WO2010005032A1 - Procédé de formation de motif - Google Patents

Procédé de formation de motif Download PDF

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Publication number
WO2010005032A1
WO2010005032A1 PCT/JP2009/062464 JP2009062464W WO2010005032A1 WO 2010005032 A1 WO2010005032 A1 WO 2010005032A1 JP 2009062464 W JP2009062464 W JP 2009062464W WO 2010005032 A1 WO2010005032 A1 WO 2010005032A1
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WO
WIPO (PCT)
Prior art keywords
mold
gas
transfer material
material layer
pattern
Prior art date
Application number
PCT/JP2009/062464
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English (en)
Japanese (ja)
Inventor
信支 坂井
玉乃 平澤
Original Assignee
東洋合成工業株式会社
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Filing date
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Publication of WO2010005032A1 publication Critical patent/WO2010005032A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0053—Moulding articles characterised by the shape of the surface, e.g. ribs, high polish
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0003—Discharging moulded articles from the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing

Definitions

  • the present invention relates to a pattern forming method using imprint lithography, and more particularly to a pattern forming method suitable for manufacturing a fine pattern such as a semiconductor integrated circuit or an optical element.
  • Nanoimprint lithography is a process for filling a material to be transferred by pressing a mold having a fine uneven pattern against the material to be transferred such as a resist, and then releasing the mold from the material to be transferred. A pattern is formed (see, for example, Patent Document 1).
  • an object of the present invention is to provide a pattern forming method by imprint lithography that is excellent in mold releasability.
  • the present inventors have solved the above problems by generating a gas or supplying a gas to the interface region between the mold and the transfer material layer. We have found that we can do it and have arrived at the present invention.
  • the first aspect of the present invention is a filling step in which a transfer material layer made of a transfer material and a mold on which an uneven pattern is formed are brought into contact with each other to fill the transferred material into the uneven pattern of the mold,
  • a gas application step of applying a gas to an interface region between the mold and the transfer material layer in a state in which the transfer material layer and the mold are brought into contact with each other and the uneven material pattern of the mold is filled with the transfer material;
  • a pattern forming method comprising: a mold release step of releasing the mold from the transfer material layer.
  • the material to be transferred contains a gas generating agent that generates gas by stimulation, and in the gas application step, the gas generating agent is stimulated to give the mold and the transferred material.
  • the pattern forming method according to the first aspect is characterized in that gas is generated in an interface region with the material layer.
  • a third aspect of the present invention is the pattern forming method according to the second aspect, wherein the gas generating agent generates gas by light stimulation.
  • the transfer material is a photocurable composition
  • the transfer material layer and the mold are brought into contact with each other to fill the uneven material pattern of the mold with the transfer material.
  • the pattern forming method according to any one of the first to third aspects, further comprising a photocuring step of exposing the transfer material layer to a photocured layer.
  • the photocurable composition contains a compound having a photopolymerizable group, a photopolymerization initiator, and the gas generating agent. Is in the way.
  • a sixth aspect of the present invention is the pattern forming method according to the fourth or fifth aspect, characterized in that the gas applying step is performed simultaneously with the photocuring step or after the photocuring step.
  • the gas generating agent generates gas by light stimulation, and the wavelength region of light for curing the photocurable composition in the photocuring step is gas in the gas applying step.
  • the pattern forming method according to any one of the fourth to sixth aspects, which is different from the wavelength region of the light that generates the light.
  • the transfer material is solid, and in the filling step, the transfer material layer is heated and softened, and then the transfer material layer and the mold are brought into contact with each other. 4.
  • a ninth aspect of the present invention is the pattern forming method according to any one of the first to third aspects, wherein the transfer material is solid and the filling step is performed at room temperature.
  • a tenth aspect of the present invention is the pattern forming method according to any one of the first to ninth aspects, wherein the mold has an uneven pattern with a pitch of 1 ⁇ m or less.
  • An eleventh aspect of the present invention is the pattern forming method according to any one of the first to tenth aspects, wherein the mold has an uneven pattern having an aspect ratio of 1.0 or more. .
  • the mold releasability from the transfer material layer is improved, There is an effect that a pattern in which the concave / convex pattern of the mold is precisely transferred to the transfer material layer can be easily formed.
  • the pattern forming method of the present invention includes a filling step of bringing a transfer material layer made of a transfer material into contact with a mold on which an uneven pattern is formed and filling the transfer material with the uneven pattern of the mold, and a transfer material layer The mold is released from the transfer material layer, and a gas application step for causing a gas to be present in the interface region between the mold and the transfer material layer in a state where the transfer material is filled in the uneven pattern of the mold by bringing the mold into contact with the mold And a mold release step.
  • a transfer material layer 2 made of a transfer material formed on a substrate 1 and a mold 3 having an uneven pattern are prepared.
  • the material to be transferred is filled into the concave / convex pattern of the mold 3 by bringing the material layer 2 and the mold 3 into contact with each other by pressing or the like (filling step).
  • the mold 3, the transferred material layer 2, and the transfer material layer 2 are brought into contact with the mold 3 and the uneven material pattern of the mold 3 is filled with the transferred material.
  • a gas is generated or supplied to the interface region 4 to apply the gas to the interface region 4 (gas application step).
  • the mold 3 is released from the transfer material layer 2 to form a pattern in which the uneven pattern of the mold 3 is transferred to the transfer material layer 2 (release). Process).
  • gas is intentionally introduced into the interface region 4 between the mold 3 and the transfer material layer 2, that is, the region existing between the surface of the transfer material layer 2 and the surface where the uneven pattern of the mold 3 is in contact.
  • the interface region 4 between the mold 3 and the transfer material layer 2 can be brought into a pressurized state or the like by performing a gas application process in which gas is generated by supplying or supplying gas. Therefore, the mold 3 and the transferred material layer 2 have good releasability, so that a pattern in which the concave / convex pattern of the mold 3 is accurately transferred without pattern defects can be formed, and the mold is easily released. be able to.
  • the transfer material layer 2 is cured with light, and thus the transfer material layer 2 contracts due to the curing, and the interface region 4 may be in a reduced pressure state, which may make release difficult.
  • the depressurized state of the interface region 4 is eliminated or a pressurized state is achieved by the gas application step, so that the mold 3 is easily released.
  • the transfer material constituting the transfer material layer 2 contains a gas generating agent that generates gas by stimulation, and the gas generating agent is stimulated in the gas application step.
  • the gas is generated from the method of generating the gas from the transfer material layer 2, the method of generating the gas from the substrate 1 or any layer provided on the substrate 1, and the mold itself or the mold release treatment agent applied to the mold.
  • a method of applying gas to the interface region 4 can be used.
  • a gas permeable mold 3 is used, or a gas supply port for supplying gas to the interface region 4 is provided in the mold 3.
  • a method of generating gas and a method of supplying gas to the interface region 4 may be used in combination. Note that it is preferable to generate gas from the transfer material layer 2 in terms of ease of process.
  • the type of gas generated or supplied to the interface region 4 is not particularly limited, but is preferably an inert gas such as N 2 or CO 2 from the viewpoint of safety.
  • imprint lithography is roughly classified into optical imprint lithography, thermal imprint lithography, and room temperature imprint lithography.
  • the present invention will be described in detail below for each imprint lithography.
  • optical imprint lithography In optical imprint lithography, first, as shown in FIG. 2 (a), a substrate 1 at least one of which is transparent and a mold 3 on which an uneven pattern is formed are prepared, and a transfer material comprising a photocurable composition is prepared. Layer 2 is formed on substrate 1 (transfer material layer forming step). In FIG. 2, the transfer material layer 2 is formed on the substrate 1. However, the transfer material layer 2 may be provided on the mold 3, or provided on both the substrate 1 and the mold 3. May be.
  • the mold 3 may have a desired uneven pattern on the surface.
  • the material of the mold 3 include transparent materials such as quartz glass and synthetic resin, as well as materials that do not transmit light such as metals such as silicon, silicon carbide, silicon oxide, and nickel, and metal oxides.
  • a material that generates gas from the mold itself such as a resin containing a gas generating agent, may be used.
  • the appearance of the mold 3 may be the same as that of the mold 3 used in normal optical imprint lithography. For example, the appearance may be a rectangular parallelepiped shape or a roll shape.
  • the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold 3 used in normal optical imprint lithography, but is not limited thereto. It is not what is done. For example, it is good also as the mold 3 which formed the recessed part by forming the hollow in the surface of the material of a mold, and the part which protruded relatively to the surface side becomes a convex part in this case. Moreover, it is good also as the mold 3 which formed the convex part by providing a permite
  • each concave portion of the concave / convex pattern may be a square, a rectangle, a half moon shape, or a shape similar to those shapes.
  • Each concave portion has a depth of about 1 nm to 100 ⁇ m and an opening width of 1 nm, for example. It may be about 100 ⁇ m.
  • the mold release property is particularly bad, and the uneven pattern of the mold 3 is precisely The problem that it is impossible to obtain a transfer material layer having a transferred pattern is likely to occur.
  • the pattern pitch is 1 ⁇ m or less, and the unevenness of the aspect ratio is 1.0 or more. Even if the mold 3 having a pattern is used, the releasability is improved. Accordingly, the uneven pattern can be transferred to the transfer material, and can be easily released without applying a large force to the release.
  • the aspect ratio represents y / x where x is the diameter or the minimum length of one side of the concave portion or convex portion, and y is the depth of the concave portion or the height of the convex portion. Further, the pitch is the width of the concave portion and the convex portion represented by P in FIG.
  • the surface of the mold 3 may be subjected to a mold release treatment.
  • a known release treatment agent exemplified by a perfluoro- or hydrocarbon-based polymer compound, an alkoxysilane compound or a trichlorosilane compound, diamond-like carbon, or the like is used by a gas phase method or a liquid phase method. Can be done.
  • gas when gas is generated from the mold release treatment agent in the gas application step described later, it is replaced with a mold release treatment agent that generates a gas such as an azide compound or an azo compound having a functional group such as perfluoro or hydrocarbon. That's fine.
  • the mold 3 is made into gas permeable materials, such as a silicon
  • gas permeable materials such as a silicon
  • the substrate 1 may be any substrate as long as the material to be transferred 2 can be provided by applying or dropping the material to be transferred.
  • the substrate used in a pattern forming method by normal optical imprint lithography it is preferable that the transfer material layer 2 can be applied with a substantially uniform thickness.
  • Specific examples include semiconductor substrates such as silicon wafers, compound semiconductors such as GaAs, InAs, and GaN, transparent inorganic substrates such as glass, quartz, and sapphire, ceramic substrates, polycarbonate, PET (polyethylene terephthalate), and triacetyl cellulose.
  • a synthetic resin substrate, a metal, a metal oxide, etc. are mentioned.
  • the transparent substrate 1 examples include a glass substrate, a quartz substrate, a sapphire substrate, and a transparent synthetic resin substrate.
  • the surface of the substrate 1 may be subjected to pretreatment in order to improve adhesion to the transfer material layer 2 or to improve the application state of the transfer material layer 2.
  • Specific examples of the pretreatment include wet surface cleaning, surface modification by plasma and ozone cleaning, treatment with an adhesion improver such as a silane coupling agent, and the like.
  • the transfer material layer 2 may be provided directly on the substrate 1, or the transfer material layer 2 may be formed on a single layer or a plurality of arbitrary layers provided on the substrate 1.
  • the optional layer include a novolac resin layer and a layer made of a spin-on-glass material. Moreover, you may generate gas from these arbitrary layers.
  • the transfer material constituting the transfer material layer 2 is a solid, liquid, or fluid photocurable composition.
  • the photocurable composition include a photodimer type having a photodimer group such as a cinnamate ester resin, a photocrosslink type containing a photocrosslinker such as a cyclized rubber resist, an ene / thiol type, a radical, and a cation. And photopolymerization type. From the viewpoint of ease of the filling step and miscibility with the gas generating agent described later, the photocurable composition is more preferably liquid or fluid, and the photopolymerization type is most preferable from the viewpoint of versatility.
  • the photopolymerizable photocurable composition contains a compound having a photopolymerizable group and a photopolymerization initiator.
  • the compound having a photopolymerizable group refers to a compound having a radical polymerizable group or a cationic polymerizable group.
  • the radical polymerizable group include acryloyl group, methacryloyl group and vinyl group.
  • Examples of the cationically polymerizable group include epoxy groups, vinyl ethers, oxetanes, oxolanes, spirooxoesters, and thiiranes.
  • the compounds having a photopolymerizable group may be used alone or in combination of two or more, and a compound having a radical polymerizable group and a compound having a cationic polymerizable group may be used in combination.
  • the photopolymerization initiator refers to a compound that generates an active species such as a radical or a cation capable of initiating polymerization of the compound having the photopolymerizable group upon irradiation with light.
  • Photopolymerization initiators can be classified into radical polymerization initiators and cationic polymerization initiators.
  • radical polymerization initiators include benzophenone, benzyldimethyl ketal, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, titanocenes and oxime esters, trihalomethyltriazines, and other trihalomethyls And a compound having a group.
  • Examples of the cationic polymerization initiator include aromatic sulfonium salts and aromatic iodonium salts.
  • the polymerization initiators may be used alone or in combination of two or more, and a radical polymerization initiator and a cationic polymerization initiator may be used in combination. Furthermore, you may use a sensitizer with a photoinitiator.
  • the content of the compound having a photopolymerizable group in the photocurable composition is preferably 50 to 99.99 parts by weight with respect to 100 parts by weight of the total amount of the photocurable composition.
  • the amount is less than 50 parts by weight, the amount of the photopolymerizable group is small.
  • the amount exceeds 99.99 parts by weight the ratio of the photopolymerization initiator to the compound having the photopolymerizable group is decreased. This is because of a decrease.
  • the compound having a photopolymerizable group having two or more photopolymerizable groups in one molecule is contained in an amount of 5 parts by weight or more, preferably 20 parts by weight or more with respect to 100 parts by weight of the total amount of the photocurable composition. Is desirable.
  • the content of the photopolymerization initiator in the photocurable composition is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the compound having a photopolymerizable group. If it is less than 0.01 part by weight, the ratio of the photopolymerization initiator to the compound having a photopolymerizable group is lowered, and the photocurability is lowered. Moreover, when it exceeds 20 weight part, it is because the solubility of the photoinitiator with respect to a photocurable composition falls and it is not practical.
  • the photocurable composition includes a nonphotocurable oligomer, a nonphotocurable polymer, an adhesion-imparting agent (for example, a silane coupling agent), an organic solvent, and a leveling agent as long as the performance is not adversely affected.
  • Additives such as plasticizers, fillers, antifoaming agents, flame retardants, stabilizers, antioxidants, fragrances, thermal crosslinking agents, and polymerization inhibitors may be contained. In addition, these may be contained alone or in combination of two or more.
  • the photocurable composition when generating gas in the interface area
  • Stimulation includes light, heat, impact, etc., but the process is easy and can be applied to heat-sensitive substrates and transfer materials, so use a gas generating agent that generates gas by light stimulation. Is preferred.
  • the gas generating agent that generates gas by thermal stimulation for example, a gas generating agent that generates gas by thermal stimulation at 40 to 200 ° C. is preferable.
  • gas may be generated in steps other than the gas application step, and if it is higher than 200 ° C., there is a risk of thermal decomposition when the material to be transferred is an organic substance when thermally stimulated. Because.
  • Gas generating agents include azide compounds that generate gas by light stimulation, thermal stimulation or impact, azo compounds, diazo compounds, diazonium salts, nitrobenzyl carbamate compounds that generate gas by light stimulation or thermal stimulation, and gas by heat stimulation. And organic or inorganic peroxides generating ⁇ -ketocarboxylic acid or derivatives thereof. Specific examples include azidobenzaldehyde that generates nitrogen, azidobenzalmethylcyclohexanones, azobisisobutyronitrile, azobis compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and aromatic diazonium salts.
  • Naphthoquinonediazide compounds Naphthoquinonediazide compounds, diazomer drum acids that generate nitrogen, carbon monoxide and acetone, nitrobenzyl carbamate compounds that generate carbon monoxide, t-BOC compounds and photoacids of hydroxystyrene that generate isobutylene and carbon dioxide
  • Examples include combinations of generators.
  • the addition amount of the gas generating agent is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the photocurable composition. If it is less than 0.1, the improvement in releasability may not be significant, and if it exceeds 50 parts by weight, the mixing property with the transfer material may be insufficient.
  • the gas generant may be the same as or different from the photodimer group, photocrosslinker or photopolymerization initiator contained in the photocurable composition, but the photodimer group, photocrosslinker or photopolymerization may be used.
  • the photocuring step and the gas application step described later can be made different steps. If the photocuring step and the gas application step are separate steps, the respective functions can be exhibited in each step, and problems that occur when photocuring and gas generation occur simultaneously, for example, the transferred material in which the generated gas is cured This is preferable because there is no inconvenience such as trapping inside the layer 2 and causing bubble defects.
  • the photocuring step and the gas application step are separate steps.
  • the wavelength region of light that the photocurable composition cures is the same as the wavelength region of light that generates gas from the gas generating agent.
  • the photocuring step and the gas application step can be made separate steps. .
  • the photocurable composition is preferably in a liquid state near room temperature. Specifically, it is preferable that the photocurable composition has fluidity enough to fill the uneven pattern of the mold 3.
  • the viscosity is 10 Pa ⁇ s or less at 25 ° C.
  • the method of measuring using the B-type viscometer made from TOKIMEC is mentioned, for example.
  • a method for forming the transfer material layer 2 on the substrate or the mold using the transfer material made of such a photocurable composition is not particularly limited.
  • the transfer material diluted with a solvent or the like as necessary is used.
  • the application and dripping include spin coating, roll coating, dip coating, gravure coating, die coating, curtain coating, inkjet coating, and dispenser coating.
  • the thickness of the transfer material layer 2 may be set in consideration of the amount of the photocurable composition filled in the concave portion of the concave / convex pattern formed on the mold 3, for example, the depth of the concave portion of the concave / convex pattern. Good. Further, the transfer material layer 2 may be provided so as to cover the entire surface of the mold 3 and the substrate 1, or may be provided so as to cover only a part thereof.
  • the transfer material layer 2 and the mold 3 are opposed to each other, as shown in FIG.
  • the surface on which the uneven pattern of the mold 3 is formed is brought into contact with the material to be transferred into the uneven pattern of the mold 3 (filling step).
  • a conventional apparatus for optical imprint lithography can be used.
  • the transfer material layer 2 is exposed and cured in a state where the transfer material layer 2 and the mold 3 are brought into contact with each other and the uneven pattern of the mold 3 is filled in the transfer material.
  • a photocured layer photocuring step
  • the transfer material layer 2 may be cured and contracted to form a space at the interface between the transfer material layer 2 and the mold 3.
  • the light source used for exposure may be any light source that can irradiate light having a wavelength at which the photocurable composition is cured.
  • Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arcs, mercury xenon lamps, excimer lasers such as XeCl, KrF and ArF, ultraviolet or visible light lasers, and ultraviolet light. Or visible light LED etc. are mentioned.
  • the light irradiation amount may be an amount that can cure the transfer material layer 2. When industrially carrying out the present invention, it is usually preferable to select an irradiation dose within a range of 10 J / cm 2 or less.
  • the photocurable composition contains a gas generating agent that generates gas by light stimulation
  • the wavelength region of light irradiated in the photocuring step is preferably light in a wavelength region that does not generate gas. This is to prevent the generated gas from being trapped inside the cured transfer material layer 2 and causing bubble defects.
  • the transferred material layer (photocured layer) 2 and the mold 3 are brought into contact with each other, and the mold 3 and the transferred material layer are filled with the uneven pattern of the mold 3 in the transferred material layer.
  • Gas is applied to the interface region 4 with the material layer 2 (gas application step).
  • the gas generating step may be performed with light having a wavelength that allows the gas generating agent to sensitize and generate gas.
  • the exposure method may be the same as the photocuring step, but the wavelength region of light for curing the photocurable composition is not the same as the wavelength region of light for generating gas from the gas generating agent,
  • the sensitivity to light of the wavelength is different between the gas generating agent and the photodimeric group, the photocrosslinking agent, or the photopolymerization initiator, the wavelength of the light that generates the gas in the wavelength region of light that photocures the photocurable composition.
  • substantially only photo-curing proceeds and substantially no gas is generated from the gas generating agent.
  • substantially only gas generation proceeds and substantially no gas is generated.
  • the transfer material layer 2 contains a gas generating agent that generates gas by thermal stimulation
  • the transfer material layer 2 is heated to a temperature at which the gas generating agent can generate gas in the gas application step. do it.
  • the photocuring step only photocuring substantially proceeds and gas is not generated from the gas generating agent.
  • the gas application step only gas generation proceeds substantially and photocuring does not proceed substantially.
  • the transfer material layer 2 contains a gas generating agent that generates gas by impact
  • the transfer material layer 2 is given an impact that can generate gas in the gas application step. Good.
  • the mold release treatment agent applied to the mold 3, or the substrate 1 or any layer on the substrate 1 to supply the gas to the interface region 4 the mold 3 A gas may be generated in the interface region 4 by applying a stimulus such as light, heat or impact to the agent, the substrate 1 or any layer on the substrate 1.
  • the gas when gas is supplied to the interface region 4 between the mold 3 and the transfer material layer 2, the gas passes through the mold 3 having a gas permeable mold 3 or a supply port for supplying gas to the interface region 4. Then, the gas may be supplied to the interface region 4 from the outside.
  • the transfer material layer 2 is cured and contracted during the photocuring process, and the interface region 4 between the mold 3 and the transfer material layer 2 is in a reduced pressure state.
  • the mold 3 tends to be difficult to release due to the close contact between the mold 3 and the mold 3 or the like.
  • the gas is applied to the interface region 4 in the gas application step, so that the interface region 4 is released from the reduced pressure state or is in a pressurized state. As a result, a precise pattern can be easily formed.
  • the gas application process may be performed after or after the photocuring process, and the gas application process and the photocuring process may be the same process, but the generated gas is confined within the cured transfer material layer 2.
  • a gas application step after the photocuring step.
  • a gas generating agent that generates gas by thermal stimulation is used, and in the photocuring process, the photocurable composition is cured so that no gas is substantially generated from the gas generating agent, thereby completing the curing of the transfer material layer 2.
  • a gas provision process can be performed after a photocuring process by generating gas from a gas generating agent by thermal stimulation in a gas provision process.
  • the wavelength region of light for photocuring the photocurable composition is different from the wavelength region of light for generating gas.
  • the gas application step can be performed after the photocuring step by causing the gas generating agent to be exposed to light in the gas application step to generate a gas.
  • the mold 3 is released from the transfer material layer 2, thereby forming on the substrate 1 a pattern in which the uneven pattern of the mold 3 is transferred to the transfer material layer 2.
  • the pattern forming method of the present invention includes a gas application step for intentionally generating gas or supplying gas to the interface region 4 between the mold 3 and the transfer material layer 1, the mold 3 and the transfer material Since the mold releasability with the layer 2 is improved, a pattern in which the concave / convex pattern of the mold 3 is accurately transferred without pattern defects can be formed, and the mold can be easily released.
  • thermal imprint lithography ⁇ Thermal imprint lithography>
  • thermal imprint lithography first, as shown in FIG. 3A, a substrate 1 and a mold 3 on which an uneven pattern is formed are prepared, and a transfer material layer 2 that is a solid is disposed on the substrate 1.
  • the transfer material layer 2 is formed on the substrate 1 (transfer material layer forming step).
  • the transfer material layer 2 is formed on the substrate 1.
  • the transfer material layer 2 may be provided on the mold 3, or provided on both the substrate 1 and the mold 3. Also good.
  • the solid material 2 to be transferred is a solid plate or the like having sufficient mechanical strength and thickness, the material layer 2 need not be formed on the substrate 1 or the mold 3.
  • the transfer material layer forming step can be omitted.
  • the mold 3 may have a desired uneven pattern on the surface.
  • the material of the mold 3 include transparent materials such as quartz glass and synthetic resin, as well as materials that do not transmit light such as metals such as silicon, silicon carbide, silicon oxide, and nickel, and metal oxides.
  • a material that generates gas from the mold itself such as a resin containing a gas generating agent, may be used.
  • the appearance of the mold 3 may be the same as the appearance of the mold 3 used in normal thermal imprint lithography. For example, the appearance may be a rectangular parallelepiped shape or a roll shape.
  • the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold 3 used in normal thermal imprint lithography, but is not limited thereto. It is not what is done. For example, it is good also as the mold 3 which formed the recessed part by forming the hollow in the surface of the material of a mold, and the part which protruded relatively to the surface side becomes a convex part in this case. Moreover, it is good also as the mold 3 which formed the convex part by providing a permite
  • each concave portion of the concave / convex pattern may be a square, a rectangle, a half moon, or a shape similar to those shapes.
  • Each concave portion has a depth of about 1 nm to 100 ⁇ m and an opening width of 1 nm, for example. It may be about 100 ⁇ m.
  • the mold release property is particularly bad, and the uneven pattern of the mold 3 is precisely The problem that it is impossible to obtain a transfer material layer having a transferred pattern is likely to occur.
  • the pattern pitch is 1 ⁇ m or less, and the unevenness of the aspect ratio is 1.0 or more. Even if the mold 3 having a pattern is used, the releasability is improved. Accordingly, the uneven pattern can be transferred to the transfer material, and can be easily released without applying a large force to the release.
  • the surface of the mold 3 may be subjected to a mold release treatment.
  • a known release treatment agent exemplified by a perfluoro- or hydrocarbon-based polymer compound, an alkoxysilane compound or a trichlorosilane compound, diamond-like carbon, or the like is used by a gas phase method or a liquid phase method. Can be done.
  • a mold release treatment agent that generates a gas such as an azide compound or azo compound having a functional group such as perfluoro type or hydrocarbon type is used. That's fine.
  • the mold 3 is made into gas permeable materials, such as a silicon
  • gas permeable materials such as a silicon
  • the substrate 1 may be any substrate as long as the material to be transferred 2 can be provided by applying or dropping the material to be transferred.
  • a substrate used in a pattern forming method by normal thermal imprint lithography it is preferable that the transfer material layer 2 has a substantially uniform thickness.
  • Specific examples include semiconductor substrates such as silicon wafers, compound semiconductors such as GaAs, InAs, and GaN, transparent inorganic substrates such as glass, quartz, and sapphire, ceramic substrates, synthetic resin substrates such as polycarbonate, PET, and triacetyl cellulose, metals Or a metal oxide etc. are mentioned.
  • the transparent substrate 1 include a glass substrate, a quartz substrate, a sapphire substrate, and a transparent synthetic resin substrate.
  • the surface of the substrate 1 may be subjected to pretreatment in order to improve adhesion to the transfer material layer 2 or to improve the application state of the transfer material layer 2.
  • pretreatment include wet surface cleaning, surface modification by plasma and ozone cleaning, treatment with an adhesion improver such as a silane coupling agent, and the like.
  • the transfer material layer 2 may be provided directly on the substrate 1, or the transfer material layer 2 may be formed on a single layer or a plurality of arbitrary layers provided on the substrate 1.
  • the optional layer include a novolac resin layer and a layer made of a spin-on-glass material. Moreover, you may generate gas from these arbitrary layers.
  • the transfer material constituting the transfer material layer 2 may be any material that is softened by heating and has a property that the transfer material layer 2 and the mold 3 can be brought into contact with each other to fill the uneven material pattern of the mold 3 with the transfer material. Good. Examples thereof include thermoplastic resins such as polymethyl methacrylate and polylactic acid, thermoplastic resin compositions containing these, and inorganic substances such as glass and metals.
  • the transfer material may have a reactive group such as a photopolymerizable group.
  • a non-photocurable oligomer, a non-photocurable polymer, an adhesion-imparting agent (for example, a silane coupling agent), an organic solvent, a leveling agent, Additives such as a plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, and a polymerization inhibitor may be contained. In addition, these may be contained alone or in combination of two or more.
  • the transfer material when gas is generated in the interface region 4 between the mold 3 and the transfer material layer 2 in the subsequent gas application step, the transfer material contains a gas generating agent that generates gas by stimulation.
  • Stimulation includes light, heat, impact, etc., but the process is easy and can be applied to heat-sensitive substrates and transfer materials, so use a gas generating agent that generates gas by light stimulation. Is preferred.
  • the gas generating agent that generates gas by thermal stimulation for example, a gas generating agent that generates gas by thermal stimulation at 40 to 200 ° C. is preferable.
  • gas may be generated in steps other than the gas application step, and if it is higher than 200 ° C., there is a risk of thermal decomposition when the material to be transferred is an organic substance when thermally stimulated. Because.
  • Gas generating agents include azide compounds that generate gas by light stimulation, thermal stimulation or impact, azo compounds, diazo compounds, diazonium salts, nitrobenzyl carbamate compounds that generate gas by light stimulation or thermal stimulation, and gas by heat stimulation. And organic or inorganic peroxides generating ⁇ -ketocarboxylic acid or derivatives thereof. Specific examples include azidobenzaldehyde that generates nitrogen, azidobenzalmethylcyclohexanones, azobisisobutyronitrile, azobis compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and aromatic diazonium salts.
  • Naphthoquinonediazide compounds Naphthoquinonediazide compounds, diazomer drum acids that generate nitrogen, carbon monoxide and acetone, nitrobenzyl carbamate compounds that generate carbon monoxide, t-BOC compounds and photoacids of hydroxystyrene that generate isobutylene and carbon dioxide
  • Examples include combinations of generators.
  • the addition amount of the gas generating agent is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the transfer material. If it is less than 0.1, the improvement in releasability may not be significant, and if it exceeds 50 parts by weight, the mixing property with the transfer material may be insufficient.
  • the gas generating agent is preferably one that can make the filling step for heating and the gas application step separate from each other. If the filling step and the gas application step are separate steps, the respective functions can be performed in each step, and problems that occur when filling and gas generation occur simultaneously, for example, the generated gas is generated inside the transfer material layer 2. This is preferable because there is no inconvenience such as a bubble defect trapped in
  • the gas application step is a step of irradiating light, which is a separate step from the filling step of heating.
  • the temperature at which the transfer material is softened in the filling step and the temperature at which gas is generated from the gas generating agent in the gas applying step are different.
  • the filling step and the gas application step can be made separate.
  • the thickness of the transfer material layer 2 may be set in consideration of the amount of the transfer material filled in the concave portion of the uneven pattern formed on the mold 3, for example, the depth of the concave portion of the uneven pattern. Further, the transfer material layer 2 may be provided so as to cover the entire surface of the mold 3 and the substrate 1, or may be provided so as to cover only a part thereof.
  • the solid transfer material layer 2 is heated. By heating, the transferred material layer 2 is softened more than before heating. After the softening, as shown in FIG. 3B, the transferred material layer 2 is brought into contact with the surface on which the uneven pattern of the mold 3 is formed, and the uneven material pattern of the mold 3 is filled with the transferred material. Thereafter, the transfer material layer 2 is cooled to near room temperature to cure the transfer material layer 2 (filling step).
  • the heating temperature depends on the characteristics of the material to be transferred, but may be heated until the material to be transferred becomes viscoelastic enough to fill the uneven pattern of the mold 3.
  • the temperature heated in the filling step is a temperature that does not generate gas. This is to prevent the generated gas from being trapped inside the transfer material and causing bubble defects.
  • both the transfer material layer 2 and the mold 3 horizontal to bring the transfer material layer 2 and the mold 3 into contact with each other. There is no need to limit it to keeping.
  • a force of about 0.01 to 100 MPa may be applied as necessary.
  • a conventional apparatus for thermal imprint lithography can be used.
  • the transfer material layer 2 and the mold 3 are brought into contact with each other and the uneven pattern of the mold 3 is filled with the transfer material layer. Gas is generated or supplied to the interface region 4 (gas application step).
  • the gas generating step may be performed with light having a wavelength that allows the gas generating agent to sensitize and generate gas.
  • the light source used for exposure may be any light source that can irradiate light having a wavelength generated by gas. Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arcs, mercury xenon lamps, excimer lasers such as XeCl, KrF and ArF, ultraviolet or visible light lasers, and ultraviolet light. Or visible light LED etc. are mentioned.
  • the irradiation amount of light may be an amount that can generate gas. When the present invention is industrially carried out, it is usually preferable to select an irradiation dose within a range of 10 J / cm 2 or less.
  • the transfer material layer 2 contains a gas generating agent that generates gas by thermal stimulation
  • the transfer material layer 2 is heated to a temperature at which the gas generating agent can generate gas in the gas application step. do it.
  • the transfer material layer 2 contains a gas generating agent that generates gas by impact
  • the transfer material layer 2 is given an impact that can generate gas in the gas application step. Good.
  • the mold release treatment agent applied to the mold 3, or the substrate 1 or any layer on the substrate 1 to supply the gas to the interface region 4 the mold 3 A gas may be generated in the interface region 4 by applying a stimulus such as light, heat or impact to the agent, the substrate 1 or any layer on the substrate 1.
  • the gas when gas is supplied to the interface region 4 between the mold 3 and the transfer material layer 2, the gas passes through the mold 3 having a gas permeable mold 3 or a supply port for supplying gas to the interface region 4. Then, the gas may be supplied to the interface region 4 from the outside.
  • the mold 3 and the transfer material layer 2 are closely adhered to each other, so that the mold 3 is released. May be difficult.
  • the gas is applied to the interface region 4 by the gas application step, the interface region 4 is in a pressurized state or the like, so that the mold 3 can be easily released and a precise pattern can be easily formed. Can be formed.
  • the gas application step may be performed after the cooling in the filling step or before, but the generated gas is confined inside the cured transfer material layer 2 and is cooled after the cooling in order to avoid bubble defects. More preferably, the applying step is performed.
  • the mold 3 is released from the transfer material layer 2, thereby forming on the substrate 1 a pattern in which the uneven pattern of the mold 3 is transferred to the transfer material layer 2.
  • the pattern forming method of the present invention includes a gas application step for intentionally generating gas or supplying gas to the interface region 4 between the mold 3 and the transfer material layer 1, the mold 3 and the transfer material Since the mold releasability with the layer 2 is improved, a pattern in which the concave / convex pattern of the mold 3 is accurately transferred without pattern defects can be formed, and the mold can be easily released.
  • the transfer material has a reactive group such as a photopolymerizable group, in order to improve the strength of the molded product after cooling in the filling step, gas application step or release step.
  • An optional step such as photocuring may be performed.
  • room temperature imprint lithography In room temperature imprint lithography, first, as shown in FIG. 4A, a substrate 1 and a mold 3 on which an uneven pattern is formed are prepared, and a transfer material layer 2 that is a solid is disposed on the substrate 1. In the same manner, the transfer material layer 2 is formed on the substrate 1 (transfer material layer forming step). In FIG. 4, the transfer material layer 2 is formed on the substrate 1. However, the transfer material layer 2 may be provided on the mold 3, or provided on both the substrate 1 and the mold 3. Also good. Furthermore, if the solid material 2 to be transferred is a solid plate or the like having sufficient mechanical strength and thickness, the material layer 2 need not be formed on the substrate 1 or the mold 3. The transfer material layer forming step can be omitted.
  • the mold 3 may have a desired uneven pattern on the surface.
  • the material of the mold 3 include transparent materials such as quartz glass and synthetic resin, as well as materials that do not transmit light such as metals such as silicon, silicon carbide, silicon oxide, and nickel, and metal oxides.
  • a material that generates gas from the mold itself such as a resin containing a gas generating agent, may be used.
  • the appearance of the mold 3 may be the same as that of the mold 3 used in normal room temperature imprint lithography. For example, the appearance may be a rectangular parallelepiped shape or a roll shape.
  • the uneven pattern formed on the surface of the mold 3 may be the same as the uneven pattern formed on the surface of the mold 3 used in normal room temperature imprint lithography, but is not limited thereto. It is not what is done. For example, it is good also as the mold 3 which formed the recessed part by forming the hollow in the surface of the material of a mold, and the part which protruded relatively to the surface side becomes a convex part in this case. Moreover, it is good also as the mold 3 which formed the convex part by providing a permite
  • each concave portion of the concave / convex pattern may be a square, a rectangle, a half moon shape, or a shape similar to those shapes.
  • Each concave portion has a depth of about 1 nm to 100 ⁇ m and an opening width of 1 nm, for example. It may be about 100 ⁇ m.
  • the mold release property is particularly bad, and the uneven pattern of the mold 3 is precisely The problem that it is impossible to obtain a transfer material layer having a transferred pattern is likely to occur.
  • the pattern pitch is 1 ⁇ m or less, and the unevenness of the aspect ratio is 1.0 or more. Even if the mold 3 having a pattern is used, the releasability is improved. Accordingly, the uneven pattern can be transferred to the transfer material, and can be easily released without applying a large force to the release.
  • the surface of the mold 3 may be subjected to a mold release treatment.
  • a known release treatment agent exemplified by a perfluoro- or hydrocarbon-based polymer compound, an alkoxysilane compound or a trichlorosilane compound, diamond-like carbon, or the like is used by a gas phase method or a liquid phase method. Can be done.
  • a mold release treatment agent that generates a gas such as an azide compound or azo compound having a functional group such as perfluoro type or hydrocarbon type is used. That's fine.
  • gas supply material such as a silicon
  • the substrate 1 may be any substrate as long as the material to be transferred 2 can be provided by applying or dropping the material to be transferred.
  • a substrate used in a pattern forming method by normal room temperature imprint lithography it is preferable that the transfer material layer 2 can be applied with a substantially uniform thickness.
  • Specific examples include semiconductor substrates such as silicon wafers, compound semiconductors such as GaAs, InAs, and GaN, transparent inorganic substrates such as glass, quartz, and sapphire, ceramic substrates, synthetic resin substrates such as polycarbonate, PET, and triacetyl cellulose, metals Or a metal oxide etc. are mentioned.
  • the transparent substrate 1 include a glass substrate, a quartz substrate, a sapphire substrate, and a transparent synthetic resin substrate.
  • the surface of the substrate 1 may be subjected to pretreatment in order to improve adhesion to the transfer material layer 2 or to improve the application state of the transfer material layer 2.
  • pretreatment include wet surface cleaning, surface modification by plasma and ozone cleaning, treatment with an adhesion improver such as a silane coupling agent, and the like.
  • the transfer material layer 2 may be provided directly on the substrate 1, or the transfer material layer 2 may be formed on a single layer or a plurality of arbitrary layers provided on the substrate 1.
  • the optional layer include a novolac resin layer and a layer made of a spin-on-glass material. Moreover, you may generate gas from these arbitrary layers.
  • the transfer material constituting the transfer material layer 2 may be any material that can be filled in the shape of the concave-convex pattern of the mold 3 by pressing near room temperature.
  • the transfer material may have a reactive group such as a heat crosslinkable group or a polymerizable group, and may contain other polymer, monomer, crosslinker, or the like as necessary.
  • room temperature means about 20 to 30 ° C.
  • a non-photocurable oligomer, a non-photocurable polymer, an adhesion-imparting agent (for example, a silane coupling agent), an organic solvent, a leveling agent, a plastic is used for the material to be transferred as long as the performance is not adversely affected.
  • Additives such as an agent, a filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, and a polymerization inhibitor may be contained. In addition, these may be contained alone or in combination of two or more.
  • the transfer material contains a gas generating agent that generates gas by stimulation.
  • Stimulation includes light, heat, impact, etc., but the process is easy and can be applied to heat-sensitive substrates and transfer materials, so use a gas generating agent that generates gas by light stimulation. Is preferred.
  • the gas generating agent that generates gas by thermal stimulation for example, a gas generating agent that generates gas by thermal stimulation at 40 to 200 ° C. is preferable.
  • gas may be generated in steps other than the gas application step, and if it is higher than 200 ° C., there is a risk of thermal decomposition when the material to be transferred is an organic substance when thermally stimulated. Because.
  • Gas generating agents include azide compounds that generate gas by light stimulation, thermal stimulation or impact, azo compounds, diazo compounds, diazonium salts, nitrobenzyl carbamate compounds that generate gas by light stimulation or thermal stimulation, and gas by heat stimulation. And organic or inorganic peroxides generating ⁇ -ketocarboxylic acid or derivatives thereof. Specific examples include azidobenzaldehyde that generates nitrogen, azidobenzalmethylcyclohexanones, azobisisobutyronitrile, azobis compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and aromatic diazonium salts.
  • Naphthoquinonediazide compounds Naphthoquinonediazide compounds, diazomer drum acids that generate nitrogen, carbon monoxide and acetone, nitrobenzyl carbamate compounds that generate carbon monoxide, t-BOC compounds and photoacids of hydroxystyrene that generate isobutylene and carbon dioxide
  • Examples include combinations of generators.
  • the addition amount of the gas generating agent is not particularly limited, but is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the transfer material. If it is less than 0.1, the improvement in releasability may not be significant, and if it exceeds 50 parts by weight, the mixing property with the transfer material may be insufficient.
  • the thickness of the transfer material layer 2 may be set in consideration of the amount of the transfer material filled in the concave portion of the uneven pattern formed on the mold 3, for example, the depth of the concave portion of the uneven pattern. Further, the transfer material layer 2 may be provided so as to cover the entire surface of the mold 3 and the substrate 1, or may be provided so as to cover only a part thereof.
  • the transfer material layer 2 and the mold 3 are made to face each other, and as shown in FIG. 4B, the transfer material layer 2 and the surface of the mold 3 on which the uneven pattern is formed are brought into contact with each other. Then, the material to be transferred is filled in the uneven pattern of the mold 3 (filling step).
  • room temperature imprint lithography when the mold 3 and the transfer material layer 2 are brought into contact with each other, a force of about 0.01 to 100 MPa is applied to bring the mold 3 and the transfer material layer 2 into close contact with each other. A conventional apparatus for room temperature imprint lithography can be used. Further, it is preferable to keep both the transfer material layer 2 and the mold 3 horizontal to bring the transfer material layer 2 and the mold 3 into contact with each other. However, if there is no problem in the pattern to be obtained, the transfer material layer 2 and the mold 3 are limited to being kept horizontal. do not have to.
  • the transferred material layer 2 and the mold 3 are brought into contact with each other and the mold 3 and the transferred material layer 2 are filled with the uneven pattern of the mold 3 in the transferred material layer.
  • Gas is generated or supplied to the interface region 4 (gas application step).
  • the transfer material layer 2 contains a gas generating agent that generates a gas by light stimulation
  • the gas application step if the gas generating agent is exposed to light in a wavelength region where the gas generating agent can be exposed to generate gas.
  • the light source used for exposure may be any light source that can irradiate light having a wavelength generated by gas. Examples of light sources include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, xenon lamps, carbon arcs, mercury xenon lamps, excimer lasers such as XeCl, KrF and ArF, ultraviolet or visible light lasers, and ultraviolet light. Or visible light LED etc. are mentioned.
  • the irradiation amount of light may be an amount that can generate gas. When the present invention is industrially carried out, it is usually preferable to select an irradiation dose within a range of 10 J / cm 2 or less.
  • the transfer material layer 2 contains a gas generating agent that generates gas by thermal stimulation
  • the transfer material layer 2 is heated to a temperature at which the gas generating agent can generate gas in the gas application step. do it.
  • the transfer material layer 2 contains a gas generating agent that generates gas by impact
  • the transfer material layer 2 is given an impact that can generate gas in the gas application step. Good.
  • the mold release treatment agent applied to the mold 3, or the substrate 1 or any layer on the substrate 1 to supply the gas to the interface region 4 the mold 3 A gas may be generated in the interface region 4 by applying a stimulus such as light, heat or impact to the agent, the substrate 1 or any layer on the substrate 1.
  • the gas when gas is supplied to the interface region 4 between the mold 3 and the transfer material layer 2, the gas passes through the mold 3 having a gas permeable mold 3 or a supply port for supplying gas to the interface region 4. Then, the gas may be supplied to the interface region 4 from the outside.
  • the mold 3 is released from the transfer material layer 2, thereby forming on the substrate 1 a pattern in which the uneven pattern of the mold 3 is transferred to the transfer material layer 2.
  • the pattern forming method of the present invention includes a gas application step that intentionally generates gas or supplies gas to the interface region 4 between the mold 3 and the transfer material layer 2, the mold 3 and the transfer material Since the mold releasability with the layer 2 is improved, a pattern in which the concave / convex pattern of the mold 3 is accurately transferred without pattern defects can be formed, and the mold can be easily released.
  • the material to be transferred contains a component that is cured by light or a component that is cured by heat, in order to improve the strength of the molded product, as shown in FIG. Or you may have the process of hardening the to-be-transferred material layer 2 with a heat
  • thermoplastic composition B Polymethylmethacrylate (Mw 120,000) was dissolved in propylene glycol methyl ether acetate while stirring to prepare 20% by weight of thermoplastic composition B.
  • Photocurable composition 1 10 parts by weight of azidobenzaldehyde was blended as a gas generating agent that generates gas by light stimulation with respect to 100 parts by weight of the photocurable composition A, and the mixture was stirred and mixed at room temperature to prepare a photocurable composition 1.
  • Room temperature imprint composition 4 10 parts by weight of azidobenzaldehyde as a gas generating agent that generates gas by light stimulation is mixed with 100 parts by weight of a solid content of a spin-on-glass material (trade name: Accuglass 512B, manufactured by Honeywell), and stirred at room temperature. Room temperature imprint composition 4 was prepared.
  • Example 1 The photocurable composition 1 was applied on a PET substrate with a bar coater so as to have a thickness of about 20 ⁇ m, and a transfer material layer made of the photocurable composition 1 was formed. Next, a nickel mold having a line and space pattern with a line width of 100 nm, a depth of 100 nm, and a pitch of 200 nm (no mold release treatment) is pressed against the transfer material layer to bring the mold into close contact, and the photocurable composition is put into the pattern. 1 is fully filled, and then exposed to light from the PET substrate side using an ultra-high pressure mercury lamp, and the photocuring and gas generation steps of the transfer material layer made of the photocurable composition 1 are performed at the same time.
  • the material layer was photocured and a gas was generated from the gas generating agent to give the gas to the interface region between the mold and the transfer material layer.
  • the exposure amount was 1000 mJ / cm 2 .
  • Example 2 The photocurable composition 2 was applied onto a glass substrate with a bar coater so as to have a thickness of about 20 ⁇ m, and a transfer material layer made of the photocurable composition 2 was formed. Next, a nickel mold having a line and space pattern with a line width of 100 nm, a depth of 100 nm, and a pitch of 200 nm (no mold release treatment) is pressed against the transfer material layer to bring the mold into close contact, and the photocurable composition is put into the pattern. 2 was sufficiently filled, and then the transfer material layer made of the photocurable composition 2 was photocured by exposure from the glass substrate side using an ultrahigh pressure mercury lamp. The exposure amount was 200 mJ / cm 2 .
  • the glass substrate is heated on a hot plate at 100 ° C. for 10 minutes, and gas is generated from dimethyl 2,2′-azobis (2-methylpropionate), which is a gas generating agent. Gas was applied to the interface area with the layer. When the mold was released after cooling, the mold was easily released, and no defects were found in the formed photocured product.
  • Example 3 The photocurable composition 1 was applied on a PET substrate with a bar coater so as to have a thickness of about 20 ⁇ m, and a transfer material layer made of the photocurable composition 1 was formed. Next, a nickel mold having a line and space pattern with a line width of 100 nm, a depth of 100 nm, and a pitch of 200 nm (no mold release treatment) is pressed against the transfer material layer to bring the mold into close contact, and the photocurable composition is put into the pattern.
  • Example 4 The thermoplastic composition 3 was applied onto a glass substrate with a bar coater, and then baked on a hot plate at 80 ° C. for 5 minutes to form a transfer material layer made of the thermoplastic composition 3.
  • the thickness of the transfer material layer was about 20 ⁇ m.
  • the glass substrate on which the transfer material layer was formed was heated to 150 ° C. to soften the transfer material layer made of the thermoplastic composition 3.
  • a nickel mold having a line-and-space pattern with a line width of 100 nm, a depth of 100 nm, and a pitch of 200 nm is pressed and adhered thereto, and the thermoplastic composition 3 is applied to the pattern by pressing with a force of 10 MPa for 5 minutes. After filling, it was cooled to near room temperature.
  • Example 5 The room temperature imprint composition 4 was spin-coated on a glass substrate and then baked on a hot plate at 80 ° C. for 5 minutes to form a transfer material layer composed of the room temperature imprint composition 4.
  • the thickness of the transfer material layer was about 10 ⁇ m.
  • a nickel mold having a line-and-space pattern with a line width of 100 nm, a depth of 100 nm, and a pitch of 200 nm is pressed against the transfer material layer to bring the mold into close contact with the transfer material layer, and a force of 30 MPa.
  • the pattern was filled with the room temperature imprint composition 4 under pressure for 5 minutes.
  • Example 1 The same operation as in Example 1 was performed except that the photocurable composition A containing no gas generating agent was used instead of the photocurable composition 1. As a result, it was difficult to release the mold, and a part of the photocured material adhered to the mold side and a defect occurred.
  • thermoplastic resin solution B containing no gas generating agent was used instead of the thermoplastic composition 3.
  • Example 3 The same operation as in Example 5 was performed except that a spin-on glass material (trade name: Accuglass 512B, manufactured by Honeywell) containing no gas generant was used instead of the room temperature imprint composition 4. As a result, it was difficult to release the mold, and a part of the spin-on-glass material adhered to the mold side and a defect occurred.
  • a spin-on glass material trade name: Accuglass 512B, manufactured by Honeywell

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Abstract

L’invention concerne un procédé de formation de motif par impression lithographique présentant une excellente capacité de démoulage. Le procédé de formation de motif comprend : une étape de remplissage dans laquelle une couche de matériau de réception de transfert (2) composée d'un matériau de réception de transfert et un moule (3) comprenant un motif présentant un évidement et une saillie sont amenés en contact l'un avec l'autre, le matériau de réception de transfert remplissant ainsi le motif présentant un évidement et une saillie du moule (3) ; une étape de fourniture de gaz dans laquelle un gaz est fourni à une région d'interface (4) entre le moule (3) et la couche de matériau de réception de transfert (2), tout en maintenant la couche de matériau de réception de transfert (2) et le moule (3) en contact l'un avec l'autre, le motif présentant un évidement et une saillie du moule (3) étant rempli du matériau de réception de transfert ; et une étape de démoulage dans laquelle le moule (3) est dégagé de la couche de matériau de réception de transfert (2).
PCT/JP2009/062464 2008-07-09 2009-07-08 Procédé de formation de motif WO2010005032A1 (fr)

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JP2010103464A (ja) * 2008-09-26 2010-05-06 Toshiba Corp インプリント方法
JP2010262980A (ja) * 2009-04-30 2010-11-18 Jsr Corp ナノインプリントリソグラフィー用硬化性組成物及びナノインプリント方法
JP2011159881A (ja) * 2010-02-02 2011-08-18 Fujifilm Corp インプリント用硬化性組成物、パターン形成方法およびパターン
JP2012062238A (ja) * 2010-09-18 2012-03-29 Sekisui Chem Co Ltd ガス発生剤及びマイクロポンプ
WO2013062068A1 (fr) 2011-10-24 2013-05-02 Canon Kabushiki Kaisha Procédé de formation d'un film
WO2013094660A1 (fr) 2011-12-19 2013-06-27 Canon Kabushiki Kaisha Procédé d'obtention de produit durci et procédé de formation de motif
WO2014057823A1 (fr) * 2012-10-09 2014-04-17 Canon Kabushiki Kaisha Composition photodurcissable et procédé de fabrication d'un film
JP2014150259A (ja) * 2014-02-21 2014-08-21 Toyo Gosei Kogyo Kk 光硬化性組成物、モールド、樹脂、光学素子の製造方法及び半導体集積回路の製造方法
JP2014154600A (ja) * 2013-02-05 2014-08-25 Tokyo Ohka Kogyo Co Ltd インプリントによるパターン形成方法
JP2014196284A (ja) * 2013-03-05 2014-10-16 キヤノン株式会社 感光性ガス発生剤、光硬化性組成物
JP2014229820A (ja) * 2013-05-24 2014-12-08 富士通株式会社 配線基板の製造方法および配線基板製造用の型
JP2015005760A (ja) * 2014-07-31 2015-01-08 キヤノン株式会社 インプリント装置、および物品の製造方法
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