WO2014024958A1 - 微細凸状パターン構造体の製造方法及び微細凸状パターン構造体製造システム - Google Patents
微細凸状パターン構造体の製造方法及び微細凸状パターン構造体製造システム Download PDFInfo
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- WO2014024958A1 WO2014024958A1 PCT/JP2013/071477 JP2013071477W WO2014024958A1 WO 2014024958 A1 WO2014024958 A1 WO 2014024958A1 JP 2013071477 W JP2013071477 W JP 2013071477W WO 2014024958 A1 WO2014024958 A1 WO 2014024958A1
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- convex pattern
- fine convex
- fine
- pattern structure
- pattern
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
Definitions
- the present invention relates to a method for manufacturing a fine convex pattern structure and a system for manufacturing the fine convex pattern structure, and particularly relates to a method and system for manufacturing the fine convex pattern structure using a nanoimprint technique.
- the nanoimprint technology is a pattern formation technology that uses a mold member (mold) having a fine concavo-convex pattern formed on the surface of a substrate, and transfers the fine concavo-convex pattern to a workpiece by transferring the fine concavo-convex pattern at the same magnification.
- a fine concavo-convex pattern having a fine concavo-convex pattern is obtained by curing the resin in a state where the mold is pressed against a resin having fluidity and then peeling the mold from the cured resin or the like.
- a structure is formed.
- a fine convex pattern structure (for example, a resin pattern such as a pillar shape or a line and space shape) having a fine convex pattern formed in this way is, for example, a nanopillar array structure such as a cell culture sheet, or a moth eye.
- the fine convex pattern is a resin pattern surface. It is required to be set up substantially perpendicular to the above.
- the fine convex pattern may fall down.
- the mold or the resin to be transferred is made of a flexible material, or while rotating a belt-shaped imprint mold or a mold having a fine concave pattern formed on the surface of a rotating body, it is conveyed in a predetermined direction.
- the force in the in-plane direction applied to the fine convex pattern is large.
- the collapse of the fine convex pattern becomes more serious.
- the present invention provides a nano-imprint technique for forming a fine convex pattern structure having a fine convex pattern protruding in a predetermined direction regardless of the structure (shape, etc.) of the fine convex pattern.
- An object of the present invention is to provide a method for manufacturing with high accuracy and a system for manufacturing the fine convex pattern structure.
- the fine convex pattern structure formed by the nanoimprint technology can be used as an end product as it is or as an etching mask for etching a predetermined substrate.
- the shape pattern is required to be erected in a substantially orthogonal direction of the plane portion. Therefore, it is necessary to form the fine convex pattern so as not to be inclined.
- the fine convex pattern is inclined after the transfer process using the imprint mold, if the inclined fine convex pattern can be erected in the substantially orthogonal direction of the plane portion, the fine convex pattern is The fine convex pattern structure can be manufactured by the nanoimprint technique without worrying about the inclination.
- the present inventors have intensively studied to solve the above problems, and as a result, by applying a predetermined force to the fine convex pattern, the inclined fine convex pattern is substantially orthogonal to the plane portion. As a result, the present invention has been completed.
- the present invention is a method of manufacturing a fine convex pattern structure having a flat portion and a fine convex pattern protruding from the flat portion in a predetermined direction with respect to the flat portion, the fine convex pattern Using the imprint mold having a fine concave pattern corresponding to the above, forming a fine convex pattern protruding from the plane portion under the condition that the fine convex pattern is inclined to the plane portion side with respect to the predetermined direction, Provided is a method for producing a fine convex pattern structure, wherein at least the inclined fine convex pattern is caused to generate electric charges, thereby causing the fine convex pattern to protrude in a predetermined direction with respect to the planar portion ( Invention 1).
- the fine convex pattern is formed on the condition that the fine convex pattern is inclined to the plane portion side with respect to the predetermined direction with respect to the flat portion, so that the fine convex pattern is removed when the imprint mold is removed. Since the stress acting on the pattern can be reduced, the ease of peeling of the imprint mold can be improved, and the occurrence of defects such as defects in the fine convex pattern can be suppressed.
- the fine convex pattern may be inclined toward the plane portion side with respect to a predetermined direction.
- the fine convex pattern can be projected in a predetermined direction with respect to the plane portion by using the repulsive force, according to the above invention (Invention 1), the fine projection protruding in the predetermined direction with respect to the plane portion.
- the fine convex pattern structure having a pattern can be manufactured with high accuracy using the nanoimprint technology.
- the contact state on the contact surface between each of the plurality of line-shaped fine convex patterns and the imprint mold is different. Therefore, when the imprint mold is peeled along the line direction of the fine convex pattern, the ease of peeling at the part where the peeling of each line-like fine convex pattern and the imprint mold starts may be different. . Further, when the imprint mold is peeled along the line direction of the fine convex pattern, it is difficult to incline the fine convex pattern, so that stress applied in the in-plane direction to the fine convex pattern escapes. It becomes difficult.
- a defect such as a defect may occur in the line-shaped fine convex pattern at the peeling start portion, and the length in the longitudinal direction of the line-shaped fine convex pattern may become uneven.
- the imprint mold is peeled in a direction intersecting (substantially orthogonal) to the line direction, the stress applied in the in-plane direction by healing the fine convex pattern can be easily released by inclining the fine convex pattern. Therefore, although the uniformity of the length in the longitudinal direction of the formed line-shaped fine convex pattern is improved, the line-shaped fine convex pattern is inclined along the peeling direction of the imprint mold.
- the dimensional accuracy of the fine convex pattern can be improved by forming the fine convex pattern so as to be inclined toward the plane part side from the predetermined direction.
- the fine convex pattern can be protruded in a predetermined direction with respect to the flat portion using the electric repulsive force.
- a fine convex pattern structure having a fine convex pattern protruding in a predetermined direction can be manufactured with high accuracy.
- the “planar portion” means a surface that serves as a base portion of the protruding fine convex structure portion, and may be a flat surface or a non-flat surface such as a concave surface, a convex surface, or a curved surface. May be.
- invention 1 by making the said fine convex pattern structure exist in the atmosphere which can charge the said fine convex pattern structure, an electric charge is produced in the said inclined fine convex pattern.
- invention 2 At least the fine convex pattern may be dielectrically polarized or electrostatically induced to generate an electric charge in the inclined fine convex pattern (Invention 3).
- the fine convex pattern structure may be made of an insulating material (Invention 4), and the fine convex pattern structure contains a conductive material. It is made of a material, and at least the fine convex pattern may be in an electrically floating state, and an electric charge may be generated in the inclined fine convex pattern (Invention 5).
- the present invention is a method of manufacturing a fine convex pattern structure having a flat portion and a fine convex pattern protruding from the flat portion in a predetermined direction with respect to the flat portion, and at least the fine convex shape
- the pattern is made of a resin material that can be shrunk by applying energy from the outside, and an imprint mold having a fine concave pattern corresponding to the fine convex pattern is used, and the fine convex pattern is in the predetermined direction.
- the fine convex pattern is characterized in that the fine convex pattern protrudes in a predetermined direction with respect to the planar portion by applying energy from To provide a method of manufacturing a structure (invention 6).
- the fine convex pattern is formed on the condition that the fine convex pattern is inclined to the plane portion side with respect to the predetermined direction with respect to the flat portion, so that the fine convex pattern is removed when the imprint mold is removed. Since the stress acting on the pattern can be reduced, the ease of peeling of the imprint mold can be improved, and the occurrence of defects such as defects in the fine convex pattern can be suppressed.
- the fine convex pattern may be inclined to the plane portion side with respect to a predetermined direction, but by applying energy from the outside to the inclined fine convex pattern.
- the plane portion according to the invention (invention 6)
- a fine convex pattern structure having a fine convex pattern protruding in a predetermined direction can be accurately manufactured using a nanoimprint technique.
- the contact state on the contact surface between each of the plurality of line-shaped fine convex patterns and the imprint mold is different. Therefore, when the imprint mold is peeled along the line direction of the fine convex pattern, the ease of peeling at the part where the peeling of each line-like fine convex pattern and the imprint mold starts may be different. . Further, when the imprint mold is peeled along the line direction of the fine convex pattern, it is difficult to incline the fine convex pattern, so that stress applied in the in-plane direction to the fine convex pattern escapes. It becomes difficult.
- a defect such as a defect may occur in the line-shaped fine convex pattern at the peeling start portion, and the length in the longitudinal direction of the line-shaped fine convex pattern may become uneven.
- the imprint mold is peeled in a direction intersecting (substantially orthogonal) to the line direction, stress in the in-plane direction with respect to the fine convex pattern can be easily released by inclining the fine convex pattern. Therefore, although the uniformity of the length in the longitudinal direction of the formed line-shaped fine convex pattern is improved, the line-shaped fine convex pattern is inclined along the peeling direction of the imprint mold.
- the dimensional accuracy of the fine convex pattern can be improved by forming the fine convex pattern so as to be inclined toward the plane part side from the predetermined direction.
- the fine convex pattern is applied to the plane portion by using the contraction force of the resin material constituting the fine convex pattern. Since it can be made to protrude in the direction, a fine convex pattern structure having a fine convex pattern protruding in a predetermined direction with respect to the plane portion can be manufactured with high accuracy.
- the relatively extended side surface of the said fine convex pattern is irradiated with an active energy ray with respect to the relatively extended side surface of the said inclined fine convex pattern.
- the chemical structure of the resin material on the relatively extending side surface of the fine convex pattern is changed to change the fine convex pattern.
- the relatively extending side surfaces of the material may be contracted (Invention 8).
- the cross-linking reaction of the resin material may be advanced to contract the relatively extending side surfaces of the fine convex pattern (Invention 9), or the molecules of the resin material
- the relatively extending side surface of the fine convex pattern may be contracted by cutting the chain (Invention 10).
- the relatively extending side surface of the fine convex pattern may be thermally contracted (Invention 11).
- the fine convex pattern structure is irradiated with an electron beam, an ion beam, an ultraviolet ray, an infrared ray, a visible ray, a laser beam, an X-ray or a gamma ray to thereby form the fine convex pattern. It is preferable to shrink the relatively extending side surface (Invention 12).
- the present invention is a system for manufacturing a fine convex pattern structure having a flat portion and a fine convex pattern protruding from the flat portion in a predetermined direction with respect to the flat portion, the fine convex pattern Inclination that forms a fine convex pattern that protrudes from the planar portion under the condition that the fine convex pattern is inclined to the planar portion side with respect to the predetermined direction, using an imprint mold having a fine concave pattern corresponding to A fine projection comprising: a pattern forming portion; and a charge imparting portion that causes the fine convex pattern to protrude in a predetermined direction with respect to the planar portion by generating a charge on at least the inclined fine convex pattern.
- a pattern-structure manufacturing system is provided (Invention 13).
- the present invention includes a flat portion and a fine convex pattern protruding from the flat portion in a predetermined direction with respect to the flat portion, and at least the fine convex pattern is contracted by external energy application.
- An inclined pattern forming portion that forms a fine convex pattern that protrudes from the planar portion under a condition that it is inclined to the flat portion side relative to a direction, and a side surface of the inclined fine convex pattern that is formed by the inclined pattern forming portion
- the fine convex pattern is Providing a fine convex pattern structure manufacturing system characterized by comprising an energy applying portion to project in a predetermined direction with respect to surface portion (invention 14).
- a method for accurately producing a fine convex pattern structure having a fine convex pattern protruding in a predetermined direction and the fine pattern A system for manufacturing a convex pattern structure can be provided.
- FIG. 1 is a flowchart showing a method for producing a fine convex pattern structure according to the first embodiment of the present invention by a cut end face.
- FIG. 2 is a flowchart showing another example (No. 1) of the step of transferring the fine concave pattern of the imprint mold to the imprinting resin film in the first and second embodiments of the present invention by a cut end face.
- FIG. 3 is a flowchart showing another example (part 2) of the step of transferring the fine concave pattern of the imprint mold to the imprint resin film in the first and second embodiments of the present invention by a cut end surface. .
- FIG. 1 is a flowchart showing a method for producing a fine convex pattern structure according to the first embodiment of the present invention by a cut end face.
- FIG. 2 is a flowchart showing another example (No. 1) of the step of transferring the fine concave pattern of the imprint mold to the imprinting resin film in the first and second embodiments of the present invention by
- FIG. 4 is a cut end view showing another example of the step of forming the fine convex pattern that is inclined using the imprint mold in the first embodiment of the present invention.
- FIG. 5 is a perspective view which shows the other example (the 1) which has the fine convex-shaped pattern which inclines in the 1st Embodiment of this invention which has the fine convex-shaped pattern which inclines.
- FIG. 6 is a block diagram showing a schematic configuration of the fine convex pattern structure manufacturing system in the first embodiment of the present invention.
- FIG. 7 is a flowchart showing a method of manufacturing a fine convex pattern structure according to the second embodiment of the present invention by a cut end face.
- FIG. 8 is a cut end view showing a preferred example of the process of irradiating active energy rays in the second embodiment of the present invention.
- FIG. 9 is a cut end view showing another example of a fine convex pattern structure having an inclined fine convex pattern manufactured in the second embodiment of the present invention.
- FIG. 10 is a block diagram showing a schematic configuration of a fine convex pattern structure manufacturing system in the second embodiment of the present invention.
- FIG. 11 is a perspective view which shows the other example (the 2) which has the fine convex pattern which inclines in the 1st Embodiment of this invention which has the fine convex pattern which inclines.
- FIG. 12 is a cut end view showing a specific example of a fine convex pattern structure having an inclined fine convex pattern manufactured in the first and second embodiments of the present invention.
- FIG. 13 is an SEM photograph showing a fine convex pattern after peeling off the imprint mold in Example 1.
- 14 is an SEM photograph showing the substrate after the dry etching process in Example 1.
- FIG. 15 is a SEM photograph showing a fine convex pattern before electron beam irradiation in Example 2.
- FIG. 16 is an SEM photograph showing a fine convex pattern after electron beam irradiation in Example 2.
- FIG. 17 is a SEM photograph showing a fine convex pattern before electron beam irradiation in Example 3.
- FIG. 18 is an SEM photograph showing a fine convex pattern after electron beam irradiation in Example 3.
- FIG. 19 is an SEM photograph showing a fine convex pattern after electron beam irradiation in Example 4.
- FIG. 1 is a flowchart showing a method for producing a fine convex pattern structure according to the first embodiment of the present invention by a cut end face.
- a predetermined substrate for example, a silicon substrate, a metal substrate, a glass substrate, a quartz substrate, or the like
- the fine concave pattern 32 corresponding to the fine convex pattern 12 in the fine convex pattern structure 10 to be manufactured is formed on the imprinting resin film 13 on the substrate 14.
- the imprint mold 30 having a pressure is pressed, and the imprint resin film 13 is cured in this state (see FIG. 1B).
- the resin material constituting the imprint resin film 13 is a resin material generally used for forming a fine uneven pattern by a nanoimprint method (insulating resin material such as a thermoplastic resin, a thermosetting resin, a photo-curable resin). Conductive resin materials, etc.).
- resin materials examples include olefin-based, styrene-based, ethylene-based, ester-based, thiophoene-based, aniline-based, nylon-based, polyether-based, urethane-based, epoxy-based, phenol-based, acrylic-based, polyimide-based, Resin materials such as polyacetylene; silicone resins such as polydimethylsiloxane and polysiloxane; polypropylene, polycarbonate, polyamide, polyacetal, polyether ether ketone (PEEK), acrylonitrile butadiene styrene resin (ABS), polyphenylene sulfide resin (PPS), poly Examples include phenyloline oxide, polyvinylidene fluoride, polysulfone, polylactic acid, polyethylene terephthalate (PET), and vinyl chloride.
- PES polyphenylene sulfide resin
- the conductive resin material is obtained by doping a resin material such as a thermosetting resin or a thermoplastic resin with an electron acceptor or an electron donor such as a conductive metal, a carbon compound, or iodine.
- a resin material such as a thermosetting resin or a thermoplastic resin
- an electron acceptor or an electron donor such as a conductive metal, a carbon compound, or iodine.
- the resin material that can be doped with the electron acceptor or the electron donor include polyolefin, polyamide, polyimide, polyacetylene, polythiophene, polyaniline, polyester, phenol resin, epoxy resin, acrylic resin, polyurethane, and the like.
- the method for forming the imprint resin film 13 on the substrate 14 is not particularly limited.
- the imprint resin film 13 can be formed on the substrate 14 using a spin coater or the like.
- the imprint mold 30 is pressed against the imprint resin film 13 formed in advance on the predetermined substrate 14 to cure the imprint resin film 13 (FIG. 1).
- the present invention is not limited to such an embodiment.
- the resin material is discretely dropped on the substrate 14 by an ink jet method or the like, and the imprint mold 30 is brought into contact with the resin material to spread the resin material, and in the fine concave pattern 32 of the imprint mold 30.
- the resin material 131 may be filled and cured (see FIGS.
- thermoplastic resin film 131 composed of the thermoplastic resin is heated to a temperature higher than the glass transition temperature of the thermoplastic resin. Then, the imprint mold 30 may be pressed to cure the thermoplastic resin (see FIGS. 3A and 3B).
- the method of curing the imprint resin film 13 pressed by the imprint mold 30 is the type of resin material constituting the imprint resin film 13 (cured type). It can be appropriately selected depending on the case.
- the imprint mold 30 is peeled off from the cured resin film for imprint 13 (see FIG. 1C).
- the fine convex pattern 12 is formed under the condition that the fine convex pattern 12 protrudes in the direction ID inclined with respect to the orthogonal direction CD of the plane portion 11.
- the fine convex pattern structure 10 which has the plane part 11 and the fine convex pattern 12 which protrudes in direction ID which inclines with respect to orthogonal direction CD of the plane part 11 is manufactured.
- the flat surface portion 11 is constituted by a resin residual film remaining on the substrate 14 as a portion corresponding to a portion other than the fine concave pattern 32 of the imprint mold 30.
- the “orthogonal direction CD of the flat surface portion 11” is a side view of the fine convex pattern structure 10 in which the fine convex pattern 12 is positioned upward and the flat surface portion 11 is positioned downward.
- a plane part that passes through the intersection of a line segment (axis line) passing through the center in the width direction of the fine convex pattern 12 and the plane part 11 in both the side view and the side view from another direction orthogonal to the one direction. 11 means a direction orthogonal to the tangent line, and when the plane part 11 is a non-flat surface, “orthogonal direction CD of the plane part 11” means the direction in each fine convex pattern 12. To do.
- the fine convex pattern 12 which protrudes in direction ID which inclines with respect to orthogonal direction CD of the plane part 11 formed in 1st Embodiment is shown schematically in FIG.1 (c).
- the side surface in the example shown in FIG. 12, the left direction in the inclined direction of the fine convex pattern 12
- the side view the side surface (in the example shown in FIG. 12, the side view).
- Each of the left side surface 12b and the side surface 12a on the tilt direction side (the right side surface in the example shown in FIG. 12) has a substantially curved shape, and the thickness of the fine convex pattern 12 ( length in the width direction) W 12 are substantially the same throughout the axial direction of one fine convex pattern 12. If it is the fine convex pattern 12 which has such a shape, it can be made to protrude in the substantially orthogonal direction with respect to the plane part 11 in the process mentioned later (refer FIG.1 (e)).
- an imprint mold A method of peeling the imprint mold 30 from the imprinting resin film 13 so that not only the force in the vertical direction against the flat surface portion 11 but also the force in the in-plane direction acts on the fine convex pattern 12 when peeling 30. Can be mentioned.
- the imprint mold 30 may be peeled off so that the peeling boundary portion between the imprint resin film 13 (substrate 14) and the imprint mold 30 has an inclination angle.
- the imprint mold 30 is peeled off so that stress applied in the in-plane direction to the fine convex pattern 12 is mainly applied to the fine convex pattern 12 in the direction of the minimum dimension when the mold 30 is peeled off.
- stress applied to the fine convex pattern 12 when the imprint mold 30 is peeled can be reduced.
- the occurrence of defects such as these can be suppressed, and the fine convex pattern 12 with high dimensional accuracy can be formed.
- the line-shaped fine convex pattern 12 having a high accuracy in the length in the longitudinal direction (line length) can be formed.
- the direction of peeling of the imprint mold 30 is most preferably a direction intersecting the line direction of the fine convex pattern 12, but peeling is performed along the line direction. If the change in the shape of the fine convex pattern 12 that occurs in the process is within an allowable range, the imprint mold 30 may be peeled off along the line direction, and the line direction and the component in the direction intersecting the line direction are included. The imprint mold 30 may be peeled in the direction.
- the resin sheet 15 made of the resin material is fixed in a certain direction.
- the rotation of the belt-shaped imprint mold 301 or the columnar imprint mold 302 is synchronized with the conveyance of the resin sheet 15, and the belt-shaped imprint mold 301 or the columnar imprint mold 302 and the resin sheet 15
- the method etc. which are made to contact continuously can be illustrated (refer Fig.4 (a), (b)).
- the line direction of the line-shaped fine convex pattern 12 is When intersecting (substantially orthogonal) the transport direction X of the resin sheet 15, the fine convex pattern 12 protruding in the direction ID inclined with respect to the orthogonal direction CD of the planar portion 11 can be formed.
- the size and aspect ratio of the pattern 12 can be determined by the type of resin material constituting the fine convex pattern 12, the shape of the fine convex pattern 12 (line shape, pillar shape, cross shape, L shape, etc.), etc.
- the fine convex pattern 12 has a dimension and an aspect ratio that can protrude in the tilt direction ID by the above-described method.
- the type of resin material constituting the imprinting resin film 13 and the shape of the fine convex pattern 12 in the fine convex pattern structure 10 to be manufactured (line shape, pillar shape, cross shape, L shape, etc.)
- the size and / or the aspect ratio of the fine convex pattern 12 to be formed is peeled by pulling up the imprint mold 30 in the direction CD orthogonal to the plane portion 11, the fine convex pattern 12 is formed.
- the fine convex pattern 12 is planarized by peeling the imprint mold 30 so as to be pulled up in the orthogonal direction CD with respect to the flat portion 11. It can project in the direction ID inclined with respect to the orthogonal direction CD of the part 11.
- the fine convex pattern structure 10 having the pillar-shaped fine convex pattern 12 when the dimension of the fine convex pattern 12 is about 100 nm or less and the aspect ratio is about 2.0 or more,
- the inclined fine convex pattern 12 can be formed without depending on the peeling method of the imprint mold 30.
- the dimension of the fine convex pattern 12 (about 100 nm or less) is determined when the cylindrical pillar-shaped fine convex pattern 12 having an aspect ratio of 2.0 is formed using the resin material as described above. This is an example of the dimension definition that can form the fine convex pattern 12 protruding in the ID, and even if the dimension exceeds 100 nm, the fine convex pattern protruding in the tilt direction ID can be formed.
- the fine convex pattern 12 protruding in the tilt direction ID can be formed even if the aspect ratio is less than 2.0.
- a plurality of fine convex patterns 12 are formed in the fine convex pattern structure 10. May be included, all the fine convex patterns 12 may be inclined, or some of the fine convex patterns 12 may be inclined.
- the inclined fine convex pattern 12 protrudes in a direction substantially orthogonal to the plane portion 11 (FIG. 1).
- the thickness of the flat surface portion 11 is preferably a thickness that can generate charges on the surface of the flat surface portion 11.
- the fine convex pattern structure 10 formed on the substrate 14 is used, for example, as a mask for etching the substrate 14, generally, by an ashing process or the like as a pretreatment of the etching process of the substrate 14.
- the residual resin film remaining on the substrate 14 is removed, but with the ashing of the residual resin film, the fine convex pattern 12 may be deformed or the dimension of the fine convex pattern 12 may be changed. As a result, the etching accuracy of the substrate 14 may decrease.
- the fine convex pattern structure 10 is used as a mask at the time of etching the substrate 14, it is desired to make the thickness of the resin residual film extremely small.
- the thickness of the resin residual film (planar portion 11) is the deformation or dimension of the fine convex pattern 12 accompanying the removal of the resin residual film. It is desirable that the thickness be such that an electric charge can be effectively generated on the surface of the residual resin film (planar portion 11) while taking into consideration the influence on the change and the like.
- the flat portion 11 constituted by the resin residual film has a thickness that can only be charged to such an extent that it is difficult to protrude the inclined fine convex pattern 12 in a direction substantially orthogonal to the flat portion 11.
- the substrate 14 is an insulating substrate or is not grounded even if it is a conductive substrate. If there is, the substrate 14 that is significantly thicker than the flat surface portion 11 is charged, so that the inclined fine convex pattern 12 is formed by utilizing the electric repulsive force between the charged substrate 14 and the fine convex pattern 12. It can project in a direction substantially orthogonal to the flat portion 11.
- the substrate 14 is a conductive substrate and is grounded when generating a charge in the fine convex pattern structure 10
- the plane portion 11 is extremely thin, Part of the charge generated in the portion 11 may escape to the substrate 14 side.
- the fine convex pattern 12 and the planar portion 11 are in a state that can sufficiently hold the charge even if the charge that escapes to the conductive substrate 14 is subtracted.
- the resin material constituting the flat portion 11 has a high dielectric constant, and the thickness and area of the flat portion 11 (area on the contact surface with the substrate 14) is as large as possible. preferable.
- the center in the width direction of the bottom portion of the fine convex pattern 12 (the portion in contact with the upper surface of the flat portion 11), and the fine convex pattern 12 means that the angle formed with respect to the plane portion 11 by the line segment passing through the center in the width direction of the top portion 12 (the axis line of the fine convex pattern 12) is substantially 90 °, and the angle formed with respect to the plane portion 11 is As long as it is within an allowable range depending on the use of the fine convex pattern structure 10 (use of a lithography mask or the like), specifically, it may be within 90 ° ⁇ 10 °.
- the interval between the adjacent fine convex patterns 12 and 12 is such that the electric repulsive force is such that the inclined fine convex pattern 12 can protrude in the substantially orthogonal direction of the plane portion 11.
- the distance is such that it acts between the fine convex patterns 12, 12, particularly when the height of the fine convex pattern 12 is smaller than the distance between the adjacent fine convex patterns 12, 12.
- the distance is preferably about twice or less the dimension (width) of the fine convex pattern 12.
- the method for generating a charge in the fine convex pattern structure 10 is not particularly limited as long as it is a method capable of generating a charge having the same polarity on the surface of the flat portion 11 and the surface of the fine convex pattern 12,
- the fine convex pattern structure 10 exists in an atmosphere in which the fine convex pattern structure 10 such as a plasma atmosphere can be charged.
- the fine convex pattern structure 10 is made to exist in an electric field generated by an electric field generator or the like, and the fine convex pattern structure Charge of the same polarity (negative charge or positive charge) is applied to the surface of the planar portion 11 and the fine convex pattern 12 by 10 dielectric polarization or electrostatic induction.
- the like method to Zaisa is. These methods may be appropriately selected according to the thickness of the fine convex pattern 12, the type of the resin material, and the like as described above.
- the fine convex pattern structure 10 When a method of causing the fine convex pattern structure 10 to exist in a plasma atmosphere formed using a dry etching apparatus is selected as a method for generating a charge in the fine convex pattern structure 10, the fine convex pattern structure An output that does not substantially etch the body 10 (particularly, the resin residual film or the substrate 14) (for example, plasma that provides a desired etching rate of the substrate 14 when dry etching is performed using a dry etching apparatus).
- the plasma atmosphere is formed at an output of about 80% or less, preferably about 50 to 70% of the output), so that a high-frequency current is not applied to the electrode on which the fine convex pattern structure 10 is mounted if desired. It is preferable that the positive ions in the plasma are not easily drawn into the fine convex pattern structure 10 side.Thereby, an electric charge can be generated in the fine convex pattern structure 10 without etching the fine convex pattern formation in the plasma atmosphere.
- the conditions for generating high-density charges are equivalent to or close to the conditions in which the substrate 14 and the like are easily etched, such as temporarily increasing the plasma output, for example.
- the bias voltage for drawing ions to the substrate 14 side is lowered (for example, the output of the drawing electrode electrically connected to the substrate 14 is lowered). It is necessary to set conditions for generating a high-density charge such that the etching amount of the substrate 14 or the like is negligible, such as using an etchant with a low etching rate such as.
- the inclined fine convex pattern 12 can be protruded in the substantially orthogonal direction of the flat portion 11 on the surfaces of the fine convex pattern 12 and the flat portion 11.
- the electric repulsive force generates an electric charge having an amount of electric charge.
- the amount of electric charge includes the size and aspect ratio of the fine convex pattern 12, the physical properties of the resin material constituting the fine convex pattern 12 (for example, elastic modulus), the degree of inclination of the fine convex pattern 12 (inclination angle), It can be appropriately set according to the interval between the adjacent fine convex patterns 12 and 12.
- the fine convex pattern 12 and the plane part 11 are comprised by the conductor (for example, conductive polymer etc.), when the fine convex pattern 12 and the plane part 11 comprised by a conductor are earth
- the conductor for example, conductive polymer etc.
- the fine convex pattern structure 10 (the fine convex pattern 12 and the planar portion 11) is composed of a conductive polymer.
- the charge application region EA in the fine convex pattern structure 10 and For example, a method of dividing another area OA through the slit 16 may be used.
- the other area OA thus formed is grounded, so that charge is generated only in the charge application area EA, and only the fine convex pattern 12 in the charge application area EA is substantially perpendicular to the plane portion 11. Can be projected.
- the fine convex portions between the fine convex pattern 12 and the flat portion 11 or adjacent to each other By generating charges of the same polarity (for example, negative charges) on the surfaces of the flat surface portion 11 and the fine convex pattern 12 as described above, the fine convex portions between the fine convex pattern 12 and the flat portion 11 or adjacent to each other.
- the fine convex pattern 12 is deformed in a direction away from the plane part 11 by the electric repulsive force between the pattern patterns 12 and 12, and protrudes in a substantially orthogonal direction of the plane part 11 (see FIG. 1E).
- the charge generated in the fine convex pattern structure 10 is released (FIG. 1 (f)). If the fine convex pattern structure 10 remains charged, various adverse effects may occur. For example, if the electric charge remains, fine foreign substances existing in the surrounding environment are easily attracted, and they are attached to the fine convex pattern structure 10, and the fine convex shape on the substrate 14 later. When the substrate 14 is etched using the pattern structure 10 as a mask, the etching accuracy may be reduced.
- the fine convex pattern structure 10 having the flat portion 11 and the fine convex pattern 12 made of a predetermined resin material or the like is used as it is as a final product (for example, a nanopillar array structure such as a cell culture sheet, a moth-eye film, a microneedle.
- a nanopillar array structure such as a cell culture sheet, a moth-eye film, a microneedle.
- a deflection film, a metamaterial, a hydrophilic film, a water-repellent film, or the like there is a possibility that a predetermined function may not be achieved due to the characteristics of the foreign matter attached to the fine convex pattern structure 10.
- the fine convex pattern 12 may be damaged due to electric charges (static electricity). Therefore, by discharging the charges from the fine convex pattern structure 10, it is possible to suppress the adverse effects caused by the charging of the fine convex pattern structure 10 as described above.
- the method for releasing electric charges from the fine convex pattern structure 10 is not particularly limited.
- the method of summing etc. is mentioned.
- the step shown in FIG. 1D when charges are generated on the surface of the fine convex pattern structure 10 by causing the fine convex pattern structure 10 to exist in a plasma atmosphere.
- the fine convex pattern 12 protruding in the substantially orthogonal direction of the plane portion 11 is inclined again by applying an electric repulsive force.
- the above-described discharging step (FIG. 1 (f)) may be omitted.
- the fine convex pattern structure 10 remains charged in an environment where the above adverse effect due to the discharge of the electric charge from the fine convex pattern structure 10 does not occur or the possibility of the adverse effect is extremely low. If the next process can be carried out even in the state, it is not necessary to release the charge from the fine convex pattern structure 10, and the above-described discharge process (FIG.
- a dry etching apparatus is used in the process shown in FIG.
- the plasma output is adjusted to such an extent that the etching amount can be substantially ignored or not etched, and if desired, the fine convex shape can be formed without applying a high-frequency current to the electrode on which the fine convex pattern structure 10 is placed.
- the dry etching process may be performed by increasing the plasma output without releasing the charge from the fine convex pattern structure 10 existing in the plasma atmosphere. With such a method, it is possible to perform the next dry etching process as it is while projecting the fine convex pattern 12 in a direction substantially orthogonal to the flat surface portion 11, and to improve the throughput. preferable.
- the manufacturing method of the fine convex pattern structure according to the first embodiment described above includes a cell culture sheet having a nanopillar array structure, and a moth-eye structure (a structure simulating an eyelet having a size of several tens to several hundreds of nanometers).
- a film moss eye film having a micro-convex pattern of the order
- a deflection film controlling the vibration direction of light, for example, a line and space in a specific direction, and this is the incident direction of light
- it is particularly suitable for manufacturing a device that selectively blocks or transmits light.
- an imprint mold 30 having a nanohole array structure corresponding to the nanopillar array structure is pressed against the resin film 13 for imprinting (FIG. 1 ( b)). Then, by carrying out the steps of FIG. 1C to FIG. 1F, a cell culture sheet in which the nanopillar array structure (fine convex pattern 12) protrudes in a direction substantially orthogonal to the planar portion 11 can be manufactured. it can.
- the cell culture sheet having the nanopillar array structure is used, the cells contact the fine convex pattern 12. Therefore, it may not be desirable to form a release agent layer on the imprint mold 30. This is because the release agent layer may be toxic to cells.
- the stress at the time of mold release of imprint mold 30 can be reduced by manufacturing the cell culture sheet which has a nano pillar array structure by a 1st embodiment.
- an aluminum substrate having a plurality of fine recesses is formed by anodizing the surface of the aluminum substrate.
- An etching process is performed to enlarge a plurality of fine recesses.
- the aluminum substrate having a plurality of fine recesses formed as described above is used as an imprint mold, and the aluminum substrate is pressed against the imprint resin film.
- the aluminum base material is a belt-shaped imprint mold 301 or a columnar imprint mold 302, and the belt-shaped or columnar imprint.
- the molds 301 and 302 and the resin sheet 15 are continuously brought into contact with each other.
- the moth-eye film in which the fine convex pattern 12 protrudes in a direction substantially orthogonal to the flat portion 11.
- the moth-eye film can be mass-produced by continuously contacting the resin sheet 15 using belt-shaped or columnar imprint molds 301, 302, but gradually belt-shaped or columnar imprint molds 301, 302 The mold release performance of 302 may be reduced.
- the moth-eye film in which the fine convex pattern 12 protrudes in a direction substantially orthogonal to the plane portion 11 can be manufactured with high accuracy.
- deviation film it can manufacture by producing the mold which has a line and space structure, for example, and passing through the process similar to a moth-eye film.
- the fine convex pattern 12 is formed under the condition that the fine convex pattern 12 protrudes in the inclined direction. Therefore, when the imprint mold 30 is peeled from the imprint resin film 13, it is possible to suppress the occurrence of defects such as defects in the fine convex pattern 12. At the same time, by generating an electric charge in the inclined fine convex pattern 12, the fine convex pattern 12 can be projected in a substantially orthogonal direction with respect to the flat portion 11 by using an electric repulsive force. Thus, the fine convex pattern structure 10 having the fine convex pattern 12 protruding in a direction substantially orthogonal to 11 can be manufactured with high accuracy.
- the manufacturing method of the fine convex pattern structure according to the first embodiment since the inclined fine convex pattern 12 can be protruded in a direction substantially orthogonal to the plane portion 11, in the conventional nanoimprint, Even the fine convex pattern structure 10 having the fine convex pattern 12 having a fine dimension and a high aspect ratio that is not formed because the pattern collapses can be manufactured with high accuracy.
- FIG. 6 is a block diagram showing a schematic configuration of the fine convex pattern structure manufacturing system in the present embodiment.
- the fine convex pattern structure manufacturing system 50 includes a fine convex pattern structure 10 having a flat portion 11 and a fine convex pattern 12 protruding from the flat portion 11.
- An inclined pattern forming portion 51 manufactured under the condition that the fine convex pattern 12 protrudes in a direction ID inclined with respect to the orthogonal direction CD of the plane portion 11, and a fine convex pattern structure manufactured by the inclined pattern forming portion 51.
- It has the charge provision part 52 which makes the fine convex pattern 12 which inclines protrude in the substantially orthogonal direction of the plane part 11 by producing an electric charge in the body 10.
- the inclined pattern forming unit 51 is configured by a single device or a plurality of devices generally used for manufacturing the fine convex pattern structure 10. For example, the substrate stage on which the substrate 14 is placed, and the imprint mold 30 is held so that the surface of the imprint mold 30 on which the fine concave pattern 32 is formed faces the substrate 14 placed on the substrate stage.
- Optical nanoimprint apparatus or thermal nanoimprint apparatus including a holding unit, an imprint chamber in which an imprint process is performed, or the like; belt-shaped or rotating body-shaped imprint molds 301 and 302, and a long sheet-shaped transfer target (resin sheet 15 Etc.), a sheet nanoimprint apparatus or the like that can produce a long sheet-like fine convex pattern structure 10 by pressing the belt-like or rotating body-like imprint molds 301 and 302 against the transfer object. (See FIGS. 4A and 4B).
- the holding portion is applied so that the in-plane stress acts on the fine convex pattern 12.
- a mechanism capable of operating By providing such a mechanism, the fine convex pattern structure 10 having the fine convex pattern 12 protruding in the direction ID inclined with respect to the orthogonal direction CD of the plane part 11 can be manufactured.
- the fine convex pattern 12 is necessarily in the in-plane direction. Stress acts (the fine convex pattern 12 is pulled in a direction opposite to the conveyance direction X of the transfer target (resin sheet or the like)). Therefore, the fine convex pattern structure 10 which has the fine convex pattern 12 which protrudes in direction ID which inclines with respect to orthogonal direction CD of the plane part 11 can be manufactured.
- the device configuration is particularly limited.
- a plasma generator having a plasma chamber
- a dry etching apparatus having a plasma generator, an electric field generator, and the like.
- the fine convex pattern structure 10 having the fine convex pattern 12 that is inclined is manufactured by the inclined pattern forming unit 51, and the charge applying unit 52 Electric charges are generated in the fine convex pattern structure 10.
- the plane repulsive force which acts between the fine convex pattern 12 and the plane part 11 or between the adjacent fine convex patterns 12 and 12 is utilized, and the substantially orthogonal direction with respect to the plane part 11. It is possible to manufacture the fine convex pattern structure 10 having the fine convex pattern 12 projecting in the direction.
- the fine convex pattern structure 10 is manufactured under the condition that the fine convex pattern 12 is inclined in the inclined pattern forming unit 51.
- the fine convex pattern 12 inclined by the charge imparting portion 52 protrudes in a direction substantially orthogonal to the plane portion 11. Therefore, the fine convex pattern structure 10 having the fine convex pattern 12 protruding in a direction substantially orthogonal to the flat portion 11 can be manufactured with high accuracy.
- the inclined fine convex pattern 12 can be protruded in a direction substantially orthogonal to the plane portion 11, so that the pattern in the conventional nanoimprint is Even if it is the fine convex pattern structure 10 which has the fine convex pattern 12 of the fine dimension and high aspect ratio which were not formed because it falls down, it can manufacture accurately.
- FIG. 7 is a flowchart showing a method of manufacturing a fine convex pattern structure according to the second embodiment of the present invention by a cut end face.
- the imprint resin film 23 is formed, as in the method for manufacturing the fine convex pattern structure according to the first embodiment.
- a predetermined substrate for example, a silicon substrate, a metal substrate, a glass substrate, a quartz substrate, etc.
- the imprint mold 40 having the fine concave pattern 42 corresponding to the fine convex pattern 22 in the fine convex pattern structure 20 is pressed, and the imprint resin film 23 is cured in this state (see FIG. 7B).
- a resin material constituting the imprint resin film 23 As a resin material constituting the imprint resin film 23, a resin material generally used for forming a fine uneven pattern by a nanoimprint method (an insulating resin material such as a thermoplastic resin, a thermosetting resin, or a photocurable resin) is used. ), which can be shrunk by external energy application. As such a resin material, the thing similar to what was illustrated as a resin material which comprises the resin film 13 for imprint in 1st Embodiment can be used.
- an insulating resin material such as a thermoplastic resin, a thermosetting resin, or a photocurable resin
- the same method as that of the first embodiment can be adopted for the method of forming the imprint resin film 23 on the substrate 24.
- the resin material is discretely dropped onto the substrate 24 by an ink jet method or the like, and the imprint mold 40 is brought into contact with the resin material. While spreading the resin material, the resin material may be filled into the fine concave pattern 42 of the imprint mold 40 and cured (see FIGS. 2A and 2B), or may be made of a thermoplastic resin.
- the resin film 231 may be heated above the glass transition temperature of the thermoplastic resin, and the imprint mold 40 may be pressed in this state to cure the resin (see FIGS. 3A and 3B).
- the method of curing the imprint resin film 23 is the same as the method in the first embodiment.
- the imprint mold 40 is peeled from the cured resin film for imprint 23 (see FIG. 7C).
- the fine convex pattern 22 is formed under the condition that the fine convex pattern 22 protrudes in the direction ID inclined with respect to the orthogonal direction CD of the plane portion 21.
- the fine convex pattern structure 20 which has the plane part 21 and the fine convex pattern 22 which protrudes in direction ID which inclines with respect to the orthogonal direction CD of the plane part 21 is manufactured.
- the flat surface portion 21 is configured by a resin residual film remaining on the substrate 24 as a portion corresponding to a portion other than the fine concave pattern 42 of the imprint mold 40, and the thickness of the flat surface portion 21. The length can be appropriately set according to the use of the fine convex pattern structure 20 to be manufactured.
- the fine convex pattern 22 which protrudes in direction ID which inclines with respect to orthogonal direction CD of the plane part 21 formed in 2nd Embodiment is schematically shown in FIG.7 (c).
- the side surface in the example shown in FIG. 12, the left direction in the inclined direction of the fine convex pattern 22
- Both the left side surface 22b and the inclined side surface (in the example shown in FIG. 12, the right side surface side surface) 22a have a substantially arcuate shape
- the thickness of the fine convex pattern 22 ( The length in the width direction) W 22 is substantially the same over the entire axial direction of one fine convex pattern 22. If it is the fine convex pattern 22 which has such a shape, it can be made to protrude in the substantially orthogonal direction with respect to the plane part 21 in the process mentioned later (refer FIG.7 (e)).
- the first embodiment As a condition for projecting the fine convex pattern 22 in the direction ID inclined with respect to the orthogonal direction CD of the plane portion 21, that is, as a method for projecting the fine convex pattern 22 in the inclined direction ID, the first embodiment is used.
- the imprinting resin for example, not only the force in the vertical direction against the flat surface portion 21 but also the force in the in-plane direction acts on the fine convex pattern 22 when the imprint mold 40 is peeled off.
- membrane 23 can be mentioned.
- the imprint mold 40 may be peeled off so that the peeling boundary portion between the imprint resin film 23 (substrate 24) and the imprint mold 40 has an inclination angle.
- the imprint mold 40 is peeled so that the stress applied in the in-plane direction to the fine convex pattern 22 is applied to the fine convex pattern 22 in the direction of the minimum dimension when the mold 40 is peeled off.
- stress applied to the fine convex pattern 22 when the imprint mold 40 is peeled can be reduced.
- the occurrence of defects such as these can be suppressed, and the fine convex pattern 22 with high dimensional accuracy can be formed.
- the line-shaped fine convex pattern 22 having a high accuracy in the length in the longitudinal direction (line length) can be formed.
- the direction of peeling of the imprint mold 40 is most preferably a direction intersecting the line direction of the fine convex pattern 22, but peeling is performed along the line direction. If the change in the shape of the fine convex pattern 22 that occurs in the process is within an allowable range, the imprint mold 40 may be peeled along the line direction, and the component has a component in the line direction and a direction intersecting the line direction. The imprint mold 40 may be peeled in the direction.
- the resin sheet 25 made of the resin material is fixed in a certain direction.
- the rotation of the belt-shaped imprint mold 401 or the columnar imprint mold 402 is synchronized with the conveyance of the resin sheet 25, and the belt-shaped imprint mold 401 or the columnar imprint mold 402 and the resin sheet 25 are The method etc. which are made to contact continuously can be illustrated (refer Fig.4 (a), (b)).
- the line direction of the line-shaped fine convex pattern 22 is When intersecting (substantially orthogonal) the transport direction X of the resin sheet 25, the fine convex pattern 22 protruding in the direction ID inclined with respect to the orthogonal direction CD of the plane portion 21 can be formed.
- the dimension and aspect ratio of the pattern 22 can be determined by the type of resin material constituting the fine convex pattern 22, the shape of the fine convex pattern 22 (line shape, pillar shape, cross shape, L shape, etc.), etc.
- the fine convex pattern 22 has a dimension and an aspect ratio that can protrude in the inclination direction ID by the above-described method.
- the resin material constituting the fine convex pattern 22 is contracted to cause the fine convex pattern 22 protruding in the inclination direction ID to protrude in a substantially orthogonal direction.
- the dimension and aspect ratio of the fine convex pattern 22 protruding in the substantially orthogonal direction vary from the design dimension and aspect ratio.
- the amount of change in the dimension and aspect ratio is determined by the shrinkage rate of the resin material constituting the fine convex pattern 22. Therefore, the dimension and aspect ratio of the fine convex pattern 22 protruding in the tilt direction ID can be appropriately set according to the allowable range of the change amount of the dimension and aspect ratio of the fine convex pattern 22.
- the type of resin material constituting the imprint resin film 23 and the shape of the fine convex pattern 22 in the fine convex pattern structure 20 to be manufactured (line shape, pillar shape, cross shape, L shape, etc.)
- the size and / or aspect ratio of the fine convex pattern 22 to be formed is raised by peeling the imprint mold 40 in the orthogonal direction CD with respect to the plane portion 21, the fine convex pattern 22 is formed.
- the fine convex pattern 22 is planarized by peeling the imprint mold 40 so as to pull up in the orthogonal direction CD with respect to the flat portion 21.
- the part 21 can be projected in a direction ID that is inclined with respect to the orthogonal direction CD.
- the dimension of the fine convex pattern 22 is about 1.0 ⁇ m or less and the aspect ratio is about 1.5 or more.
- the fine convex pattern 22 protruding in the tilt direction ID can be formed without depending on the peeling method of the imprint mold 40.
- the dimension of the fine convex pattern 22 (about 1.0 ⁇ m or less) is defined when a cylindrical pillar-shaped fine convex pattern 22 having an aspect ratio of 1.5 is formed using a resin material as described above. This is an example of a dimension that can form the fine convex pattern 22 protruding in the inclination direction ID, and even if the dimension exceeds 1.0 ⁇ m, the fine convex pattern protruding in the inclination direction ID can be formed. it can.
- the fine convex pattern 22 protruding in the tilt direction ID can be formed even if the aspect ratio is less than 1.5.
- the fine convex pattern 22 is formed when the fine convex pattern 22 protruding in the direction ID inclined with respect to the orthogonal direction CD of the plane portion 21 is formed.
- the structure 20 includes a plurality of fine convex patterns 22, all the fine convex patterns 22 may protrude in the inclination direction ID, or some of the fine convex patterns 22 may be in the inclination direction. You may make it protrude in ID.
- the fine convex pattern structure according to the second embodiment is applied from the outside.
- the contraction force of the fine convex pattern 22 caused by the energy the inclined fine convex pattern 22 can be protruded in the substantially orthogonal direction of the plane part 21, and the plane part 21 and the substantially orthogonal direction of the plane part 21 It is possible to manufacture a fine convex pattern structure 20 having a fine convex pattern 22 that protrudes into the shape (see FIG. 7E).
- Examples of a method for applying energy to the fine convex pattern 22 include, for example, an active energy beam irradiation device (electron beam irradiation device, charged particle beam irradiation device such as an ion beam irradiation device; ultraviolet irradiation device, infrared irradiation device, visible light irradiation) Active energy rays (charged particle beams such as electron beams and ion beams); ultraviolet rays, infrared rays, visible rays, etc., using a beam irradiation device such as an apparatus or a laser beam irradiation device; a radiation irradiation device such as an X-ray irradiation device or a gamma ray irradiation device And a method of irradiating the fine convex pattern 22 with a light beam such as a laser beam; radiation such as an X-ray and a gamma ray).
- the type of the active energy ray 26 irradiated to the fine convex pattern 22 can be appropriately selected according to the type of the resin material constituting the fine convex pattern 22.
- the resin material constituting the fine convex pattern 22 is a photocurable resin and the photocurable resin is contracted using a crosslinking (polymerization) reaction
- the photocurable resin generally has a wavelength of 400 nm.
- ultraviolet rays are selected as the active energy ray
- the polymerization initiator contained in the photocurable resin has an optimum absorption wavelength.
- the pattern 22 contracts in a short time. Therefore, it is necessary to strictly control the irradiation amount of ultraviolet rays so that the fine convex pattern 22 does not shrink too much. That is, it is necessary to select energy to be used from the viewpoint of controllability.
- the type of active energy ray 26 can be appropriately selected depending on the type of material constituting the fine convex pattern 22.
- the effect exerted by the second embodiment is the fine convex pattern It depends on the thickness and physical properties of the resin constituting the resin 22. Specifically, when the light is applied to the fine convex pattern 22 composed of a resin material having a transmittance of 30% or less with respect to the wavelength of light to be used, and composed of a resin material having a transmittance of 90% or more.
- the curing mode of the resin is different.
- the surface irradiated with the light is more contracted, but in the fine convex pattern 22 composed of a resin material having a transmittance of 90% or more Will shrink substantially uniformly. Due to the difference in the light transmittance of such a resin material, in the fine convex pattern 22 composed of a resin material having a high light transmittance (for example, 90%), the entire fine convex pattern 22 is substantially uniform.
- the fine convex pattern 22 Due to the shrinkage, it is difficult to project the fine convex pattern 22 in a substantially orthogonal direction of the flat surface portion 21, but the fine convex pattern 22 made of a resin material having a low light transmittance (for example, 30%). In this case, it becomes easy to project the fine convex pattern 22 in a substantially orthogonal direction of the plane portion 21. Further, when the fine convex pattern 22 is projected in the substantially orthogonal direction of the plane portion 21 by light irradiation, there is a concern that the resin material may be further contracted by the reflected light from the substrate 24.
- an optical system such as a direction of irradiating the fine convex pattern 22 with light or scattered light. It is preferable to consider the physical properties corresponding to the transmittance (absorption rate) of the resin material constituting the fine convex pattern 22 and the reactivity with respect to the wavelength.
- an electron beam is selected as the active energy ray 26 (when an electron beam irradiation device is selected as the active energy ray irradiation device), energy is easily consumed near the surface of the resin facing the irradiation direction. It is possible to cause a strong change with respect to the surface of the resin (electron beam irradiation surface), and it is possible to project the fine convex pattern 22 in a substantially orthogonal direction of the flat portion 21. Note that the electron beam irradiation conditions are also preferably selected as appropriate.
- a fine convex pattern 22 having a thickness of 20 nm or less as viewed in the irradiation direction from an electron beam irradiation source is irradiated with an electron beam generated by a low acceleration voltage of about 0.1 to 10 kV.
- the resin material which comprises the surface irradiated with the electron beam among the side surfaces of the convex pattern 22 can be more effectively contracted, the side surface (electron beam) facing the electron beam irradiation surface of the fine convex pattern 22 Since the resin material constituting the non-irradiated surface is hardly contracted, the fine convex pattern 22 can be protruded in the substantially orthogonal direction of the flat surface portion 21.
- the side surface 22a on the left side in side view is relatively elongated, and the side surface on the inclined side (the side surface on the right side in the side view in the example shown in FIG. 7) 22b is relatively contracted.
- the amount of energy applied to the relatively extending side surface 22a among the side surfaces of the inclined fine convex pattern 22 is as follows. Energy is imparted to the fine convex pattern 22 so as to increase. By increasing the amount of energy applied to the side surface 22a that is relatively extended, the amount of contraction of the side surface 22a that is relatively extended becomes larger than that of the side surface 22b that is relatively contracted. As a result, the fine convex pattern 22 can be protruded in a direction substantially orthogonal to the plane portion 21.
- an active energy ray (electron beam, ion beam, ultraviolet ray, infrared ray, visible ray, laser beam, X-ray, gamma ray, etc.) 25 is present on the relatively extending side surface 22a of the inclined fine convex pattern 22. It is preferable to irradiate mainly, and for this purpose, the active energy ray source (in consideration of the inclination direction and the inclination angle of the fine convex pattern 22, the interval between the adjacent fine convex patterns 22, 22, etc.
- an installation position of an electron gun or an ion gun a light source of ultraviolet rays, infrared rays, visible light, laser light; irradiation source of X-rays, gamma rays, etc.) and set an irradiation direction of active energy rays.
- the side surface 22a of the fine convex pattern 22 is efficiently irradiated by irradiating the active energy ray 26 from above the fine convex pattern structure 20 in a direction CD orthogonal to the plane portion 21. While the active energy ray 26 can be irradiated to the side surface 22a, the side surface 22a of the fine convex pattern 22 is less likely to be irradiated with the active energy ray 26. The amount of energy applied can be increased.
- the fine convex pattern structure 20 having the pattern 22 can be manufactured.
- the side surface of the fine convex pattern 22 depends on the inclination angle of the fine convex pattern 22, the interval between the adjacent fine convex patterns 22, 22, and the like.
- the irradiation direction of the active energy ray 26 may be set so that the active energy ray 26 is efficiently irradiated by 22a.
- the fine convex pattern 22 is inclined toward the right side, and the fine convex pattern 22 is inclined (the fine convex pattern with respect to the orthogonal direction CD of the plane portion 21).
- the angle ⁇ formed by the inclination direction ID of 22 is large, and a part of the side surface 22a of one fine convex pattern 22 is hidden by the adjacent fine convex pattern 22 when the fine convex pattern structure 20 is viewed from above.
- the inclination of the fine convex pattern 22 (the angle ⁇ formed by the inclination direction ID of the fine convex pattern 22 with respect to the orthogonal direction CD of the flat surface portion 21) is small, and the fine convex pattern structure 20 has one fineness when viewed from above.
- the irradiation direction of the active energy ray 26 is set to the lower right direction (see FIG. 8B).
- the inclination direction ID of the fine convex pattern 22 is not necessarily a constant direction, and each fine convex pattern 22 may be inclined in various directions. In such a case, it is preferable to irradiate the active energy rays 26 from above the fine convex pattern structure 20 along the direction CD perpendicular to the plane portion 21 (see FIG. 7D).
- the fine convex pattern structure 20 is divided into a plurality of regions based on the inclination direction ID of the fine convex pattern 22, and the irradiation direction of the active energy ray 26 according to the inclination direction ID of the fine convex pattern 22 in each region. And the active energy ray 26 may be irradiated from the set direction for each divided region. By doing in this way, the active energy ray 26 can be effectively irradiated to the side surfaces 22a of all the fine convex patterns 22 in the fine convex pattern structure 20, and it protrudes in a direction substantially orthogonal to the plane portion 21.
- the fine convex pattern structure 20 having the fine convex pattern 22 to be manufactured can be accurately manufactured.
- the shrinkage of the fine convex pattern 22 due to the application of energy is the shrinkage caused by the change in the chemical structure of the resin material constituting the fine convex pattern 22, and the energy applied to the fine convex pattern 22.
- This is considered to be caused by at least one mechanism of shrinkage or the like caused by the heat generated by.
- the shrinkage caused by the change in the chemical structure of the resin material for example, the shrinkage caused by the progress of the crosslinking (polymerization) reaction of the resin material constituting the fine convex pattern 22;
- the constituent resin material is a material having a ring structure, and shrinkage caused by densification of the resin material in the fine convex pattern 22 due to the ring structure becoming a linear structure by ring opening;
- the molecular chain of the resin material constituting the pattern 22 is cut, and some molecules are removed so as not to affect the structure of the fine convex pattern 22 (so that the fine convex pattern 22 is not damaged).
- the active energy ray-curable resin can proceed with a crosslinking (polymerization) reaction, but the molecular chain can be cut.
- An active energy ray 26 having a low energy intensity is irradiated toward the side surface 22 a of the fine convex pattern 22.
- the cross-linking (polymerization) reaction of the active energy ray-curable resin in the vicinity of the portion irradiated with the active energy ray 26 (side surface 22a) proceeds, and the vicinity of the side surface 22a of the fine convex pattern 22 is further contracted. .
- the inclined fine convex pattern 22 can be protruded in the substantially orthogonal direction of the plane portion 21.
- the resin material which comprises the fine convex pattern 22 is a resin material which has a ring structure
- strength which can advance the ring-opening reaction of the said ring structure is made into the fine convex pattern 22 Irradiation toward the side surface 22a.
- the ring-opening reaction of the resin material in the vicinity of the portion irradiated with the active energy ray 26 (side surface 22a) proceeds to change the ring structure into a linear structure, thereby increasing the density of the resin material in the vicinity of the side surface 22a. Therefore, the vicinity of the side surface 22a of the fine convex pattern 22 is further contracted, and the inclined fine convex pattern 22 can be protruded in the substantially orthogonal direction of the plane portion 21.
- the active energy rays 26 having such an energy intensity that the molecular chains of the resin material constituting the fine convex pattern 22 can be cut and some molecules can be desorbed are directed toward the side surface 22 a of the fine convex pattern 22. Irradiate. As a result, the molecular chain of the resin material in the vicinity of the portion irradiated with the active energy ray 26 (side surface 22a) is cut and a part of the molecules is detached, and the vicinity of the side surface 22a of the fine convex pattern 22 is further contracted. As a result, the inclined fine convex pattern 22 a can be protruded in the substantially orthogonal direction of the plane portion 21.
- the active energy ray 26 may be continuously irradiated onto the fine convex pattern 22, but by irradiating the active energy ray 26 in a pulse shape, the fine convex pattern structure 20 It is preferable that excessive energy is not applied to the fine convex pattern 22. If excessive energy is applied to the fine convex pattern 22, the portion other than the portion to be contracted (side surface 22a of the fine convex pattern 22) mainly contracts. 20 may be deformed.
- the active energy ray irradiation conditions including the pulse width and pulse pause time of the active energy ray irradiation are the type of resin material constituting the fine convex pattern structure 20, the size and aspect ratio of the fine convex pattern 22, What is necessary is just to set suitably to such an extent that the inclination of the fine convex pattern 22 can be corrected according to the inclination angle etc. of the fine convex pattern 22 and the deformation of the fine convex pattern structure 20 is not caused.
- a slit 27 is formed in the flat portion 21, or the fine convex pattern structure is formed. It is preferable to suppress the propagation of energy by providing a layer having a characteristic that blocks the propagation of energy such as heat insulation, insulation, and absorption between the substrate 20 and the substrate 24.
- the method for producing a fine convex pattern structure according to the second embodiment described above is applicable to a cell culture sheet having a nanopillar array structure, a moth-eye structure (a structure simulating a moth eye, and several tens to several hundreds of nm).
- a film moss eye film having a micro-convex pattern of the order
- a deflection film controlling the vibration direction of light, for example, a line and space in a specific direction, and this is the incident direction of light
- it is particularly suitable for manufacturing a device that selectively blocks or transmits light.
- an imprint mold 40 having a nanohole array corresponding to the nanopillar array structure is pressed against the imprint resin film 23 (FIG. 7B). )reference). Then, by performing the steps of FIG. 7C to FIG. 1E, a cell culture sheet in which the nanopillar array structure (fine convex pattern 22) protrudes in a direction substantially orthogonal to the flat portion 21 can be manufactured. it can.
- the cell culture sheet having the nanopillar array structure is used, the cells contact the fine convex pattern 22. Therefore, it may not be desirable to form a release agent layer on the imprint mold 40. This is because the release agent layer may be toxic to cells.
- an aluminum substrate having a plurality of fine recesses is formed by anodizing the surface of the aluminum substrate.
- An etching process is performed to enlarge a plurality of fine recesses.
- the aluminum substrate having a plurality of fine recesses formed as described above is used as an imprint mold, and the aluminum substrate is pressed against the imprint resin film.
- the aluminum base material is a belt-shaped imprint mold 401 or a columnar imprint mold 402, and the belt-shaped or columnar imprint.
- the molds 401 and 402 and the resin sheet 25 are continuously contacted. Thereafter, by performing the steps of FIG. 7C to FIG.
- the moth-eye film in which the fine convex pattern 22 protrudes in a direction substantially orthogonal to the flat portion 21 can be mass-produced by continuously contacting the resin sheet 25 using a belt-like or columnar imprint mold 401, 402, but gradually belt-like or columnar imprint mold 401, The mold release performance of 402 may be reduced. Even in such a case, according to the second embodiment, the moth-eye film in which the fine convex pattern 22 protrudes in a direction substantially orthogonal to the plane portion 21 can be manufactured with high accuracy.
- deviation film it can manufacture by producing the mold which has a line and space structure, for example, and passing through the process similar to a moth-eye film.
- the fine convex pattern 22 is formed under the condition that the fine convex pattern 22 protrudes in the inclined direction. Therefore, when the imprint mold 40 is peeled from the imprint resin film 23, it is possible to suppress the occurrence of defects such as defects in the fine convex pattern 22. At the same time, by applying energy from the outside to the relatively extending side surface 22a of the inclined fine convex pattern 22, the micro convex pattern 22 is utilized by utilizing the contraction force of the resin material constituting the fine convex pattern 22.
- the fine convex pattern structure 20 having the micro-projection pattern 22 protruding in the direction substantially orthogonal to the plane part 21 is accurately manufactured. be able to.
- the manufacturing method of the fine convex pattern structure according to the second embodiment since the inclined fine convex pattern 22 can be protruded in a direction substantially orthogonal to the plane portion 21, in the conventional nanoimprint, Even the fine convex pattern structure 20 having the fine convex pattern 22 having a fine dimension and a high aspect ratio that is not formed because the pattern collapses can be manufactured with high accuracy.
- FIG. 10 is a block diagram showing a schematic configuration of a fine convex pattern structure manufacturing system according to the second embodiment.
- the fine convex pattern structure manufacturing system 60 in the second embodiment includes a fine convex pattern structure 20 having a flat portion 21 and a fine convex pattern 22 protruding from the flat portion 21.
- An inclined pattern forming portion 61 manufactured under the condition that the fine convex pattern 20 protrudes in a direction ID inclined with respect to the orthogonal direction CD of the plane portion 21, and a fine convex pattern structure manufactured by the inclined pattern forming portion 61.
- an energy applying part 62 that causes the inclined fine convex pattern 22 to protrude in a substantially orthogonal direction of the plane part 21.
- the inclined pattern forming unit 61 is configured by a single device or a plurality of devices generally used for manufacturing the fine convex pattern structure 20, and the specific device configuration is the first embodiment. The thing similar to the inclination pattern formation part 51 in FIG.
- the energy applying unit 62 As the energy applying unit 62, as long as it can apply energy to the side surface 22a of the fine convex pattern 22 in the fine convex pattern structure 20 and contract the resin material on the side surface 22a, the energy applying unit 62 is particularly limited to the device configuration.
- active energy beam irradiation devices such as electron beam irradiation devices, ion beam irradiation devices, ultraviolet irradiation devices, infrared irradiation devices, visible light irradiation devices, laser beam irradiation devices, X-ray irradiation devices, gamma ray irradiation devices, etc. It is done.
- the inclined pattern forming unit 61 manufactures the fine convex pattern structure 20 having the inclined fine convex pattern 22, and the energy applying unit 62 Thus, energy is applied to the side surface 22a of the inclined fine convex pattern 22.
- the fine convex pattern structure 20 which has the plane part 21 and the fine convex pattern 22 which protrudes in the substantially orthogonal direction with respect to the plane part 21 can be manufactured.
- the fine convex pattern structure 20 is manufactured under the condition that the fine convex pattern 22 is inclined in the inclined pattern forming unit 61.
- the fine convex pattern 22 inclined by the energy application unit 62 protrudes in a direction substantially orthogonal to the plane portion 21. Therefore, the fine convex pattern structure 20 having the fine convex pattern 22 protruding in a direction substantially orthogonal to the flat portion 21 can be manufactured with high accuracy.
- the fine convex pattern structure manufacturing system in the second embodiment since the inclined fine convex pattern 22 can be protruded in a direction substantially orthogonal to the plane portion 21, the pattern is not obtained in the conventional nanoimprint. Even the fine convex pattern structure 20 having the fine convex pattern 22 having a fine dimension and a high aspect ratio that has not been formed because of falling down can be accurately manufactured.
- the entire fine convex pattern structure 10 is charged.
- the present invention is not limited to such an embodiment. Charge may be generated only in a part of the region, and the fine convex pattern 12 inclined in the region may be protruded in a substantially orthogonal direction of the plane part 11.
- the fine convex pattern structure 10 is manufactured under the condition that only the fine convex pattern 12 in the partial region of the fine convex pattern structure 10 protrudes in the inclination direction ID. Charges may be generated only in the region.
- the fine convex pattern structure 10 (the flat portion 11 and the fine convex patterns 121 and 122) to be manufactured is made of a conductive polymer, and the fine convex pattern structure 10 is made of a glass substrate or the like.
- the first fine convex pattern 121 protrudes in the substantially orthogonal direction of the plane portion 11
- the 2nd fine convex pattern 122 protrudes in the direction inclined with respect to the substantially orthogonal direction of the plane part 11 (refer FIG.11 (b)).
- the second fine convex pattern 122 is formed to have a highly accurate line length.
- the second fine convex pattern 122 protrudes in a direction inclined with respect to the substantially orthogonal direction of the plane portion 11, but the first fine convex pattern 121 and the first The region where the two fine convex patterns 122 are formed is divided through the slits 16, and the region where the first fine convex patterns 121 are formed is grounded, so that the second fine Electric charges can be generated only in the region where the convex pattern 122 is formed, and the inclined second fine convex pattern 122 can be protruded in the substantially orthogonal direction of the plane portion 11 (see FIG. 11A). ).
- a part of the fine convex pattern structure 20 is irradiated with active energy rays only on a part of the fine convex pattern 22 (side surface 22a thereof). Energy may be applied only to the fine convex pattern 22 in the region, and the fine convex pattern 22 inclined in the region may be protruded in a substantially orthogonal direction of the plane portion 21.
- the fine convex patterns 12 and 22 that are inclined are charged or given energy
- the fine convex patterns 12 and 22 are formed on the flat portions 11 and 21. It may further include a step of confirming whether or not it protrudes in a substantially orthogonal direction.
- a method for confirming whether or not the fine convex patterns 12 and 22 protrude in a substantially orthogonal direction of the flat portions 11 and 21 for example, a method for observing and evaluating the shape, or a change in the shape is used. A method for determining the presence or absence of inclination from the information is included.
- the fine convex pattern structures 10 and 20 are imaged from the top or side using a laser microscope, SEM, or the like to confirm the presence or absence of the inclination of the fine convex patterns 12 and 22, or AFM or the like.
- the probe can be brought close to or in contact with the fine convex pattern structures 10 and 20 to check whether the fine convex patterns 12 and 22 are inclined.
- the resolution in response to the fine convex patterns 12 and 22 is not sufficient, and it is difficult to identify the fine convex patterns 12 and 22, but in the substantially orthogonal direction of the planar portions 11 and 21.
- the contrast of the image By comparing with an image of a region where it is known that protruding fine convex patterns 12 and 22 exist, or by comparing such an image with an image captured at the same resolution, the contrast of the image.
- the presence or absence of inclination of the fine convex patterns 12 and 22 can be confirmed based on the difference in optical characteristics such as color, and the fine convex patterns 12 and 22 are measured based on measurement data such as transmittance, refractive index, and reflectance. The presence or absence of the inclination may be confirmed, and further, these methods may be used in combination.
- the second embodiment when energy is applied to the fine convex pattern 22 by irradiating the inclined fine convex pattern 22 with an electron beam using an SEM or the like, The presence or absence of the inclination of the fine convex pattern 22 can also be confirmed while irradiating a line.
- the fine convex pattern structures 10 and 20 having the fine convex patterns 12 and 22 projecting in a direction substantially orthogonal to the planar portions 11 and 21 are manufactured.
- the protrusion angle of the fine convex patterns 12 and 22 after the electric charges are generated in the shape pattern structures 10 and 20 or the energy is applied (the fine convex patterns 12 and 22 are upward and the flat portions 11 and 21 are downward)
- the plane portion 11 passes through the intersection of the line segment (axis line) passing through the center in the width direction of the fine convex patterns 12 and 22 and the flat portions 11 and 21.
- 21 is an angle formed by the axis with respect to the tangent line) than the protrusion angle of the fine convex patterns 12 and 22 when the imprint molds 30 and 40 are peeled off from the imprint resin films 13 and 23.
- a method for producing a fine convex pattern structure 10 or 20 comprising approaching substantially perpendicular direction to the surface portion 11 and 21.
- a method of manufacturing the fine convex pattern structures 10 and 20 having the fine convex patterns 12 and 22 projecting in the direction orthogonal to the plane portions 11 and 21 will be described as an example.
- the present invention is also applied to a method of manufacturing a fine convex pattern structure in which the fine convex pattern in the target fine convex pattern structure is inclined at a predetermined angle (projects in the inclined direction). Can be applied.
- the charge is generated in the fine convex pattern, or energy is applied to the fine convex pattern.
- the fine convex pattern can be projected at the predetermined angle.
- an imprint mold having a fine concave pattern, where the side wall of the fine concave pattern has an angle corresponding to the inclination angle of the fine convex pattern As a method of forming a fine convex pattern that is inclined at a predetermined angle, an imprint mold having a fine concave pattern, where the side wall of the fine concave pattern has an angle corresponding to the inclination angle of the fine convex pattern.
- a method using an imprint mold constituted by an inclined surface that is inclined can be exemplified.
- Example 1 A plurality of line shapes are formed by UV nanoimprinting using an imprint mold 30 having a fine concave pattern 32 corresponding to the fine convex pattern 12 to be formed on one surface of the quartz substrate 14 using an ultraviolet curable resin material.
- the fine convex pattern 12 (design dimension: 100 nm, aspect ratio: 3.0, pitch between adjacent fine convex patterns 12: 100 nm) was formed, and the fine convex pattern structure 10 was produced.
- the imprint mold 30 was peeled along the direction substantially orthogonal to the line direction (longitudinal direction) of the line-shaped fine convex pattern 12.
- the fine convex pattern structure 10 produced as described above and in which the fine convex pattern 12 collapsed was subjected to a dry etching process using ICP-RIE.
- a plasma atmosphere is formed as an ICP output (60% of the ICP output that can achieve the target quartz etching rate) to such an extent that the UV curable resin and quartz are not etched.
- the ICP is such that the fine convex pattern structure 10 exists in the plasma atmosphere for 10 seconds without applying a high frequency current to the electrode on which the pattern structure 10 is mounted, and then the desired quartz etching rate is obtained. Raised to output.
- Example 1 The fine convex pattern structure 10 manufactured by the same method as in Example 1 is subjected to dry etching treatment, except that the output is such that the target quartz etching rate is obtained through the dry etching treatment. did. Observation of the quartz substrate 14 after the dry etching treatment in this way with an SEM confirmed that the quartz substrate 14 was dry-etched in a state where the collapse of the fine convex pattern 12 was reflected. .
- Example 1 As is clear from the results of Example 1 and Comparative Example 1, as described in Example 1, by reducing the ICP output to such an extent that the ultraviolet curable resin and the quartz substrate 14 are not etched in the dry etching process, The pattern structure 10 (fine convex pattern 12) can be charged, and the resulting electric repulsive force can cause the fine convex pattern 12 to protrude in a direction substantially orthogonal to the plane portion 11.
- a line pattern standing upright on the quartz substrate 14 could be formed by increasing the output of the ICP in that state and performing a dry etching process.
- Example 2 A cycloolefin-based thermoplastic resin film (product name: ZEONOR, manufactured by Nippon Zeon Co., Ltd.) is heated to a predetermined temperature, and the imprint mold 40 having a hole-shaped fine concave pattern is pressed to be substantially perpendicular to the upper surface of the resin film. By pulling up the imprint mold 40 in the direction and releasing the mold, the fine convex pattern structure 20 having the pillar-shaped fine convex pattern 22 and the planar portion 21 was manufactured.
- the dimension of the fine convex pattern 22 in the fine convex pattern structure 20 was set to 250 nm
- the aspect ratio was 2.0
- the interval between the adjacent fine convex patterns 22 and 22 was set to 250 nm.
- the thickness of the resin film was 2.0 mm.
- the fine convex pattern structure 20 thus manufactured was observed using an SEM (manufactured by JEOL Ltd., product name: JSM-7001F). As is apparent from the SEM photograph of FIG. The collapse of the pattern 22 was confirmed (electron beam irradiation amount: 5.8 ⁇ C / cm 2 ). And when the electron beam was continuously irradiated to the fine convex pattern structure 20 at the acceleration voltage of 800 V using the SEM until the electron beam integrated dose reached 58.0 ⁇ C / cm 2 , the SEM photograph of FIG. As is clear from the above, the fine convex pattern 22 could be protruded in a direction substantially orthogonal to the plane portion 21.
- Example 3 A fine convex pattern structure 20 was produced in the same manner as in Example 2 except that the cycloolefin-based thermoplastic resin film was changed to a polystyrene resin film.
- the fine convex pattern structure 20 was observed using an SEM (manufactured by JEOL Ltd., product name: JSM-7001), the fine convex pattern structure 20 was observed as is apparent from the SEM photograph of FIG. The collapse of the pattern 22 was confirmed (electron beam irradiation amount: 5.8 ⁇ C / cm 2 ). And when the electron beam was continuously irradiated to the fine convex pattern structure 20 at the acceleration voltage of 800 V using the SEM until the electron beam integrated dose reached 63.8 ⁇ C / cm 2 , the SEM photograph of FIG. As is clear from the above, the fine convex pattern 22 could be protruded in a direction substantially orthogonal to the plane portion 21.
- Example 4 Only a partial region of the fine convex pattern structure 20 of Example 2 was continuously irradiated with an electron beam using an SEM at an acceleration voltage of 800 V until the integrated electron beam dose reached 63.8 ⁇ C / cm 2 . However, as is apparent from the SEM photograph of FIG. 19, only the fine convex pattern 22 in the electron beam irradiation region could be protruded in a direction substantially orthogonal to the plane portion 21.
- Example 4 From the result of Example 4, by irradiating only a partial region of the fine convex pattern structure 20 with an electron beam, only the fine convex pattern 22 in the partial region is substantially orthogonal to the plane portion 21. It is thought that it can be made to protrude. Further, since only the fine convex pattern 22 in the portion irradiated with the electron beam can be protruded in a direction substantially orthogonal to the plane portion 21, the energy of the irradiated electron beam is a fine convex pattern structure outside the irradiation region. It is thought that it acted only in the irradiation region without diffusing into the body 20.
- the fine convex pattern 22 inclined by irradiating the fine convex pattern structure 20 having the fine convex pattern 22 with an electron beam because the electron beam is mainly irradiated to the relatively extended side surface in the resin, the resin material on the side surface irradiated with the electron beam is more contracted by the action of the energy of the electron beam, As a result, it is presumed that the fine convex pattern 22 could be protruded in a direction substantially orthogonal to the plane portion 21.
- the present invention is useful for producing a fine convex pattern structure by a nanoimprint method.
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Abstract
Description
[微細凸状パターン構造体の製造方法]
本発明の第1の実施形態について図面を参照しながら説明する。図1は、本発明の第1の実施形態に係る微細凸状パターン構造体の製造方法を切断端面により示すフロー図である。
続いて、上述した第1の実施形態に係る微細凸状パターン構造体の製造方法を実施し得るシステムについて説明する。図6は、本実施形態における微細凸状パターン構造体製造システムの概略構成を示すブロック図である。
[微細凸状パターン構造体の製造方法]
本発明の第2の実施形態について図面を参照しながら説明する。図7は、本発明の第2の実施形態に係る微細凸状パターン構造体の製造方法を切断端面により示すフロー図である。
続いて、上述した第2の実施形態に係る微細凸状パターン構造体の製造方法を実施し得るシステムについて説明する。図10は、第2の実施形態における微細凸状パターン構造体製造システムの概略構成を示すブロック図である。
石英基板14の一方面上に、紫外線硬化性樹脂材料を用い、形成しようとする微細凸状パターン12に対応する微細凹状パターン32を有するインプリントモールド30を用いたUVナノインプリントにより、複数のライン形状の微細凸状パターン12(設計寸法:100nm、アスペクト比:3.0、隣接する微細凸状パターン12間のピッチ:100nm)を形成し、微細凸状パターン構造体10を作製した。なお、インプリントモールド30の剥離時に、ライン形状の微細凸状パターン12のライン方向(長手方向)に略直交する方向に沿ってインプリントモールド30を剥離した。
ドライエッチング処理を通じて、ICPの出力を目的とする石英のエッチングレートが得られるような出力とした以外は、実施例1と同様の方法により作製した微細凸状パターン構造体10にドライエッチング処理を施した。このようにしてドライエッチング処理を施した後の石英基板14をSEMにて観察したところ、微細凸状パターン12の倒れが反映された状態で石英基板14がドライエッチングされていることが確認された。
シクロオレフィン系熱可塑性樹脂フィルム(製品名:ゼオノア,日本ゼオン社製,大きさ:10mm角,厚み:2.0mm)の一方の面のみに電子線を照射し(加速電圧:800V,電子線積算照射量:188.6μC/cm2)、電子線照射前後における当該フィルムの平坦度(反り)を、Flatmaster(コーニング社製)により計測した。その結果、電子線照射後に照射面側が凹むようにして反り返っていることが確認された。この結果から、電子線を照射することにより、上記樹脂フィルムの電子線照射面において樹脂がより収縮することが判明した。
シクロオレフィン系熱可塑性樹脂フィルム(製品名:ゼオノア,日本ゼオン社製)を所定の温度に加熱し、ホール状の微細凹状パターンを有するインプリントモールド40を押圧し、当該樹脂フィルムの上面に対する略垂直方向にインプリントモールド40を引き上げて離型することで、ピラー状の微細凸状パターン22及び平面部21を有する微細凸状パターン構造体20を製造した。なお、微細凸状パターン構造体20における微細凸状パターン22の寸法を250nm、アスペクト比を2.0、隣接する微細凸状パターン22,22の間隔を250nmと設定した。また、樹脂フィルムの厚さは2.0mmであった。
シクロオレフィン系熱可塑性樹脂フィルムをポリスチレン樹脂フィルムに変更した以外は、実施例2と同様にして微細凸状パターン構造体20を製造した。
実施例2の微細凸状パターン構造体20の一部の領域のみにSEMを用いて加速電圧800Vにて電子線積算照射量が63.8μC/cm2になるまで電子線を連続して照射したところ、図19のSEM写真から明らかなように、当該電子線の照射領域内の微細凸状パターン22のみを平面部21に対する略直交方向に突出させることができた。
11,21…平面部
12,22…微細凸状パターン
30,40,301,302,401,402…インプリントモールド
32,42…微細凹状パターン
50,60…微細凸状パターン構造体製造システム
51,61…傾斜パターン形成部
52…電荷付与部
62…エネルギー付与部
Claims (14)
- 平面部と、当該平面部から当該平面部に対する所定の方向に突出する微細凸状パターンとを有する微細凸状パターン構造体を製造する方法であって、
前記微細凸状パターンに対応する微細凹状パターンを有するインプリントモールドを用い、前記微細凸状パターンが前記所定の方向よりも前記平面部側に傾斜する条件で、前記平面部から突出する微細凸状パターンを形成し、
少なくとも前記傾斜した微細凸状パターンに電荷を生じさせることにより、前記微細凸状パターンを前記平面部に対する所定の方向に突出させる
ことを特徴とする微細凸状パターン構造体の製造方法。 - 前記微細凸状パターン構造体を帯電させることが可能な雰囲気下に当該微細凸状パターン構造体を存在させることにより、前記傾斜した微細凸状パターンに電荷を生じさせることを特徴とする請求項1に記載の微細凸状パターン構造体の製造方法。
- 少なくとも前記微細凸状パターンを誘電分極又は静電誘導させることにより、前記傾斜した微細凸状パターンに電荷を生じさせることを特徴とする請求項1に記載の微細凸状パターン構造体の製造方法。
- 前記微細凸状パターン構造体は、絶縁性材料により構成されていることを特徴とする請求項1~3のいずれかに記載の微細凸状パターン構造体の製造方法。
- 前記微細凸状パターン構造体は、導電性材料を含む材料により構成されており、
少なくとも前記微細凸状パターンを電気的フローティング状態として、前記傾斜した微細凸状パターンに電荷を生じさせることを特徴とする請求項1~3のいずれかに記載の微細凸状パターン構造体の製造方法。 - 平面部と、当該平面部から当該平面部に対する所定の方向に突出する微細凸状パターンとを有する微細凸状パターン構造体を製造する方法であって、
少なくとも前記微細凸状パターンが、外部からのエネルギーの付与により収縮し得る樹脂材料により構成されており、
前記微細凸状パターンに対応する微細凹状パターンを有するインプリントモールドを用い、前記微細凸状パターンが前記所定の方向よりも前記平面部側に傾斜する条件で、前記平面部から突出する微細凸状パターンを形成し、
前記傾斜した微細凸状パターンの側面のうちの相対的に伸長している側面に対して外部からエネルギーを付与することにより、前記微細凸状パターンを前記平面部に対する所定の方向に突出させる
ことを特徴とする微細凸状パターン構造体の製造方法。 - 前記傾斜した微細凸状パターンの相対的に伸長している側面に対し活性エネルギー線を照射することにより、前記微細凸状パターンの相対的に伸長している側面を収縮させることを特徴とする請求項6に記載の微細凸状パターン構造体の製造方法。
- 前記微細凸状パターンの相対的に伸長している側面における前記樹脂材料の化学構造を変化させて前記微細凸状パターンの相対的に伸長している側面を収縮させることを特徴とする請求項7に記載の微細凸状パターン構造体の製造方法。
- 前記樹脂材料の架橋反応を進行させて前記微細凸状パターンの相対的に伸長している側面を収縮させることを特徴とする請求項8に記載の微細凸状パターン構造体の製造方法。
- 前記樹脂材料の分子鎖を切断することにより前記微細凸状パターンの相対的に伸長している側面を収縮させることを特徴とする請求項8に記載の微細凸状パターン構造体の製造方法。
- 前記微細凸状パターンの相対的に伸長している側面を熱収縮させることを特徴とする請求項7に記載の微細凸状パターン構造体の製造方法。
- 前記微細凸状パターン構造体に電子線、イオンビーム、紫外線、赤外線、可視光線、レーザー光線、X線又はガンマ線を照射することにより、前記微細凸状パターンの相対的に伸長している側面を収縮させることを特徴とする請求項6~11のいずれかに記載の微細凸状パターン構造体の製造方法。
- 平面部と、当該平面部から当該平面部に対する所定の方向に突出する微細凸状パターンとを有する微細凸状パターン構造体を製造するシステムであって、
前記微細凸状パターンに対応する微細凹状パターンを有するインプリントモールドを用い、前記微細凸状パターンが前記所定の方向よりも前記平面部側に傾斜する条件で、前記平面部から突出する微細凸状パターンを形成する傾斜パターン形成部と、
少なくとも前記傾斜した微細凸状パターンに電荷を生じさせることにより、前記微細凸状パターンを前記平面部に対する所定の方向に突出させる電荷付与部と
を備えることを特徴とする微細凸状パターン構造体製造システム。 - 平面部と、当該平面部から当該平面部に対する所定の方向に突出する微細凸状パターンとを有し、少なくとも前記微細凸状パターンが外部からのエネルギーの付与により収縮し得る樹脂材料により構成されている微細凸状パターン構造体を製造するシステムであって、
前記微細凸状パターンに対応する微細凹状パターンを有するインプリントモールドを用い、前記微細凸状パターンが前記所定の方向よりも前記平面部側に傾斜する条件で、前記平面部から突出する微細凸状パターンを形成する傾斜パターン形成部と、
前記傾斜パターン形成部により形成された前記傾斜した微細凸状パターンの側面のうちの相対的に伸長している側面に対して外部からエネルギーを付与することにより、前記微細凸状パターンを前記平面部に対する所定の方向に突出させるエネルギー付与部と
を備えることを特徴とする微細凸状パターン構造体製造システム。
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JPWO2015159825A1 (ja) * | 2014-04-15 | 2017-04-13 | 東レ株式会社 | 表面に突起を有する構造体 |
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