WO2017030151A1 - Method for manufacturing matrix - Google Patents

Abstract

A method for manufacturing a matrix having an uneven pattern includes the steps of: supplying a photocuring material onto a high-refractive-index medium 130 and forming a photocuring material film 210; and radiating a plurality of luminous fluxes 330, 370, 390 at mutually different incidence directions and an incidence angle equal to or greater than a critical angle from the high-refractive-index medium 130 to a predetermined region of an interface 230 of the photocuring material film 210 with the high-refractive-index medium 130, and, through use of a multi-beam interference evanescent wave thereby generated, curing the photocuring material film 210 in the vicinity of the predetermined region. Provided is a novel method for manufacturing a matrix for forming an uneven pattern in a mold used for nanoimprinting.

Description

Manufacturing method of mother mold

The present invention relates to a method for producing a matrix of a nanoimprint mold.

As a method for forming a fine uneven pattern such as a semiconductor integrated circuit, a nanoimprint method is known in addition to the lithography method. The nanoimprint method is a technology that allows a nanometer order pattern to be transferred from the mold onto the substrate by sandwiching the resin between the mold and the substrate. Depending on the materials used, the thermal nanoimprint method, the optical nanoimprint method, etc. It is being considered. Among these, the photo-nanoimprint method includes i) application of a curable resin layer, ii) pressing of a mold onto the curable resin layer, iii) photocuring of the curable resin layer, and iv) peeling of the mold from the curable resin layer. It is excellent in that nano-sized processing can be realized by such a simple process. In particular, since a photocurable resin that is cured by light irradiation is used, the time required for the pattern transfer process is short, and high throughput can be expected. Therefore, it is expected to be put to practical use not only in semiconductor devices but also in many fields such as optical members such as organic EL elements and LEDs, members having various functions such as water repellency, antireflection and antifogging, MEMS and biochips. ing.

Examples of a method for producing a master pattern for forming an uneven pattern of a mold used for nanoimprint include a photolithography method, a cutting method, an electron beam direct drawing method, a particle beam processing method, and an operation probe processing method. Further, one of the co-applicants of the present application described in Patent Document 1 a method using self-organization (microphase separation) by heating of a block copolymer, and in Patent Document 2 in a solvent atmosphere of the block copolymer. Patent Document 3 discloses a method using self-organization, and discloses a method for forming irregularities due to wrinkles on a polymer surface by heating and cooling a deposited film on the polymer film.

In addition, the other of the co-applicants of the present application discloses a method and apparatus for producing a member having a complicated three-dimensional shape using evanescent light in Patent Document 4.

WO2012 / 096368 WO2013 / 161454 WO2011 / 007878 JP 2005-238650 A

An object of the present invention is to provide a novel manufacturing method of a mother die for forming an uneven pattern of a mold used for nanoimprinting.

According to the first aspect of the present invention, a photocurable material is supplied onto the high refractive index medium to form a photocurable material film;
A predetermined region at the interface between the high refractive index medium and the photocuring material film is irradiated with a plurality of light beams from the high refractive index medium side in different incident directions and incident angles greater than a critical angle. There is provided a method for manufacturing a mother die having a concavo-convex pattern including curing the photocurable material film in the vicinity of the predetermined region by a double beam interference evanescent wave.

The manufacturing method of the mother die having the concavo-convex pattern may further include removing an uncured portion of the photocuring material film.

In the method of manufacturing a master having the uneven pattern, the plurality of light beams may be three light beams.

In the manufacturing method of the master having the uneven pattern, the time average of the intensity distribution of the double beam interference evanescent wave may include a maximum value or a minimum value having different values in one spatial period.

In the manufacturing method of the mother die having the concavo-convex pattern, the concavo-convex pattern may include convex portions or concave portions having different heights in one cycle.

In the manufacturing method of the mother die having the concavo-convex pattern, the plurality of light fluxes may be generated using a filter having a plurality of light transmission portions arranged concentrically. The light quantity of the plurality of light beams and / or the azimuth angle at which the plurality of light beams enter the predetermined region may be controlled by the filter.

According to the second aspect of the present invention, laminating a metal layer by electroforming on the concavo-convex pattern of the mother die produced by the method of producing a mother die having the concavo-convex pattern of the first aspect;
A method for producing a mold is provided, which includes peeling a mother die having the concavo-convex pattern from the metal layer.

According to the third aspect of the present invention, there is provided a method for producing a member having a concavo-convex pattern including transferring the concavo-convex pattern of the mold obtained by the mold production method of the second aspect.

In the method for manufacturing a master having an uneven pattern according to the present invention, the photocuring material film is cured by a double beam interference evanescent wave generated by interfering with the evanescent light of a plurality of light beams, and therefore the incident angle of the incident light beam (light wave) A complicated uneven pattern can be formed by changing the direction or the like. The mother die obtained by the method for producing a mother die having an uneven pattern according to the present invention has various functions such as members used in various devices such as organic EL elements and solar cells, water repellency, antireflection, and antifogging. It is extremely effective for manufacturing members.

FIG. 1 is a flowchart showing a method for manufacturing a mother die having a concavo-convex pattern. FIG. 2 is a diagram conceptually illustrating the principle of generation of evanescent light. FIG. 3 is a diagram conceptually illustrating an embodiment of a manufacturing apparatus for a mother die having a concavo-convex pattern. FIG. 4 is a diagram conceptually showing another embodiment of a manufacturing apparatus for a mother die having a concavo-convex pattern. FIG. 5 is a conceptual diagram illustrating an example of a pressing process and a peeling process in the method for manufacturing an optical substrate. FIG. 6 is a diagram conceptually showing a cross-sectional structure of a light-emitting element including an optical substrate manufactured using a mother die. FIG. 7 is a diagram conceptually showing the irradiation directions of three light beams in the simulations of the first to third embodiments. 8A and 8B show the time average of the intensity distribution of the three-beam interference evanescent wave obtained in Example 1, and FIGS. 8C and 8D show the three-beams obtained in Example 2. FIG. The time average of the intensity distribution of the interference evanescent wave is shown. FIGS. 8E and 8F show the time average of the intensity distribution of the three-beam interference evanescent wave obtained in Example 3. FIG.

Hereinafter, a method for producing a mother die having a concavo-convex pattern according to the present invention, a method for producing a mold using a mother die having a concavo-convex pattern obtained thereby, a method for producing an optical substrate using the mold, and the optical substrate An embodiment of a light emitting device manufactured using the same will be described with reference to the drawings.

[Manufacturing method of matrix having uneven pattern]
An embodiment of a method for manufacturing a mother die having an uneven pattern will be described. As shown in FIG. 1, the manufacturing method of the mother mold having the concavo-convex pattern mainly includes a step S1 of supplying a photocurable material on a high refractive index medium to form a photocurable material film, and a high refractive index medium. And a step S2 of irradiating a predetermined region on the interface of the photocurable material film with a plurality of light beams (light waves).

<Photocuring material film formation process>
First, a photocurable material is supplied onto a high refractive index medium to form a photocurable material film (low refractive index medium) (step S1 in FIG. 1). The photocuring material is a material that is cured by light, and for example, KC1162, KC104, etc. manufactured by JSR Corporation can be used. The high refractive index medium has a refractive index greater than that of the photocuring material. As the high refractive index medium, for example, S-LAH79 manufactured by Ohara, SF6 manufactured by Schott, N-SF66, a prism made of sapphire, a solid immersion lens, or the like can be used. As a method for supplying the photocurable material onto the high refractive index medium, any method may be used. For example, any method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an ink jet method may be used. The coating method can be used.

<Light beam irradiation process>
Next, a predetermined region at the interface between the high refractive index medium and the photocuring material film is irradiated with a plurality of light beams from the high refractive index medium side at different incident directions and incident angles greater than the critical angle (step of FIG. 1). S2). In the present application, the different incident directions of a plurality of light beams means that at least one of the incident angles and azimuth angles of the plurality of light beams is different. Here, the azimuth angle is the angle around the normal of the interface in the traveling direction of the projected light beam when the traveling direction (ray vector) of the light beam is projected onto the interface between the high refractive index medium and the photocuring material film. (For example, angle φ1 in FIG. 7).

Evanescent light is generated when a light beam is irradiated on the interface between the high refractive index medium and the photocurable material film at an incident angle greater than the critical angle from the high refractive index medium side. FIG. 2 is a conceptual diagram showing the principle of generation of evanescent light. As shown in FIG. 2, when the light beam 70 is irradiated from the high refractive index medium 10 side to the interface 50 between the high refractive index medium 10 and the photocuring material film 30 at an incident angle θ that is equal to or greater than the critical angle, the light beam 70 is The light is totally reflected at the interface 50 between the film 10 and the photocurable material film 30. At this time, since there is an electric field amplitude at the interface 50, the leakage of electromagnetic energy occurs. This leaked energy is the evanescent light 90. The evanescent light 90 decreases exponentially in a direction perpendicular to the interface 50 and is localized in a region of about the wavelength of the light beam 70.

The electric field E of the evanescent light 90 at the interface 50 is described by the following formula (1) using the Maxwell equation and Snell's law. Where θ is the incident angle of the luminous flux 70, A is the amplitude of the electric field E, ω is the angular frequency, t is the time, λ is the wavelength, k is the wave number, n ₁ is the refractive index of the high refractive index medium, and n ₂ is the light. The refractive index of the curable material is represented, and the axis orthogonal to the interface 50 is the z axis, and the axis where the interface 50 and the light plane (incident surface) intersect is the x axis.

In the manufacturing method of the present embodiment, a plurality of light beams are irradiated to a predetermined region at the interface between the high refractive index medium and the photocuring material film. An Ar ion laser, a He—Cd laser, or the like can be used as a light source for a plurality of light beams. The plurality of light beams may have the same wavelength. The wavelengths of the plurality of light beams are not particularly limited as long as the light curing material can be cured.

By irradiating a predetermined region of the interface between the high refractive index medium and the photocuring material film with an incident angle greater than the critical angle, a plurality of light beams of evanescent light are generated in the predetermined region. Interference between these evanescent lights generates interference waves (double-beam (multi-beam) interference evanescent waves). As shown in the examples described later, by controlling the conditions of the incident angle, azimuth angle, amplitude, relative phase, and polarization state of a plurality of light beams to be irradiated, the waveform of the double light beam interference evanescent wave is controlled to obtain a desired waveform. The double beam interference evanescent wave can be generated. That is, it is possible to generate a double beam interference evanescent wave having a desired intensity distribution in the vicinity of the interface between the high refractive index medium and the photocuring material film. For example, as shown in Example 3 described later, the time-averaged intensity distribution (time average of the intensity distribution) includes local maximum values (or local minimum values) having different values in one period (spatial period). A simple double beam interference evanescent wave can be generated.

A part of the photocuring material film is exposed by the double beam interference evanescent wave generated as described above. The exposed photocurable material film is cured into a shape corresponding to the intensity distribution of the double beam interference evanescent wave. Therefore, the photocurable material film can be cured into a desired shape by controlling the intensity distribution of the double beam interference evanescent wave according to the irradiation conditions of a plurality of light beams. As described above, since the evanescent light is localized in the region of the wavelength of the light beam at the interface between the high refractive index medium and the photocuring material film, only the portion existing in this region of the photocuring material film is cured.

Next, an uncured portion of the photocuring material film is dissolved and removed using a solvent that dissolves the photocuring material. Thereby, a matrix having a concavo-convex pattern in which a cured photocurable material film is formed on a high refractive index medium is obtained. The obtained mother mold can be used as a mother mold for producing a mold having an uneven pattern used for nanoimprinting. The concave / convex pattern of the matrix has a shape corresponding to the shape of the cured photocuring material film, that is, the intensity distribution of the double beam interference evanescent wave. Therefore, by controlling the intensity distribution of the double beam interference evanescent wave according to the irradiation conditions of a plurality of light beams, it is possible to form a matrix having uneven patterns of various shapes. For example, as described above, the photocuring material film is exposed with the double beam interference evanescent wave in which the time-averaged intensity distribution includes maximum values (or minimum values) having different values in one period (spatial period). By doing so, it is possible to form a matrix having a concavo-convex pattern including convex portions (or concave portions) having different heights in one cycle (spatial cycle). Such a concavo-convex pattern is referred to as a “three-dimensional pseudorandom pattern” in the present application. In conventional methods such as photolithography, it is difficult to form a three-dimensional pseudo-random pattern, but it is possible to form a three-dimensional pseudo-random pattern by using a double beam interference evanescent wave as in the manufacturing method of this embodiment. Become.

Note that the size and shape of the predetermined region where the double-beam interference evanescent wave is generated depend on the size and shape of the light emitting surface of the light source. Therefore, for example, by using a light source having a large light emission area as a light source for a plurality of light beams, a mother die having a large-area uneven pattern can be formed.

[Manufacturing apparatus for mother mold having uneven pattern (first embodiment)]
FIG. 3 shows an embodiment of a manufacturing apparatus used for the manufacturing method of the mother die having the concavo-convex pattern described above. 3 mainly includes a laser light source 110 that emits an initial light beam 300, a prism 130 that is a high refractive index medium, and an initial light beam 300 that is branched into three light beams 330, 370, and 390. And a branching optical system 150 to be incident on the CCD camera 170. A photocuring material film 210 is formed on the surface of the prism 130 opposite to the light beam incident side. The three light beams 330, 370, and 390 generated by the branching optical system 150 are incident on the prism 130 and are irradiated on the interface 230 between the prism 130 and the photocurable material film 210.

The branching optical system 150 includes polarizing beam splitters 151a and 151b, a beam splitter 153, half- wave plates 155a, 155b and 155c, a polarizing plate 157, mirrors 159a, 159b, 159c, 159d and 159e as optical components.

The laser light source 110 emits an initial light beam 300. The initial light beam 300 is linearly polarized light in this embodiment. The emitted initial light beam 300 passes through the half-wave plate 155a, and then is split (branched) into the first transmitted light 310 that is the p-polarized component and the first reflected light 350 that is the s-polarized component in the polarization beam splitter 151a. ) The vibration direction of the first transmitted light 310 is the vertical direction of the paper surface of FIG. 3, and the vibration direction of the first reflected light 350 is a direction perpendicular to the paper surface of FIG.

The first transmitted light 310 passes through the half-wave plate 155b and the polarizing plate 157, and its vibration direction (polarization direction) and intensity are adjusted. Next, the first transmitted light 310 is reflected by the mirror 159a and then enters the polarization beam splitter 151b. In the polarization beam splitter 151b, the first transmitted light 310 is split into second transmitted light (first light flux) 330 that is a p-polarized component and second reflected light (not shown) that is an s-polarized component. The second transmitted light 330 passes through the half-wave plate 155c and its vibration direction is changed to a direction perpendicular to the paper surface of FIG. Next, the second transmitted light 330 enters the prism 130 through a surface different from the surface on which the photocurable material film 210 of the prism 130 is formed, and is irradiated to the interface 230 between the prism 130 and the photocurable material film 210.

On the other hand, the first reflected light 350 generated in the polarization beam splitter 151a is reflected by the mirror 159b and then enters the beam splitter 153. In the beam splitter 153, the first reflected light 350 is divided into a third transmitted light 370 (second light beam) and a third reflected light (third light beam) 390. The third transmitted light 370 is reflected by the mirror 159c and the mirror 159e, and then enters the prism 130 through a surface different from the surface on which the photocuring material film 210 of the prism 130 is formed. The interface 230 of the film 210 is irradiated. The vibration direction of the third transmitted light 370 is a direction perpendicular to the paper surface of FIG. The third reflected light 390 is reflected by the mirror 159d and then enters the prism 130 through a surface different from the surface on which the photocuring material film 210 of the prism 130 is formed. The interface 230 is irradiated. The vibration direction of the third reflected light 390 is a direction perpendicular to the paper surface of FIG.

The incident angle of the first light beam 330, the second light beam 370, and the third light beam 390 to the interface 230 can be adjusted from the position and orientation of each optical component of the branching optical system 150. In the manufacturing apparatus 100, the first light beam 330, the second light beam 370, and the third light beam 390 are all applied to a predetermined region of the interface 230 at an incident angle that is equal to or greater than the critical angle. Therefore, the first light beam 330, the second light beam 370, and the third light beam 390 are totally reflected at a predetermined region of the interface 230.

At this time, in a predetermined region of the interface 230, the electromagnetic energy oozes out to the photocurable material film 210 side, that is, evanescent light is generated. The evanescent light generated from the first light beam 330, the second light beam 370, and the third light beam 390 interferes to generate an interference wave (three-beam interference evanescent wave). Since the three-beam interference evanescent wave is localized in a region of the wavelength of the light beam near the interface 230, a portion existing in this region of the photo-curing material film 210 is exposed to form an intensity distribution of the three-beam interference evanescent wave. Cured to the corresponding shape.

The process of exposure and curing of the photocurable material film 210 by the three-beam interference evanescent wave can be observed by the CCD camera 170 and the imaging lens 171.

In the manufacturing apparatus 100 of FIG. 3, the photocuring material film 210 is exposed and cured by irradiating the interface 230 with three light beams. However, by appropriately changing the branching optical system 150, two light beams or four or more light beams are generated. It is also possible to expose and cure the photo-curing material film 210.

The manufacturing apparatus 100 may further include a control unit (not shown) that controls the laser light source 110, the optical components of the branching optical system 150, the CCD camera 170, and the like.

[Manufacturing device for mother mold having uneven pattern (second embodiment)]
FIG. 4 shows another embodiment of a manufacturing apparatus used in a method for manufacturing a mother die having an uneven pattern. 4 mainly includes a laser light source 510 that emits an initial light beam 700, a liquid light guide 530, a relay optical system 550, a filter 560, and a container 590 for filling a photocuring material, A high numerical aperture objective lens 586 and a CCD camera 570 are provided.

The laser light source 510 emits an initial light beam 700. The initial light beam 700 may be linearly polarized light.

The liquid light guide 530 includes a resin tube and a light guide liquid filled therein. The refractive index of the light guide liquid is higher than the refractive index of the resin tube. Thus, when light is incident from one end in the liquid light guide 530, the light propagates while repeating total reflection in the liquid light guide 530 and is emitted from the other end.

The relay optical system 550 includes a plurality of lenses 551a, 551b, and 551c, and a beam splitter 553. The relay optical system 550 is not limited to the configuration illustrated in FIG. 4, and any number and any type of relay optical system 550 may be used as long as the configuration can guide the light 710 from the liquid light guide 530 to the high numerical aperture objective lens 586. You may comprise with an optical element.

The filter 560 is provided in the optical path between the liquid light guide 530 and the high numerical aperture objective lens 586. The filter 550 has a plurality of light transmission parts arranged concentrically, and generates a number of light beams according to the number of the plurality of light transmission parts. The filter 560 may be, for example, a hole in a metal plate such as aluminum or stainless steel provided with a light transmission part. Alternatively, an optical substrate such as quartz or BK7 glass may be vapor-deposited with chromium or the like to provide a light transmission part, and in this case, by adjusting the transmittance of the light transmission part, The amount of light can be adjusted.

The container 590 includes a side wall 592 and a bottom surface 594. A bottom surface 594 of the container 590 serves as a base material that supports the photocurable material film 210. The bottom surface 594 is made of a high refractive index medium.

The high numerical aperture objective lens 586 is disposed outside the bottom surface 594 of the container 590 and is in close contact with the bottom surface 594 of the container 590 via the optical oil 584. The refractive indices of the high numerical aperture objective lens 586, the bottom surface 594 of the container 590 and the optical oil 584 may be equal. In this configuration, the high numerical aperture objective lens 586, the optical oil 584, and the bottom surface 594 of the container 590 are equivalent to configuring one solid immersion lens (solid immersion lens) 580. Here, the term “solid immersion lens” is used to refer to a portion that is in contact with the photocurable material film 210 that is an object of exposure, although the optical oil (liquid) 584 is in contact with the high numerical aperture objective lens 586. This is because the bottom surface 594 of the container 590 is solid. Instead of the optical oil 584, another high refractive index fluid may be used. Instead of the high numerical aperture objective lens 586 and the optical oil 584 of the solid immersion lens 580, a solid immersion lens (super hemispherical lens) itself may be used.

In the manufacturing apparatus 500, the initial light beam 700 generated from the laser light source 510 propagates in the liquid light guide 530 through the entrance 530 a of the liquid light guide 530. The light 710 emitted from the emission port 530b of the liquid ride guide 530 passes through the plurality of lenses 551a of the relay optical system 550. Next, when the light 710 passes through the filter 560, a plurality of light beams 730 corresponding to the number and position of the light transmitting portions of the filter are generated. The plurality of light beams 730 pass through the lenses 551 b and 551 c, and then partially reflected by the beam splitter 553 toward the solid immersion lens 580.

The plurality of light beams 730 incident on the solid immersion lens 580 are applied to the interface between the solid immersion lens 580 and the photocuring material film 610 (that is, the interface between the bottom surface 594 of the container 590 and the photocuring material film 610). Each of the plurality of light beams 730 is applied to a predetermined region of the interface 630 at an incident angle greater than the critical angle. Therefore, the plurality of light beams 730 are totally reflected at a predetermined region of the interface 630.

At this time, evanescent light is generated on the photocurable material film 610 side in a predetermined region of the interface 630. The evanescent light generated from the plurality of light beams 730 interferes to generate an interference wave (double light beam interference evanescent wave). Since the double beam interference evanescent wave is localized in the region of the wavelength of the light beam in the vicinity of the interface 630, a portion existing in this region of the photo-curing material film 610 is exposed to the intensity distribution of the double beam interference evanescent wave. Cured to the corresponding shape.

The exposure and curing process of the photocuring material film 610 by the double beam interference evanescent wave can be observed by the CCD camera 570, the imaging lens 571, and the mirror 573.

The manufacturing apparatus 500 may further include a control unit (not shown) that controls the laser light source 510, each optical component of the relay optical system 550, the CCD camera 570, and the like.

Since the manufacturing apparatus 500 uses the filter 560 to generate a plurality of light beams, the configuration of the optical system is simple. Further, the number of light beams can be easily increased or decreased by changing the number of light transmitting portions of the filter 560. Further, the azimuth angle at which the plurality of light beams 730 are incident on a predetermined region of the interface 630 can be controlled by the position of the light transmission portion of the filter 560.

[Mold manufacturing method]
A mold for transferring the concavo-convex pattern can be manufactured from the mother die having the concavo-convex pattern manufactured by the above manufacturing method. As will be described later, another member such as an optical substrate can be manufactured by transferring the uneven pattern of the mold. The mold manufactured from the matrix having such a concavo-convex pattern includes a metal mold and a film-like resin mold. The resin constituting the resin mold includes rubber such as natural rubber or synthetic rubber. A method for manufacturing such a mold will be described below.

First, a seed layer serving as a conductive layer for electroforming is formed on a matrix having an uneven pattern by electroless plating, sputtering, vapor deposition, or the like. The seed layer is preferably 10 nm or more in order to make the current density uniform in the subsequent electroforming process and to make the thickness of the metal layer deposited by the subsequent electroforming process constant. Examples of seed layer materials include nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold / cobalt alloy, gold / nickel alloy, boron / nickel alloy, solder, copper / nickel / chromium An alloy, a tin-nickel alloy, a nickel-palladium alloy, a nickel-cobalt-phosphorus alloy, or an alloy thereof can be used.

Next, a metal layer is deposited on the seed layer by electroforming (electroplating). The thickness of the metal layer can be, for example, 10 to 30000 μm in total including the thickness of the seed layer. Any of the above metal species that can be used as a seed layer can be used as a material for the metal layer deposited by electroforming. The formed metal layer desirably has an appropriate hardness and thickness from the viewpoint of ease of processing such as pressing, peeling and cleaning of the resin layer for forming a subsequent mold.

The metal layer including the seed layer obtained as described above is peeled off from the matrix having the concavo-convex pattern to obtain a metal substrate. The peeling method may be physically peeled off, and the material for forming the concave / convex pattern of the matrix is removed by dissolving it using an organic solvent that dissolves them, for example, toluene, tetrahydrofuran (THF), chloroform or the like. Also good. When the metal substrate is peeled from the mother die, the remaining material components can be removed by washing. As a cleaning method, wet cleaning using a surfactant or the like, or dry cleaning using ultraviolet rays or plasma can be used. Further, for example, remaining material components may be adhered and removed using an adhesive or an adhesive. The metal substrate (metal mold) having the pattern transferred from the mother die thus obtained can be used as a mold for transferring the concavo-convex pattern.

Furthermore, a film-like resin mold can be produced by transferring the concavo-convex structure (pattern) of the metal substrate to a film-like support substrate using the obtained metal substrate. For example, after the curable resin is applied to the support substrate, the resin layer is cured while pressing the uneven structure of the metal substrate against the resin layer. As a supporting substrate, for example, a substrate made of an inorganic material such as glass or silicon, silicone resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl methacrylate (PMMA) ), Polystyrene (PS), polyimide (PI), polyarylate and other resin substrates, and substrates made of metal materials such as nickel, copper, and aluminum. The thickness of the support substrate can be in the range of 1 to 500 μm.

As the curable resin, a resin such as photo-curing and thermosetting, moisture-curing type, chemical-curing type (two-component mixing) can be used. Specifically, for example, epoxy type, acrylic type, methacrylic type, vinyl ether type, oxetane type, urethane type, melamine type, urea type, polyester type, polyolefin type, phenol type, cross-linkable liquid crystal type, fluorine type, silicone type And various resins such as polyamide-based monomers, oligomers, and polymers. The thickness of the curable resin is preferably in the range of 0.5 to 500 μm. If the thickness is less than the lower limit, the height of the irregularities formed on the surface of the cured resin layer tends to be insufficient, and if the thickness exceeds the upper limit, the influence of the volume change of the resin that occurs during curing increases and the irregular shape is well formed. It may not be possible.

Examples of the method for applying the curable resin include spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, curtain coating, ink jet, and sputtering. Various coating methods such as a method can be employed. Furthermore, the conditions for curing the curable resin vary depending on the type of resin used. For example, the curing temperature is in the range of room temperature to 250 ° C., and the curing time is in the range of 0.5 minutes to 3 hours. Preferably there is. Further, a method of curing by irradiating energy rays such as ultraviolet rays or electron beams may be used. In that case, the irradiation amount is preferably in the range of 20 mJ / cm ² to 10 J / cm ² .

Next, the metal substrate is removed from the cured resin layer after curing. The method for removing the metal substrate is not limited to the mechanical peeling method, and a known method can be adopted. A film-like resin mold having a cured resin layer in which unevenness is formed on a support substrate that can be obtained in this way can be used as a mold for transferring an uneven pattern.

In addition, by applying a rubber-based resin material on the concavo-convex structure (pattern) of the metal substrate obtained by the above-described method, curing the applied resin material, and peeling from the metal substrate, the concavo-convex pattern of the metal substrate can be obtained. A transferred rubber mold can be produced. The obtained rubber mold can be used as a mold for transferring an uneven pattern. Natural rubber and synthetic rubber can be used as the rubber-based resin material, and silicone rubber or a mixture or copolymer of silicone rubber and other materials is particularly preferable. Examples of the silicone rubber include polyorganosiloxane, cross-linked polyorganosiloxane, polyorganosiloxane / polycarbonate copolymer, polyorganosiloxane / polyphenylene copolymer, polyorganosiloxane / polystyrene copolymer, polytrimethylsilylpropyne, poly 4-methylpentene or the like is used. Silicone rubber is cheaper than other resin materials, has excellent heat resistance, high thermal conductivity, elasticity, and is not easily deformed even under high temperature conditions. Is suitable. Furthermore, since the silicone rubber-based material has high gas and water vapor permeability, the solvent and water vapor of the transfer material can be easily transmitted. Therefore, when a rubber mold is used for the purpose of transferring a concavo-convex pattern to a film of a resin material or an inorganic material precursor solution, a silicone rubber-based material is preferable. The surface free energy of the rubber material is preferably 25 mN / m or less. Thereby, the releasability when transferring the concave / convex pattern of the rubber mold to the coating film on the substrate becomes good, and transfer defects can be prevented. The rubber mold can be, for example, 50 to 1000 mm long, 50 to 3000 mm wide, and 1 to 50 mm thick. Moreover, you may perform a mold release process on the uneven | corrugated pattern surface of a rubber mold as needed.

[Optical substrate manufacturing method]
The member which has an uneven | corrugated pattern can be manufactured by the nanoimprint method using the mold for uneven | corrugated pattern transfer manufactured with the above-mentioned manufacturing method. An optical substrate is taken as an example of such a member, and the manufacturing method thereof will be described below. The optical substrate manufacturing method mainly includes a solution preparation step for preparing a precursor solution of an inorganic material, a coating step for applying the prepared precursor solution to the substrate, a mold having a concavo-convex pattern on a coating film (precursor) By transferring the concavo-convex pattern to the coating film by curing the coating film while being pressed against the film), a pressing process for pressing the mold for transferring the concavo-convex pattern, a pre-baking process for pre-baking the coating film pressed against the mold, It has the peeling process which peels a mold from a coating film, and the hardening process which carries out the main curing of the coating film. An optical substrate manufactured by such a manufacturing method includes a concavo-convex structure layer onto which a concavo-convex pattern of a mold is transferred.

<Solution adjustment process>
When forming a concavo-convex structure layer made of an inorganic material, a precursor solution of the inorganic material is prepared. Examples of inorganic materials include Si-based materials such as silica, SiN, and SiON, Ti-based materials such as TiO ₂ , ITO (indium tin oxide) -based materials, ZnO, ZnS, ZrO ₂ , and Al ₂ O. ₃ , inorganic materials such as BaTiO ₃ and SrTiO ₂ .

Further, polysilazane may be used as a precursor of the inorganic material. Polysilazane is oxidized and ceramicized (silica modification) by heating or irradiation with energy rays such as excimer to form silica, SiN or SiON. “Polysilazane” is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N _{4 made of} Si—N, Si—H, N—H, etc., and ceramics such as both intermediate solid solutions SiO _X N _Y. It is a precursor inorganic polymer. A compound that is converted to ceramics at a relatively low temperature and is modified to silica or the like as represented by the following general formula (1) described in JP-A-8-112879 is more preferable.

General formula (1):
—Si (R1) (R2) —N (R3) —
In the formula, R1, R2, and R3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

Among the compounds represented by the general formula (1), perhydropolysilazane (also referred to as PHPS) in which all of R 1, R 2 and R 3 are hydrogen atoms, and the hydrogen part bonded to Si is partially an alkyl group or the like. Substituted organopolysilazanes are particularly preferred.

As another example of polysilazane to be ceramicized at low temperature, silicon alkoxide-added polysilazane obtained by reacting polysilazane with silicon alkoxide (for example, JP-A No. 5-23827), glycidol-added polysilazane obtained by reacting glycidol ( For example, JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (for example, JP-A-6-240208), a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate ( For example, JP-A-6-299118), an acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (for example, JP-A-6-306329), and metal fine particles are added. Metal fine particles Pressurized polysilazane (e.g., JP-A-7-196986) and the like can also be used.

As the solvent of the polysilazane solution, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. In order to promote the modification to a silicon oxide compound, an amine or metal catalyst may be added.

When polysilazane is used as a precursor of an inorganic material, curing of the coating film may be promoted by heating in the curing step described later, or the precursor solution is cured by irradiation of energy rays such as excimer to form an inorganic material. May be.

<Application process>
The precursor solution of the inorganic material prepared as described above is applied on the substrate. The substrate is not particularly limited, and a known transparent substrate can be appropriately used. For example, a substrate made of a transparent inorganic material such as glass; polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.), acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, styrene resin ( For example, an ABS resin or the like), a cellulose resin (such as triacetyl cellulose), a polyimide resin (such as a polyimide resin or a polyimide amide resin), or a substrate made of a resin such as a cycloolefin polymer can be used.

As a coating method of the precursor solution, any coating method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an ink jet method can be used. The bar coating method, the die coating method and the spin coating method are preferable because the precursor solution can be uniformly applied and the application can be completed quickly before the precursor film is cured.

After applying the precursor solution, the substrate may be held in the air or under reduced pressure in order to evaporate the solvent in the coating film (precursor film). If this holding time is short, the viscosity of the coating film becomes too low to transfer the uneven pattern to the coating film, and if the holding time is too long, the polymerization reaction of the precursor proceeds and the viscosity of the coating film becomes too high. The uneven pattern cannot be transferred to the film. Further, after the precursor solution is applied, the coating film is cured as the solvent evaporates, and the physical properties such as the viscosity of the coating film change in a short time. In view of the stability of the uneven pattern formation, it is desirable that the drying time range in which pattern transfer can be satisfactorily wide is desirable. This includes the drying temperature (holding temperature), drying pressure, precursor material type, precursor material type. It can be adjusted by the mixing ratio, the amount of solvent used at the time of preparing the precursor solution (precursor concentration), and the like. In addition, since the solvent in the coating film (precursor film) evaporates just by holding the substrate as it is, it is not always necessary to perform an aggressive drying operation such as heating or blowing, and the substrate on which the coating film is formed is left as it is. It may be left for a certain period of time or may be transported for a predetermined time in order to perform a subsequent process.

<Transfer process>
Subsequently, a concavo-convex pattern is formed on the coating film using a mold for concavo-convex pattern transfer. As the mold, the above-described film-shaped mold or metal mold can be used, but it is desirable to use a flexible or flexible film-shaped mold. At this time, the mold may be pressed against the precursor film using a pressing roll. In the roll process using a pressure roll, the time for contact between the mold and the coating film is short compared to the press type, so that pattern breakage due to differences in the thermal expansion coefficients of the mold, the substrate, and the stage on which the substrate is installed is prevented. Can prevent gas bubbles from being generated in the pattern due to bumping of the solvent in the precursor film, and gas traces can remain, and because of line contact with the substrate (coating film), transfer pressure In addition, the peeling force can be reduced, and it is easy to cope with an increase in area, and there is an advantage that bubbles are not caught during pressing. Further, the substrate may be heated while pressing the mold. As an example of pressing a mold against a coating film (precursor film) using a pressing roll, as shown in FIG. 5, a film-like mold 140 is fed between the pressing roll 122 and the substrate 40 conveyed immediately below the pressing roll 122. The uneven pattern of the film mold 140 can be transferred to the coating film 64 on the substrate 40. That is, when the film mold 140 is pressed against the coating film 64 by the pressing roll 122, the film mold 140 and the substrate 40 are transported synchronously, and the surface of the coating film 64 on the substrate 40 is covered with the film mold 140. To do. At this time, the film mold 140 and the substrate 40 are brought into close contact with each other by rotating while pressing the pressing roll 122 against the back surface of the film mold 140 (the surface opposite to the surface on which the concavo-convex pattern is formed). In order to feed the long film-shaped mold 140 toward the pressing roll 122, it is convenient to use the film-shaped mold 140 as it is from the film roll around which the long film-shaped mold 140 is wound.

After pressing the mold against the precursor film, the precursor film may be calcined. By pre-baking, the precursor is converted into an inorganic material, the coating film is cured, the concavo-convex pattern is solidified, and is less likely to collapse during peeling. When pre-baking is performed, it is preferably heated in the atmosphere at a temperature of room temperature to 300 ° C. Note that the preliminary firing is not necessarily performed. In addition, when a material that generates acid or alkali by adding light such as ultraviolet rays to the precursor solution is added, instead of pre-baking the precursor film, for example, ultraviolet rays such as excimer UV light are used. The coating film may be cured by irradiation with energy rays.

After pressing the mold or pre-baking the precursor film, the mold is peeled off from the coating film (precursor film or inorganic material film formed by converting the precursor film). A known peeling method can be employed as a mold peeling method.

<Curing process>
After the mold is peeled from the coating film (uneven structure layer) on which the unevenness is formed, the uneven structure layer may be fully cured. In this manufacturing method, the concavo-convex structure layer can be fully cured by the main baking. When a precursor that is converted to silica by the sol-gel method is used, a hydroxyl group and the like contained in silica (amorphous silica) constituting the concavo-convex structure layer is detached by the main calcination, and the concavo-convex structure layer becomes stronger. The main baking is preferably performed at a temperature of 200 to 1200 ° C. for about 5 minutes to 6 hours. At this time, when the concavo-convex structure layer is made of silica, it becomes amorphous or crystalline, or a mixed state of amorphous and crystalline depending on the firing temperature and firing time. Note that the curing step is not necessarily performed. In addition, when a material that generates an acid or an alkali by irradiating the precursor solution with light such as ultraviolet rays, energy represented by ultraviolet rays such as excimer UV light is used instead of firing the concavo-convex structure layer. By irradiating the line, the concavo-convex structure layer can be fully cured.

As described above, the optical substrate 400 (see FIG. 6) in which the uneven structure layer 60 is formed on the substrate 40 can be manufactured.

Incidentally, as a precursor of the inorganic material to be applied in the coating step, in place of the precursor of the _{silica, TiO 2, ZnO, ZnS,} ZrO 2, Al 2 O 3, BaTiO 3, SrTiO 2, precursors such as ITO The body may be used.

In addition to the sol-gel method, the concavo-convex structure layer may be formed by using a dispersion of fine particles of an inorganic material, a liquid phase deposition (LPD), or the like.

In the manufacturing method of the above embodiment, the concavo-convex structure layer made of an inorganic material is formed. However, the concavo-convex structure layer may be made of a curable resin in addition to the above-described inorganic material. As the curable resin, for example, a resin such as photo-curing and thermosetting, moisture-curing type, and chemical-curing type (two-component mixing) can be used. Specifically, epoxy, acrylic, methacrylic, vinyl ether, oxetane, urethane, melamine, urea, polyester, polyolefin, phenol, cross-linkable liquid crystal, fluorine, silicone, polyamide And various resins such as monomers, oligomers and polymers.

When forming the concavo-convex structure layer using a curable resin, for example, after applying the curable resin to the substrate, by curing the coating film while pressing the mold for transferring the concavo-convex pattern to the applied curable resin layer, The concave / convex pattern of the mold can be transferred to the curable resin layer. The curable resin may be applied after being diluted with an organic solvent. As the organic solvent used in this case, a solvent capable of dissolving the uncured resin can be selected and used. For example, it can be selected from known solvents such as alcohol solvents such as methanol, ethanol and isopropyl alcohol (IPA), and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone (MIBK). Examples of the method for applying the curable resin include spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, curtain coating, ink jet, and sputtering. Various coating methods such as a method can be employed. As the mold for transferring the concavo-convex pattern, for example, a desired mold such as a film mold or a metal mold can be used. Furthermore, the conditions for curing the curable resin vary depending on the type of resin used. For example, the curing temperature is in the range of room temperature to 250 ° C., and the curing time is in the range of 0.5 minutes to 3 hours. Preferably there is. Further, a method of curing by irradiating energy rays such as ultraviolet rays or electron beams may be used. In that case, the irradiation amount is preferably in the range of 20 mJ / cm ² to 10 J / cm ² .

Moreover, you may use a silane coupling agent as a material of an uneven structure layer. Thereby, for example, when an organic EL element is manufactured using the manufactured optical substrate, adhesion between the uneven structure layer and a layer such as an electrode formed thereon can be improved. Resistance in a cleaning process and a high-temperature treatment process in an element manufacturing process is improved. The type of the silane coupling agent used in the concavo-convex structure layer is not particularly limited. For example, RSiX ₃ (R is selected from a vinyl group, a glycidoxy group, an acrylic group, a methacryl group, an amino group, and a mercapto group. An organic functional group containing at least one selected from the above, and X is a halogen element or an alkoxyl group). Examples of methods for applying the silane coupling agent include spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, curtain coating, ink jet, and sputtering. Various coating methods such as a method can be employed. Thereafter, a cured film can be obtained by drying under appropriate conditions according to each material. For example, heat drying may be performed at 100 to 150 ° C. for 15 to 90 minutes.

The material of the concavo-convex structure layer may be an inorganic material or a curable resin material containing an ultraviolet absorbing material. The ultraviolet absorbing material has an action of suppressing deterioration of the film by absorbing ultraviolet rays and converting light energy into a harmless form such as heat. As the ultraviolet absorber, conventionally known ones can be used. For example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, or the like can be used.

In the manufacturing method described above, a coating film (precursor film) is formed on a substrate and a mold is pressed against the coating film to manufacture a concavo-convex structure layer. Instead, a precursor is formed on the concavo-convex pattern of the mold. An uneven structure layer can also be formed on a substrate by forming a body film, bonding the precursor film to the substrate, and peeling the mold. In this case, as a method of forming the precursor film on the mold, in addition to the coating method described in the above coating step, physical vapor deposition (PVD) method such as vapor deposition and sputtering, chemical vapor deposition (CVD) method, and the like A method using a known dry process can also be used. In this case, metal, metal oxide, metal nitride, metal oxynitride, metal sulfide, metal carbide, metal halide, and mixtures thereof (metal oxynitride, metal oxyhalide, metal nitride carbide, etc.), etc. An uneven structure layer made of can be formed.

The concavo-convex structure layer formed on the mold using the dry process can be bonded to the substrate by the following method, for example. First, an adhesive is applied on the substrate. The substrate and the mold are overlapped so that the adhesive layer on the substrate adheres to the uneven structure layer on the mold, and the adhesive is cured. Thereby, a board | substrate and an uneven | corrugated structure layer are joined via an adhesive agent. Next, the mold is peeled from the uneven structure layer. Thereby, an optical substrate having a concavo-convex structure layer formed on the substrate can be formed.

Furthermore, the surface of the concavo-convex structure layer (the surface of the coating layer when a coating layer is formed) may be subjected to a hydrophobic treatment. A known method may be used for the hydrophobizing treatment. For example, if the surface is silica, it can be hydrophobized with dimethyldichlorosilane, trimethylalkoxysilane, or the like, or trimethylsilyl such as hexamethyldisilazane. A method of hydrophobizing with an agent and silicone oil may be used, or a surface treatment method of metal oxide powder using supercritical carbon dioxide may be used.

In addition to the above coating layer, various functional layers may be provided on the surface of the concavo-convex structure layer. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and an ultraviolet absorption layer, a mechanical functional layer such as a hard coat layer and a stress relaxation layer, an antistatic layer, and a conductive layer. Examples thereof include an electric functional layer, an antifogging layer, an antifouling layer, and a printing layer.

In addition, although the method of manufacturing an optical substrate using a film-like mold as a mold for concavo-convex pattern transfer has been described, an optical substrate can be manufactured in the same manner as the above manufacturing method even if a hard mold such as a metal mold or a quartz mold is used. can do. When using a hard mold, it is preferable to use a flexible substrate such as a film substrate as the substrate. In addition to the optical substrate, members having various functions such as insulation, conductivity, anti-fogging, heat insulation, antifouling, dielectric, hydrophilic, and water repellent can be produced by the same method.

In the following examples, the intensity distribution of the double beam interference evanescent wave was calculated by simulation. In a state where a photo-curing material film is formed on a high-refractive index medium such as a prism, the interface between the high-refractive index medium and the photo-curing material film is the xy plane, and the photo-curing material film side is the positive direction of the z-axis and high refraction The xyz axis was determined with the rate medium side as the negative direction of the z axis. As conceptually shown in FIG. 7, when the first light beam 330, the second light beam 370, and the third light beam 390 are irradiated to the interface (that is, the xy plane) between the high refractive index medium and the photocuring material film. The time average of the intensity distribution of the three-beam interference evanescent wave in the xy plane was calculated. In Examples 1 to 3, the calculation was performed assuming that each of the light beams 330, 370, and 390 is s-polarized light (that is, the vibration in the z direction in FIG. 7 is 0).

Example 1
As shown in FIG. 7, when the first light beam 330 is irradiated onto the xy plane with an incident angle of θ ₁ and an angle (azimuth angle) around the z-axis from the positive x-axis direction of φ ₁ , the first light beam 330 is irradiated. An electric field wave (electric field vector) E ₁ of 330 is expressed by the following equation (2). T ₁ (amplitude in consideration of polarization), k ₁ (wave vector), and r (position vector) in equation (2) are expressed by the following equations (3), (4), and (5), respectively. c is the speed of light, λ is the wavelength, ω is the angular frequency (ω = 2πc / λ), ε ₁ is the initial phase, A ₁ is the electric field amplitude, k is the wave number in the vacuum (k = 2π / λ), and n ₁ is high The refractive index of the refractive index medium, n ₂ represents the refractive index of the photocuring material.

When the incident angles of the second light beam 370 and the third light beam 390 are θ ₂ and θ ₃ , and the angles around the z-axis from the positive direction of the x-axis are φ _{2 and} φ _{3 ,} respectively _, (5) and in the same manner, the electric field wave _{E 3} of the second electric field waves _{E 2} and the third light flux 370 of the light beam 390 is represented.

The first electric field wave _{E 1} of the light beam 330, the wave _{E 2} of the electric field of the second beam 370, a combined wave _{E 3} of the electric field of the third light flux 390, Wolfram Research Inc. formula processing software Mathematica (registered trademark ) To obtain the electric field E of the interference wave of the evanescent light (three-beam interference evanescent wave) generated by the first light beam 330, the second light beam 370, and the third light beam 390. it can.

Furthermore, the intensity I of the three-beam interference evanescent wave is calculated from the following formula (6), and the time average <I> _t of the intensity I can be obtained by the following formula (7). Note that τ represents a period (τ = λ / c).

In this example, (θ ₁ , θ ₂ , θ ₃ ) = (70 °, 70 °, 70 °), (φ ₁ , φ ₂ , φ ₃ ) = (30 °, 150 °, 270 °), The time average of the intensity distribution of the three-beam interference evanescent wave at the xy plane, that is, the interface (z = 0) between the high refractive index medium and the photocuring material film was obtained. Note that c = 3.0 × 10 ⁸ m / s, λ = 488 × 10 ⁻⁹ m, n ₁ = 1.78, and n ₂ = 1.5. When the refractive index of the high refractive index material is 1.78 and the refractive index of the photocuring material is 1.5, the critical angle is about 50 °, so that each of the light beams 330, 370, and 390 satisfies the total reflection condition. ing.

8A and 8B show the time average of the intensity distribution of the obtained three-beam interference evanescent wave. In FIGS. 8A and 8B and FIGS. 8C to 8F described later, the light intensity is plotted in a two-dimensional plane as height information, and FIGS. 8A and 8C. , (E) are oblique perspective views, and FIGS. 8 (b), (d), and (f) are upward perspective views. In this example, the time average of the intensity distribution of the three-beam interference evanescent wave has a distribution in which mountains having the same intensity are densely arranged.

Example 2
Example 1 except that (θ ₁ , θ ₂ , θ ₃ ) = (70 °, 70 °, 60 °), (φ ₁ , φ ₂ , φ ₃ ) = (0 °, 180 °, 330 °) Similarly, the time average of the intensity distribution of the three-beam interference evanescent wave was obtained. The time average of the intensity distribution of the obtained three-beam interference evanescent wave is shown in FIGS. In this example, the time average of the intensity distribution of the three-beam interference evanescent wave has a distribution in which the wave shape is cut obliquely on the ridge where the antinodes of standing waves are connected.

Example 3
Example 1 except that (θ ₁ , θ ₂ , θ ₃ ) = (80 °, 80 °, 60 °), (φ ₁ , φ ₂ , φ ₃ ) = (0 °, 180 °, 0 °) Similarly, the time average of the intensity distribution of the three-beam interference evanescent wave was obtained. The time average of the intensity distribution of the obtained three-beam interference evanescent wave is shown in FIGS. In the three-beam interference evanescent wave of this example, the amplitude of the standing wave was continuously changed, and the beat was generated. As shown in FIGS. 8E and 8F, the time average of the intensity distribution of the three-beam interference evanescent wave according to the present embodiment includes maximal values having different values in one spatial period.

As shown in Examples 1 to 3, a three-beam interference evanescent wave having various intensity distributions can be generated by changing the incident direction of each beam. Also, by changing the incident direction of each light beam, a three-beam interference evanescent wave having a time average of intensity distribution that includes a maximum value or a minimum value having different values in one cycle as in the third embodiment is generated. It is also possible to make it.

In Examples 1 to 3, the simulation result in the case of using three light beams has been described. However, two light beams may be irradiated to a predetermined region at the interface between the high refractive index medium and the photocuring material film. It is possible to form an intensity distribution having a shape extending in one direction. Compared to such a two-beam interference evanescent wave, the three-beam evanescent wave may have a more complicated intensity distribution as described above. Further, four or more light beams may be used, and the double light beam interference evanescent wave in that case can have an even more complicated intensity distribution. Further, by exposing the photocuring material film with such a double beam interference evanescent wave having various intensity distributions, the photocuring material film can be cured into a shape corresponding to the intensity distribution of the double beam interference evanescent wave. This cured photo-curing material film can be used as a matrix of a mold used in the nanoimprint method, and the uneven pattern of the matrix is related to the shape of the cured photo-curing material film, that is, the intensity distribution of the double beam interference evanescent wave. Have a corresponding shape. For example, by using a three-beam interference evanescent wave in which the time average of the intensity distribution includes a maximum value or a minimum value having different values in one period as in the third embodiment, the height is mutually increased in one period. A matrix having a concavo-convex pattern including different convex portions or concave portions, that is, a three-dimensional pseudo-random pattern, can be formed.

As mentioned above, although embodiment and the Example of this invention were described, the manufacturing method of the mother mold | die which has an uneven | corrugated pattern of this invention is not limited to the said embodiment, In the range of the technical idea described in the claim Can be modified as appropriate. Moreover, the manufacturing apparatus of the mother mold having the uneven pattern according to the present invention is not limited to the configuration of the above embodiment, and the arrangement of various components may be different from the arrangement shown in the drawings of the present application. For example, the configuration may be such that the incident angle, azimuth angle, amplitude, relative phase, polarization state, and the like of a plurality of light beams to be irradiated can be controlled. The matrix having the concavo-convex pattern obtained by the production method of the present invention is, for example, an organic substrate for various devices such as organic EL lighting, liquid crystal display elements, solar cells, microlens arrays, nanoprism arrays, optical waveguides, etc. Manufacture of optical elements, optical components such as lenses, LEDs, solar cells, antireflection films, semiconductor chips, patterned media, data storage, electronic paper, LSI, etc., packaging of goods, food and industrial products, pharmaceuticals, etc. It can be suitably used for applications in the bio field such as the manufacture of packaging members for preventing alteration, immunoassay chips, and cell culture sheets. Further, a light reflecting member, a light scattering member, an insulating member, an electrode pattern member, a conductive member, an antifogging member, a heat insulating member, an antifouling member, an optical waveguide member, a dielectric member, a non-reflective member, a low reflection member, a polarization functional member, It can also be used for the production of members having various functions, such as light diffractive members, hydrophilic members, and water repellent members.

DESCRIPTION OF SYMBOLS 10 High refractive index medium, 30 Photocurable material film, 40 Substrate 50 Interface, 60 Uneven structure layer, 64 Coating film, 70 Light flux 90 Evanescent light, 92 1st electrode, 94 Organic layer 98 2nd electrode, 100, 500 Uneven pattern Manufacturing apparatus for mother mold having 101 101 sealing member, 103 sealing adhesive layer, 110 laser light source 130 high refractive index medium, 140 mold, 150 branch optical system 200 light emitting element, 210 photocurable material film, 230 interface 300 initial light flux , 330 First light flux, 370 Second light flux 390 Third light flux, 400 Optical substrate

Claims (9)

1. Supplying a photocurable material on the high refractive index medium to form a photocurable material film;
   A predetermined region at the interface between the high refractive index medium and the photocuring material film is irradiated with a plurality of light beams from the high refractive index medium side in different incident directions and incident angles greater than a critical angle. A method of manufacturing a mother die having a concavo-convex pattern, comprising: curing the photocurable material film in the vicinity of the predetermined region by a double beam interference evanescent wave.
2. Furthermore, the manufacturing method of the mother die which has an uneven | corrugated pattern of Claim 1 including removing the uncured part of the said photocuring material film | membrane.
3. 3. The method for manufacturing a mother die having an uneven pattern according to claim 1, wherein the plurality of light beams are three light beams.
4. The matrix of the matrix having the concavo-convex pattern according to any one of claims 1 to 3, wherein the time average of the intensity distribution of the double beam interference evanescent wave includes a maximum value or a minimum value having different values in one spatial period. Production method.
5. The method for producing a mother die having a concavo-convex pattern according to any one of claims 1 to 4, wherein the concavo-convex pattern includes convex portions or concave portions having different heights in one cycle.
6. 6. The method for manufacturing a mother die having a concavo-convex pattern according to claim 1, wherein the plurality of light fluxes are generated using a filter having a plurality of light transmission portions arranged concentrically.
7. The method for manufacturing a mother die having a concavo-convex pattern according to claim 6, wherein the filter controls the light amount of the plurality of light beams and / or the azimuth angle at which the plurality of light beams enter the predetermined region.
8. Laminating a metal layer by electroforming on the concavo-convex pattern of the mother die produced by the method for producing a mother die having the concavo-convex pattern according to any one of claims 1 to 7,
   A method for producing a mold, comprising peeling a mother die having the concavo-convex pattern from the metal layer.
9. The manufacturing method of the member which has an uneven | corrugated pattern including transferring the uneven | corrugated pattern of the mold obtained by the manufacturing method of the mold of Claim 8.
   

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