100 ⁇ m.
- group atomic group
- substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “light” includes not only light in a wavelength region such as ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, and electromagnetic waves, but also radiation. Examples of radiation include microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used.
- the light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
- the weight average molecular weight (Mw) in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.
- the temperature in the present invention is 23 ° C. unless otherwise specified.
- the kit of the present invention comprises a curable composition for imprints and an underprint film forming composition for imprints
- the undercoat film forming composition for imprints is a polymer having a polymerizable functional group (hereinafter, “ Hansen Solubility Parameter Distance (which may be referred to as a “specific polymer”) and the component having the highest content in the curable composition for imprints, which has a lower boiling point and thermal decomposition temperature of 480 ° C. or higher.
- ⁇ HSP (see Formula 1 below) is a compound having 2.5 or less (hereinafter sometimes referred to as “specific compound”).
- the underlayer film-forming composition for imprints containing a polymer having a polymerizable functional group can be baked at a high temperature. Even in this case, the specific compound can be left in the lower layer film without being volatilized. Furthermore, the specific polymer forms a film having good interface strength with the base material and strength, and can secure adhesion with a cured product formed from the curable composition for imprints.
- the present invention will be described in detail.
- the Hansen solubility parameter distance ( ⁇ HSP) between the specific compound and the component (maximum amount component) having the largest content contained in the curable composition for imprints is 2.5 or less. 2.2 or less, more preferably 2.0 or less, further preferably 1.8 or less, and may be 1.5 or less.
- the lower limit is ideally 0, but 1.0 or more is a practical level.
- ⁇ HSP [4.0 ⁇ ( ⁇ D 2 + ⁇ P 2 + ⁇ H 2 )] 0.5 Formula (1)
- ⁇ D Dispersion term component (d component 1) of the Hansen solubility parameter vector of the component with the highest content contained in the curable composition for imprints, and Hansen solubility of the compound contained in the underlayer film forming composition for imprints Difference of parameter vector from variance term component (d component 2) (d component 1-d component 2)
- ⁇ P the polar term component (p component 1) of the Hansen solubility parameter vector of the component with the highest content contained in the curable composition for imprints, and the Hansen solubility of the compound contained in the underlayer film forming composition for imprints Difference in polarity term component (p component 2) of parameter vector (p component 1 ⁇ p component 2)
- ⁇ H the hydrogen bond term component (h component 1) of the Hansen solubility parameter vector of the component with the highest content contained in the curable composition for imprints, and Hansen, a compound contained in the underlayer film forming composition
- the target component is the maximum amount component of the curable composition for imprints and the specific compound in the composition for forming an underlayer film for imprint. Adopt large amounts of ingredients for evaluation.
- the compounding quantity of an applicable component is the same, the calculated value of a compound with high surface tension is employ
- the maximum amount component refers to the one whose mass is the maximum amount.
- a specific compound plays the role which raises affinity with the curable composition for imprints by making HSP close
- the composition for forming an underlayer film for imprinting includes a polymer having a polymerizable functional group (specific polymer).
- the type of the specific polymer is not particularly defined as long as it contains a polymerizable functional group.
- the specific polymer is usually a compound having a weight average molecular weight of 2,000 or more, preferably 4,000 or more, more preferably 6,000 or more, and further preferably 10,000 or more.
- the upper limit of a weight average molecular weight is not specifically defined, For example, 200,000 or less is preferable, 70,000 or less is more preferable, 50,000 or less is further more preferable.
- the film stability during the baking process can be improved, and the surface state during the formation of the imprint lower layer film can be further improved.
- the weight average molecular weight (Mw) in this invention means what was measured by the gel permeation chromatography (GPC) unless otherwise stated.
- liquidity is maintained because said molecular weight becomes an appropriate range, and the wettability of the curable composition for imprints improves.
- Specified polymer has a polymerizable functional group.
- the polymerizable functional group include (meth) acryloyl group, epoxy group, oxetane group, methylol group, methylol ether group, vinyl ether group and the like. From the viewpoint of ease of polymerization, a (meth) acryloyl group is particularly preferable.
- the polymerizable functional group defined and exemplified herein is referred to as a polymerizable functional group Ps.
- the specific polymer preferably has a polar functional group Tf in order to strengthen the adhesion to the substrate.
- a preferred range is defined by a urea group-containing group (—NR N CONR N 2 ), a urethane group (—OCONR N 2 , —NR N COOR Q2 ), a cyano group, an oxygen atom (ether group), and the following linking group L.
- (Oligo) alkyleneoxy group cyclic ether group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms), lactone group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 4 are more preferable), a sulfonyl group-containing group (—SO 2 R Q3 ), a sulfonic acid group (—SO 2 (OH)), a sulfinic acid group (—SO 2 ).
- sulfonyl group-containing groups sulfonic acid groups, sulfinic acid groups, sulfonamido groups, sulfonimidyl group-containing groups, phosphoric acid groups, phosphoric ester groups, cyano groups, carboxyl groups, amino groups and hydroxyl groups are particularly preferred.
- Sulfonyl group-containing groups, sulfonic acid groups, phosphoric acid groups, and hydroxyl groups are more preferred. Definition of R N is as described below.
- R Q1 is independently an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 1 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 21 carbon atoms, preferably 7 to 15 carbon atoms). More preferably, 7 to 11 are more preferable, an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), and an alkynyl group (preferably 2 to 12 carbon atoms are preferable). 6 is more preferred, and 2 to 3 is more preferred) an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10).
- R Q2 is a hydrogen atom or a substituent defined by R Q1 above.
- R Q3 is a substituent of the above R Q1 or OR Q1 .
- R Q1 to R Q3 may have a substituent T as long as the effects of the present invention are exhibited. For example, a hydroxyl group, amino group, carboxyl group or the like may be substituted.
- the adhesion with the substrate interface tends to be improved.
- at least one of the specific polymer and the specific compound preferably has a polar functional group Tf, and more preferably the specific polymer has a compound having a polar functional group Tf.
- both the specific polymer and the specific compound may have a polar functional group Tf.
- the aspect in which compounds other than a specific polymer and a specific compound have polar functional group Tf is also contained in the scope of the present invention.
- An example of an embodiment of the specific polymer is a polymer including a structural unit including a polymerizable functional group.
- the total of the structural units containing a polymerizable functional group occupy 90 mol% or more of all the structural units.
- the structural unit containing a polymerizable functional group may contain only 1 type, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the aspect in which the structural unit containing a polymerizable functional group contains the polar functional group Tf is also preferable.
- Another example of the embodiment of the specific polymer is a polymer including a structural unit including a polymerizable functional group and a structural unit including the polar functional group.
- the total of the structural unit containing a polymerizable functional group and the structural unit containing the polar functional group occupy 90 mol% or more of all the structural units.
- the molar ratio between the structural unit containing a polymerizable functional group and the structural unit containing the polar functional group is preferably 10 to 95:90 to 5, more preferably 30 to 93: 7 to 70.
- it is 40 to 90:10 to 60.
- the structural unit containing a polymerizable functional group and the structural unit containing the polar functional group may each be included one by one or two or more. When 2 or more types are included, the total amount is preferably within the above range.
- the specific polymer is exemplified by acrylic resin, novolac resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, and melamine resin, and acrylic resin and novolac resin are preferable, and acrylic resin is more preferable.
- the acrylic resin includes not only a polymer of acrylate monomers but also a polymer of methacrylate monomers.
- R 1 is a hydrogen atom or a methyl group.
- L 1 is a single bond or a divalent linking group.
- the linking group include the following linking group L, and the following linking group Lh is preferred.
- a single bond, an oxygen atom, a carbonyl group, —NR N —, an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and combinations thereof are preferable. More preferred are atoms, carbonyl groups, or combinations thereof, or phenylene groups.
- N11 and n12 are numbers that total 100 or less, and are copolymerization ratios based on the molar ratio of each structural unit.
- n11 is preferably 10 to 95, more preferably 20 to 90, and still more preferably 30 to 80.
- n12 is preferably 5 to 90, and more preferably 10 to 80. When the total of n11 and n12 is 100 or less, it means that other structural units are copolymerized to 100.
- N13 and n14 are numbers that total 100 or less, and are copolymerization ratios based on the molar ratio of each structural unit.
- n13 is preferably 10 to 95, more preferably 20 to 90, and still more preferably 30 to 80.
- n14 is preferably 5 to 95, more preferably 10 to 80, and still more preferably 20 to 70. When the total of n13 and n14 is 100 or less, it means that other structural units are copolymerized to be 100.
- R 11 is a substituent having a polymerizable functional group, and is preferably a substituent represented by the following formula (T1). -(L 3 ) t3 -[(L 2 ) t2- (P) t1 ] t4 (T1)
- L 2 is a t1 + 1-valent linking group, and is a cyclic or linear or branched alkane structure group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 and even more preferably 1 to 20), cyclic or linear Or a group having a branched alkene structure (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms), a group having a cyclic or straight chain or branched alkyne structure (preferably having 2 to 40 carbon atoms).
- a group having an aryl structure preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and further preferably 6 to 10
- a group having a heteroaryl structure It preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- Preferred examples of the ring structure of the aryl structure group include the following hydrocarbon aromatic ring aCy.
- Examples of the preferable ring structure of the heteroaryl structure group include the following examples of the aromatic heterocyclic ring hCy.
- L 2 may have a substituent T as long as the effects of the present invention are achieved. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to L 2 in the formula via a linking group L or not to form a ring.
- T2 is 0 or 1.
- L 3 is a linking group (preferably a linking group L described later), and among them, an acyclic linking group is preferable, and an alkylene group, an alkenylene group, an alkyleneoxy group, an oxygen atom, a carbonyl group, or a group thereof.
- the group which concerns on a combination is more preferable.
- L 3 may have a substituent T as long as the effects of the present invention are exhibited. For example, an embodiment in which a hydroxyl group is substituted on an alkyleneoxy group or an alkylene chain of an alkyleneoxy group can be given as a preferred example.
- substituents T When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to L 3 in the formula through or without a linking group L to form a ring.
- T3 is 0 or 1.
- P is a polymerizable functional group, and the above-described polymerizable functional group Ps is preferable. In the present invention, it is particularly preferable to apply a (meth) acryloyl group.
- T1 is preferably 1 to 6, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
- t4 is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
- L 3 can be a trivalent or higher linking group.
- the alkylene group can be an alkanetriyl group or an alkanetetrayl group.
- R 12 is a substituent having no polymerizable functional group, and is preferably a substituent represented by the following formula (T2). -(L 3 ) t3 -[(L 2 ) t2- (Q) t1 ] t4 (T2)
- L 2 L 3, t1, t2, t3, t4 is the same as L 2, L 3, t1, t2, t3, t4 in formula (T1), and preferred ranges are also the same.
- Q is a hydrogen atom or a polar functional group Tf, preferably a polar functional group Tf.
- R 13 is represented by the following formula (T3). -(L 4 ) -T 1 (T3) L 4 is a linking group Lh having a single bond or a hetero atom, preferably an oxygen atom, a carbonyl group, —NR N — or a combination thereof, more preferably an oxygen atom, a carbonyl group or a combination thereof, preferable.
- T 1 is a substituent represented by the above formula (T1).
- R 14 is represented by the following formula (T4). -(L 4 ) -T 2 (T4) L 4 represents the same meaning as L 4 in formula (T3). T 2 is preferably a substituent represented by the above formula (T2).
- the benzene ring contained in the main chain of the structural unit in the formula (2) may have a substituent T as long as the effects of the present invention are exhibited.
- substituents T they may be the same as or different from each other.
- an example having a hydroxyl group or an alkoxyl group is also mentioned as a preferred form.
- the copolymerization ratio of other structural units may be adjusted within a range where the effects of the present invention are exhibited.
- the molar ratio is preferably 0.5 or more and 50 or less, and more preferably 1 or more and 30 or less.
- hydrocarbon aromatic ring aCy examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, acenaphthylene ring, biphenyl ring, terphenyl ring, indene ring, indane ring, triphenylene ring, tetraphenylene ring, Examples include a phenylene ring, a pyrene ring, a chrysene ring, a perylene ring, a tetrahydronaphthalene ring, and the like.
- the aromatic ring may have a structure in which a plurality of aromatic rings are connected with or without a connecting group L, and examples thereof include a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring.
- examples of the structure in which a plurality of benzene rings are linked include those represented by the following formulas Ar1 to Ar5.
- a 1 is a divalent linking group, and examples of the linking group L are preferable.
- An alkylene group which may be substituted with a fluorine atom (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms being preferred) Further preferred are a carbonyl group, an oxygen atom, a sulfonyl group, a sulfinyl group, and —NR N —.
- a 2 represents a nitrogen atom, a trivalent linking group containing a phosphorus atom, or a methine group.
- Ar2 having three rings is a divalent linking group.
- Ar1 to Ar5 may further have a substituent T.
- a bond may be located and linked to the substituent T.
- aromatic heterocyclic ring hCy examples include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Triazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine Ring, phenoxazine ring and the like.
- alicyclic ring fCy examples include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydro Naphthalene ring, decahydronaphthalene ring, hexahydroindane ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, bicyclononane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring, oxane ring, dioxane ring, dioxolane ring, Examples include an oxiran
- the linking group Lh containing a hetero atom includes an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, —NR N —, an (oligo) alkyleneoxy group (of the alkylene group in one constituent unit).
- the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), or these Examples of the linking group include a combination.
- the number of atoms constituting the linking group Lh containing a hetero atom is preferably from 1 to 100, more preferably from 1 to 70, particularly preferably from 1 to 50, excluding hydrogen atoms.
- the number of linking atoms of Lh is preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 15, and still more preferably 1 to 10.
- the (oligo) alkyleneoxy group means an alkyleneoxy group or an oligoalkyleneoxy group.
- the (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
- substituent T examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). 7 to 11 is more preferable), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), and an alkynyl group (preferably having 2 to 12 carbon atoms are preferable).
- an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms
- arylalkyl group preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms. 7 to 11 is more preferable
- an alkenyl group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still
- hydroxyl group preferably having 0 to 24 carbon atoms, more preferably 0 to 12 and further preferably 0 to 6
- thiol group carboxyl group, aryl group (carbon Numbers 6 to 22 are preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable, and a heteroaryl group (C 1 to 22 is preferable, and 1 to 16 is more preferable) 1 to 12 are more preferable)
- an alkoxyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3
- an aryloxy group preferably having 6 to 22 carbon atoms and 6 to 18 carbon atoms.
- 6 to 10 are more preferable
- an acyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms
- an acyloxy group preferably 2 to 12 carbon atoms are preferable 2 To 6 are more preferable, and 2 to 3 are more preferable
- an aryloyl group preferably having 7 to 23 carbon atoms, more preferably 7 to 19 and further preferably 7 to 11
- an aryloyloxy group 7. to 23 carbon atoms.
- Sulfamoyl group (preferably having 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, still more preferably 0 to 3 carbon atoms), sulfo group, alkylsulfonyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). 1 to 3 are more preferable), an arylsulfonyl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and a heterocyclic group (preferably 1 to 12 carbon atoms are preferable 1 to 3 carbon atoms).
- a 5-membered ring or 6-membered ring is preferable, (meth) acryloyl group, (meth) acryloyloxy group, halogen atom (for example, fluorine atom, chlorine atom, Bromine atom, iodine atom), oxo group ( ⁇ O), imino group ( ⁇ NR N ), alkylidene group ( ⁇ C (R N ) 2 ) and the like.
- halogen atom for example, fluorine atom, chlorine atom, Bromine atom, iodine atom
- oxo group oxo group
- imino group ⁇ NR N
- alkylidene group ⁇ C (R N ) 2
- RN is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms).
- an alkynyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms
- an aryl group preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms.
- a heteroaryl group preferably having 1 to 22 carbon atoms, more preferably 1 to 16 and further preferably 1 to 12).
- R N may have a respective group defined by substituent T to the extent that the effects of the present invention.
- the alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be linear or cyclic, and may be linear or branched.
- the substituent T may further have a substituent T.
- the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloyloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.
- an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) 2 to 3 are more preferable), an alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and further preferably 2 to 3), an (oligo) alkyleneoxy group (of the alkylene group in one structural unit)
- the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and the arylene group ( Preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), oxygen atom, sulfur atom, sulfonyl group, carbonyl group, thi
- the alkylene group may have the following substituent T.
- the alkylene group may have a hydroxyl group.
- the number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms.
- the number of connected atoms means the number of atoms located in the shortest path among the atomic groups involved in the connection. For example, in the case of —CH 2 — (C ⁇ O) —O—, there are 6 atoms involved in the connection, and 4 atoms excluding hydrogen atoms. On the other hand, the shortest atom involved in the connection is —C—C—O—, which is three.
- the number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6.
- the alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched.
- the content of the specific polymer in the composition for forming an underlayer film for imprinting is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. More preferably. As an upper limit, it is preferable that it is 10 mass% or less, It is more preferable that it is 7 mass% or less, It is further more preferable that it is 5 mass% or less, It is still more preferable that it is 4 mass% or less, 3 mass % Or less is even more preferable, and it may be 1% by mass or less and 0.7% by mass or less.
- the content of the specific polymer in the nonvolatile component is preferably 5% by mass or more, more preferably 20% by mass or more, and 30% by mass. % Or more is more preferable.
- As an upper limit it is preferable that it is 90 mass% or less, It is more preferable that it is 70 mass% or less, It is further more preferable that it is 60 mass% or less.
- the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
- Only 1 type may be used for a specific polymer, and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.
- Examples of the specific polymer include polymers used in the following examples, but the present invention is not construed as being limited thereto.
- the specific compound contained in the composition for forming an underprint film used in the present invention is a component having the highest content contained in the curable composition for imprints at the lower of the boiling point and the thermal decomposition temperature at 480 ° C or higher.
- the Hansen solubility parameter distance ( ⁇ HSP) is 2.5 or less.
- the specific compound preferably has a boiling point of 480 ° C. or higher.
- the specific compound needs to have a boiling point (bp1) of 480 ° C. or higher, more preferably 500 ° C. or higher, and further preferably 550 ° C. or higher.
- the upper limit is not particularly defined, but is preferably 800 ° C. or lower, for example. When the boiling point is below the lower limit, the low molecular weight specific compound volatilizes during baking after coating, and outgassing may occur.
- Difference (bp1-bp2) between the boiling point (bp1) of the specific compound contained in the composition for forming an underlayer film for imprinting and the boiling point (bp2) of the component having the largest amount in the curable composition for imprinting described later Is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 150 ° C. or higher, and even more preferably 170 ° C. or higher.
- the upper limit of the difference between the boiling points can be, for example, 300 ° C. or less.
- the specific compound is preferably a low molecular weight compound relative to the specific polymer.
- the molecular weight is preferably less than 2,000, more preferably 1,500 or less, further preferably 1,300 or less, and even more preferably 1,000 or less. As a lower limit, it is practical that it is 100 or more.
- the specific compound preferably has in the molecule a group that can be polymerized with the polymerizable functional group of the specific polymer (hereinafter sometimes simply referred to as “polymerizable group”).
- the number of polymerizable groups in one molecule of the specific compound is preferably 2 or more, and more preferably 3 or more.
- the upper limit is preferably 6 or less, and may be 5 or less and 4 or less. It is particularly preferable that the specific compound has three polymerizable groups in one molecule.
- the specific compound having a lower molecular weight functions as a cross-linking agent for forming a three-dimensional cross-link between main chains of a higher molecular weight specific polymer by having a plurality of polymerizable groups.
- the polymerizable group is not particularly defined as long as it is a group that can be polymerized with the polymerizable functional group of the specific polymer, and examples thereof include (meth) acryloyl group, epoxy group, vinyl group, and vinyl ether group. What corresponds to the functional group Ps is preferable, an epoxy group and a (meth) acryloyl group are more preferable, and a (meth) acryloyl group is more preferable. Moreover, it is preferable that at least one kind of the polymerizable group contained in the specific compound and the polymerizable functional group of the specific polymer are common.
- the specific compound may have a polar functional group Tf in order to strengthen the adhesion to the substrate.
- a preferred range is defined by a urea group-containing group (—NR N CONR N 2 ), a urethane group (—OCONN N 2 , —NR N COOR Q 2 ), a cyano group, an oxygen atom (ether group), and the following linking group L.
- (Oligo) alkyleneoxy group, cyclic ether group (2 to 12 carbon atoms are preferred, 2 to 6 are more preferred, 2 to 3 are more preferred), lactone group (2 to 12 carbon atoms are preferred, 2 to 6 are preferred) even more preferably from 2 to 4), a sulfonyl group-containing group (-SO 2 R Q3), a sulfonic acid group (-SO 2 (OH)), sulfinic acid group (- O 2 OH)), a sulfonamido group (-SO 2 NR N 2), sulfonimide yl group-containing group (-S (O) (NR N ) R Q1), a phosphoric acid group (-O (P O) ( OH) 2 ), phosphate groups (—O (P ⁇ O) (OH) (OR Q1 ), —O (P ⁇ O) (OR Q1 ) 2 ), and the like.
- a sulfonyl group-containing group, a sulfonic acid group, a sulfinic acid group, a sulfonamide group, a sulfonimidyl group-containing group, a phosphoric acid group, a phosphoric ester group, a cyano group, a carboxyl group, an amino group, and a hydroxyl group are particularly preferable.
- the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 20.0, and more preferably 17.0 to 19.0. More preferably, it is more preferably 17.5 to 19.0, even more preferably 18.0 to 19.0;
- the polar term component (p component) is preferably 3.5 to 8.0, more preferably 4.0 to 8.0, and preferably 4.0 to 7.5. More preferably, 4.0 to 5.5 is more preferable;
- the hydrogen bond term component (component h) is preferably from 4.0 to 8.0, more preferably from 4.0 to 7.5, and from 4.5.2 to 5.5. More preferably it is.
- the dispersion term component, polar term component, and hydrogen bond term component of the HSP vector of the specific compound are each set by the method described in the examples described later.
- the viscosity of the specific compound at 23 ° C. is preferably 2,000 mPa ⁇ s or less, and more preferably 1,000 mPa ⁇ s or less. Moreover, it is preferable that it is 3 mPa * s or more. It is more preferably 10 mPa ⁇ s or more, and further preferably 50 mPa ⁇ s or more. If the viscosity exceeds the above upper limit, the fluidity of the low molecular weight specific compound at the time of cross-linking by baking is lowered and it is difficult to form cross-links, so the adhesion may be lowered.
- the value measured based on the method as described in an after-mentioned Example is employ
- the surface tension of the specific compound is preferably 35 mN / m or more, more preferably 38 mN / m or more, and further preferably 40 mN / m or more.
- the upper limit is not particularly defined, but is preferably 45 mN / m or less, for example. If the surface tension is lower than the lower limit, the surface energy of the imprint underlayer film formed after baking may decrease, and the wettability of the imprint curable composition may deteriorate.
- As the viscosity of the specific compound a value measured based on the method described in Examples below is adopted.
- L 30 is a q3 + 1 valent linking group and has the same meaning as L 2 described above.
- the preferred range is a group having the above hydrocarbon aromatic ring aCy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), or a group having an alkane structure (having 2 to 40 carbon atoms).
- (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one constituent unit is preferably 1-12, more preferably 1-6, To 3 is more preferable; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), or a combination thereof.
- L 30 may have the substituent T.
- a plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different.
- R 31 and R 32 each independently represent a hydrogen atom or a methyl group.
- L 31 and L 32 each independently represent a single bond or a linking group Lh having the above hetero atom.
- L 30 and L 31 or L 32 may combine with or without a linking group L to form a ring.
- L 30 , L 31 and L 32 may have the substituent T.
- a plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different.
- L 31 and L 32 may be bonded to each other or L 30 to form a ring.
- the site of L32 is a hydrogen atom.
- the compound represented by the formula (3) preferably has the above-mentioned polar functional group Tf in the molecule.
- a polar functional group Tf may be formed together with the carbonyl group and the oxygen atom in the formula.
- the content of the specific compound in the composition for forming an underlayer film for imprinting is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. More preferably it is. As an upper limit, it is preferable that it is 10 mass% or less, It is more preferable that it is 7 mass% or less, It is further more preferable that it is 5 mass% or less, It is still more preferable that it is 4 mass% or less, 3 mass % Or less, still more preferably 1% by mass or less, and may be 0.7% by mass or less.
- the content of the specific compound in the nonvolatile component is preferably 5% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
- an upper limit it is preferable that it is 90 mass% or less, It is more preferable that it is 70 mass% or less, It is further more preferable that it is 60 mass% or less.
- blended the polymer can be exhibited suitably, and it becomes easy to prepare a uniform thin film.
- the amount is not more than the above upper limit value, the effect of using the solvent is suitably exhibited, and it becomes easy to form a uniform film over a wide area.
- the specific compound used in the imprint underlayer film forming composition is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, and 40 parts by mass or more, with respect to 100 parts by mass of the specific polymer. It may be 60 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more.
- the upper limit is preferably 500 parts by weight or less, more preferably 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, 130 parts by weight or less, 110 parts by weight or less. There may be. By adopting such a configuration, it becomes possible to express the adhesion and filling properties in a well-balanced manner. Only 1 type may be used for a specific compound and it may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the viscosity of the specific compound is preferably 3,000 mPa ⁇ s or less, more preferably 2,000 mPa ⁇ s or less, further preferably 1,500 mPa ⁇ s or less, and 1,000 mPa ⁇ s or less. It is more preferable that The lower limit of the viscosity of the specific compound is preferably 5 mPa ⁇ s or more, more preferably 10 Pa ⁇ s or more, may be 20 mPa ⁇ s or more, and may be 50 mPa ⁇ s or more. .
- the surface tension of the specific compound at 23 ° C. is preferably 37.0 mN / m or more, and more preferably 38.0 mN / m or more.
- the upper limit of the surface tension is not particularly defined, but is, for example, 48.0 mN / m or less.
- the surface tension ( ⁇ 1) of the specific compound contained in the composition for forming an underprint film for imprint is larger than the surface tension ( ⁇ 2) of the component having the largest blending amount in the curable composition for imprints.
- the difference is ⁇ 1- ⁇ 2 and is preferably 2.0 mN / m or more, more preferably 2.5 mN / m or more, and further preferably 3.0 mN / m or more.
- the undercoat film-forming composition for imprinting may contain an alkylene glycol compound.
- the alkylene glycol compound preferably has 3 to 1000 alkylene glycol structural units, more preferably 4 to 500, still more preferably 5 to 100, and more preferably 5 to It is more preferable to have 50 pieces.
- the weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10,000, more preferably 200 to 5,000, still more preferably 300 to 3,000, and even more preferably 300 to 1,000.
- Alkylene glycol compounds are polyethylene glycol, polypropylene glycol, mono- or dimethyl ether, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, monooleate, monoadipate, monosuccinate.
- the acid ester include polyethylene glycol and polypropylene glycol.
- the surface tension of the alkylene glycol compound at 23 ° C. is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more.
- the upper limit of the surface tension is not particularly defined, but is, for example, 48.0 mN / m or less.
- the alkylene glycol compound When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. Further preferred.
- One type of alkylene glycol compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the underlayer film forming composition for imprints may contain a polymerization initiator, and preferably contains at least one of a thermal polymerization initiator and a photopolymerization initiator.
- a polymerization initiator By including a polymerization initiator, the reaction of the polymerizable group contained in the composition for forming a lower layer film for imprinting is promoted, and the adhesion tends to be improved.
- a photopolymerization initiator is preferred.
- the photopolymerization initiator a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.
- a plurality of photopolymerization initiators may be used in combination.
- radical photopolymerization initiator known compounds can be arbitrarily used.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
- acylphosphine compound examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
- Commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
- the content of the photopolymerization initiator used in the composition for forming an underprint film for imprinting is, for example, 0.0001 to 5% by mass, preferably 0.0005 to 3% by mass in the nonvolatile component. %, More preferably 0.01 to 1% by mass.
- the total amount becomes the said range.
- non-volatile component mix blended with the underlayer film formation composition for imprints
- thermal polymerization initiator, a polymerization inhibitor, antioxidant, a leveling agent, a thickener, surfactant, etc. are 1 It may contain seeds or two or more.
- thermal polymerization initiator and the like each component described in JP2013-036027A, JP2014-090133A, JP2013-189537A can be used.
- the description in the above publication can be referred to.
- it can also be set as the structure which does not contain surfactant substantially in the underlayer film forming composition for imprints. “Substantially not contained” means 0.1% by mass or less of the nonvolatile component in the composition for forming a lower layer film for imprinting.
- the composition for forming an underlayer film for imprinting preferably contains a solvent (a solvent for the underlayer film).
- the solvent is preferably a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less.
- the nonvolatile component finally forms the lower layer film.
- the composition for forming an underlayer film for imprinting preferably contains 99.0% by mass or more of the solvent for the lower layer film, more preferably 99.5% by mass or more, and may be 99.6% by mass or more.
- the liquid means that the viscosity at 23 ° C. is 100,000 mPa ⁇ s or less.
- the solvent only 1 type may be contained in the underlayer film forming composition for imprint, and 2 or more types may be contained. When 2 or more types are included, the total amount is preferably within the above range.
- the boiling point of the solvent for the lower layer film is preferably 230 ° C. or less, more preferably 200 ° C. or less, further preferably 180 ° C. or less, further preferably 160 ° C. or less, and 130 ° C. or less. Is more preferable.
- the lower limit is practically 23 ° C, but more practically 60 ° C or more.
- the solvent for the lower layer film is preferably an organic solvent.
- the solvent is preferably a solvent having any one or more of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among these, it is preferable to use an aprotic polar solvent.
- alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected.
- alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (eg 1-methoxy-2-propanol), ethoxypropanol (eg 1-ethoxy-2-propanol), propoxypropanol (eg 1-propoxy-2- Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol).
- methoxypropanol eg 1-methoxy-2-propanol
- ethoxypropanol eg 1-ethoxy-2-propanol
- propoxypropanol eg 1-propoxy-2- Propanol
- methoxybutanol eg 1-methoxy-2-butanol, 1-
- the propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate. It is particularly preferred.
- propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
- lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
- the acetate ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate.
- alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
- chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone or methyl amyl ketone are preferred.
- cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
- lactone ⁇ -butyrolactone is preferable.
- alkylene carbonate propylene carbonate is preferable.
- an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
- ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
- a solvent having a flash point (hereinafter also referred to as a p component) of 30 ° C. or higher.
- a solvent having a flash point hereinafter also referred to as a p component
- propylene glycol monomethyl ether p component: 47 ° C.
- ethyl lactate p component: 53 ° C.
- ethyl 3-ethoxypropionate p component: 49 ° C.
- methyl amyl ketone (p component: 42 ° C)
- cyclohexanone (p component: 30 ° C)
- pentyl acetate p component: 45 ° C
- methyl 2-hydroxyisobutyrate p component: 45 ° C
- ⁇ -butyrolactone p component: 101 ° C
- propylene carbonate P component: 132 ° C.
- propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
- solvents for the lower layer film water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate At least one is more preferable.
- a conventionally known storage container can be used as the storage container for the composition for forming an underlayer film for imprint.
- the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
- the surface free energy of the imprint underlayer film formed from the imprint underlayer film forming composition of the present invention is preferably 30 mN / m or more, more preferably 40 mN / m or more, and 50 mN / m or more. More preferably.
- the upper limit is preferably 200 mN / m or more, more preferably 150 mN / m or more, and still more preferably 100 mN / m or more.
- the surface free energy can be measured, for example, using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. at 23 ° C. using a glass plate.
- the curable composition for imprints contains a compound having ⁇ HSP that is a Hansen solubility parameter distance with a specific compound of 2.5 or less.
- the said compound is a component (maximum amount component) with most content contained in the curable composition for imprints.
- the maximum component preferably occupies 20% by mass or more of the composition, more preferably occupies 30% by mass or more, and further preferably occupies 40% by mass or more. It is more preferable to occupy 50% by mass or more, and even more preferable to occupy 51% by mass or more.
- the upper limit is not particularly defined, but may be, for example, 95% by mass or less, further 85% by mass or less, and particularly 75% by mass or less.
- HSP Hansen Solubility Parameter
- the dispersion term component (component d) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and more preferably 16.0 to 18.5. Even more preferred;
- the polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and 4.0 to 5.0. Even more preferred;
- the hydrogen bond term component (component h) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5.
- the dispersion component, the polar term component, and the hydrogen bond term component of the HSP vector which are the maximum amount components, are set by the methods described in the examples described later.
- the maximum amount component satisfies the above range, but it is more preferable that components other than the maximum amount component also satisfy the above range. More preferably, 80% by mass or more of the curable composition satisfies the above range.
- the curable composition for imprints preferably contains a polymerizable compound, and more preferably the polymerizable compound constitutes the maximum amount component.
- the polymerizable compound may have one polymerizable functional group or 2 or more in one molecule.
- At least one of the polymerizable compounds contained in the curable composition for imprints preferably contains 2 to 5 polymerizable functional groups, more preferably 2 to 4 polymerizable molecules per molecule. More preferably, three are more preferable.
- At least one of the polymerizable compounds contained in the curable composition for imprints preferably includes at least one of an aromatic ring (for example, the above-described hydrocarbon aromatic ring aCy) and an alicyclic ring, and includes an aromatic ring.
- the aromatic ring is preferably a benzene ring.
- the molecular weight of the polymerizable compound is preferably 100 to 900.
- At least one of the polymerizable compounds is preferably represented by the following formula (I-1).
- L 20 is a group having the same meaning as L 30 in the above formula (3), and a preferred range thereof is also the same.
- R 21 and R 22 each independently represents a hydrogen atom or a methyl group.
- L 21 and L 22 each independently represent a single bond or a linking group Lh having the above hetero atom.
- L 20 and L 21 or L 22 may be bonded via a linking group L or not to form a ring.
- L 20 , L 21 and L 22 may have the substituent T.
- a plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different.
- L 20 having a substituent when q2 is 0 and L 20 is a terminal substituent, the aromatic ring (for example, benzene ring) constituting L 20 is preferably an alkyl group (having 1 to 12 carbon atoms).
- An embodiment in which 1 to 6 is more preferable, and 1 to 3 is more preferable is a preferred example.
- q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.
- Examples of the polymerizable compound include compounds used in the following examples, compounds described in paragraphs 0017 to 0024 and Examples of JP 2014-090133 A, and compounds described in paragraphs 0024 to 0089 of JP 2015-009171 A.
- Compounds, compounds described in paragraphs 0023 to 0037 of JP-A-2015-070145, and compounds described in paragraphs 0012 to 0039 of international publication 2016/152597 can be exemplified, but the present invention is limited thereto. It is not interpreted.
- the polymerizable compound is preferably contained in the curable composition for imprints in an amount of 30% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, more preferably 55% by mass or more, and 60% by mass. % May be 70% or more. Moreover, it is preferable that an upper limit is less than 99 mass%, it is further more preferable that it is 98 mass% or less, and it can also be 97 mass% or less.
- the boiling point of the polymerizable compound is preferably set and blended and designed in relation to the specific compound contained in the above-described imprint underlayer film forming composition.
- the boiling point of the polymerizable compound is preferably 500 ° C. or less, more preferably 450 ° C. or less, and further preferably 400 ° C. or less.
- the lower limit is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and further preferably 240 ° C. or higher.
- the curable composition for imprints may contain additives other than the polymerizable compound.
- Other additives may include a polymerization initiator, a surfactant, a sensitizer, a mold release agent, an antioxidant, a polymerization inhibitor, and the like.
- Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP2013-036027A, JP2014-090133A, and JP2013-189537A. The contents of which are incorporated herein.
- the description of the above publication can be referred to for the preparation of the curable composition for imprints and the method for forming the film (pattern forming layer), and the contents thereof are incorporated herein.
- the viscosity of the curable composition for imprints is preferably 20.0 mPa ⁇ s or less, more preferably 15.0 mPa ⁇ s or less, still more preferably 11.0 mPa ⁇ s or less, 9 More preferably, it is 0.0 mPa ⁇ s or less. Although it does not specifically limit as a lower limit of the said viscosity, For example, it can be 5.0 mPa * s or more. The viscosity is measured according to the method described in Examples described later.
- the surface tension ( ⁇ Resist) of the curable composition for imprints is preferably 28.0 mN / m or more, more preferably 30.0 mN / m or more, and may be 32.0 mN / m or more. .
- the upper limit value of the surface tension is not particularly limited, but is preferably 40.0 mN / m or less, from the viewpoint of imparting the relationship with the lower layer film and inkjet suitability, and 38.0 mN / m. More preferably, it may be 36.0 mN / m or less.
- the surface tension of the curable composition for imprints is measured according to the method described in Examples described later.
- the Onishi parameter of the curable composition for imprints is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.7 or less.
- the lower limit value of the Onishi parameter of the curable composition for imprints is not particularly defined, but may be, for example, 1.0 or more, or 2.0 or more.
- the Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formulas for the nonvolatile components of the curable composition for imprints.
- Onishi parameter sum of the number of carbon, hydrogen and oxygen atoms / (number of carbon atoms-number of oxygen atoms)
- the content of the solvent in the curable composition for imprints is preferably 5% by mass or less of the curable composition for imprints, more preferably 3% by mass or less, and 1% by mass. More preferably, it is as follows.
- the curable composition for imprints is a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, and still more preferably a weight average molecular weight of 10,000 or more. ) May not be substantially contained. “Containing substantially no polymer” means, for example, that the polymer content is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not contained at all. Is more preferable.
- the container for the curable composition for imprints used in the present invention a conventionally known container can be used.
- the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
- a preferred embodiment of the kit of the present invention includes a laminate formed from the kit.
- the laminate of the present embodiment comprises an underlayer film formed from the above-described imprint underlayer film-forming composition, and an imprint layer formed from the above-mentioned curable composition for imprints and located on the surface of the underlayer film. It is preferable to have.
- the manufacturing method is not particularly limited, a manufacturing method including applying the curable composition for imprints to the surface of the lower layer film formed from the lower layer film forming composition for imprints using the kit described above. Can be mentioned.
- the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method (IJ method).
- the method for producing a laminate includes a step of applying the above-mentioned imprinting lower layer film-forming composition in a layer form on a substrate. Preferably includes heating at 50 to 65 ° C.).
- a pattern forming method includes a step of applying the above-described composition for forming an underlayer film for imprinting to a substrate to form a layer film for imprinting (underlayer film forming process), A step of applying the curable composition (application step), a step of exposing the curable composition for imprint in a state where the mold is brought into contact with the curable composition for imprint, and a step of peeling the mold (mold contact step, Light irradiation step, mold release step).
- the curable composition for imprints is preferably provided on the surface of the lower layer film.
- Lower layer formation process the lower layer film 2 is formed on the substrate 1 as shown in FIGS.
- the lower layer film is preferably formed by applying the lower film forming composition for imprinting in a layer form on the substrate.
- An adhesion film may be provided on the surface of the substrate 1 under the lower layer film.
- the application method of the composition for forming an underlayer film for imprinting on the substrate is not particularly defined, and generally known application methods can be employed. Specifically, as an application method, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or an inkjet method. And a spin coating method is preferable.
- a solvent is volatilized (dried) with a heat
- the thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, may be 5 nm or more, may be 7 nm or more, It may be 10 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, and may be 15 nm or less.
- a silicon substrate is not particularly defined, and the description in paragraph 0103 of JP 2010-109092 A (the publication number of the corresponding US application is US 2011/0183127) can be referred to, and the contents thereof are incorporated in this specification. It is.
- the curable composition 3 for imprinting is applied to the surface of the lower layer film 2.
- the method for applying the curable composition for imprints is not particularly defined, and the description in paragraph 0102 of JP 2010-109092 A (the publication number of the corresponding US application is US 2011/0183127) can be referred to. Are incorporated herein.
- the curable composition for imprints is preferably applied to the surface of the lower layer film by an inkjet method. Moreover, you may apply
- the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to dispose the droplets on the surface of the lower layer film with an interval between the droplets.
- the interval between the droplets is preferably 10 to 1000 ⁇ m.
- the liquid drop interval is the arrangement interval of the ink jet nozzles.
- the volume ratio of the lower film 2 and the film-like curable composition for imprint 3 applied on the lower film is preferably 1: 1 to 500, more preferably 1:10 to 300. A ratio of 1:50 to 200 is more preferable.
- the manufacturing method of the laminated body which concerns on preferable embodiment of this invention is a method of manufacturing using the kit of this invention, Comprising: On the surface of the lower layer film formed from the said composition for lower layer films for imprints Applying a curable composition for imprints.
- the manufacturing method of the laminated body which concerns on preferable embodiment of this invention includes the process of applying the said underlayer film formation composition for imprints on a board
- Mold contact process For example, as shown in FIG. 1 (4), the curable composition for imprints 3 is brought into contact with the mold 4 having a pattern for transferring the pattern shape. Through such a process, a desired cured product pattern (imprint pattern) is obtained. Specifically, in order to transfer a desired pattern to the film-shaped curable composition for imprints, the mold 4 is pressed against the surface of the film-shaped curable composition for imprints 3.
- the mold may be a light transmissive mold or a light non-transmissive mold.
- a light-transmitting mold it is preferable to irradiate the curable composition 3 with light from the mold side.
- a light-impermeable mold it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side.
- a light transmissive mold and irradiate light from the mold side it is more preferable to use a light transmissive mold and irradiate light from the mold side.
- the mold that can be used in the present invention is a mold having a pattern to be transferred.
- the mold pattern manufacturing method in particular is not restrict
- cured material pattern manufacturing method which concerns on preferable embodiment of this invention can also be used as a mold.
- the material constituting the light-transmitting mold used in the present invention is not particularly limited, but includes a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), and polycarbonate resin, a transparent metal vapor-deposited film, and polydimethylsiloxane. Examples thereof include a flexible film, a photocured film, and a metal film, and quartz is preferable.
- the non-light-transmitting mold material used when a light-transmitting substrate is used is not particularly limited as long as it has a predetermined strength.
- Specific examples include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. There are no particular restrictions.
- the mold pressure is preferably selected from a range in which the residual film of the curable composition for imprint hitting the mold convexity is reduced while ensuring the uniformity of mold transfer.
- the curable composition for imprints is irradiated with light to form a cured product.
- the irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount necessary for curing.
- the amount of irradiation necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints.
- an ultraviolet light is illustrated.
- the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity.
- a pre-stage of light irradiation if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light.
- a preferable degree of vacuum at the time of light irradiation is in the range of 10 ⁇ 1 Pa to normal pressure.
- the exposure illuminance is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 .
- the exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second.
- Exposure amount is preferably in a range of 5 ⁇ 1000mJ / cm 2, and more preferably in the range of 10 ⁇ 500mJ / cm 2.
- the film-shaped curable composition for imprints is cured by light irradiation, and then is further cured by applying heat to the cured pattern as necessary. A process may be included.
- the temperature for heat-curing the curable composition for imprints after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
- the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
- the cured product and the mold are separated (FIG. 1 (5)).
- the obtained cured product pattern can be used for various applications as described later. That is, in this invention, the laminated body which has further the hardened
- the cured product pattern formed by the method for producing a cured product pattern is used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element.
- the present invention discloses a circuit board manufacturing method including a step of obtaining a cured product pattern by a cured product pattern manufacturing method according to a preferred embodiment of the present invention.
- the step of performing etching or ion implantation on the substrate using the cured product pattern obtained by the method of manufacturing the cured product pattern as a mask, and the formation of the electronic member You may have a process.
- the circuit board is preferably a semiconductor element. That is, the present invention discloses a semiconductor device manufacturing method including the pattern forming method. Furthermore, the present invention discloses a method for manufacturing an electronic device, which includes a step of obtaining a circuit board by the method for manufacturing a circuit board, and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
- a grid pattern is formed on a glass substrate of a liquid crystal display device using the pattern formed by the above-described cured product pattern manufacturing method, and polarized light having a large screen size (for example, 55 inches or more than 60 inches) with little reflection and absorption It is possible to manufacture the plate at a low cost.
- a polarizing plate described in JP-A-2015-132825 and International Publication No. 2011-132649 can be produced. One inch is 25.4 mm.
- the cured product pattern formed in the present invention is also useful as an etching resist (lithographic mask) as shown in FIGS.
- the cured product pattern As an etching resist, first, for example, a silicon substrate (such as a silicon wafer) on which a thin film such as SiO 2 is formed as a substrate, and the cured product pattern manufacturing method on the substrate, for example, A fine cured material pattern of nano or micron order is formed.
- a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed.
- the lower limit of the size of the cured product pattern formed by the cured product pattern manufacturing method is not particularly defined, but can be, for example, 1 nm or more.
- cured material pattern A method for manufacturing an imprint mold is also disclosed.
- a desired cured product pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
- the cured product pattern has particularly good etching resistance against dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a lithography mask.
- FIG. 2 is a plan view schematically showing a wet spread state of the curable composition for imprints when the curable composition for imprints is applied to the surface of the lower layer film by an inkjet method.
- IJ inkjet
- droplets of the curable composition for imprints 22 are dropped on the surface of the lower layer film 21 at equal intervals.
- FIG. 2A When the mold is brought into contact therewith, the droplets spread on the lower layer film 21 and become film-shaped curable compositions for imprints 22a, 22b, 22c (FIGS. 2B, 2C, 2C). (D)).
- the state of the curable composition for imprints 22b is completely on the lower layer film 21.
- a film that does not spread is formed. That is, a region 23 having a thin film thickness or no film may be generated. If it becomes like this, the part in which the curable composition for imprints is not fully filled will arise in the pattern of a mold, and the part without a pattern will be made in an imprint layer. For example, when etching is performed using a pattern of an imprint layer having a defect or an insufficiently thick portion in such a part as a mask, a thin region or a region 23 without a film and another region 22b.
- the lower layer film forming composition for imprints of the present invention the interfacial tension between the lower layer film formed thereby and the curable composition for imprints is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state of FIG. As a result, the curable composition for imprints can be filled in the mold accurately and sufficiently, and good patterning with uniform thickness can be achieved in the formed imprint layer. In addition, the improvement of filling property enables high-speed imprinting, which can lead to an improvement in throughput.
- the pattern formed by the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging element, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), and a liquid crystal display.
- a recording medium such as a magnetic disk
- a light receiving element such as a solid-state imaging element
- a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
- a liquid crystal display such as a magnetic disk
- a light receiving element such as a solid-state imaging element
- a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence)
- a liquid crystal display such as a liquid crystal display.
- Optical devices such as devices (LCD), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropattern formation using self-assembly of block copolymers (directed self-assembly, DSA) Can be preferably used for producing a guide pattern or the like.
- LCD liquid crystals
- DSA directed self-assembly
- composition for forming underlayer film for imprint The compounds listed in Tables 1 to 3 below were blended to prepare an underlayer film forming composition. This was filtered with a Nylon (nylon) filter having a filter diameter of 0.02 ⁇ m and a PTFE (polytetrafluoroethylene) filter having a filter diameter of 0.001 ⁇ m.
- Nylon nylon
- PTFE polytetrafluoroethylene
- ⁇ HSP Hansen solubility parameter distance
- HSPiP HSP calculation software
- each component (d component, p component, h component) of the Hansen solubility parameter vector was calculated by inputting the structural formula of each compound into the above software in the SMILES format.
- ⁇ D, ⁇ P, and ⁇ H are obtained from each component (d component, p component, h component) of the Hansen solubility parameter of the corresponding component, and are applied to the equation (1). Calculated.
- the calculated value of the compound (maximum amount component) with the largest blending amount (mass) was adopted (when the blending amount was the same, the calculated value of the compound with high surface tension was adopted. .)
- the weight average molecular weight (Mw) of the resin was defined as a polystyrene equivalent value according to gel permeation chromatography (GPC measurement).
- the apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) were used as columns.
- THF tetrahydrofuran
- Detection was performed using a UV light (ultraviolet) wavelength 254 nm detector.
- the viscosities are E type rotational viscometer RE85L (measurement range: 0.6 to 1200 mPa ⁇ s) and RE85H (measurement range: 6.4 to 12800 mPa ⁇ s) manufactured by Toki Sangyo Co., Ltd., standard cone rotor (1 Measured by adjusting the temperature of the sample cup to 23 ° C. using ° 34 ′ ⁇ R24). The unit is mPa ⁇ s. Other details regarding the measurement conformed to JISZ8803: 2011. Two samples were prepared for each level and measured three times each. A total of 6 arithmetic average values were adopted as evaluation values.
- the surface tension was measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is expressed in mN / m. Two samples were prepared for each level and measured three times each. A total of 6 arithmetic average values were adopted as evaluation values.
- A Average diameter of IJ droplet> 500 ⁇ m
- B 400 ⁇ m ⁇ IJ droplet average diameter ⁇ 500 ⁇ m
- C 300 ⁇ m ⁇ IJ droplet average diameter ⁇ 400 ⁇ m
- D Average diameter of IJ droplets ⁇ 300 ⁇ m
- the curable composition for imprints adjusted to a temperature of 23 ° C. is ejected onto the surface of the lower layer film obtained above with a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fuji Film Daimatics. Then, the droplets were applied on the surface of the lower layer film so as to form a square array with an interval of about 100 ⁇ m.
- the quartz substrate was pressed against the curable composition for imprints, and the curable composition for imprints was planarized. Further, using a high-pressure mercury lamp from the mold side, exposure was performed at 300 mJ / cm 2 , and then the quartz substrate was peeled off to obtain a flat film.
- the flat film surface was observed using an optical microscope (Olympus STM6-LM), and the filling property was evaluated according to the following criteria.
- D A region where inkjet droplets were not connected to each other and a flat film could not be formed was confirmed.
- any one of the curable compositions for imprints whose temperature was adjusted to 25 ° C. was dropped into a droplet of 6 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fuji Film Dimatics.
- the ink was discharged in a quantity and applied onto the lower layer film so that the droplets were arranged in a square array with an interval of about 100 ⁇ m to form a pattern forming layer (a layered curable composition for imprints).
- the copolymerization ratios of the copolymers in Table 5 and Table 6 are as follows (mass basis): Left structural unit Right structural unit 1-2 80 20 1-3 90 10 1-4 95 5 1-6 50 50
- Comparative Example 2 the specific polymer did not have a polymerizable functional group, and adhesion and resistance to peeling defects were inferior. Moreover, in preferable embodiment of this invention, in addition to wettability, it turned out that it can be set as especially excellent in a fillability, adhesive force, a peeling defect, and a coating surface shape.
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Abstract
Description
本発明はかかる課題を解決することを目的とするものであって、インプリント用硬化性組成物の上記下層膜に対する濡れ性、および、上記下層膜とインプリント用硬化性組成物から形成される硬化物との優れた密着性をもたらす両組成物を含むキット、インプリント用下層膜形成組成物、パターン形成方法、および半導体デバイスの製造方法の提供を目的とする。
上記インプリント用下層膜形成組成物が、重合性官能基を有するポリマーと、沸点と熱分解温度のうち低い方が480℃以上で、インプリント用硬化性組成物中に含まれる最も含有量が多い成分とのハンセン溶解度パラメータ距離であるΔHSPが2.5以下である化合物とを含む、キット;
ハンセン溶解度パラメータ距離であるΔHSPは下記数式(1)により導かれる;
ΔHSP=[4.0×(ΔD2+ΔP2+ΔH2)]0.5 数式(1)
ΔD:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの分散項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの分散項成分との差;
ΔP:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの極性項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの極性項成分の差;
ΔH:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの水素結合項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差。
<2>上記インプリント用下層膜形成組成物に含まれる化合物が、上記ポリマーの重合性官能基と重合可能な基を1分子内に複数有する、<1>に記載のキット。
<3>上記ポリマーおよび上記インプリント用下層膜形成組成物に含まれる化合物の少なくとも一方が極性官能基を有する、<1>たは<2>に記載のキット。
<4>上記極性官能基がスルホニル基含有基、スルホン酸基、リン酸基、およびヒドロキシル基からなる群の少なくとも1種を有する、<3>に記載のキット。
<5>上記ポリマーが有する重合性官能基が(メタ)アクリロイル基である、<1>~<4>のいずれか1つに記載のキット。
<6>上記ポリマーがアクリル樹脂である、<1>~<5>のいずれか1つに記載のキット。
<7>上記ポリマーの重量平均分子量が4,000以上である、<1>~<6>のいずれか1つに記載のキット。
<8>上記インプリント用下層膜形成組成物に含まれる化合物の23℃における粘度が2,000mPa・s以下である、<1>~<7>のいずれか1つに記載のキット。
<9>上記インプリント用下層膜形成組成物に含まれる化合物の23℃における表面張力が38mN/m以上である、<1>~<8>のいずれか1つに記載のキット。
<10>上記インプリント用下層膜形成組成物に含まれる化合物が、上記ポリマーが有する重合性官能基と重合可能な基を分子内に3つ有する、<1>~<9>のいずれか1つに記載のキット。
<11>上記ポリマーの重合性官能基と重合可能な基が(メタ)アクリロイル基である、<1>~<10>のいずれか1つに記載のキット。
<12>上記ポリマー100質量部に対する上記インプリント用下層膜形成組成物に含まれる化合物の量が25質量部以上400質量部以下である、<1>~<11>のいずれか1つに記載のキット。
<13>上記インプリント用下層膜形成組成物がさらに熱重合開始剤および光重合開始剤の少なくとも1種を含む、<1>~<12>のいずれか1つに記載のキット。
<14>上記インプリント用下層膜形成組成物がさらに溶剤を含み、インプリント用下層膜形成組成物の99.0質量%以上を上記溶剤が占める、<1>~<13>のいずれか1つに記載のキット。
<15>インプリント用硬化性組成物中の最も配合量の多い成分の沸点と、上記インプリント用下層膜形成組成物に含まれる化合物の沸点との差が150℃以上である、<1>~<14>のいずれか1つに記載のキット。
<16>インプリント用硬化性組成物中の最も配合量の多い成分の表面張力より、上記インプリント用硬化性組成物に含まれる化合物の表面張力の方が大きい、<1>~<15>のいずれか1つに記載のキット。
<17>インプリント用硬化性組成物と組み合わせて用いるインプリント用下層膜形成組成物であって、上記インプリント用下層膜形成組成物が、重合性官能基を有するポリマーと、沸点と熱分解温度のうち低い方が480℃以上で、インプリント用硬化性組成物中に含まれる最も含有量が多い成分とのハンセン溶解度パラメータ距離であるΔHSPが2.5以下である化合物とを含むインプリント用下層膜形成組成物;
ハンセン溶解度パラメータ距離であるΔHSPは下記数式(1)により導かれる;
ΔHSP=[4.0×(ΔD2+ΔP2+ΔH2)]0.5 数式(1)
ΔD:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの分散項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの分散項成分との差;
ΔP:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの極性項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの極性項成分の差;
ΔH:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの水素結合項成分と、上記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差。
<18>上記インプリント用下層膜形成組成物に含まれる化合物が、上記ポリマーの重合性官能基と重合可能な基を分子内に複数有する、<17>に記載のインプリント用下層膜形成組成物。
<19><1>~<16>のいずれか1つに記載のキットに含まれるインプリント用下層膜形成組成物を基板に適用しインプリント用下層膜を形成する工程、
上記キットに含まれるインプリント用硬化性組成物を上記インプリント用下層膜に適用する工程、
上記インプリント用硬化性組成物にモールドを接触させた状態で上記インプリント用硬化性組成物を露光する工程および
上記モールドを剥離する工程
を含む、パターン形成方法。
<20>上記インプリント用下層膜を形成する工程がスピンコート法を含む、<19>に記載のパターン形成方法。
<21>上記インプリント用硬化性組成物を適用する工程がインクジェット法を含む、<19>または<20>に記載のパターン形成方法。
<22><19>~<21>のいずれか1つに記載のパターン形成方法を含む半導体デバイスの製造方法。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートを表す。
本明細書において、「インプリント」は、好ましくは、1nm~10mmのサイズのパターン転写をいい、より好ましくは、およそ10nm~100μmのサイズのパターン転写(ナノインプリント)をいう。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において、「光」には、紫外、近紫外、遠紫外、可視、赤外等の領域の波長の光や、電磁波だけでなく、放射線も含まれる。放射線には、例えばマイクロ波、電子線、極端紫外線(EUV)、X線が含まれる。また248nmエキシマレーザー、193nmエキシマレーザー、172nmエキシマレーザーなどのレーザー光も用いることができる。これらの光は、光学フィルタを通したモノクロ光(単一波長光)を用いてもよいし、複数の波長の異なる光(複合光)でもよい。
本発明における重量平均分子量(Mw)は、特に述べない限り、ゲルパーミエーションクロマトグラフィ(GPC)で測定したものをいう。
本発明における温度は、特に述べない限り、23℃とする。
本発明における沸点とは、1気圧(1atm=1013.25hPa)における沸点をいう。
このメカニズムは推定であるが、沸点と熱分解温度のうち低い方が480℃以上の化合物(特定化合物)として、インプリント用硬化性組成物とのハンセン溶解度パラメータ距離が小さい化合物を用いることにより、下層膜とインプリント用硬化性組成物との親和性が向上し良好な濡れ性を達成できる。また、特定化合物として沸点と熱分解温度のうち低い方が480℃以上の化合物を用いることにより、重合性官能基を有するポリマー(特定ポリマー)を含むインプリント用下層膜形成組成物を高温でベイクしても、特定化合物を揮発させずに下層膜中に残すことができる。さらに、特定ポリマーが基材との界面密着性が良好でかつ強度のある膜を形成し、インプリント用硬化性組成物から形成される硬化物との密着性を確保することができる。
以下、本発明について詳細に説明する。
本発明のキットは、特定化合物と、インプリント用硬化性組成物中に含まれる最も含有量が多い成分(最大量成分)との間のハンセン溶解度パラメータ距離(ΔHSP)が2.5以下であり、2.2以下であることが好ましく、2.0以下であることがより好ましく、1.8以下であることがさらに好ましく、1.5以下であってもよい。下限値は、0が理想であるが、1.0以上でも十分実用レベルである。ΔHSPを2.5以下とすることで、インプリント用硬化性組成物との親和性が向上し、インプリント用下層膜上でのインプリント用硬化性組成物の濡れ性が向上する。
ハンセン溶解度パラメータ距離(ΔHSP)は下記数式(1)により導かれる。
ΔHSP=[4.0×(ΔD2+ΔP2+ΔH2)]0.5 数式(1)
ΔD:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの分散項成分(d成分1)と、インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの分散項成分(d成分2)との差(d成分1-d成分2)
ΔP:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの極性項成分(p成分1)と、インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの極性項成分(p成分2)の差(p成分1-p成分2)
ΔH:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの水素結合項成分(h成分1)と、インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの水素結合項成分(h成分2)の差(h成分1-h成分2)
HSPベクトルの分散項成分、極性項成分、水素結合項成分は、それぞれ、後述する実施例に記載の方法で設定される。本発明においては、上記対象成分が、インプリント用硬化性組成物の最大量成分と、インプリント用下層膜形成組成物中の特定化合物であるが、特定化合物が複数ある場合には、その最大量成分を評価に採用する。なお、該当成分の配合量が同一の場合は表面張力の高い化合物の計算値を採用する。最大量成分は、質量が最大量であるものをいう。
特定化合物は、上記のようにインプリント用硬化性組成物の最大量成分(好ましくは重合性化合物)とHSPを近づけることで、インプリント用硬化性組成物との親和性を上げる役割を果たす。これにより、良好な濡れ性を実現し、ひいては、好ましい実施形態において良好な密着性をも達成することができる。
<<特定ポリマー>>
インプリント用下層膜形成組成物は、重合性官能基を有するポリマー(特定ポリマー)を含む。特定ポリマーの種類は、重合性官能基を含む限り、特に定めるものではない。
特定ポリマーは、通常、重量平均分子量が2,000以上の化合物であり、4,000以上が好ましく、6,000以上がより好ましく、10,000以上がさらに好ましい。重量平均分子量の上限は特に定めるものではないが、例えば、200,000以下が好ましく、70,000以下がより好ましく、50,000以下がさらに好ましい。重量平均分子量を上記下限値以上とすることにより、ベイク処理時の膜安定性が向上し、インプリント下層膜形成時の面状をより向上させることができる。また、重量平均分子量を上記上限値以下とすることにより、溶剤への溶解性が高くなり、スピンコー等による適用がより容易となる。なお、本発明における重量平均分子量(Mw)は、特に述べない限り、ゲルパーミエーションクロマトグラフィ(GPC)で測定したものをいう。また、上記の分子量が適正な範囲となることで流動性が維持され、インプリント用硬化性組成物の濡れ性が向上する。
RQ2は水素原子または上記RQ1で規定される置換基である。
RQ3は上記RQ1またはORQ1の置換基である。
RQ1~RQ3は、本発明の効果を奏する範囲で置換基Tを有していてもよい。例えば、ヒドロキシル基、アミノ基、カルボキシル基などが置換していてもよい。
本発明では、特定ポリマーと特定化合物の少なくとも一方が極性官能基Tfを有することが好ましく、特定ポリマーが極性官能基Tfを有する化合物を有することがより好ましい。もちろん、特定ポリマーと特定化合物の両方が極性官能基Tfを有していてもよい。
また、特定ポリマーおよび特定化合物以外の化合物が、極性官能基Tfを有している態様も本発明の範囲に含まれる。
-(L3)t3-[(L2)t2-(P)t1]t4 (T1)
L2はt1+1価の連結基であり、環状または直鎖もしくは分岐のアルカン構造の基(炭素数1~40が好ましく、1~30がより好ましく、1~20がさらに好ましい)、環状または直鎖もしくは分岐のアルケン構造の基(炭素数2~40が好ましく、2~30がより好ましく、2~20がさらに好ましい)、環状または直鎖もしくは分岐のアルキン構造の基(炭素数2~40が好ましく、2~30がより好ましく、2~20がさらに好ましい)、アリール構造の基(炭素数6~22が好ましく、6~18がより好ましく、6~10がさらに好ましい)、ヘテロアリール構造の基(炭素数1~22が好ましく、1~18がより好ましく、1~10がさらに好ましい)であることが好ましい。アリール構造の基の好ましい環構造としては、下記の炭化水素芳香族環aCyの例が挙げられる。ヘテロアリール構造の基の好ましい環構造としては、下記の芳香族複素環hCyの例が挙げられる。環状のアルカン構造の基、アルケン構造の基、アルキン構造の基の好ましい環構造としては、下記の脂環fCyの例が挙げられる。L2は本発明の効果を奏する範囲で置換基Tを有していてもよい。置換基Tは複数あるとき互いに結合して、あるいは連結基Lを介してまたは介さずに式中のL2と結合して環を形成していてもよい。
-(L3)t3-[(L2)t2-(Q)t1]t4 (T2)
-(L4)-T1 (T3)
L4は単結合またはヘテロ原子を有する連結基Lhであり、なかでも酸素原子、カルボニル基、-NRN-またはその組み合わせが好ましく、酸素原子、カルボニル基またはその組み合わせがより好ましく、酸素原子がさらに好ましい。T1は上記式(T1)で表される置換基である。
-(L4)-T2 (T4)
L4は式(T3)におけるL4と同義である。T2は上記式(T2)で表される置換基が好ましい。
RNは水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3がさらに好ましい)であり、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3がさらに好ましい)、アルキニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3がさらに好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10がさらに好ましい)、ヘテロアリール基(炭素数1~22が好ましく、1~16がより好ましく、1~12がさらに好ましい)であり、なかでも、水素原子、メチル基、エチル基、またはプロピル基が好ましい。RNは本発明の効果を奏する範囲でさらに置換基Tで規定される各基を有していてもよい。
各置換基に含まれるアルキル部位、アルケニル部位、およびアルキニル部位は鎖状でも環状でもよく、直鎖でも分岐でもよい。上記置換基Tが置換基を取りうる基である場合にはさらに置換基Tを有してもよい。例えば、アルキル基はハロゲン化アルキル基となってもよいし、(メタ)アクリロイルオキシアルキル基、アミノアルキル基やカルボキシアルキル基になっていてもよい。
特定ポリマーの不揮発性成分(組成物中の溶剤以外の成分をいう、以下同じ)中の含有率は、5質量%以上であることが好ましく、20質量%以上であることがより好ましく、30質量%以上であることがさらに好ましい。上限としては、90質量%以下であることが好ましく、70質量%以下であることがより好ましく、60質量%以下であることがさらに好ましい。
この量を上記下限値以上とすることで、ポリマーを配合したことによる効果を好適に発揮させることができ、また、均一な薄膜を調製しやすくなる。一方上記上限値以下とすることにより、溶剤を用いた効果が好適に発揮され、広い面積に均一な膜を形成しやすくなる。
特定ポリマーは、1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合、合計量が上記範囲となることが好ましい。
本発明で用いるインプリント用下層膜形成組成物に含まれる特定化合物は、沸点と熱分解温度のうち低い方が480℃以上でインプリント用硬化性組成物中に含まれる最も含有量が多い成分とのハンセン溶解度パラメータ距離(ΔHSP)が2.5以下である化合物である。特定化合物は、沸点が480℃以上であることが好ましい。
なお、インプリント用下層膜形成組成物の特定化合物を2種以上採用するときには、沸点の対比は最も沸点の低い化合物を対象とする。
重合可能な基とは、特定ポリマーが有する重合性官能基と重合可能な基である限り特に定めるものではなく、(メタ)アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基が例示され、上記重合性官能基Psに相当するものが好ましく、エポキシ基および(メタ)アクリロイル基がより好ましく、(メタ)アクリロイル基がさらに好ましい。
また、特定化合物に含まれる重合可能な基と特定ポリマーが有する重合性官能基は、少なくとも1種が共通することが好ましい。
(i)分散項成分(d成分)は、14.0~20.0であることが好ましく、15.0~20.0であることがより好ましく、17.0~19.0であることがさらに好ましく、17.5~19.0であることが一層好ましく、18.0~19.0であることがより一層好ましい;
(ii)極性項成分(p成分)は、3.5~8.0であることが好ましく、4.0~8.0であることがより好ましく、4.0~7.5であることがさらに好ましく、4.0~5.5が一層好ましい;
(iii)水素結合項成分(h成分)は、4.0~8.0であることが好ましく、4.0~7.5であることがより好ましく、4.5.2~5.5であることがさらに好ましい。
上記特定化合物の、HSPベクトルの分散項成分、極性項成分、水素結合項成分は、それぞれ、後述する実施例に記載の方法で設定される。
また、特定化合物に限らず、不揮発性成分が複数ある場合には、特定化合物以外の少なくとも1種も上記の範囲を満たすことが好ましく、特定化合物以外の不揮発性成分の80質量%以上が上記の範囲を満たすことがより好ましく、すべての成分が上記の範囲にあることがさらに好ましい。
L30は、q3+1価の連結基であり、上記のL2と同義である。ただし好ましい範囲は、上記炭化水素芳香族環aCyを有する基(炭素数6~22が好ましく、6~18がより好ましく、6~10がさらに好ましい)、アルカン構造の基(炭素数2~40が好ましく、4~30がより好ましく、6~24がさらに好ましい)、(オリゴ)アルキレンオキシ基(1つの構成単位中のアルキレン基の炭素数は1~12が好ましく、1~6がより好ましく、1~3がさらに好ましい;繰り返し数は1~50が好ましく、1~40がより好ましく、1~30がさらに好ましい)、またはこれらの組合せが好ましい。L30は上記置換基Tを有していてもよい。置換基Tは複数が結合して環を形成してもよい。置換基Tが複数あるとき互いに同じでも異なっていてもよい。
R31およびR32はそれぞれ独立に水素原子またはメチル基を表す。
L31およびL32はそれぞれ独立に単結合または上記ヘテロ原子を有する連結基Lhを表す。L30とL31またはL32は連結基Lを介してまたは介さずに結合して環を形成していてもよい。L30、L31およびL32は上記置換基Tを有していてもよい。置換基Tは複数が結合して環を形成してもよい。置換基Tが複数あるとき互いに同じでも異なっていてもよい。L31およびL32は互いにまたはL30と結合して環を形成していてもよい。
q3は0~5の整数であり、1~5の整数が好ましく、1~3がより好ましく、1または2がさらに好ましい。q3=0のとき、L30は置換基となる。L30が置換基となるとき、L32の部位は水素原子となる。
特定化合物の不揮発性成分中の含有率は、5質量%以上であることが好ましく、20質量%以上であることがより好ましく、30質量%以上であることがさらに好ましい。上限としては、90質量%以下であることが好ましく、70質量%以下であることがより好ましく、60質量%以下であることがさらに好ましい。
この量を上記下限値以上とすることで、ポリマーを配合したことによる効果を好適に発揮させることができ、また、均一な薄膜を調製しやすくなる。一方上記上限値以下とすることにより、溶剤を用いた効果が好適に発揮され、広い面積に均一な膜を形成しやすくなる。
特定化合物は、1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合、合計量が上記範囲となることが好ましい。
インプリント用下層膜形成組成物に含まれる特定化合物の表面張力(η1)の方が、インプリント用硬化性組成物中の最も配合量の多い成分の表面張力(η2)より大きいことが好ましい。その差は、η1-η2で、2.0mN/m以上であることが好ましく、2.5mN/m以上であることがより好ましく、3.0mN/m以上であることがさらに好ましい。このような構成とすることにより、インプリント用硬化性組成物との濡れ性をより良好にすることが可能となる。
この表面張力は、後記実施例に記載の方法に基づき測定した値を採用する。
インプリント用下層膜形成組成物は、アルキレングリコール化合物を含んでいてもよい。アルキレングリコール化合物は、アルキレングリコール構成単位を3~1000個有していることが好ましく、4~500個有していることがより好ましく、5~100個有していることがさらに好ましく、5~50個有していることが一層好ましい。アルキレングリコール化合物の重量平均分子量(Mw)は150~10000が好ましく、200~5000がより好ましく、300~3000がさらに好ましく、300~1000が一層好ましい。
アルキレングリコール化合物は、ポリエチレングリコール、ポリプロピレングリコール、これらのモノまたはジメチルエーテル、モノまたはジオクチルエーテル、モノまたはジノニルエーテル、モノまたはジデシルエーテル、モノステアリン酸エステル、モノオレイン酸エステル、モノアジピン酸エステル、モノコハク酸エステルが例示され、ポリエチレングリコール、ポリプロピレングリコールが好ましい。
アルキレングリコール化合物の23℃における表面張力は、38.0mN/m以上であることが好ましく、40.0mN/m以上であることがより好ましい。表面張力の上限は特に定めるものではないが、例えば48.0mN/m以下である。このような化合物を配合することにより、下層膜の直上に設けるインプリント用硬化性組成物の濡れ性をより向上させることができる。
アルキレングリコール化合物は、1種のみ用いてもよいし、2種以上用いてもよい。2種以上用いる場合、合計量が上記範囲となることが好ましい。
インプリント用下層膜形成組成物は、重合開始剤を含んでいてもよく、熱重合開始剤および光重合開始剤の少なくとも1種を含むことが好ましい。重合開始剤を含むことにより、インプリント用下層膜形成組成物に含まれる重合性基の反応が促進し、密着性が向上する傾向にある。インプリント用硬化性組成物との架橋反応性を向上させる観点から光重合開始剤が好ましい。光重合開始剤としては、ラジカル重合開始剤、カチオン重合開始剤が好ましく、ラジカル重合開始剤がより好ましい。また、本発明において、光重合開始剤は複数種を併用してもよい。
アシルホスフィン化合物としては、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドなどが挙げられる。また、市販品であるIRGACURE-819やIRGACURE1173、IRGACURE-TPO(商品名:いずれもBASF製)を用いることができる。
インプリント用下層膜形成組成物に配合される不揮発性成分としては、上記化合物の他に、熱重合開始剤、重合禁止剤、酸化防止剤、レベリング剤、増粘剤、界面活性剤等を1種または2種以上含んでいてもよい。
熱重合開始剤等については、特開2013-036027号公報、特開2014-090133号公報、特開2013-189537号公報に記載の各成分を用いることができる。含有量等についても、上記公報の記載を参酌できる。
また、本発明では、インプリント用下層膜形成組成物が実質的に界面活性剤を含まない構成とすることもできる。実質的に含まないとは、インプリント用下層膜形成組成物中の不揮発性成分の0.1質量%以下であることをいう。
インプリント用下層膜形成組成物は溶剤(下層膜用溶剤)を含むことが好ましい。溶剤は例えば、23℃で液体であって沸点が250℃以下の化合物が好ましい。通常、不揮発性成分が最終的に下層膜を形成する。インプリント用下層膜形成組成物は、下層膜用溶剤を99.0質量%以上含むことが好ましく、99.5質量%以上含むことがより好ましく、99.6質量%以上であってもよい。本発明において、液体とは、23℃における粘度が100,000mPa・s以下であることをいう。
溶剤は、インプリント用下層膜形成組成物に、1種のみ含まれていてもよいし、2種以上含まれていてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
下層膜用溶剤の沸点は、230℃以下であることが好ましく、200℃以下であることがより好ましく、180℃以下であることがさらに好ましく、160℃以下であることが一層好ましく、130℃以下であることがより一層好ましい。下限値は23℃であることが実際的であるが、60℃以上であることがより実際的である。沸点を上記の範囲とすることにより、下層膜から溶剤を容易に除去でき好ましい。
乳酸エステルとしては、乳酸エチル、乳酸ブチル、または乳酸プロピルが好ましい。
酢酸エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソアミル、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、または酢酸3-メトキシブチルが好ましい。
アルコキシプロピオン酸エステルとしては、3-メトキシプロピオン酸メチル(MMP)、または、3-エトキシプロピオン酸エチル(EEP)が好ましい。
鎖状ケトンとしては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、アセトン、4-ヘプタノン、1-ヘキサノン、2-ヘキサノン、ジイソブチルケトン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトンまたはメチルアミルケトンが好ましい。
環状ケトンとしては、メチルシクロヘキサノン、イソホロンまたはシクロヘキサノンが好ましい。
ラクトンとしては、γ-ブチロラクトンが好ましい。
アルキレンカーボネートとしては、プロピレンカーボネートが好ましい。
本発明のインプリント用下層膜形成組成物から形成されたインプリント用下層膜の表面自由エネルギーが30mN/m以上であることが好ましく、40mN/m以上であることがより好ましく、50mN/m以上であることがさらに好ましい。上限としては、200mN/m以上であることが好ましく、150mN/m以上であることがより好ましく、100mN/m以上であることがさらに好ましい。
表面自由エネルギーの測定は、例えば、協和界面科学(株)製、表面張力計 SURFACE TENS-IOMETER CBVP-A3を用い、ガラスプレートを用いて23℃で行うことができる。
インプリント用硬化性組成物は、特定化合物とのハンセン溶解度パラメータ距離であるΔHSPが2.5以下である化合物を含む。上記化合物は、インプリント用硬化性組成物に含まれる最も含有量が多い成分(最大量成分)である。インプリント用硬化性組成物は、上記最大量成分が、組成物の20質量%以上を占めることが好ましく、30質量%以上を占めることがより好ましく、40質量%以上を占めることがさらに好ましく、50質量%以上を占めることが一層好ましく、51質量%以上を占めることがより一層好ましい。上限値については、特に定めるものではないが、例えば、95質量%以下、さらには85質量%以下、特には75質量%以下とすることができる。
上記最大量成分のハンセン溶解度パラメータ(HSP)ベクトルの:
(i)分散項成分(d成分)は、14.0~20.0であることが好ましく、15.0~19.0であることがより好ましく、16.0~18.5であることがさらに好ましい;
(ii)極性項成分(p成分)は、3.5~8.0であることが好ましく、3.8~6.0であることがより好ましく、4.0~5.0であることがさらに好ましい;
(iii)水素結合項成分(h成分)は、4.0~8.0であることが好ましく、4.7~7.0であることがより好ましく、5.2~6.5であることがさらに好ましい。
上記最大量成分の、HSPベクトルの分散項成分、極性項成分、水素結合項成分は、それぞれ、後述する実施例に記載の方法で設定される。なお、インプリント用硬化性組成物の含有成分が複数ある場合には、最大量成分が上記の範囲を満たすが、最大量成分以外の成分も上記の範囲を満たすことがより好ましく、インプリント用硬化性組成物の80質量%以上の成分が上記範囲を満たすことがさらに好ましい。
インプリント用硬化性組成物は重合性化合物を含むことが好ましく、この重合性化合物が最大量成分を構成することがより好ましい。重合性化合物は、一分子中に重合性官能基を1つ有していても、2つ以上有していてもよい。インプリント用硬化性組成物に含まれる重合性化合物の少なくとも1種は、重合性官能基を一分子中に2~5つ含むことが好ましく、2~4つ含むことがより好ましく、2または3つ含むことがさらに好ましく、3つ含むことが一層好ましい。
インプリント用硬化性組成物に含まれる重合性化合物の少なくとも1種は、芳香族環(例えば、上記炭化水素芳香族環aCy)および脂環の少なくとも一方を含むことが好ましく、芳香族環を含むことがさらに好ましい。芳香族環はベンゼン環が好ましい。
重合性化合物の分子量は100~900が好ましい。
上記重合性化合物の少なくとも1種は、下記式(I-1)で表されることが好ましい。
L20は、上記式(3)のL30と同義の基であり、その好ましい範囲も同じである。
R21およびR22はそれぞれ独立に水素原子またはメチル基を表す。
L21およびL22はそれぞれ独立に単結合または上記ヘテロ原子を有する連結基Lhを表す。L20とL21またはL22は連結基Lを介してまたは介さずに結合して環を形成していてもよい。L20、L21およびL22は上記置換基Tを有していてもよい。置換基Tは複数が結合して環を形成してもよい。置換基Tが複数あるとき互いに同じでも異なっていてもよい。L20が置換基を有する例としては、q2が0でL20が末端の置換基となるとき、L20を構成する芳香族環(例えばベンゼン環)にアルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3がさらに好ましい)が置換した態様を好ましい例として挙げることができる。
q2は0~5の整数であり、0~3の整数が好ましく、0~2の整数がより好ましく、0または1がさらに好ましい。
インプリント用硬化性組成物は、重合性化合物以外の添加剤を含有してもよい。他の添加剤としては、重合開始剤、界面活性剤、増感剤、離型剤、酸化防止剤、重合禁止剤等を含んでいてもよい。
本発明で用いることができるインプリント用硬化性組成物の具体例としては、特開2013-036027号公報、特開2014-090133号公報、特開2013-189537号公報に記載の組成物が例示され、これらの内容は本明細書に組み込まれる。また、インプリント用硬化性組成物の調製、膜(パターン形成層)の形成方法についても、上記公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。
インプリント用硬化性組成物の粘度は、20.0mPa・s以下であることが好ましく、15.0mPa・s以下であることがより好ましく、11.0mPa・s以下であることがさらに好ましく、9.0mPa・s以下であることが一層好ましい。上記粘度の下限値としては、特に限定されるものでは無いが、例えば、5.0mPa・s以上とすることができる。粘度は、後述する実施例に記載の方法に従って測定される。
大西パラメータはインプリント用硬化性組成物の不揮発性成分について、それぞれ、全構成成分の炭素原子、水素原子および酸素原子の数を下記式に代入して求めることができる。
大西パラメータ=炭素原子、水素原子および酸素原子の数の和/(炭素原子の数-酸素原子の数)
インプリント用硬化性組成物は、ポリマー(好ましくは、重量平均分子量が1,000を超える、より好ましくは重量平均分子量が2,000を超える、さらに好ましくは重量平均分子量が10,000以上のポリマー)を実質的に含有しない態様とすることもできる。ポリマーを実質的に含有しないとは、例えば、ポリマーの含有量がインプリント用硬化性組成物の0.01質量%以下であることをいい、0.005質量%以下が好ましく、全く含有しないことがより好ましい。
本発明のキットの好ましい実施形態として、このキットから形成される積層体が挙げられる。本実施形態の積層体は、上記インプリント用下層膜形成組成物から形成された下層膜と、上記インプリント用硬化性組成物から形成され、上記下層膜の表面に位置するインプリント層とを有することが好ましい。その製造方法は特に限定されないが、上記のキットを用いて、インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む製造方法が挙げられる。このとき、インプリント用硬化性組成物は、インクジェット法(IJ法)により、上記下層膜の表面に適用することが好ましい。さらに、積層体の製造方法は、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を40~70℃(好ましくは50~65℃)で加熱することを含むことが好ましい。
本発明の好ましい実施形態にかかるパターンの形成方法は、上記インプリント用下層膜形成組成物を基板に適用しインプリント用下層膜を形成する工程(下層膜形成工程)、下層膜にインプリント用硬化性組成物を適用する工程(適用工程)、インプリント用硬化性組成物にモールドを接触させた状態でインプリント用硬化性組成物を露光する工程およびモールドを剥離する工程(モールド接触工程、光照射工程、離型工程)を含む。インプリント用硬化性組成物は、下層膜の表面に設けることが好ましい。
以下、パターン形成方法(硬化物パターンの製造方法)について、図1に従って説明する。本発明の構成が図面により限定されるものではないことは言うまでもない。
下層膜形成工程では、図1(1)(2)に示す様に、基板1上に、下層膜2を形成する。下層膜は、インプリント用下層膜形成組成物を基板上に層状に適用して形成することが好ましい。下層膜の下で、基板1の表面に密着膜を設けてもよい。
また、基板上にインプリント用下層膜形成組成物を層状に適用した後、好ましくは、熱によって溶剤を揮発(乾燥)させて、薄膜である下層膜を形成する。
適用工程では、例えば、図1(3)に示すように、上記下層膜2の表面に、インプリント用硬化性組成物3を適用する。
インプリント用硬化性組成物の適用方法としては、特に定めるものでは無く、特開2010-109092号公報(対応US出願の公開番号は、US2011/0183127)の段落0102の記載を参酌でき、この内容は本明細書に組み込まれる。上記インプリント用硬化性組成物は、インクジェット法により、上記下層膜の表面に適用することが好ましい。また、インプリント用硬化性組成物を、多重塗布により塗布してもよい。インクジェット法などにより下層膜の表面に液滴を配置する方法において、液滴の量は1~20pL程度が好ましく、液滴間隔をあけて下層膜表面に配置することが好ましい。液滴間隔としては、10~1000μmの間隔が好ましい。液滴間隔は、インクジェット法の場合は、インクジェットのノズルの配置間隔とする。
さらに、下層膜2と、下層膜上に適用した膜状のインプリント用硬化性組成物3の体積比は、1:1~500であることが好ましく、1:10~300であることがより好ましく、1:50~200であることがさらに好ましい。
また、本発明の好ましい実施形態に係る積層体の製造方法は、本発明のキットを用いて製造する方法であって、上記インプリント用下層膜用成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む。さらに、本発明の好ましい実施形態に係る積層体の製造方法は、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を、好ましくは100~300℃で、より好ましくは130~260℃で、さらに好ましくは150~230℃で、加熱(ベイク)することを含むことが好ましい。加熱時間は、好ましくは30秒~5分である。
モールド接触工程では、例えば、図1(4)に示すように、上記インプリント用硬化性組成物3とパターン形状を転写するためのパターンを有するモールド4とを接触させる。このような工程を経ることにより、所望の硬化物パターン(インプリントパターン)が得られる。
具体的には、膜状のインプリント用硬化性組成物に所望のパターンを転写するために、膜状のインプリント用硬化性組成物3の表面にモールド4を押接する。
本発明で用いることのできるモールドは、転写されるべきパターンを有するモールドである。上記モールドが有するパターンは、例えば、フォトリソグラフィや電子線描画法等によって、所望する加工精度に応じて形成できるが、本発明では、モールドパターン製造方法は特に制限されない。また、本発明の好ましい実施形態に係る硬化物パターン製造方法によって形成したパターンをモールドとして用いることもできる。
本発明において用いられる光透過性モールドを構成する材料は、特に限定されないが、ガラス、石英、ポリメチルメタクリレート(PMMA)、ポリカーボネート樹脂などの光透過性樹脂、透明金属蒸着膜、ポリジメチルシロキサンなどの柔軟膜、光硬化膜、金属膜等が例示され、石英が好ましい。
本発明において光透過性の基板を用いた場合に使われる非光透過型モールド材としては、特に限定されないが、所定の強度を有するものであればよい。具体的には、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基板、SiC、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの基板などが例示され、特に制約されない。
また、インプリント用硬化性組成物とモールドとの接触を、ヘリウムガスまたは凝縮性ガス、あるいはヘリウムガスと凝縮性ガスの両方を含む雰囲気下で行うことも好ましい。
光照射工程では、上記インプリント用硬化性組成物に光を照射して硬化物を形成する。光照射工程における光照射の照射量は、硬化に必要な最小限の照射量よりも十分大きければよい。硬化に必要な照射量は、インプリント用硬化性組成物の不飽和結合の消費量などを調べて適宜決定される。
照射する光の種類は特に定めるものではないが、紫外光が例示される。
また、本発明に適用されるインプリントリソグラフィにおいては、光照射の際の基板温度は、通常、室温とするが、反応性を高めるために加熱をしながら光照射してもよい。光照射の前段階として、真空状態にしておくと、気泡混入防止、酸素混入による反応性低下の抑制、モールドとインプリント用硬化性組成物との密着性向上に効果があるため、真空状態で光照射してもよい。また、上記硬化物パターン製造方法中、光照射時における好ましい真空度は、10-1Paから常圧の範囲である。
露光に際しては、露光照度を1~500mW/cm2の範囲にすることが好ましく、10~400mW/cm2の範囲にすることがより好ましい。露光の時間は特に限定されないが、0.01~10秒であることが好ましく、0.5~1秒であることがより好ましい。露光量は、5~1000mJ/cm2の範囲にすることが好ましく、10~500mJ/cm2の範囲にすることがより好ましい。
上記硬化物パターン製造方法においては、光照射により膜状のインプリント用硬化性組成物(パターン形成層)を硬化させた後、必要に応じて、硬化させたパターンに熱を加えてさらに硬化させる工程を含んでいてもよい。光照射後にインプリント用硬化性組成物を加熱硬化させるための温度としては、150~280℃が好ましく、200~250℃がより好ましい。また、熱を付与する時間としては、5~60分間が好ましく、15~45分間がさらに好ましい。
離型工程では、上記硬化物と上記モールドとを引き離す(図1(5))。得られた硬化物パターンは後述する通り各種用途に利用できる。
すなわち、本発明では、上記下層膜の表面に、さらに、インプリント用硬化性組成物から形成される硬化物パターンを有する、積層体が開示される。また、本発明で用いるインプリント用硬化性組成物からなるパターン形成層の膜厚は、使用する用途によって異なるが、0.01μm~30μm程度である。
さらに、後述するとおり、エッチング等を行うこともできる。
上述のように上記硬化物パターンの製造方法によって形成された硬化物パターンは、液晶表示装置(LCD)などに用いられる永久膜や、半導体素子製造用のエッチングレジスト(リソグラフィ用マスク)として使用することができる。特に、本発明では、本発明の好ましい実施形態に係る硬化物パターンの製造方法により硬化物パターンを得る工程を含む、回路基板の製造方法を開示する。さらに、本発明の好ましい実施形態に係る回路基板の製造方法では、上記硬化物パターンの製造方法により得られた硬化物パターンをマスクとして基板にエッチングまたはイオン注入を行う工程と、電子部材を形成する工程と、を有していてもよい。上記回路基板は、半導体素子であることが好ましい。すなわち、本発明では、上記パターン形成方法を含む半導体デバイスの製造方法を開示する。さらに、本発明では、上記回路基板の製造方法により回路基板を得る工程と、上記回路基板と上記回路基板を制御する制御機構とを接続する工程と、を有する電子機器の製造方法を開示する。
また、上記硬化物パターン製造方法によって形成されたパターンを利用して液晶表示装置のガラス基板にグリッドパターンを形成し、反射や吸収が少なく、大画面サイズ(例えば55インチ、60インチ超)の偏光板を安価に製造することが可能である。例えば、特開2015-132825号公報や国際公開第2011/132649号に記載の偏光板が製造できる。なお、1インチは25.4mmである。
本発明で形成された硬化物パターンは、図1(6)(7)に示す通り、エッチングレジスト(リソグラフィ用マスク)としても有用である。硬化物パターンをエッチングレジストとして利用する場合には、まず、基板として例えばSiO2等の薄膜が形成されたシリコン基板(シリコンウェハ等)等を用い、基板上に上記硬化物パターン製造方法によって、例えば、ナノまたはミクロンオーダーの微細な硬化物パターンを形成する。本発明では特にナノオーダーの微細パターンを形成でき、さらにはサイズが50nm以下、特には30nm以下のパターンも形成できる点で有益である。上記硬化物パターン製造方法で形成する硬化物パターンのサイズの下限値については特に定めるものでは無いが、例えば、1nm以上とすることができる。
また、本発明では、基板上に、本発明の好ましい実施形態に係る硬化物パターンの製造方法により硬化物パターンを得る工程と、得られた上記硬化物パターンを用いて上記基板にエッチングを行う工程と、を有する、インプリント用モールドの製造方法も開示する。
ウェットエッチングの場合にはフッ化水素等、ドライエッチングの場合にはCF4等のエッチングガスを用いてエッチングすることにより、基板上に所望の硬化物パターンを形成することができる。硬化物パターンは、特にドライエッチングに対するエッチング耐性が良好である。すなわち、上記硬化物パターン製造方法によって形成されたパターンは、リソグラフィ用マスクとして好ましく用いられる。
これに対し、本発明のインプリント用下層膜形成組成物によれば、これにより形成される下層膜とインプリント用硬化性組成物との界面張力が改善され濡れ性が向上している。そのため、より確実に図2(d)の状態の隅々にまで広がったインプリント用硬化性組成物22cとなる。その結果、全体にわたってインプリント用硬化性組成物がモールドに的確かつ十分に充填され、形成されたインプリント層において厚さにムラのない良好なパターニングを達成することができる。また、充填性の向上により高速のインプリントが可能となりスループットの改善にもつなげることができる。
なお、上記の説明では、インクジェット法によりインプリント用硬化性組成物を下層膜上に適用する例を挙げて本発明の好ましい実施形態にかかる作用機序について説明したが、これにより本発明が限定して解釈されるものではない。例えば、スクリーン塗布やスピンコートなどにおいても、良好な濡れ性と優れた充填性は加工上および製品品質上の利点につながり、発明の効果を好適に発揮し得るものである。
下表1~3に記載の各化合物を配合し、下層膜形成組成物を調製した。これをフィルタ径0.02μmのNylon(ナイロン)フィルタおよびフィルタ径0.001μmのPTFE(ポリテトラフルオロエチレン)フィルタでろ過した。
下表4に記載の各種化合物を混合し、さらに重合禁止剤として4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン-1-オキシルフリーラジカル(東京化成社製)を重合性化合物の合計量に対して200質量ppm(0.02質量%)となるように加え、インプリント用硬化性組成物を調製した。これをフィルタ径0.02μmのNylon(ナイロン)フィルタおよびフィルタ径0.001μmのPTFE(ポリテトラフルオロエチレン)フィルタでろ過した。
ハンセン溶解度パラメータおよび沸点はHSP計算ソフトHSPiPにて計算した。具体的には、各化合物の構造式をSMILES形式にて上記ソフトに入力することで、ハンセン溶解度パラメータベクトルの各成分(d成分、p成分、h成分)を算出した。
ハンセン溶解度パラメータ距離(ΔHSP)については、該当する成分のハンセン溶解度パラメータの各成分(d成分、p成分、h成分)からそれぞれΔD、ΔP、ΔHを求め、数式(1)の式にあてはめることで算出した。
なお、該当成分が複数ある場合は、最も配合量(質量)の多い化合物(最大量成分)での計算値を採用した(配合量が同一の場合は表面張力の高い化合物の計算値を採用した。)。
樹脂の重量平均分子量(Mw)は、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義した。装置はHLC-8220(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000およびTSKgel Super HZ2000(東ソー(株)製)を用いた。溶離液は、THF(テトラヒドロフラン)を用いた。検出は、UV線(紫外線)の波長254nm検出器を使用した。
粘度は、東機産業(株)製のE型回転粘度計RE85L(測定範囲:0.6~1200mPa・s)およびRE85H(測定範囲:6.4~12800mPa・s)、標準コーン・ロータ(1°34’×R24)を用い、サンプルカップを23℃に温度調節して測定した。単位は、mPa・sで示した。測定に関するその他の詳細はJISZ8803:2011に準拠した。1水準につき2つの試料を作製し、それぞれ3回測定した。合計6回の算術平均値を評価値として採用した。
表面張力は、協和界面科学(株)製、表面張力計 SURFACE TENS-IOMETER CBVP-A3を用い、ガラスプレートを用いて23℃で行った。単位は、mN/mで示した。1水準につき2つの試料を作製し、それぞれ3回測定した。合計6回の算術平均値を評価値として採用した。
シリコンウェハ(4インチ:1インチ=25.4mm)上に、表1~3に記載の成分を配合して調製したインプリント用下層膜形成組成物をスピンコートし、表1~3に記載のベイク温度でホットプレートを用いて加熱し、下層膜を形成した。下層膜の膜厚はエリプソメータにより測定した。
上記で得られた下層膜表面に、表4に示すインプリント用硬化性組成物を、富士フイルムダイマティックス製インクジェットプリンターDMP-2831を用いて、ノズルあたり6pLの液滴量で吐出して、下層膜の表面に液滴が縦4個および横4個の合計16個が約880μm間隔の正方配列となるように塗布した。塗布3秒後の液滴形状を撮影し、液滴の平均直径を測定した。1水準につき2つの試料を用い、それぞれ3回測定した。合計6回の算術平均値を評価値として採用した。
A:IJ液滴の平均直径>500μm
B:400μm<IJ液滴の平均直径≦500μm
C:300μm<IJ液滴の平均直径≦400μm
D:IJ液滴の平均直径≦300μm
上記で得られた下層膜表面に、23℃に温度調整したインプリント用硬化性組成物を、富士フイルムダイマティックス製、インクジェットプリンターDMP-2831を用いて、ノズルあたり1pLの液滴量で吐出して、上記下層膜の表面に液滴が約100μm間隔の正方配列となるように塗布した。次に、インプリント用硬化性組成物に、石英基板を押接し、インプリント用硬化性組成物を平坦化した。さらに、モールド側から高圧水銀ランプを用い、300mJ/cm2の条件で露光した後、石英基板を剥離することで平坦膜を得た。
光学顕微鏡(オリンパス製STM6-LM)を用いて上記平坦膜表面を観察して、充填性を下記の基準で評価した。
A:インプリントエリアにおいて、未充填の領域(インプリント用硬化性組成物の硬化物が存在しない領域)が発生していなかった。
B:インプリントエリアの一部の領域において、インクジェット液滴境界での未充填が確認された。
C:インプリントエリアの全面に渡って、インクジェット液滴境界での未充填が確認された。
D:インクジェット液滴同士がつながらず平坦膜を形成できていない領域が確認された。
上記で得られた下層膜表面に、25℃に温度調整したインプリント用硬化性組成物を、富士フイルムダイマティックス製、インクジェットプリンターDMP-2831を用いて、ノズルあたり6pLの液滴量で吐出して、下層膜上に液滴が約100μm間隔の正方配列となるように塗布し、パターン形成層とした。次に、特開2014-024322号公報の実施例6に示す密着層形成組成物をスピンコートした石英ウエハをパターン形成層にHe雰囲気下(置換率90%以上)で押接し、インプリント用硬化性組成物を押印した。押印後10秒が経過した時点で、モールド側から高圧水銀ランプを用い、150mJ/cm2の条件で露光した。露光後にモールドを剥離する際に必要な力を測定し、下層膜の密着力Fとした
A:F≧30N
B:25N≦F<30N
C:20N≦F<25N
D:F<20N
上記で得られた下層膜表面に、25℃に温度調整したインプリント用硬化性組成物のいずれかを、富士フイルムダイマティックス製、インクジェットプリンターDMP-2831を用いて、ノズルあたり6pLの液滴量で吐出して、下層膜上に液滴が約100μm間隔の正方配列となるように塗布し、パターン形成層(層状のインプリント用硬化性組成物)とした。次に、パターン形成層に、石英モールド(線幅28nm、深さ60nmのラインパターン)をHe雰囲気下(置換率90%以上)で押接し、インプリント用硬化性組成物をモールドに充填した。押印後10秒が経過した時点で、モールド側から高圧水銀ランプを用い、150mJ/cm2の条件で露光した後、モールドを剥離することでパターン形成層にパターンを転写させた。転写したパターンの剥れ有無を光学顕微鏡観察(マクロ観察)およびSEM観察(走査型電子顕微鏡によるミクロ観察)にて確認した。
A:パターン剥れが確認されなかった
B:マクロ観察では剥れは確認されなかったが、ミクロ観察にてパターンの剥れが確認された
B:マクロ観察にて一部領域(離型終端部)に剥れが確認された
C:マクロ観察にて転写エリア前面にわたり剥れが確認された
上記で得られた下層膜表面の表面粗さ(Ra)をJIS B 0601の4.2.1に従い、原子間力顕微鏡(AFM)を用いて測定した。測定エリアは10μm角、測定周波数は0.5Hzとした。単位は、nmである。
A:Ra≦0.4
B:0.4<Ra≦0.6
C:0.6<Ra≦1.0
D:Ra>1.0
左の構成単位 右の構成単位
1-2 80 20
1-3 90 10
1-4 95 5
1-6 50 50
一方、上記のポリマーと組み合わせる化合物が、ΔHSPの値を満たさない場合(比較例1、5、6)、化合物の沸点が低い場合(比較例3、4)は濡れ性において劣っていた。比較例2は、特定ポリマーが重合性官能基を有しておらず、密着性および剥離欠陥の耐性が劣っていた。
また、本発明の好ましい実施形態においては、濡れ性に加え、充填性、密着力、剥れ欠陥、塗布面状において特に優れたものとすることができることが分かった。
2 下層膜
3 インプリント用硬化性組成物
4 モールド
21 下層膜
22 インプリント用硬化性組成物
Claims (22)
- インプリント用硬化性組成物と、インプリント用下層膜形成組成物を含むキットであって、
前記インプリント用下層膜形成組成物が、重合性官能基を有するポリマーと、沸点と熱分解温度のうち低い方が480℃以上で、インプリント用硬化性組成物中に含まれる最も含有量が多い成分とのハンセン溶解度パラメータ距離であるΔHSPが2.5以下である化合物とを含む、キット;
ハンセン溶解度パラメータ距離であるΔHSPは下記数式(1)により導かれる;
ΔHSP=[4.0×(ΔD2+ΔP2+ΔH2)]0.5 数式(1)
ΔD:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの分散項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの分散項成分との差;
ΔP:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの極性項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの極性項成分の差;
ΔH:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの水素結合項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差。 - 前記インプリント用下層膜形成組成物に含まれる化合物が、前記ポリマーの重合性官能基と重合可能な基を1分子内に複数有する、請求項1に記載のキット。
- 前記ポリマーおよび前記インプリント用下層膜形成組成物に含まれる化合物の少なくとも一方が極性官能基を有する、請求項1または2に記載のキット。
- 前記極性官能基がスルホニル基含有基、スルホン酸基、リン酸基、およびヒドロキシル基からなる群の少なくとも1種を有する、請求項3に記載のキット。
- 前記ポリマーが有する重合性官能基が(メタ)アクリロイル基である、請求項1~4のいずれか1項に記載のキット。
- 前記ポリマーがアクリル樹脂である、請求項1~5のいずれか1項に記載のキット。
- 前記ポリマーの重量平均分子量が4,000以上である、請求項1~6のいずれか1項に記載のキット。
- 前記インプリント用下層膜形成組成物に含まれる化合物の23℃における粘度が2,000mPa・s以下である、請求項1~7のいずれか1項に記載のキット。
- 前記インプリント用下層膜形成組成物に含まれる化合物の23℃における表面張力が38mN/m以上である、請求項1~8のいずれか1項に記載のキット。
- 前記インプリント用下層膜形成組成物に含まれる化合物が、前記ポリマーが有する重合性官能基と重合可能な基を分子内に3つ有する、請求項1~9のいずれか1項に記載のキット。
- 前記ポリマーの重合性官能基と重合可能な基が(メタ)アクリロイル基である、請求項1~10のいずれか1項に記載のキット。
- 前記ポリマー100質量部に対する前記インプリント用下層膜形成組成物に含まれる化合物の量が25質量部以上400質量部以下である、請求項1~11のいずれか1項に記載のキット。
- 前記インプリント用下層膜形成組成物がさらに熱重合開始剤および光重合開始剤の少なくとも1種を含む、請求項1~12のいずれか1項に記載のキット。
- 前記インプリント用下層膜形成組成物がさらに溶剤を含み、インプリント用下層膜形成組成物の99.0質量%以上を前記溶剤が占める、請求項1~13のいずれか1項に記載のキット。
- インプリント用硬化性組成物中の最も配合量の多い成分の沸点と、前記インプリント用下層膜形成組成物に含まれる化合物の沸点との差が150℃以上である、請求項1~14のいずれか1項に記載のキット。
- インプリント用硬化性組成物中の最も配合量の多い成分の表面張力より、前記インプリント用硬化性組成物に含まれる化合物の表面張力の方が大きい、請求項1~15のいずれか1項に記載のキット。
- インプリント用硬化性組成物と組み合わせて用いるインプリント用下層膜形成組成物であって、
前記インプリント用下層膜形成組成物が、重合性官能基を有するポリマーと、沸点と熱分解温度のうち低い方が480℃以上で、インプリント用硬化性組成物中に含まれる最も含有量が多い成分とのハンセン溶解度パラメータ距離であるΔHSPが2.5以下である化合物とを含むインプリント用下層膜形成組成物;
ハンセン溶解度パラメータ距離であるΔHSPは下記数式(1)により導かれる;
ΔHSP=[4.0×(ΔD2+ΔP2+ΔH2)]0.5 数式(1)
ΔD:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの分散項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの分散項成分との差;
ΔP:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの極性項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの極性項成分の差;
ΔH:インプリント用硬化性組成物中に含まれる最も含有量が多い成分のハンセン溶解度パラメータベクトルの水素結合項成分と、前記インプリント用下層膜形成組成物に含まれる化合物のハンセン溶解度パラメータベクトルの水素結合項成分の差。 - 前記インプリント用下層膜形成組成物に含まれる化合物が、前記ポリマーの重合性官能基と重合可能な基を分子内に複数有する、請求項17に記載のインプリント用下層膜形成組成物。
- 請求項1~16のいずれか1項に記載のキットに含まれるインプリント用下層膜形成組成物を基板に適用しインプリント用下層膜を形成する工程、
前記キットに含まれるインプリント用硬化性組成物を前記インプリント用下層膜に適用する工程、
前記インプリント用硬化性組成物にモールドを接触させた状態で前記インプリント用硬化性組成物を露光する工程および
前記モールドを剥離する工程
を含む、パターン形成方法。 - 前記インプリント用下層膜を形成する工程がスピンコート法を含む、請求項19に記載のパターン形成方法。
- 前記インプリント用硬化性組成物を適用する工程がインクジェット法を含む、請求項19または20に記載のパターン形成方法。
- 請求項19~21のいずれか1項に記載のパターン形成方法を含む半導体デバイスの製造方法。
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