WO2013154077A1 - Article having fine pattern on surface thereof, manufacturing method therefor, optical article, manufacturing method therefor, and method for manufacturing duplicate mold - Google Patents

Abstract

In this method for manufacturing an article having a fine pattern on the surface thereof, a cycle consisting of the following steps is repeated twice: a step in which a transfer-material film is formed on the surface of a substrate; a step in which a negative pattern on a mold is transferred to the transfer-material film; a step in which etching is performed using the transfer-material film as an etching mask; and a step in which the remaining transfer-material film is removed. In this method, a fine pattern formed in the first cycle is not etched during the etching in the second cycle. Immediately before the etching in the second cycle, the thickness (d) of the transfer-material film on top of the fine pattern formed in the first cycle satisfies the relation r∙(H/R) + t < d (where r represents the rate at which the transfer-material film is etched, H represents the target etching depth, R represents the rate at which the substrate is etched, and t represents the thickness of the remaining film).

Description

Article having fine pattern on surface and method for producing the same, optical article, method for producing the same, and method for producing replica mold

The present invention relates to an article having a fine pattern on its surface and a method for producing the same, and an optical article, a method for producing the same, and a method for producing a replica mold.

As a method for producing an optical article having a fine pattern on its surface (for example, a wire grid polarizing element having a line-and-space fine pattern, an antireflection member having a moth-eye structure, etc.), a nanoimprint lithography method has attracted attention. As a method for producing the optical article by the nanoimprint lithography method, for example, the following method is known.
Apply the coating composition on the surface of the substrate, irradiate the light in a state where the photocurable resin composition is sandwiched between the mold and the substrate having a reverse pattern of the target fine pattern on the surface, A method of forming a cured resin layer having a desired fine pattern on the surface of a substrate after separating the mold after curing the photocurable resin composition.

A mold used in the nanoimprint lithography method is usually produced by forming a fine reversal pattern on the surface of a silicon or quartz substrate by an electron beam drawing method. However, since the mold has the following problems, it is difficult to increase the area of the mold.
-It takes a long time to form a fine reversal pattern on the surface of a quartz substrate by an electron beam drawing method. Since the apparatus used for the electron beam drawing method has a high running cost per unit time, the mold becomes considerably expensive when the area of the mold is increased.

In addition, a nanoimprint mold is also produced using a stepper exposure method or a multi-beam interference exposure method. In these methods, it is possible to produce a mold having a large area at a lower cost than in the electron beam drawing method, but there is a drawback that it is difficult to produce a fine pattern sufficiently smaller than the wavelength of light. .
In addition, methods for producing regular patterns of large areas by methods such as alumina anodization and self-organization methods have also been proposed, but these methods are very easy to produce (shape, size, arrangement, etc.). There is a problem that it is limited and lacks versatility.

When the reversal pattern of the mold is a repeat of the same shape such as a line-and-space or moth-eye structure, a relatively large area is used by using a relatively small area master mold as in the following method. A method for producing a replica mold is conceivable.
(I) A reversal pattern of a relatively small area master mold is repeatedly transferred in parallel to a transfer material film (resist film) on the surface of a relatively large area substrate to form a continuous mask pattern, and the surface of the substrate A method of forming a continuous fine pattern.

However, since the method (i) has the following problems, it is actually difficult to produce a replica mold having a relatively large area.
When the master mold is pressed against the transfer material film, excess transfer material is pushed out to the periphery of the master mold, so that the periphery of the area where the reverse pattern of the master mold is transferred rises. Therefore, the master mold cannot be pressed against the transfer material film in the area adjacent to the area during the next transfer.
・ When transferring, it is necessary to cure the transfer material film by irradiating light with the master mold pressed against the transfer material film, but light leaks around the area where the reverse pattern of the master mold is transferred. As a result, the transfer material film is cured. Therefore, the master mold cannot be pressed against the transfer material film in the area adjacent to the area during the next transfer.
-When the master mold is pressed against the transfer material film, excess transfer material is pushed out to the periphery of the master mold, so it is pushed out to the area where the mask pattern is already formed adjacent to the area where the transfer is performed. The transfer material will flow and become contaminated.

As a method for solving this problem, the following method has been proposed (Patent Document 1).
(Ii) a step of forming a transfer material film on the surface of the substrate, a step of repeatedly transferring the reverse pattern of the master mold to the transfer material film, a step of etching using the transfer material film as an etching mask, and removing the remaining transfer material film The first step is to form a fine pattern having the same area as the reverse pattern of the master mold in the first cycle, and a fine pattern having the same area as the reverse pattern of the master mold in the second cycle. A method of repeating the cycle twice so that the formed second regions are adjacent and alternately arranged (see FIGS. 3 and 4 of Patent Document 1).

Japanese Unexamined Patent Publication No. 2008-247022

According to the method (ii), the plurality of first regions in which the fine pattern is formed in the first cycle can be separated from the second region in which the fine pattern is formed in the second cycle. it can. Similarly, the plurality of second regions in which the fine pattern is formed in the second cycle can be separated by the amount of the first region in which the fine pattern is formed in the first cycle. Accordingly, each problem in the method (i) is solved in each cycle of the method (ii).

However, the method (ii) has the following problems.
In the second cycle, a part of the transfer material applied on the first region of the surface of the substrate flows into the concave portion of the fine pattern formed in the first region. The thickness of the transfer material film existing thereon is reduced (see FIGS. 4 and 5 of Patent Document 1). Therefore, depending on the target etching depth, during the etching in the second cycle, the transfer material film existing on the first region is completely etched, and the fine pattern in the first region is further etched. Thus, a fine pattern having a desired shape may not be obtained. For this reason, the fine pattern of the first region becomes a defect, or the fine pattern varies between the first region and the second region.

The present invention includes a step of forming a transfer material film on the surface of a substrate, a step of transferring a mold reversal pattern to the transfer material film, a step of etching using the transfer material film as an etching mask, and removing the remaining transfer material film. In the method of manufacturing an article having a fine pattern on the surface by repeating the cycle twice, the fine pattern formed in the first cycle is etched in the second cycle. Provide a method that never happens.

The method for producing an article having a fine pattern on the surface of the present invention forms a fine pattern in each of the first region on the surface of the substrate and the second region at a position different from the first region. A method for producing an article having a fine pattern on its surface,
(A) applying a coating composition containing a transfer material to the surface of the substrate to form a first transfer material film;
(B) In the first region, the reversal pattern of the mold having the reversal pattern of the fine pattern on the surface is transferred to the first transfer material film, and the fine pattern is transferred to the first transfer material film. Forming a mask pattern corresponding to
(C) performing etching using the first transfer material film on which the mask pattern is formed as an etching mask, and forming the fine pattern in the first region of the surface of the substrate;
(D) removing the first transfer material film remaining on the surface of the substrate;
(E) applying a coating composition containing a transfer material to the surface of the substrate on which the fine pattern is formed in the first region, and forming a second transfer material film;
(F) In the second region, the reverse pattern of the mold having the reverse pattern of the fine pattern on the surface is transferred to the second transfer material film, and the fine pattern is transferred to the second transfer material film. Forming a mask pattern corresponding to
(G) performing etching using the second transfer material film on which the mask pattern is formed as an etching mask, and forming the fine pattern in the second region of the surface of the substrate;
(H) removing the second transfer material film remaining on the surface of the substrate;
Have
Immediately before the step (g), the thickness d of the second transfer material film existing on the first region on the surface of the substrate satisfies the following formula (1). And
r × (H / R) + t <d (1).
Where r is the etching rate of the second transfer material film, H is the target etching depth in the second region, R is the etching rate of the substrate, and t is It is the thickness of the remaining film between the concave portion of the mask pattern and the base material in the second region.

The first region and the second region are preferably adjacent to each other.
The base material preferably includes a plurality of the first regions and a plurality of the second regions, and the first regions and the second regions are alternately arranged.
The coating composition and its coating amount in the step (a) are the same as the coating composition and its coating amount in the step (e), and the mold and the coating in the step (b) The formation conditions of the mask pattern are the same as the formation conditions of the mold and the mask pattern in the step (f), and the etching conditions in the step (c) are the same as the etching conditions in the step (g). Preferably there is.

The article having the fine pattern of the present invention on the surface is produced by the method for producing an article having the fine pattern of the present invention on the surface.
The optical article manufacturing method of the present invention is a method of manufacturing an optical article having a fine pattern on its surface, the article having the fine pattern of the present invention on its surface, and a reverse pattern of the fine pattern of the optical article on its surface. It is used as a mold having, and the reverse pattern of the mold is transferred to the surface of a transparent substrate.
Moreover, it is preferable that the manufacturing method of the optical article of this invention has the following process.
(X) The process of apply | coating the composition for coating containing a photocurable resin as a transfer material on the surface of a transparent base material, and forming a photocurable resin layer.
(Y) An article having the fine pattern on the surface is used as a mold having a reverse pattern of the fine pattern of the optical article on the surface, and the photocurable resin layer is sandwiched between the mold and the transparent substrate. The process of irradiating light in a state and curing the photocurable resin layer to form a cured resin layer.
(Z) A step of separating the mold from the cured resin layer to obtain an optical article.
The optical article of the present invention is manufactured by the method for manufacturing an optical article of the present invention (for example, a wire grid polarizing element, an antireflection member, etc.).
The method for producing a replica mold of the present invention is to manufacture a replica mold using the article having the fine pattern of the present invention on the surface as a master mold, or to further manufacture a replica mold using the replica mold as a master mold. It is characterized by.

According to the method for manufacturing an article having a fine pattern on the surface of the present invention, the step of forming a transfer material film on the surface of the substrate, the step of transferring the reverse pattern of the mold to the transfer material film, and using the transfer material film as an etching mask In the method of manufacturing an article having a fine pattern on the surface by repeating the cycle twice, the step of performing etching and the step of removing the remaining transfer material film being performed twice, during the etching in the second cycle, The fine pattern formed in the first cycle is not etched.

The article having the fine pattern of the present invention on the surface has a relatively large fine pattern and few defects in the fine pattern and variations in shape.
According to the method for producing an optical article of the present invention, an optical article can be produced in which the fine pattern has a relatively large area and the fine pattern has few defects and variations in shape.
In the optical article of the present invention, the fine pattern has a relatively large area, and there are few defects in the fine pattern and variations in shape.
According to the method for producing a replication mold of the present invention, a replication mold can be manufactured in which a fine pattern has a relatively large area and there are few defects in the fine pattern and variations in shape.

It is a top view which shows an example of the articles | goods which have the fine pattern obtained by the manufacturing method of this invention on the surface. FIG. 2 is a II-II sectional view of an article having the fine pattern of FIG. 1 on its surface. FIG. 3 is a cross-sectional view for explaining steps (a) to (d) in the method for producing an article having a fine pattern on the surface according to the present invention. FIG. 5 is a cross-sectional view for explaining steps (e) to (h) in the method for producing an article having a fine pattern on the surface thereof according to the present invention. It is sectional drawing of the base material which has the 2nd transcription | transfer material film in which the mask pattern was formed in the surface just before a process (g). It is sectional drawing which shows an example of the optical article obtained with the manufacturing method of this invention. FIG. 5 is a cross-sectional view for explaining steps (x) to (z) in the method for producing an optical article of the present invention.

In this specification, the definition is as follows.
A fine pattern or inverted pattern refers to a shape composed of one or more protrusions and / or recesses having a minimum dimension of 1 nm to 100 μm among width, length and height (ie, depth).
The region refers to a region where a fine pattern obtained by inverting the reversal pattern for one mold is formed, that is, a region having substantially the same area as the reversal pattern of the mold.
The transfer material film is a film made of a transfer material (for example, a photocurable resin, a thermosetting resin, a thermoplastic resin, or the like), a film in which the transfer material in the film is chemically changed, or an original transfer material film. It refers to a film that has changed physically (for example, its shape has changed). Therefore, when the transfer material is a curable resin, the transfer material film before and after transferring the fine pattern of the mold changes to a chemically different state due to curing, and before or after transferring the fine pattern of the mold or etched. Although the shape of the transfer material film before and after the change has changed, these are all called transfer material films. In addition, when the transfer material is a thermoplastic resin, the shape of the transfer material film before and after the transfer of the fine pattern of the mold or before and after the etching is changed, all of which are referred to as a transfer material film.
The (meth) acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.
(Meth) acrylate refers to acrylate or methacrylate.

<Article having a fine pattern on its surface>
In the article having the fine pattern obtained by the production method of the present invention on the surface, the fine pattern is formed in each of the first region on the surface of the substrate and the second region at a position different from the first region. It has been done.

FIG. 1 is a top view showing an example of an article having a fine pattern on its surface, and FIG. 2 is a cross-sectional view taken along the line II-II in FIG. The article 10 has a fine pattern 20 composed of a plurality of convex portions 22 and concave portions 24 between the convex portions 22 on the surface of the substrate 12. On the surface, a rectangular first region (I) in which a fine pattern 20 is formed in a first cycle described later and a rectangular second region in which a fine pattern 20 is formed in a second cycle described later. (II) are adjacent to each other and alternately arranged in the X direction and the Y direction.

(Base material)
Examples of the material of the base material include silicon (for example, single crystal silicon, polysilicon, amorphous silicon, etc.), quartz, glass, silicon nitride, aluminum nitride, silicon carbide, sapphire, lithium niobate, lithium tantalate, metal (for example, Aluminum, nickel, copper, etc.), metal oxides (eg, alumina, zinc oxide, magnesium oxide, etc.), and oxide and / or metal layers (eg, chromium, aluminum, nickel, molybdenum) on the surface of these substrates , Tantalum, tungsten, ITO, tin oxide, gold, silver, copper, platinum, titanium, etc.), and various resins. As a material for the base material, silicon, quartz or glass is preferable when an article having a fine pattern to be obtained is used as a mold.

The base material may be surface-treated from the viewpoint of further improving the adhesion with a transfer material film described later. Surface treatment includes primer coating treatment, ozone treatment, UV cleaning treatment, plasma treatment, corona treatment, flame treatment, itro treatment (a kind of treatment of Combustion Chemical Vapor Deposition developed by ITRO), SPM (Sulfuric Acid Hydrogen Peroxide) Mixture) and the like. Examples of the primer include silane coupling agents, alkoxysilanes, and silazanes.

(Fine pattern)
A fine pattern is formed on the surface of the substrate. The fine pattern is a pattern formed by transferring a reverse pattern on the surface of the mold to be described later.
The fine pattern is composed of a plurality of convex portions and concave portions between the convex portions. As a convex part, the protrusion extended on the surface of a base material like the example of illustration, the processus | protrusion scattered on the surface, etc. are mentioned.

Examples of the shape of the ridge include a straight line, a curved line, a bent shape, and the like as shown in the illustrated example. As shown in the illustrated example, a plurality of ridges may exist in parallel to form stripes.
Examples of the cross-sectional shape of the ridge in the direction perpendicular to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle as shown in the illustrated example.
Examples of the shape of the protrusion include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.

The width of the ridge is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and particularly preferably 10 nm to 500 nm. The width of the ridge means the full width at half maximum in the cross section in the direction orthogonal to the longitudinal direction.
The width of the protrusion is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and particularly preferably 10 nm to 500 nm. The width of the protrusion means the full width at half maximum in the cross section perpendicular to the longitudinal direction when the bottom surface is elongated, and when the bottom surface of the protrusion is not elongated, it passes through the center of gravity in the horizontal section at a position half the height of the protrusion. Means the minimum length of a line.
The height of the convex portion (depth of the concave portion) is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and even more preferably 10 nm to 500 nm.

In a region where fine patterns are densely packed, the interval between adjacent convex portions is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and even more preferably 10 nm to 500 nm. The interval between the adjacent convex portions means the distance from the starting end of the base of the cross section of the convex portion to the starting end of the base of the cross section of the adjacent convex portion.
Each dimension is an average of dimensions measured at three locations.

The minimum dimension of the convex portion is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and particularly preferably 10 nm to 500 nm. The minimum dimension means the minimum dimension among the width, length, and height of the convex portion.
The minimum dimension of the recess is preferably 1 nm to 100 μm, more preferably 1 nm to 10 μm, and particularly preferably 10 nm to 500 nm. The minimum dimension means the minimum dimension among the width, length and depth of the recess.

(First region and second region)
The first region is a region where a fine pattern is formed by steps (a) to (d) described later. In step (b), which will be described later, a reversal pattern for one mold is transferred to form a mask pattern. In step (c), a region in which a fine pattern corresponding to the mask pattern is formed by etching is designated as one region. Count as the first region. Therefore, in the step (b), when the reversal pattern of the mold is repeatedly transferred to the first transfer material film, the same number of first regions as the number of repetitions exists on the surface of the substrate.

The second region is a region where a fine pattern is formed by steps (e) to (h) described later. In step (f) described later, a reversal pattern for one mold is transferred to form a mask pattern, and in step (g), a region where a fine pattern corresponding to the mask pattern is formed by etching Count as the second region. Therefore, in the step (f), when the reversal pattern of the mold is repeatedly transferred to the second transfer material film, the same number of second regions as the number of repetitions exists on the surface of the substrate.

The first region and the second region may be adjacent to each other or may be separated from each other. The first region and the second region are preferably adjacent to each other from the point that the fine pattern can be enlarged and the area utilization efficiency can be increased. When the first region and the second region are adjacent to each other, it is preferable that the fine pattern of the first region and the fine pattern of the second region are continuous. That is, in the case of ridges and grooves, these extend without a break in the longitudinal direction and without shifting in the width direction, and in the case of protrusions or holes, it is preferable that these exist periodically and repeatedly.

The base material may have one each of the first region and the second region, and may have either one or a plurality of both. The base material preferably has a plurality of first regions and a plurality of second regions from the viewpoint of efficiently increasing the area of the fine pattern.

In the case where the substrate has a plurality of first regions and a plurality of second regions, the first region and the second region are not caused by the problem in the conventional method (i) described above. It is preferable that the lengths of the first region and the second region that are alternately arranged are as short as possible.

(Use)
Articles having fine patterns on the surface obtained by the production method of the present invention can be used as molds, optical articles (for example, optical elements, antireflection members, etc.), biochips, microreactor chips, catalyst carriers, and the like. .
Articles having a fine pattern on the surface obtained by the production method of the present invention can be used as a mold for producing optical articles, semiconductor devices, recording media, etc. by the nanoimprint lithography method, and require a large-area mold. Suitable for the production of optical articles.

<Method for producing article having fine pattern on surface>
The method for producing an article having a fine pattern on the surface of the present invention comprises a first cycle comprising the following steps (a) to (d) and a second cycle comprising the following steps (e) to (h): It is the method which has.

(First cycle)
(A) The process of forming the 1st transfer material film | membrane 14 by apply | coating the composition for coating containing a transfer material to the surface of the base material 12, as shown in FIG.
(B) In the first region (I), as shown in FIG. 3, the reversal pattern 26 of the mold 30 having the reversal pattern 26 of the fine pattern 20 on the surface is transferred to the first transfer material film 14. A step of forming a mask pattern 28 corresponding to the fine pattern 20 on the first transfer material film 14.
(C) As shown in FIG. 3, etching is performed using the first transfer material film 14 on which the mask pattern 28 is formed as an etching mask, and the fine pattern 20 is formed in the first region (I) on the surface of the substrate 12. Forming step.
(D) A step of removing the first transfer material film 14 remaining on the surface of the substrate 12 as shown in FIG.

(Second cycle)
(E) As shown in FIG. 4, a coating composition containing a transfer material is applied to the surface of the substrate 12 on which the fine pattern 20 is formed in the first region (I), and the second transfer material Forming the film 16;
(F) As shown in FIG. 4, in the second region (II), the reversal pattern 26 of the mold 30 having the reversal pattern 26 of the fine pattern 20 on the surface is transferred to the second transfer material film 16. A step of forming a mask pattern 28 corresponding to the fine pattern 20 on the second transfer material film 16.
(G) As shown in FIG. 4, etching is performed using the second transfer material film 16 on which the mask pattern 28 is formed as an etching mask, and the fine pattern 20 is formed in the second region (II) on the surface of the substrate 12. Forming step.
(H) A step of removing the second transfer material film 16 remaining on the surface of the substrate 12 as shown in FIG.

(Manufacturing equipment)
As a manufacturing apparatus for performing the steps (a) to (h), a known manufacturing apparatus employing a nanoimprint lithography method such as a transfer apparatus described in Patent Document 1 can be cited.
The transfer device is preferably a device provided with an XY movable stage for mechanically adjusting the transfer position.

(Process (a))
The first transfer material film 14 is formed by applying a liquid coating composition containing a transfer material to the surface of the substrate 12 and drying it when the coating composition contains a solvent.

As a coating method of the coating composition, spin coating method, die coating method, dip coating method, ink jet method, potting method, roll coating method, casting method, bar coating method, spray coating method, blade coating method, gravure coating method Etc. As a coating method, a spin coating method, a die coating method, a spray coating method or an ink jet method is preferable.

When the coating composition contains a solvent, the drying temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher. If drying temperature is 60 degreeC or more, there exists an advantage which can remove a solvent in a short time. The upper limit of the drying temperature is preferably 200 ° C. from the viewpoint of suppressing thermal decomposition of the coating composition. The drying time is preferably 30 seconds to 5 minutes.

The thickness of the first transfer material film (here, when the coating composition contains a solvent, the thickness after drying), that is, the coating amount of the coating composition is the target etching depth. What is necessary is just to set suitably according to (that is, the depth of the recessed part of a fine pattern), the etching rate of a transfer material film, and the etching rate of a base material.

(Base material)
Examples of the substrate include those described above. As a material for the substrate, silicon, quartz or glass is preferable. When the transfer material is a photocurable resin, at least one of the base material and the mold is a material that transmits 40% or more of light having a wavelength at which the photopolymerization initiator of the coating composition acts.

(Transfer material)
Examples of the transfer material include a photocurable resin, a thermosetting resin, and a thermoplastic resin. From the viewpoint that the step (b) can be carried out efficiently, the transfer material is preferably a photocurable resin.
In the following description, only the case where the transfer material is a photocurable resin is described, and the case where the transfer material is a thermosetting resin or a thermoplastic resin is omitted.

(Coating composition)
The coating composition contains a photocurable resin, and optionally contains a fluorine-containing surfactant, a photopolymerization initiator, a solvent, and other additives.

As the photocurable resin, a compound having a (meth) acryloyloxy group is preferable from the viewpoint that the curing speed is high and the transparency of the cured product is high.
As a compound having a (meth) acryloyloxy group (hereinafter also referred to as a (meth) acrylate compound), a compound having 1 to 15 (meth) acryloyloxy groups per molecule is preferable.

The (meth) acrylate compound may be a relatively low molecular compound (hereinafter referred to as an acrylate monomer), and a relatively high molecular weight compound (hereinafter referred to as (meth) acrylate) having two or more repeating units. May be referred to as a system oligomer).
Examples of the (meth) acrylate compound include one or more (meth) acrylate monomers, one or more (meth) acrylate oligomers, one or more (meth) acrylate monomers (meth) And) one or more of acrylate oligomers.

The (meth) acrylate-based oligomer has a molecular structure (meta) having a molecular chain having two or more repeating units (for example, a polyurethane chain, a polyester chain, a polyether chain, a polycarbonate chain, etc.) and a (meth) acryloyloxy group. ) Acrylate oligomers, urethane bond and two or more (meth) acryloyl from the viewpoint of easy adjustment of the flexibility and surface hardness of the cured film and excellent adhesion to the substrate. A urethane (meth) acrylate oligomer having an oxy group is more preferable, and a urethane (meth) acrylate oligomer having a urethane bond and 6 to 15 (meth) acryloyloxy groups is more preferable.

The ratio of the solvent in the coating composition is preferably designed so as to obtain a target film thickness after drying, depending on the coating means used. Diluting with a solvent reduces the viscosity of the coating composition and makes it easier to apply a thin film, and evaporates the solvent after application to reduce the film thickness, which makes it easier to obtain a thin film. .

The coating composition preferably contains a fluorine-containing surfactant from the viewpoint of flatness of the transfer material film and releasability between the transfer material film and the mold.
As the fluorine-containing surfactant, a fluorine-containing surfactant having a fluorine content of 10 to 70% by mass is preferable, and a fluorine-containing surfactant having a fluorine content of 10 to 40% by mass is more preferable. The fluorine-containing surfactant may be water-soluble or fat-soluble.

As the fluorine-containing surfactant, an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, or a nonionic fluorine-containing surfactant is preferable, and the compatibility in the coating composition From the viewpoint of dispersibility in the transfer material film, a nonionic fluorine-containing surfactant is more preferable.

The proportion of the fluorine-containing surfactant in the coating composition is preferably 0.05 to 5% by mass, based on 100% by mass of the component remaining as the cured resin in the coating composition, 1 to 5% by mass is more preferable. When the ratio of the fluorine-containing surfactant is 0.05% by mass or more, the flatness of the transfer material film and the releasability between the transfer material film and the mold are good. If the ratio of a fluorine-containing surfactant is 5 mass% or less, it will be easy to maintain the state of uniform mixing stably with the other component of the coating composition, and the influence on the resin pattern shape after hardening will also be suppressed.

It is preferable that the composition for coating contains a photoinitiator from a photocurable point of view.
As photopolymerization initiators, acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, α-aminoketone photopolymerization initiator, α-hydroxyketone photopolymerization initiator Polymerization initiator, α-acyl oxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, azo Examples thereof include bisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like. From the viewpoint of sensitivity and compatibility, acetophenone photopolymerization initiator, benzoin photopolymerization initiator, α- Aminoketone photopolymerization initiator A benzophenone photopolymerization initiator is preferred.

The proportion of the photopolymerization initiator in the coating composition is preferably 0.01 to 5.0% by mass, based on 100% by mass of the component remaining as the cured resin in the coating composition. More preferably, the content is 1 to 3.0% by mass. If the ratio of the photopolymerization initiator is 0.01% by mass or more, curing can be carried out with a small amount of light, and therefore the time required for the process can be shortened. If the ratio of a photoinitiator is 5.0 mass% or less, it will be easy to mix uniformly with the other component of the coating composition, and the fall of the intensity | strength by the molecular weight fall after photocuring can be suppressed.

It is preferable that the coating composition contains a solvent. Examples of the solvent include esters, ketones, alcohols, cyclic ethers and the like.
The coating composition contains other additives such as photosensitizers, polymerization inhibitors, resins, metal oxide fine particles, carbon compounds, metal fine particles, and other organic compounds as long as the effects of the present invention are not impaired. May be included.

(Process (b))
In the first region (I), the mold 30 having a rectangular surface (the surface on which the reversal pattern 26 is formed) in contact with the first transfer material film 14 is pressed against the first transfer material film 14, thereby In a state where the first transfer material film 14 is sandwiched between the material 12, only the first transfer material film 14 sandwiched between the mold 30 and the substrate 12 is selectively irradiated with light, The first transfer material film 14 is cured. After the first transfer material film 14 is cured, the mold 30 is separated from the first transfer material film 14. In this way, the reverse pattern 26 of the mold 30 is transferred to the first transfer material film 14, and the mask pattern 28 corresponding to the fine pattern 20 is formed on the first transfer material film 14 in the first region (I). Form.

When there are a plurality of first regions (I), the step (b) is repeated for the number of first regions (I).
Further, when the step (b) is repeatedly performed, the first region (I) and the second region (II) are adjacent to each other and the X direction and the Y direction are transferred to the next step (b). It is preferable to move the mold 30 or the substrate 12 in the plane direction (X direction or Y direction) and in parallel by the second region (II) so as to be alternately arranged in each direction.
After the mask pattern 28 is formed on the first transfer material film 14 in all the first regions (I), the entire surface of the first transfer material film 14 is irradiated with light, and the regions other than the first region (I) The first transfer material film 14 is cured.

As means for moving the mold to the first region, known means such as the means described in Patent Document 1 may be used.
Adjustment of the position of the mold or the substrate when the mold is pressed against the transfer material film may be performed by a known method such as the adjustment method described in Patent Document 1.

The pressure applied from the mold to the transfer material film is preferably 0.05 MPa or more, more preferably 0.3 MPa or more, and particularly preferably 2 MPa or more. When the pressure is 0.05 MPa or more, contact between the mold and the photocurable resin is promoted, and contact failure is reduced. Further, when the pressure is 2 MPa or more, the uniformity of the thickness of the remaining film is improved. The pressure applied to the transfer material film from the mold is preferably 50 MPa or less from the viewpoint of the durability of the substrate and the mold.

The sandwiching of the transfer material film between the mold and the base material may be performed under atmospheric pressure or under reduced pressure. When the process is performed under atmospheric pressure, a large-scale apparatus for depressurization is not required, the time for the process is shortened, and volatilization of components contained in the transfer material film is suppressed. When carried out under reduced pressure, there is an advantage that the entrapment of bubbles at the time of pinching is suppressed and the photocurable resin is easily filled in the grooves and holes.

Examples of the light applied to the transfer material film include ultraviolet rays, visible rays, infrared rays, electron beams, and radiation.
Examples of ultraviolet light sources include germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, and the like.
Irradiation with light may be performed under normal pressure or under reduced pressure. Moreover, you may carry out in air and you may carry out in inert gas atmospheres, such as nitrogen atmosphere and a carbon dioxide atmosphere.

(mold)
Examples of the mold material include a non-light-transmitting material and a light-transmitting material.
Examples of the non-translucent material include silicon, metal (for example, nickel, copper, stainless steel, titanium, etc.), SiC, mica, and the like.
Examples of the light-transmitting material include quartz, glass, and various resins (for example, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin).
At least one of the mold and the base material is a material that transmits 40% or more of light having a wavelength at which the photopolymerization initiator acts.

(Process (c))
Etching is performed using the first transfer material film 14 on which the mask pattern 28 is formed as an etching mask to form the fine pattern 20 in the first region (I) on the surface of the substrate 12.
Examples of the etching method include known methods, and an etching method using a halogen-based gas is preferable.

(Process (d))
After the etching, the first transfer material film 14 remaining on the surface of the substrate 12 is removed.
Examples of the removal method include wet treatment with a stripping solution, dry treatment with oxygen plasma, vacuum ultraviolet rays, and the like, and heat treatment at a temperature that promotes thermal decomposition of the transfer material.

(Process (e))
(Formation of second transfer material film)
A liquid coating composition containing a transfer material is applied to the surface of the substrate 12 on which the fine pattern 20 is formed in the first region (I), and is dried when the coating composition contains a solvent. Thus, the second transfer material film 16 is formed.
The step (e) may be performed in the same manner as the step (a), and the description of the same contents as the step (a) is omitted.

A concave portion of the fine pattern 20 in which a part of the coating composition applied on the first region (I) on the surface of the substrate 12 in the step (e) is formed in the first region (I). Therefore, a depression 18 is formed in the second transfer material film 16 existing on the first region (I). The thickness of the second transfer material film 16 existing on the first region (I) is reduced by the amount corresponding to the depressed portion 18.

The thickness of the second transfer material film (the thickness after drying when the coating composition contains a solvent), that is, the coating amount of the coating composition is the target etching depth in the second region ( In other words, the depth of the concave portion of the fine pattern), the etching rate of the transfer material film, and the etching rate of the substrate may be set as appropriate.

(Process (f))
In the second region (II), the surface of the mold 30 on which the reverse pattern 26 is formed is pressed against the second transfer material film 16, and the second transfer material film 16 is interposed between the mold 30 and the substrate 12. In this state, only the second transfer material film 16 sandwiched between the mold 30 and the substrate 12 is selectively irradiated with light to cure the second transfer material film 16. After the second transfer material film 16 is cured, the mold 30 is separated from the second transfer material film 16. In this way, the reverse pattern 26 of the mold 30 is transferred to the second transfer material film 16, and the mask pattern 28 corresponding to the fine pattern 20 is formed on the second transfer material film 16 in the second region (II). Form.
The step (f) may be performed in the same manner as the step (b), and the description of the same contents as the step (b) is omitted.

When there are a plurality of second regions (II), the step (f) is repeated for the number of the second regions (II).
In addition, when the step (f) is repeatedly performed, the first region (I) and the second region (II) are adjacent to each other and the X direction and the Y direction are transferred to the next step (f). It is preferable to move the mold 30 or the substrate 12 in the plane direction (X direction or Y direction) and in parallel by the first region (I) so as to be alternately arranged in each direction.
After the mask pattern 28 is formed on the second transfer material film 16 in all the second regions (II), the entire surface of the second transfer material film 16 is irradiated with light, and the regions other than the second region (II) The second transfer material film 16 is cured.

When pressing the mold against the second transfer material film in the second region, the position of the mold or the substrate is corrected so that the fine pattern in the first region and the fine pattern in the second region are continuous. Preferably it is done. Correction of the position of the mold or the substrate can be performed by a known method such as a correction method described in Patent Document 1.

(Process (g))
Etching is performed using the second transfer material film 16 on which the mask pattern 28 is formed as an etching mask to form the fine pattern 20 in the second region (II) on the surface of the substrate 12.
The step (g) may be performed in the same manner as the step (c), and the description of the same contents as the step (c) is omitted.

FIG. 5 is a cross-sectional view of the base material 12 having the second transfer material film 16 on which the mask pattern 28 is formed on the surface just before the step (g).
In the present invention, immediately before the step (g), the thickness d of the second transfer material film 16 existing on the first region (I) on the surface of the substrate 12 is expressed by the following formula (1). It is necessary to be satisfied.
r × (H / R) + t <d (1).

d is the thickness of the second transfer material film 16 existing on the first region (I) on the surface of the substrate 12, that is, the depressed portion from the top of the fine pattern 20 in the first region (I). It is the distance in the thickness direction to the bottom of 18.
r is the etching rate of the second transfer material film 16. In the case where the second transfer material film 16 is etched in advance with a thickness smaller than the thickness t of the remaining film by etching using oxygen gas, when etching using halogen gas is performed, halogen gas is used. Etching rate in etching using
H is the target etching depth in the second region (II), that is, the depth of the concave portion 24 of the fine pattern 20.
R is the etching rate of the substrate 12.
t is the thickness of the remaining film between the concave portion of the mask pattern 28 and the substrate 12 in the second region (II).

“H / R” in Equation (1) is the time required to etch the substrate 12 by the target etching depth H. Therefore, “r × (H / R)” in Equation (1) is the thickness of the second transfer material film 16 that is etched while the substrate 12 is being etched by the target etching depth H.
Therefore, the thickness d is equal to the thickness of the second transfer material film 16 to be etched while the remaining film is being etched (equal to the thickness t), and the substrate 12 is etched by the target etching depth H. If the thickness is larger than the sum of the thickness (r × (H / R)) of the second transfer material film 16 that is etched during the process, the surface of the substrate 12 is obtained even at the end of the step (g). The second transfer material film 16 remains on the first region (I). Therefore, the fine pattern 20 in the first region (I) is not etched in the step (g), and the fine pattern 20 having a desired shape is obtained also in the first region (I). As a result, defects in the fine pattern 20 in the first region (I) and variations in the fine pattern 20 between the first region (I) and the second region (II) are reduced.

In order for the thickness d to satisfy the formula (1), for example, the following adjustment is performed.
(Α) The target etching depth H in the second region (II) is decreased.
(Β) The thickness d of the second transfer material film 16 existing on the first region (I) on the surface of the substrate 12 is increased.
(Γ) Increase the resist selectivity (R / r).
(Δ) Decrease the thickness t of the remaining film.
(Ε) A preliminary experiment is performed to examine the coating amount of the coating composition having a thickness d satisfying the formula (1).

About (α):
If the etching rates r, R, and thicknesses t and d cannot be changed due to restrictions on manufacturing conditions, the left side of the equation (1) can be reduced by reducing the target etching depth H.

About (β):
By the method (1) or (2) described below, the amount of the coating composition flowing into the concave portion 24 of the fine pattern 20 in the first region (I) is reduced, and the thickness d can be increased.
(1) The depth of the concave portion 24 of the fine pattern 20 in the first region (I) is decreased.
(2) The aperture ratio of the fine pattern 20 in the first region (I) (the width of the concave portion 24 / (the width of the convex portion 22 + the width of the concave portion 24)) is reduced.

About (γ):
When the material of the substrate 12 and the transfer material can be selected, the left side of the formula (1) can be reduced by selecting the material so that the resist selectivity (R / r) is increased.

About (δ):
By the following methods (1) to (4), the remaining film thickness t can be reduced and the left side of the above formula (1) can be reduced.
(1) Reduce the coating amount of the coating composition.
(2) The pressure applied from the mold 30 to the second transfer material film 16 is increased.
(3) The depth of the concave portion of the reversal pattern 26 of the mold 30 is increased.
(4) The aperture ratio of the reversal pattern 26 of the mold 30 is increased.
Since the thickness d is also reduced in the method (1), it is preferable to adjust the thickness t of the remaining film by the methods (2) to (4).

About (ε):
When the etching rate r, R, thickness t, and target etching depth H cannot be changed due to restrictions on manufacturing conditions due to the design of the article, it is necessary to change the coating amount of the coating composition in a preliminary experiment. The second transfer material film 16 is formed on the first region (I) on the surface of the material 12, and the coating amount range of the coating composition is such that the thickness d satisfies the formula (1). Investigate.

When the target fine pattern is determined in advance in the design of the article, the following methods (1) to (3) are particularly effective among (α) to (ε).
(1) (γ) Increase the resist selectivity.
(2) (δ) (2) The pressure applied from the mold 30 to the second transfer material film 16 is increased.
(3) (δ) (3) The depth of the concave portion of the reversal pattern 26 of the mold 30 is increased.

The coating composition and its coating amount in the step (a) are the same as the coating composition and its coating amount in the step (e), and the mold and the coating in the step (b) The formation conditions of the mask pattern are the same as the formation conditions of the mold and the mask pattern in the step (f), and the etching conditions in the step (c) are the same as the etching conditions in the step (g). Preferably there is. By proceeding under exactly the same conditions, it becomes possible to easily match the shapes of the fine patterns formed on the substrate in the first cycle and the second cycle, respectively.

(Process (h))
After the etching, the second transfer material film 16 remaining on the surface of the substrate 12 is removed.
Step (h) may be performed in the same manner as step (d), and the description of the same contents as step (d) will be omitted.

(Function and effect)
In the method for manufacturing an article having the fine pattern on the surface according to the present invention described above, the step of forming the transfer material film on the surface of the substrate, the step of transferring the reversal pattern of the mold to the transfer material film, the transfer material film In the method of performing the etching using the etching mask and the step of removing the remaining transfer material film as one cycle and repeating the cycle twice (that is, the method having the steps (a) to (h) described above), the second time Of the second pattern existing on the fine pattern formed in the first cycle (that is, on the first region of the surface of the substrate) immediately before the etching of the cycle (that is, step (g) described above). Since the thickness d of the transfer material film satisfies the expression (1), the second pattern is formed on the fine pattern formed in the first cycle even at the end of the second cycle etching. Copy material film remains. Therefore, the fine pattern formed in the first cycle is not etched during the etching in the second cycle.

In addition, an article having a fine pattern on the surface obtained by the production method of the present invention includes a step of forming a transfer material film on the surface of a substrate, a step of transferring a reverse pattern of a mold to the transfer material film, and etching the transfer material film. Since the process of etching as a mask and the process of removing the remaining transfer material film are defined as one cycle and the cycle is repeated twice (that is, the method having the steps (a) to (h) described above), A fine pattern has a relatively large area. Further, since the fine pattern formed in the first cycle is manufactured by a method in which the fine pattern formed in the first cycle is not etched during etching in the second cycle, there are few fine pattern defects and shape variations.

<Optical article>
The optical article of the present invention is manufactured by the optical article manufacturing method of the present invention described later.
The description of the same content as the article having the fine pattern of the present invention on the surface is omitted.

FIG. 6 is a cross-sectional view showing an example of an optical article. The optical article 40 includes a transparent substrate 42 and a cured resin layer 44 formed on the surface of the transparent substrate 42, and the cured resin layer 44 has a fine pattern 50.

(Base material)
Examples of the material of the transparent substrate 42 include quartz, glass, metal oxide, various resins, and the like.
The transparent substrate 42 may be surface-treated from the viewpoint of further improving the adhesion with the cured resin layer 44.

(Cured resin layer)
The curable resin layer 44 is formed by applying a coating composition containing a photocurable resin (that is, a photocurable resin composition) to the surface of the transparent substrate 42 and curing the photocurable resin composition by light irradiation. It is a layer formed by this.

(Fine pattern)
The cured resin layer 44 has a fine pattern 50 on the surface. The fine pattern 50 is a pattern formed by transferring a reverse pattern on the surface of the mold to be described later.
The fine pattern 50 includes a plurality of convex portions 52 and concave portions 54 between the convex portions 52. As the convex part 52, the protruding item | line extended on the surface of the cured resin layer 44 like the example of illustration, the process scattered on the surface, etc. are mentioned.
The above-described optical article can obtain a fine pattern having a relatively large area, has few defects in the fine pattern and variations in shape, and can be preferably used as an optical component such as a wire grid polarizing element or an antireflection member. .

<Method for manufacturing optical article>
The method for producing an optical article of the present invention uses an article having the fine pattern of the present invention on the surface as a mold having a reverse pattern of the fine pattern of the optical article on the surface, and uses the reverse pattern of the mold on the surface of the transparent substrate. It is a method of transcription.

Examples of methods for transferring the mold reversal pattern to the surface of the transparent substrate include photo nanoimprint lithography using a photocurable resin as a transfer material, and thermal nanoimprint lithography using a thermosetting resin or thermoplastic resin as a transfer material. Can be mentioned. The optical nanoimprint lithography method is preferable from the viewpoint that the reversal pattern of the mold can be efficiently transferred onto the surface of the transparent substrate.
In the following description, only the case where the transfer method is an optical nanoimprint lithography method will be described, and the case where the transfer method is a thermal nanoimprint lithography method will be omitted.

Examples of the method for producing an optical article of the present invention include a method having the following steps (x) to (z).
(X) A step of forming a photocurable resin layer 46 by applying a coating composition containing a photocurable resin as a transfer material to the surface of the transparent substrate 42 as shown in FIG.
(Y) As shown in FIG. 7, light is irradiated in a state where a photocurable resin layer 46 is sandwiched between a mold 60 having a reverse pattern of the fine pattern 50 on the surface and a transparent substrate 42, A step of curing the photocurable resin layer 46 to form a cured resin layer 44.
(Z) A step of obtaining the optical article 40 by separating the mold 60 from the cured resin layer 44.

(Process (x))
Step (x) may be performed in the same manner as step (a), and the description of the same contents as step (a) will be omitted.
What is necessary is just to use the thing similar to the composition for coating in a process (a) as a composition for coating in this process.

(Process (y))
Step (y) may be performed in the same manner as step (b), and the description of the same contents as step (b) is omitted.
As the mold 60, the article 10 having the fine pattern of the present invention on the surface and the mold having the reverse pattern of the fine pattern 50 of the optical article 40 on the surface are used.

(Process (z))
Examples of the method for separating the mold 60 from the cured resin layer 44 include a method in which both are fixed by vacuum suction and moved in a direction in which one is released, a method in which both are mechanically fixed and moved in a direction in which one is released. It is done.
After separating the mold 60 from the cured resin layer 44, the cured resin layer 44 may be further cured. Examples of the curing method include heat treatment and light irradiation.
By the manufacturing method including the steps (x) to (z) described above, an optical component such as a wire grid polarizing element or an antireflection member can be preferably manufactured.

(Function and effect)
In the method for producing an optical article of the present invention described above, an article having a fine pattern of the present invention on its surface having a relatively large area and a small number of fine pattern defects and shape variations is used as a mold. Therefore, an optical article having a relatively small area and a small pattern defect and shape variation can be produced by a single transfer.

An optical article obtained by the manufacturing method of the present invention is manufactured using an article having a fine pattern of the present invention on its surface as a mold, which has a relatively large fine pattern and few defects and variations in shape of the fine pattern. Therefore, the fine pattern has a relatively large area, and there are few defects and variations in the shape of the fine pattern.

<Replication mold and manufacturing method thereof>
The method for producing a replication mold of the present invention is a method for manufacturing a replication mold (that is, a child mold) using the article having the fine pattern of the present invention on the surface as a master mold.
The following method etc. are mentioned as a concrete manufacturing method of a replication mold.
A method for obtaining a replica mold by transferring a fine pattern of a master mold onto the surface of a substrate in the same manner as in the method for producing an optical article.
A method of obtaining a replica mold made of a metal substrate on which a fine pattern is transferred by depositing metal on the surface of the fine pattern of the master mold by electroforming (nickel electroforming or the like).
The obtained replica mold may be used as a master mold to further manufacture a replica mold (that is, a grandchild mold).

(Function and effect)
In the method for producing a replica mold of the present invention described above, an article having a fine pattern of the present invention on its surface having a relatively large area and a small number of fine pattern defects and shape variations is master mold. Therefore, a replica mold having a relatively large area and a small pattern defect and shape variation can be produced by one transfer.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Examples 1, 2, 4, and 7 are examples, and examples 3, 5, 6, and 8 are comparative examples.

(Thickness of transfer material film)
The thickness of the transfer material film present on the flat surface of the substrate was measured using a tabletop film thickness measurement system (F20, manufactured by Filmetrics).

The thickness d of the second transfer material film existing on the first region on the surface of the substrate was determined as follows.
For the peripheral edge of the depressed portion formed in the second transfer material film existing on the first region, the step amount is measured using a scanning probe microscope (SII Nanotechnology, L-trace, Nanoavi). went. The thickness d was determined by subtracting the step amount from the thickness of the second transfer material film present on the flat surface of the substrate.

(Residual film thickness t)
The dummy sample produced on the same conditions as an Example was cleaved, and the thickness t of the remaining film in a cut surface was measured using the scanning electron microscope (Hitachi Ltd. make, S4300).

(Evaluation of fine pattern)
A fine pattern of the obtained article was observed using a scanning probe microscope (manufactured by SII Nanotechnology, L-trace, Nanoavi) and evaluated according to the following criteria.
A: The difference in the shape of the fine pattern in the first region cannot be found when compared with the state at the end of the first cycle.
X: There is a difference when the shape of the fine pattern in the first region is compared with the state at the end of the first cycle.

(Preparation of primer)
In a vial container, 9 g of 2-propanol (manufactured by Junsei Chemical Co., Ltd., reagent for electronic industry), 4 μL of KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane), tetraethoxysilane (Tokyo Chemical Industry) A primer was prepared by weighing out 1 μg of an aqueous acetic acid solution (manufactured by Kanto Chemical Co., Ltd., special grade, 20% by mass aqueous solution) and stirring sufficiently.

(Preparation of coating composition)
In a vial container, 1.00 g of U-6H (manufactured by Shin-Nakamura Chemical Co., Ltd., urethane methacrylate type reactive oligomer), 0.03 g of S420 (manufactured by AGC Seimi Chemical Co., Ltd., nonionic fluorine-containing surfactant), IRGACURE907 ( Weigh out 0.03 g of BASF Japan Co., photopolymerization initiator), and then add 19.00 g of isobutyl acetate (Kanto Chemical Co., Ltd., Deer Special Grade), stir well, and apply coating composition. Obtained.

[Example 1]
(Process (a))
The prepared primer is dropped with a dropper onto the surface of a circular silicon substrate having a diameter of 4 inches (SUMCO Co., Ltd., thickness: 525 μm, <1.0.0> surface, single-sided mirror wafer), and 4000 rpm using a spin coater. Then, spin coating was performed for 20 seconds, followed by heat treatment at 130 ° C. for 10 minutes on a hot plate.
.

The coating composition is dropped onto the surface of the silicon substrate subjected to the primer treatment with a dropper, spin-coated at 3000 rpm for 20 seconds using a spin coater, and then heated at 70 ° C. for 2 minutes on a hot plate. Then, the solvent was removed from the coating film to form a first transfer material film. Table 1 shows the thickness of the first transfer material film.

(Process (b))
A quartz mold having a fine pattern of line and space (pattern area size: 22 mm × 22 mm, line width: 60 nm, space groove width: 60 nm, and first transfer material film in the first region, (Pitch: 120 nm, groove depth: 120 nm, external size: 22 mm × 22 mm, thickness: 6.35 mm) using a nanoimprint apparatus (manufactured by Toshiba Machine Co., Ltd., ST50) at 25 ° C. under atmospheric pressure at 3 MPa. The pressure was pressed for 40 seconds so as to be in close contact, and the fine pattern area of the quartz mold was irradiated with ultraviolet rays (1000 mJ / cm ² ) through the quartz mold in that state. Thereafter, the quartz mold was peeled off, and further, ultraviolet rays (1000 mJ / cm ² ) were irradiated in a vacuum chamber to cure the entire transfer material, thereby obtaining a silicon substrate with a mask pattern.

(Process (c))
The silicon substrate with a mask pattern was subjected to anisotropic etching by sequentially performing the following three steps using a dry etching apparatus.
1) The surface layer (thickness: 35 nm) of the first transfer material film was removed by O ₂ etching.
2) Using a fluorine-based gas (SF ₆ , C ₄ F ₈ ), the silicon substrate was dry-etched to the target etching depth H shown in Table 1. The etching time is such that the transfer material film of the actually etched sample is peeled off, and the groove depth of the silicon substrate is measured with a scanning probe microscope so that the target etching depth H is achieved. It was adjusted.
3) Ashing was performed for an excessive amount of time using O ₂ plasma, and the deposited film derived from the C ₄ F ₈ gas plasma adhered to the surface was removed.

(Process (d))
The silicon substrate subjected to dry etching was immersed in concentrated sulfuric acid heated to 80 ° C. for 20 minutes on a hot plate and then further heated to 80 ° C. (concentrated sulfuric acid: hydrogen peroxide solution (30%) = 3: 1 (volume ratio)) for 20 minutes to peel off the first transfer material film.
The pulled silicon substrate was sufficiently washed with ultrapure water and completely dried by blowing air to obtain a silicon substrate having a fine pattern formed in the first region.

(Process (e))
In the same manner as in the step (a), a primer coating treatment is performed, and then, in the same manner as in the step (a), the coating composition is applied to the surface of the silicon substrate on which the fine pattern is formed in the first region. Then, a second transfer material film was formed. Table 1 shows the thickness of the second transfer material film.

(Process (f))
The quartz mold was pressed against and adhered to the second transfer material film in the second region in the same manner as in the step (b), and the fine pattern area of the quartz mold was irradiated through the quartz mold. Thereafter, the quartz mold was peeled off, and further, ultraviolet rays (1000 mJ / cm ² ) were irradiated in a vacuum chamber to cure the entire transfer material, thereby obtaining a silicon substrate with a mask pattern. Table 1 shows the thickness d of the second transfer material film and the thickness t of the remaining film existing on the first region on the surface of the substrate.

(Steps (g) to (h))
Anisotropic etching was performed in the same manner as in step (c). The target etching depth H is shown in Table 1.
In the same manner as in the step (d), the second transfer material film was peeled off to obtain an article having a fine pattern on the surface. The evaluation results are shown in Table 1.

[Examples 2 to 8]
Except for changing the target etching depth H in the step (c), the thickness of the second transfer material film in the step (e), and the target etching depth H in the step (g) as shown in Table 1, In the same manner as in Example 1, an article having a fine pattern on the surface was obtained. The evaluation results are shown in Table 1.

The method for producing an article having a fine pattern on the surface thereof according to the present invention includes a mold used for nanoimprint lithography, an optical article (for example, an optical element, an antireflection member, etc. Specifically, it has a line-and-space fine pattern. Wire grid polarizing element, antireflection member having moth-eye structure, etc.), biochip, microreactor chip, catalyst carrier and the like.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2012-088636 filed on April 9, 2012 are incorporated herein as the disclosure of the present invention. .

DESCRIPTION OF SYMBOLS 10 Article 12 Base material 14 1st transcription | transfer material film | membrane 16 2nd transcription | transfer material film | membrane 18 Depression part 20 Fine pattern 22 Convex part 24 Concave part 26 Inversion pattern 28 Mask pattern 30 Mold 40 Optical article 42 Transparent base material 44 Curing resin layer 46 Photocurable resin layer 50 Fine pattern 52 Convex part 54 Concave part 60 Mold

Claims (11)

1. A method of manufacturing an article having a fine pattern on a surface by forming a fine pattern in each of a first region on a surface of a substrate and a second region at a position different from the first region. And
   (A) applying a coating composition containing a transfer material to the surface of the substrate to form a first transfer material film;
   (B) In the first region, the reversal pattern of the mold having the reversal pattern of the fine pattern on the surface is transferred to the first transfer material film, and the fine pattern is transferred to the first transfer material film. Forming a mask pattern corresponding to
   (C) performing etching using the first transfer material film on which the mask pattern is formed as an etching mask, and forming the fine pattern in the first region of the surface of the substrate;
   (D) removing the first transfer material film remaining on the surface of the substrate;
   (E) applying a coating composition containing a transfer material to the surface of the substrate on which the fine pattern is formed in the first region, and forming a second transfer material film;
   (F) In the second region, the reverse pattern of the mold having the reverse pattern of the fine pattern on the surface is transferred to the second transfer material film, and the fine pattern is transferred to the second transfer material film. Forming a mask pattern corresponding to
   (G) performing etching using the second transfer material film on which the mask pattern is formed as an etching mask, and forming the fine pattern in the second region of the surface of the substrate;
   (H) removing the second transfer material film remaining on the surface of the substrate;
   Have
   Just before the step (g), the fine pattern in which the thickness d of the second transfer material film existing on the first region of the surface of the base material satisfies the following formula (1) A method for manufacturing an article having a surface thereof.
   r × (H / R) + t <d (1).
   Where r is the etching rate of the second transfer material film, H is the target etching depth in the second region, R is the etching rate of the substrate, and t is It is the thickness of the remaining film between the concave portion of the mask pattern and the base material in the second region.
2. The method for producing an article having the fine pattern on the surface according to claim 1, wherein the first region and the second region are adjacent to each other.
3. The said base material has several said 1st area | region and several said 2nd area | region, and the said 1st area | region and the said 2nd area | region were arranged alternately. The manufacturing method of the articles | goods which have the fine pattern of description on the surface.
4. The coating composition and its coating amount in the step (a) are the same as the coating composition and its coating amount in the step (e),
   The forming conditions of the mold and the mask pattern in the step (b) are the same as the forming conditions of the mold and the mask pattern in the step (f),
   The method for producing an article having a fine pattern on its surface according to any one of claims 1 to 3, wherein the etching conditions in the step (c) and the etching conditions in the step (g) are the same.
5. An article having a fine pattern on its surface, produced by the method for producing an article having a fine pattern on its surface according to any one of claims 1 to 4.
6. A method for producing an optical article having a fine pattern on its surface,
   An article having the fine pattern according to claim 5 on a surface thereof as a mold having on the surface a reverse pattern of the fine pattern of the optical article, and transferring the reverse pattern of the mold onto the surface of a transparent substrate. Production method.
7. It is a method of manufacturing the optical article which has a fine pattern on the surface, Comprising: The manufacturing method of the optical article of Claim 6 which has the following process.
   (X) The process of apply | coating the composition for coating containing a photocurable resin as a transfer material on the surface of a transparent base material, and forming a photocurable resin layer.
   (Y) The article having the fine pattern according to claim 5 on the surface is used as a mold having a reverse pattern of the fine pattern of the optical article on the surface, and the photocurability is between the mold and the transparent substrate. The process of irradiating light in the state which pinched | interposed the resin layer, hardening a photocurable resin layer, and setting it as a cured resin layer.
   (Z) A step of separating the mold from the cured resin layer to obtain an optical article.
8. An optical article manufactured by the method for manufacturing an optical article according to claim 6 or 7.
9. A wire grid polarizing element or an antireflection member manufactured using the method for manufacturing an optical article according to claim 6 or 7.
10. A method for producing a replica mold, wherein a replica mold is manufactured using the article having the fine pattern according to claim 5 on its surface as a master mold.
11. A method for manufacturing a replication mold, wherein the replication mold manufactured by the method for manufacturing a replication mold according to claim 10 is used as a master mold to further manufacture a replication mold.

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