JP2012183753A - Nanoimprinting method - Google Patents

Nanoimprinting method Download PDF

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Publication number
JP2012183753A
JP2012183753A JP2011048908A JP2011048908A JP2012183753A JP 2012183753 A JP2012183753 A JP 2012183753A JP 2011048908 A JP2011048908 A JP 2011048908A JP 2011048908 A JP2011048908 A JP 2011048908A JP 2012183753 A JP2012183753 A JP 2012183753A
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Prior art keywords
silane coupling
coupling agent
curable resin
resin film
mold
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JP2011048908A
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Japanese (ja)
Inventor
Masashi Yoshida
昌史 吉田
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Fujifilm Corp
富士フイルム株式会社
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Priority to JP2011048908A priority Critical patent/JP2012183753A/en
Publication of JP2012183753A publication Critical patent/JP2012183753A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • G03F7/0751Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • G03F7/0752Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Abstract

PROBLEM TO BE SOLVED: To enable formation of the aggregate of a silane coupling agent to be reduced in nanoimprinting that includes a step of performing surface treatment by coating the surface of a substrate with the silane coupling agent.SOLUTION: In a nanoimprinting method, the surface of a substrate 2 is coated with a silane coupling agent 3 having alkyl groups of 1 or 2 adjacent to an Si atom. the surface coated with the silane coupling agent 3 is coated with a curable resin containing any of isobornyl acrylate, ethylene glycol diacrylate, and a silicone monomer compound to form a curable resin film 4. A mold 1 is pressed against the curable resin film 4 with its rugged pattern facing the curable resin film 4 to turn the curable resin film 4 cured. The mold 1 is then separated from the curable resin film 4.

Description

  The present invention relates to a nanoimprint method using a mold having a predetermined uneven pattern on its surface.

  In the production of magnetic recording media such as discrete track media (DTM) and bit patterned media (BPM), and semiconductor devices, etc., the use of pattern transfer technology that performs nanoimprinting on a curable resin applied on a substrate is expected. Yes.

  Nanoimprinting is a pattern formation technology that is an evolution of embossing technology that is well known for optical disc production. Specifically, in nanoimprinting, a mold (generally called a mold, a stamper, or a template) on which a concavo-convex pattern is formed is pressed against a curable resin applied on a substrate to dynamically deform or flow the curable resin. It is a technology that precisely transfers fine patterns. Once the mold is made, it is economical because nano-level microstructures can be easily and repeatedly molded, and it is a transfer technology with little harmful waste and emissions, so it has recently been applied to various fields. Expected.

  Conventionally, with the miniaturization of the concavo-convex pattern, from the viewpoint of the pattern formability of the curable resin (ease of forming a concavo-convex pattern as designed on the curable resin), the peelability between the mold and the curable resin Improvement is an important issue.

  Therefore, as a method for improving the peelability, by forming a release layer containing an organic compound on the surface of the mold, the adhesive force acting between the mold and the curable resin is reduced to improve the peelability. The method to be used is used.

  In addition, as another method for improving the peelability, for example, as shown in Patent Documents 1 and 2, there is a method in which a surface treatment is performed by applying a silane coupling agent in advance to the surface of a substrate to which a curable resin is applied. in use. According to this method, the adhesive force acting between the substrate and the curable resin is increased by the silane coupling agent, and the adhesive force acting between the mold and the curable resin is relatively reduced. It becomes possible to improve the property. In this case, trimethoxysilane or trichlorosilane is usually used as the silane coupling agent from the viewpoint of the bonding strength of the silane coupling agent to the substrate and cost.

Special table 2010-526426 JP 2010-152284 A

  However, when surface treatment is performed on the substrate using trimethoxysilane and trichlorosilane, aggregates of these silane coupling agents are formed on the substrate, and defects D are formed in the curable resin film as shown in FIG. There may be a problem that occurs.

  The present invention has been made in view of the above problems, and in a nanoimprint including a step of applying a surface treatment by applying a silane coupling agent to the surface of a substrate, a curable resin resulting from an aggregate of the silane coupling agent An object of the present invention is to provide a nanoimprint method that can reduce the occurrence of defects in a film.

In order to solve the above problems, the nanon printing method according to the present invention is:
In the nanoimprint method using a mold having a fine uneven pattern on the surface,
A silane coupling agent represented by the following structural formula 1 is applied to the surface of the substrate,
Forming a curable resin film by applying a curable resin to the surface coated with a silane coupling agent,
Press the mold against the curable resin film while directing the uneven pattern to the curable resin film,
After the curable resin film is cured, the mold is peeled off from the curable resin film.

Structural formula 1:

  In Structural Formula 1, R represents an alkyl group, X represents an inorganic functional group, Y represents an organic functional group, L represents a linking group or a simple bond connecting the Si atom and the organic functional group, and n represents 1 or 2.

  In the nanoimprint method according to the present invention, the alkyl group is preferably a methyl group and / or an ethyl group, and particularly preferably a methyl group.

  In the nanoimprint method according to the present invention, the silane coupling agent is 3-acryloxypropyl-dimethylmethoxysilane, 3-acryloxypropyl-methylbis-trimethylsiloxysilane, 3-acryloxypropyl-methyldichlorosilane, or 3 -Preferably acryloxypropyl-methyldimethoxysilane.

  In the nanoimprint method according to the present invention, the curable resin preferably contains any one of isobornyl acrylate, ethylene glycol diacrylate, and a silicone monomer compound.

  In the nanoimprinting method according to the present invention, it is preferable to apply a silane coupling agent by a microcontact printing method.

  Since the nanoimprint method according to the present invention uses the silane coupling agent represented by the above structural formula 1 as the silane coupling agent applied to the surface of the substrate to which the curable resin is applied, the silane coupling agents The coupling frequency is reduced. As a result, it is possible to reduce the occurrence of defects in the curable resin film due to aggregates of silane coupling agent in nanoimprint including the step of applying surface treatment by applying silane coupling agent to the surface of the substrate It becomes.

It is a schematic sectional drawing which shows 1 process of the nanoimprint method including the process of apply | coating a silane coupling agent by the microcontact method. It is a schematic sectional drawing which shows 1 process of the nanoimprint method including the process of apply | coating a silane coupling agent by the microcontact method. It is a schematic sectional drawing which shows 1 process of the nanoimprint method including the process of apply | coating a silane coupling agent by the microcontact method. It is a schematic sectional drawing which shows 1 process of the nanoimprint method including the process of apply | coating a silane coupling agent by the microcontact method. It is a schematic sectional drawing which shows 1 process of the nanoimprint method including the process of apply | coating a silane coupling agent by the microcontact method. It is a schematic sectional drawing which shows the mold used by nanoimprint. It is a schematic enlarged view which shows the cross section of a part of uneven | corrugated pattern area | region of the mold in FIG. 2A. It is a figure which shows the atomic force microscope image which displays the defect of the curable resin film on the board | substrate which implemented the surface treatment using the conventional silane coupling agent.

  Hereinafter, although an embodiment of the present invention is described using a drawing, the present invention is not limited to this. In addition, for easy visual recognition, the scale of each component in the drawings is appropriately changed from the actual one.

  1A to 1E are schematic cross-sectional views illustrating steps of the nanoimprint method of the present embodiment. 2A is a schematic cross-sectional view showing the mold, and FIG. 2B is a schematic enlarged view showing a partial cross-section of the uneven pattern region of the mold in FIG. 2A.

  As shown in FIGS. 1A to 1E, the nanoimprint method of this embodiment is a nanoimprint method using a mold 1 having a fine uneven pattern 13 on the surface, and a silane coupling agent 3 represented by the following structural formula 1 is used. Photocuring containing any of isobornyl acrylate, ethylene glycol diacrylate and silicone monomer compound on the surface coated with the silane coupling agent 3 applied to the surface of the substrate 2 (FIGS. 1A and 1B) A photocurable resin film 4 is formed by applying a photocurable resin (FIG. 1C), and the mold 1 is pressed against the photocurable resin film 4 while directing the concave / convex pattern 13 toward the photocurable resin film 4 (FIG. 1D). After the curable resin film 4 is exposed and cured, the mold 1 is peeled from the photocurable resin film 4 (FIG. 1E).

Structural formula 1:

  In Structural Formula 1, R represents an alkyl group, X represents an inorganic functional group, Y represents an organic functional group, L represents a linking group connecting the Si atom and the organic functional group, or a simple bond, and n is 1 Or 2.

(mold)
For example, as shown in FIGS. 2A and 2B, the mold 1 includes a support portion 12 and a fine uneven pattern 13 formed on the surface of the support portion 12.

  The material of the support part 12 can be, for example, metal materials such as silicon, nickel, aluminum, chromium, iron, tantalum, and tungsten, and oxides, nitrides, and carbides thereof. Specifically, examples of the material of the support portion 12 include silicon oxide, aluminum oxide, quartz glass, Pyrex (registered trademark) glass, and soda glass.

  The shape of the concavo-convex pattern 13 is not particularly limited, and is appropriately selected according to the use of nanoimprint. For example, a typical pattern is a line and space pattern as shown in FIGS. 2A and 2B. And the length of the convex part of a line & space pattern, the width W1 of a convex part, the space | interval W2 of convex parts, and the height (depth of a recessed part) H of a convex part from a recessed part bottom face are set suitably. For example, the width W1 of the convex portion is 10 to 100 nm, more preferably 20 to 70 nm, the interval W2 between the convex portions is 10 to 500 nm, more preferably 20 to 100 nm, and the height H of the convex portion is 10 to 10 nm. It is 500 nm, more preferably 30 to 100 nm. In addition, the shape of the uneven pattern 13 may be a shape in which dots having cross sections such as a rectangle, a circle, and an ellipse are arranged.

(Release layer)
In order to improve the peelability between the mold 1 and the photocurable resin film 4, it is preferable to provide a release layer on the surface of the mold 1 having the uneven pattern. The release layer is preferably a layer containing a fluorine compound, and the fluorine compound is preferably perfluoropolyether. Preferable fluorine compounds include compounds represented by the following structural formulas 2 and 3.

Structural formula 2:
C 3 F 7 (OCF 2 CF 2 CF 2) p OC 2 F 4 C 2 H 4 -Si (OCH 3) 3

  In Structural Formula 2, p represents the degree of polymerization (an integer of 1 or more).

Structural formula 3:
(CH 3 O) 3 Si- CH 2 CH 2 CH 2 -O-CH 2 CF 2 - (OCF 2 CF 2) j - (OCF 2) k -OCF 2 CH 2 -O-CH 2 CH 2 CH 2 - Si (OCH 3 ) 3

  In Structural Formula 3, j and k represent the degree of polymerization (an integer of 1 or more).

  The structural formula 3 can be generated by using Fomblin ZDOL manufactured by Augmont, for example. Fomblin ZDOL is specifically a compound represented by the following structural formula 3-1.

Structural formula 3-1:
HO-CH 2 CF 2 - ( OCF 2 CF 2) j - (OCF 2) k -OCF 2 CH 2 -OH

  In Structural Formula 3-1, j and k represent the degree of polymerization (an integer of 1 or more). The number average molecular weight is about 2000.

For example, fomblin ZDOL represented by the above structural formula 3-1 is reacted with NaH (sodium hydride) to convert hydroxyl groups at both ends to sodium oxide, and allyl bromide is reacted with this to allylate the hydroxyl groups at both ends. The obtained terminal unsaturated compound is hydrosilylated with trichlorosilane (SiHCl 3 ). Thereafter, methanol is allowed to act to replace the chlorine atom on the silicon with methoxy, whereby the compound represented by the above structural formula 3 can be obtained.

  The release layer is formed by exposing the mold 1 to a fluorine compound. Specifically, it is as follows.

  Perfluoropolyether is used diluted with a fluorine-based inert solvent to a concentration of 0.01 to 10 weight percent, preferably 0.01 to 1 weight percent, more preferably 0.01 to 0.2 weight percent. . That is, it is preferable to form the release layer by immersing the mold 1 in such a diluted solution. Examples of the fluorine-based inert solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, dichloropentafluoropropane (HCFC-225), and the like. Although the temperature at the time of immersion is not specifically limited, What is necessary is just 0 degreeC-100 degreeC. Moreover, although the time required for immersion changes according to temperature, it is usually within 10 minutes and about 1 minute is sufficient.

  The release layer can also be formed by exposing the mold 1 to perfluoropolyether vapor under reduced pressure. The atmospheric pressure in this case is not particularly limited as long as it is less than 1 atm and within a range of 0.01 atm or more. In order to expose the mold 1 to perfluoropolyether vapor, for example, the mold 1 may be left in a state where the diluted solution of perfluoropolyether is heated to vapor, or the mold 1 may be perfluoropolyether. Polyether vapor may be blown. In this case, the temperature of the steam may be about 100 ° C to 250 ° C.

  The covering degree including the density of the layer in the release layer can be appropriately designed by adjusting the time for exposing the mold 1 to the diluted solution of the fluorine compound and the concentration of the diluted solution.

(substrate)
When the mold 1 is light transmissive, the substrate 2 to be processed is not particularly limited in shape, structure, size, material, etc., and can be appropriately selected according to the purpose. The surface of the substrate 2 that is the target of pattern transfer is the curable resin coated surface. For example, when the substrate 2 is for manufacturing an information recording medium, the shape of the substrate 2 is usually a disc shape. The structure may be a single layer structure or a laminated structure. The material can be appropriately selected from those known as substrate materials, and examples thereof include silicon, tantalum, nickel, aluminum, oxides and nitrides of these metals, glass such as quartz, and resins. . These board | substrate materials may be used individually by 1 type, and may use 2 or more types together. The substrate material is preferably silicon, silicon oxide, silicon nitride, and quartz, and more preferably silicon. There is no restriction | limiting in particular as thickness of the board | substrate 2, Although it can select suitably according to the objective, 0.05 mm or more is preferable and 0.1 mm or more is more preferable. If the thickness of the substrate 2 is less than 0.05 mm, the substrate 2 may be bent when the substrate 2 and the mold 1 are bonded, and a uniform bonding state may not be ensured. On the other hand, when the mold 1 does not have optical transparency, a quartz substrate is used to enable exposure of the photocurable resin film 4. The quartz substrate is appropriately selected according to the purpose within a range having light transmittance and a thickness of 0.3 mm or more. If the thickness of the quartz substrate is less than 0.3 mm, the quartz substrate is easily damaged by handling or pressing during imprinting. Quartz is preferably fused quartz.

  As shown in FIG. 1A and the like, the substrate 2 preferably has one or more mask layers on the curable resin-coated surface. In this case, the substrate 2 includes a support substrate 2a and a mask layer 2b. The mask layer 2b plays a role of preventing the lower structure of the remaining film, that is, the substrate 2 from being etched after the remaining film is removed in the remaining film etching step. The material of the mask layer 2b is selected so that the etching selectivity of the mask layer 2b with respect to the photocurable resin film 4 becomes small. The material of the mask layer 2b is particularly preferably a metal composed of chromium, tungsten, titanium, nickel, silver, platinum, gold, and the like and oxides and nitrides thereof. Furthermore, the mask layer 2b preferably has at least one layer containing chromium, chromium oxide or chromium nitride.

(Silane coupling agent)
The silane coupling agent plays a role of increasing the adhesive force acting between the substrate and the curable resin. The silane coupling agent used in the present invention is represented by the above structural formula 1, that is, a silane coupling agent having 1 or 2 alkyl groups adjacent to the Si atom.

  The alkyl group R preferably has 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. This is because if the carbon chain of the alkyl group is too long, steric hindrance occurs in the bond with the substrate. When n = 2, one may be a methyl group and the other may be an ethyl group.

  The inorganic functional group X is a functional group that reacts with an inorganic material. Inorganic functional groups X mainly include hydrolyzable groups such as alkoxy groups (methoxy groups, ethoxy groups, etc.) and acyloxy groups (acetoxy groups, propanoyloxy groups, etc.), and halogen atoms (fluorine atoms, chlorine atoms, bromine atoms). , Iodine atom) and the like.

  The organic functional group Y is a functional group that reacts with an organic material. The organic functional group Y includes amino group, carboxyl group, hydroxyl group, aldehyde group, thiol group, isocyanate group, isothiocyanate group, epoxy group, cyano group, dimethylamino group, diethylamino group, hydrazino group, hydrazide group, vinyl sulfone. Group, vinyl group, alkoxy group and the like.

L as the linking group is an alkylene group (preferably having 1 to 20 carbon atoms), - O -, - S- , an arylene group, -CO -, - NH -, - SO 2 -, - COO -, - CONH- Or a combination thereof. L as the linking group is particularly preferably an alkylene group. On the other hand, when L is a simple bond, Y and Si are directly connected in Structural Formula 1.

  The silane coupling agent is 3-acryloxypropyl-dimethylmethoxysilane, 3-acryloxypropyl-methylbis (trimethylsiloxy) silane, 3-acryloxypropyl-methyldichlorosilane, or 3-acryloxypropyl-methyldimethoxysilane. It is particularly preferred.

(Silane coupling agent application method)
The method for applying the silane coupling agent is not particularly limited, such as a dipping method or a spin coating method. FIG. 1A and FIG. 1B show a case where a silane coupling agent is applied by a micro contact printing (μCP) method using a stamp 5. The μCP method prepares a rubber-like plastic stamp having a minute uneven pattern on the surface, attaches molecules to the top surface of the convex portion of the stamp, and adheres the top surface to the substrate, thereby forming the uneven surface. In this method, a molecular film having a pattern corresponding to the pattern is formed on a substrate. When the μCP method is used, material consumption can be minimized.

  In the present embodiment, the stamp 5 has a shape complementary to the concave / convex pattern of the mold 1, that is, the convex portion and the concave portion, so that the adhesive force between the convex portion of the concave / convex pattern of the photocurable resin film 4 and the substrate 2 increases. Have concavo-convex patterns with shapes reversed from each other (FIG. 1A). As the resin material of the stamp 5, polydimethylsiloxane is preferable. When the μCP method is performed using the stamp 5 composed of polydimethylsiloxane, the silane coupling is continuously performed about 10 times while maintaining the effect of the surface treatment per adhesion of the silane coupling agent to the stamp 5. It becomes possible to apply the agent. Details of the μCP method are disclosed in, for example, Japanese Patent Application Laid-Open No. 2010-80865.

(Curable resin film)
In the present embodiment, the curable resin film is a photocurable material, but the present invention is not limited to this, and a thermosetting material can also be applied. The nanoimprinting method of the present invention is effective regardless of the type of curable resin. Furthermore, the nanoimprint method of the present invention is more effective for a curable resin containing any of isobornyl acrylate, ethylene glycol diacrylate, and a silicone monomer compound. For example, as typical bulk materials constituting the photocurable resin, isobornyl acrylate, n-hexyl acrylate, ethylene glycol diacrylate, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are used. The photocurable resin to contain can be mentioned. A surfactant can be added as appropriate.

  The acrylate component isobornyl acrylate (IBOA) is preferably about 47% by weight of the bulk material, but can be adjusted in the range of 20-80%. As a result, IBOA is mainly responsible for the mechanical properties of the curable resin. Exemplary suppliers of IBOA are Sartomer Company, Inc., Exton, Pennsylvania. And is available under the product name SR506.

  n-Hexyl acrylate (n-HA) is preferably about 25% by weight of the bulk material, but can be adjusted in the range of 0-50%. When it is desired to further give flexibility to the curable resin, n-HA is used to lower the viscosity of the curable resin, and the curable resin is designed to have a viscosity in the range of 2 to 9 cP. An exemplary source of n-HA is Aldrich Chemical Company, Milwaukee, Wisconsin.

  The crosslinker component, ethylene glycol diacrylate (EGDA), is preferably about 25% by weight of the bulk material, but can be adjusted in the range of 10-50%. EGDA also contributes to elastic modulus and stiffness enhancement, and also plays a role in promoting cross-linking of n-HA and IBOA during polymerization of the bulk material.

  The polymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one is preferably about 3% by weight of the bulk material, but can be adjusted in the range of 1-5%. The actinic radiation to which this polymerization initiator responds is broadband ultraviolet light generated by a medium pressure mercury lamp. This polymerization initiator facilitates crosslinking and polymerization of each component of the bulk material. An exemplary source of 2-hydroxy-2-methyl-1-phenyl-propan-1-one is Ciba Specialty Chemicals, New York, Tarrytown, New York, available under the trade name DAROCUR® 1173 .

(Mold pressing process)
After reducing the atmosphere between the mold 1 and the substrate 2 to a reduced pressure or vacuum atmosphere, the residual gas is reduced by pressing the mold 1. However, under a high vacuum atmosphere, the photo-curing resin before curing volatilizes, and it may be difficult to maintain a uniform film thickness. Therefore, the residual gas is preferably reduced by setting the atmosphere between the mold 1 and the substrate 2 to a He atmosphere or a reduced pressure He atmosphere. Since He permeates the quartz substrate, the trapped residual gas (He) gradually decreases. Since it takes time to permeate He, it is more preferable to use a reduced pressure He atmosphere.

  The pressing pressure of the mold 1 is in the range of 100 kPa to 10 MPa. When the pressure is higher, the flow of the photocurable resin is promoted, and the compression of the residual gas, the dissolution of the residual gas in the photocurable resin, and the penetration of He in the quartz substrate are promoted, leading to a tact-up. However, if the applied pressure is too strong, there is a possibility that the mold 1 and the substrate 2 may be damaged when a foreign object is caught when contacting the mold. Therefore, the pressing pressure of the mold 1 is preferably 100 kPa or more and 10 MPa or less, more preferably 100 kPa or more and 5 MPa, and further preferably 100 kPa or more and 1 MPa or less. The reason why the pressure is 100 kPa or more is that when imprinting is performed in the atmosphere, when the space between the mold 1 and the substrate 2 is filled with liquid, the pressure between the mold 1 and the substrate 2 is pressurized at atmospheric pressure (about 101 kPa). Because.

(Mold peeling process)
After pressing the mold 1 to form a concavo-convex pattern on the photocurable resin film 4, the mold 1 is peeled from the photocurable resin film 4. For example, the outer edge of either the mold 1 or the substrate 2 is held and the other substrate 2 or the back surface of the mold 1 is sucked and held. The method of making it peel by carrying out relative movement in the opposite direction is mentioned. At the time of passing through this step, the width of the convex portion of the curable resin pattern coincides with the interval W2 between the convex portions of the concave-convex pattern 13 of the mold 1.

  The operation of the present invention will be described below. As shown in FIG. 3, the reason why defect D occurs in the curable resin film is that the silane coupling agents are bonded to each other to form an aggregate of the silane coupling agent on the substrate, and the curable resin is the aggregate. It is considered that the defect D is generated due to the repelling. Therefore, in order to reduce the occurrence of defects D in the curable resin film, it is necessary to reduce the bonding frequency between silane coupling agents. Bonding between the silane coupling agents occurs when the inorganic functional group X of each silane coupling agent is removed and Si atoms are bonded through O atoms. Therefore, in the present invention, the bonding of Si atoms is inhibited by using a silane coupling agent in which one or two bonds of Si atoms are replaced with an alkyl group R.

  From the above, the nanoimprint method according to the present invention uses the silane coupling agent represented by the above structural formula 1 as the silane coupling agent applied to the surface of the substrate to which the curable resin is applied. The coupling frequency between ring agents is reduced. As a result, it is possible to reduce the occurrence of defects in the curable resin film due to aggregates of silane coupling agent in nanoimprint including the step of applying surface treatment by applying silane coupling agent to the surface of the substrate It becomes.

  Examples of the nanoimprint method according to the present invention are shown below.

"Example 1"
<Preparation of photocurable resin>
The above-mentioned photocurable resin was prepared as a photocurable resin used in nanoimprinting. Specific components of the photocurable resin are as follows.
Photo-curing resin:
Isobornyl acrylate (47% by weight with respect to the total weight of the bulk material),
n-hexyl acrylate (25% by weight relative to the total weight of the bulk material),
Ethylene glycol diacrylate (25% by weight, based on the weight of the entire bulk material),
2-hydroxy-2-methyl-1-phenyl-propan-1-one (3% by weight relative to the weight of the entire bulk material), and
ZONYL® (fluorine-based surfactant, less than 1% by weight based on the weight of the bulk material).

<Surface treatment of substrate>
3-Acryloxypropyl-dimethylmethoxysilane was used as the silane coupling agent. A solution obtained by diluting 1 g of the silane coupling agent with 99 g of propylene glycol monomethyl ether acetate (PGMEA) was applied to the substrate by spin coating to perform surface treatment of the Si substrate.

<Production of photocurable resin film>
First, a photocurable resin is applied by spin coating on the surface of the Si substrate that has been subjected to the above surface treatment, and the photocurable resin is baked at a substrate temperature of 100 ° C. for 10 minutes. A resin film was prepared.

<Evaluation method>
With an atomic force microscope (AFM) (Nanoscope 3 manufactured by Digital Instruments), the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in a 10 μm × 10 μm field of view.

"Example 2"
Except for using 3-acryloxypropyl-methylbis (trimethylsiloxy) silane as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

"Example 3"
Except for using 3-acryloxypropyl-methyldichlorosilane as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

Example 4
Except that 3-acryloxypropyl-methyldimethoxysilane was used as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

“Comparative Example 1”
Except for using 3-acryloxypropyl-trimethoxysilane as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

"Comparative Example 2"
Except for using 3-acryloxypropyl-trichlorosilane as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

“Comparative Example 3”
Except for using 3-acryloxypropyl-tris (trimethylsiloxy) silane as the silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

“Comparative Example 4”
Except for using bis (trimethoxy) silylethylene as a silane coupling agent, the presence or absence of defects in the photocurable resin film was confirmed and the number of defects was counted in the same manner as in Example 1.

<Result>
Table 1 below shows the results of Examples 1 to 4 and Comparative Examples 1 to 4. As a result, when the surface treatment is performed by applying the silane coupling agent represented by the structural formula 1 on the surface of the substrate to which the curable resin is applied, the generation of aggregates of the silane coupling agent can be reduced and cured. It was confirmed that the conductive resin film can be made more uniform.

"Example 5"
A stamp made of polydimethylsiloxane having a pattern complementary to the mold was prepared. Next, a silane coupling agent was attached to the top surface of the convex portion of the stamp. Then, the silane coupling agent was apply | coated to the several board | substrate by making the said top-part surface closely_contact | adhere to a several board | substrate continuously, without attaching a silane coupling agent newly.

<Result>
The silane coupling agent could be applied according to the stamp pattern even on the substrate with the silane coupling agent applied 10 times.

DESCRIPTION OF SYMBOLS 1 Mold 2 Substrate 2a Support substrate 2b Mask layer 3 Silane coupling agent 4 Photocurable resin film 5 Stamp 12 Support part 13 Uneven pattern

Claims (9)

  1. In the nanoimprint method using a mold having a fine uneven pattern on the surface,
    A silane coupling agent represented by the following structural formula 1 is applied to the surface of the substrate,
    Applying a curable resin to the surface coated with the silane coupling agent to form a curable resin film;
    The mold is pressed against the curable resin film while directing the uneven pattern to the curable resin film,
    A nanoimprint method, comprising: curing the curable resin film, and then peeling the mold from the curable resin film.
    Structural formula 1:
    (In Structural Formula 1, R represents an alkyl group, X represents an inorganic functional group, Y represents an organic functional group, L represents a linking group or a simple bond connecting the Si atom and the organic functional group, and n represents 1 or 2.)
  2.   2. The nanoimprint method according to claim 1, wherein the alkyl group is a methyl group and / or an ethyl group.
  3.   The nanoimprint method according to claim 2, wherein the alkyl group is a methyl group.
  4.   The nanoimprint method according to claim 1, wherein the silane coupling agent is 3-acryloxypropyl-dimethylmethoxysilane.
  5.   The nanoimprint method according to claim 1, wherein the silane coupling agent is 3-acryloxypropyl-methylbis (trimethylsiloxy) silane.
  6.   The nanoimprint method according to claim 1, wherein the silane coupling agent is 3-acryloxypropyl-methyldichlorosilane.
  7.   The nanoimprint method according to claim 1, wherein the silane coupling agent is 3-acryloxypropyl-methyldimethoxysilane.
  8.   The nanoimprinting method according to any one of claims 1 to 7, wherein the silane coupling agent is applied by a microcontact printing method.
  9.   9. The nanoimprint method according to claim 1, wherein the curable resin contains any one of isobornyl acrylate, ethylene glycol diacrylate, and a silicone monomer compound.
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WO2014087817A1 (en) * 2012-12-05 2014-06-12 独立行政法人科学技術振興機構 Resin for nanoimprinting, laminate containing resin for nanoimprinting, printed board containing resin for nanoimprinting, and method for producing nanoimprint substrate

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CN104781059B (en) 2012-12-13 2017-05-10 王子控股株式会社 Mold for manufacturing optical element and production method for same, and optical element
KR101667445B1 (en) * 2013-11-22 2016-10-18 롯데첨단소재(주) Silane based compound, method for preparing the same and polycarbonate resin composition comprising the same

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US6617609B2 (en) * 2001-11-05 2003-09-09 3M Innovative Properties Company Organic thin film transistor with siloxane polymer interface
US7252862B2 (en) * 2004-08-30 2007-08-07 Hewlett-Packard Development Company, L.P. Increasing adhesion in an imprinting procedure
US8808808B2 (en) * 2005-07-22 2014-08-19 Molecular Imprints, Inc. Method for imprint lithography utilizing an adhesion primer layer
JP5282510B2 (en) 2008-09-29 2013-09-04 大日本印刷株式会社 Manufacturing method of stamp for micro contact printing (μCP)
JP5556011B2 (en) 2008-12-26 2014-07-23 荒川化学工業株式会社 Pattern forming agent, pattern forming method, and substrate on which pattern is formed

Cited By (2)

* Cited by examiner, † Cited by third party
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WO2014087817A1 (en) * 2012-12-05 2014-06-12 独立行政法人科学技術振興機構 Resin for nanoimprinting, laminate containing resin for nanoimprinting, printed board containing resin for nanoimprinting, and method for producing nanoimprint substrate
JP5689207B2 (en) * 2012-12-05 2015-03-25 独立行政法人科学技術振興機構 Nanoimprint resin composition, nanoimprint substrate, and method for producing nanoimprint substrate

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