WO2016159180A1 - 原盤の製造方法、原盤、及び光学体 - Google Patents
原盤の製造方法、原盤、及び光学体 Download PDFInfo
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- WO2016159180A1 WO2016159180A1 PCT/JP2016/060555 JP2016060555W WO2016159180A1 WO 2016159180 A1 WO2016159180 A1 WO 2016159180A1 JP 2016060555 W JP2016060555 W JP 2016060555W WO 2016159180 A1 WO2016159180 A1 WO 2016159180A1
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- resist layer
- uneven structure
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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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
- B29C33/3857—Manufacturing moulds, e.g. shaping the mould surface by machining by making impressions of one or more parts of models, e.g. shaped articles and including possible subsequent assembly of the parts
- B29C33/3878—Manufacturing moulds, e.g. shaping the mould surface by machining by making impressions of one or more parts of models, e.g. shaped articles and including possible subsequent assembly of the parts used as masters for making successive impressions
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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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/026—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing of layered or coated substantially flat surfaces
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1809—Diffraction gratings with pitch less than or comparable to the wavelength
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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
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0215—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having a regular structure
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0294—Diffusing elements; Afocal elements characterized by the use adapted to provide an additional optical effect, e.g. anti-reflection or filter
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133504—Diffusing, scattering, diffracting elements
Definitions
- the present invention relates to a method for manufacturing a master, a master, and an optical body.
- an antireflection treatment is applied to a light incident surface in order to reduce surface reflection and increase transmitted light.
- an antireflection treatment for example, it is proposed that an optical body having a micro uneven structure (for example, a moth-eye structure) having an average period of unevenness of not more than a visible light wavelength is laminated on a light incident surface.
- a micro uneven structure for example, a moth-eye structure
- Patent Document 1 discloses a method of performing dry etching using nanometer-sized island-shaped fine particles as a protective mask.
- Patent Documents 2 and 3 disclose a method for forming a micro uneven structure having a plurality of recesses less than a micrometer in the aluminum film by using anodization of the aluminum film.
- Patent Document 4 discloses a method of forming a micro uneven structure having an average period of unevenness of a predetermined wavelength or less by electron beam lithography.
- Patent Documents 1 and 2 also disclose that a transfer product having a micro concavo-convex structure formed thereon can be formed by pressing a structure having such a micro concavo-convex structure against a resin or the like. Yes.
- Patent Document 5 discloses that a fine pattern can be transferred to a large-area film by pressing a roll-shaped mold having a fine pattern formed on the outer peripheral surface thereof while rotating the film. Is disclosed.
- Patent Documents 2 to 4 in addition to the antireflection function, an antiglare function (antiglare function) is imparted to the optical body.
- an antiglare function (antiglare function) is imparted to the optical body.
- an aluminum film having coarse crystal particles distributed on the surface is prepared, and anodic oxidation and etching are repeatedly performed on the aluminum film. Thereby, an aluminum film in which the micro uneven structure is superimposed on the rough surface of the aluminum film is produced.
- Patent Documents 3 and 4 the surface of the substrate is roughened by a mechanical or scientific method, and a micro uneven structure is superimposed on the rough surface. According to these techniques, the antiglare function is realized by the rough surface formed on the substrate, and the antireflection function is realized by the micro uneven structure superimposed on the rough surface.
- JP 2012-1000 A Patent No. 4916597 JP 2009-288337 A JP 2009-128541 A JP 2014-43068 A
- the haze value is known as an evaluation index of the antiglare function.
- the haze value is an index representing the turbidity (cloudiness) of the optical body.
- the higher the haze value the higher the light scattering property of the optical body, so the antiglare function is higher.
- the optical body manufacturing technique is required to stably manufacture an optical body having a desired haze value.
- the optical bodies produced by the techniques disclosed in Patent Documents 2 to 4 have a problem that the variation in haze value among individuals is very large. Therefore, the present invention has been made in view of the above problems, and an object of the present invention is a new and improved technique capable of more stably producing an optical body having a desired haze value.
- Another object of the present invention is to provide a method for manufacturing a master, a master, and an optical body.
- a first micro uneven structure having an average period of unevenness of not more than a visible light wavelength is formed on a surface of a substrate body including at least a substrate.
- a second step of forming an inorganic resist layer on the first micro-concave structure, and forming an organic resist layer including an organic resist material and filler particles dispersed in the organic resist material on the inorganic resist layer A third step of etching, an organic resist layer and an inorganic resist layer by etching, a macro uneven structure having an average period of irregularities larger than a visible light wavelength, and a second micro having an average period of irregularities of not more than a visible light wavelength.
- the etching rate of the filler particles may be higher than the etching rate of the organic resist material.
- the average particle size of the filler particles may be 2 to 15 ⁇ m.
- the organic resist layer and the inorganic resist layer are etched by dry etching, and the etching gas used when the organic resist layer is dry etched is used when the inorganic resist layer is dry etched. It may be different from the etching gas.
- the etching gas used when dry-etching the organic resist layer includes a first etching gas and a second etching gas, and the etching rate of the organic resist material with respect to the first etching gas is an inorganic resist layer.
- the etching rate of the organic resist material with respect to the second etching gas may be lower than the etching rate of the inorganic resist layer with respect to the second etching gas.
- the etching gas used for dry etching may contain one or more atoms selected from the group consisting of carbon atoms, fluorine atoms, oxygen atoms, and hydrogen atoms.
- the first step includes forming a substrate resist layer on the surface of the substrate, thereby producing a substrate body, and forming a first micro uneven structure on the substrate resist layer.
- the etching rate of the base resist layer may be different from the etching rate of the inorganic resist layer.
- the base body is composed of a base material
- the first step is a step of forming a base resist layer on the surface of the base material, and a third micro having the same arrangement pattern as the first micro uneven structure.
- You may include the step which forms an uneven structure in a base-material resist layer, and the step which forms a 1st micro uneven structure on the surface of a base material by etching a base-material resist layer.
- the second step includes a step of forming a first inorganic resist layer on the first micro-concave structure and a step of forming a second inorganic resist layer on the first inorganic resist layer. But you can.
- a master disc manufactured by the above-described master disc manufacturing method is provided.
- an optical body in which the macro uneven structure and the second micro uneven structure formed on the master are transferred.
- the average period of the macro uneven structure formed on the master can be adjusted by adjusting the average particle diameter and concentration of the filler particles. Furthermore, the arithmetic mean roughness of the second micro uneven structure formed on the master can be adjusted by adjusting the ratio of the etching rate of the organic resist material and the etching rate of the inorganic resist layer. Therefore, an optical body having a desired arithmetic average roughness and average period can be stably produced. Although details will be described later, there is a correlation between the arithmetic average roughness and average period of the optical body and the haze value of the optical body. Therefore, an optical body having a desired haze value can be manufactured more stably.
- an optical body having a desired haze value can be more stably produced.
- FIG. 1 is a perspective view showing an example of the appearance of the master 1
- FIG. 2 is a cross-sectional view schematically showing the surface shape of the master 1
- FIG. 3 is a plan view schematically showing the surface shape of the master 1.
- 2 is a cross-sectional view obtained by cutting the master 1 along a plane passing through the central axis of the master 1 and parallel to the central axis. 3 corresponds to the circumferential direction of the master 1, and the vertical direction corresponds to the axial direction of the master 1.
- the master 1 is, for example, a master used in the nanoimprint method, and has a cylindrical shape.
- the master 1 may have a cylindrical shape or another shape (for example, a flat plate shape).
- the concavo-convex structure of the master 1 can be seamlessly transferred to a resin substrate or the like by a roll-to-roll method.
- the optical body 4 (see FIG. 15) to which the uneven structure of the master 1 is transferred can be produced with high production efficiency.
- the shape of the master 1 is preferably a cylindrical shape or a columnar shape.
- the optical body 4 to which the concavo-convex structure is transferred by the master 1 according to this embodiment is used as an antireflection film, for example.
- FIG. 1 only the micro uneven structure 13 is shown among the macro uneven structure 12 and the micro uneven structure 13 described later. Actually, the macro uneven structure 12 and the micro uneven structure 13 are superposed on the surface of the base material 11.
- the master 1 includes a base material 11, a macro uneven structure 12 formed on the surface of the base material 11, and a micro uneven structure 13 (first 2 micro uneven structures).
- the base material 11 is a glass body, for example, and is specifically formed of quartz glass. However, the base material 11 is not particularly limited as long as it has high SiO 2 purity, and may be formed of fused silica glass or synthetic quartz glass.
- the shape of the base material 11 is a cylindrical shape, but may be a columnar shape or other shapes. However, as described above, the substrate 11 is preferably cylindrical or columnar.
- the macro concavo-convex structure 12 is a concavo-convex structure formed on the base material 11, and as shown in FIG. 2, the convex part 121 that is convex in the film thickness direction of the base material 11 and the film thickness direction of the base material 11. And a concave portion 122 that is concave.
- the average period of unevenness of the macro uneven structure 12 is larger than the visible light wavelength (for example, more than 830 nm), and preferably 1 ⁇ m or more and 100 ⁇ m or less. Therefore, the macro uneven structure 12 has a so-called anti-glare structure.
- the calculation method of an average period is as follows, for example. That is, a plurality of combinations of adjacent convex portions 121 and a plurality of adjacent concave portions 122 are picked up, and these distances P1 are measured. Then, the average period may be calculated by arithmetically averaging the measured values.
- the micro uneven structure 13 is an uneven structure superimposed on the macro uneven structure 12.
- the micro concavo-convex structure 13 includes a concave portion 132 that is concave in the film thickness direction of the substrate 11 and a convex portion 131 that is located between the adjacent concave portions 132 and 132.
- the plurality of convex portions 131 are arranged at intervals, but as shown in FIG. 3, the convex portions 131 may be adjacent to each other.
- the micro uneven structure 13 may be periodically arranged on the base material 11.
- the convex portions 131 and the concave portions 132 are arranged in a staggered manner.
- a plurality of tracks (for example, tracks T1 to T3) extending in the circumferential direction are arranged at equal intervals in the axial direction on the surface of the master 1, and the convex portions 131 and the concave portions 132 are equally spaced from each track. Be placed. Further, the protrusions 131 between adjacent tracks are arranged so as to be shifted in the circumferential direction by half of the protrusions 131.
- the average period of unevenness of the micro uneven structure 13 is not more than a visible light wavelength (for example, 830 nm or less), preferably 100 nm or more and 350 nm or less, and more preferably 150 nm or more and 280 nm or less. Therefore, the micro uneven structure 13 has a so-called moth-eye structure.
- a visible light wavelength for example, 830 nm or less
- the average period is less than 100 nm, formation of the micro uneven structure 13 may be difficult, which is not preferable.
- the average period exceeds 350 nm, it is not preferable because a visible light diffraction phenomenon may occur in the optical body 4 to which the uneven structure of the master 1 is transferred.
- the average period of the micro concavo-convex structure 13 is an arithmetic average value of the distance P2 (see FIG. 2) between the convex portions 131 and the concave portions 132 adjacent to each other.
- the calculation method of an average period is as follows, for example. That is, a plurality of combinations of adjacent recesses 132 and combinations of adjacent protrusions 131 are picked up, and the distance P2 is measured.
- the distance P2 as shown in FIG. 3, the track pitch P T, is divided into a dot pitch P D.
- the two-dimensional arrangement of the micro uneven structure 13 is not limited to the example of FIG.
- the plurality of rows of tracks on which the convex portions 131 and the concave portions 132 are arranged may be linear or curved.
- the convex part 131 and the recessed part 132 are not staggered, for example, may be arranged so that the convex part 131 and the recessed part 132 may be located at the vertex of a rectangle.
- the convex portions 131 and the concave portions 132 are arranged in a rectangular lattice shape.
- the micro uneven structure 13 may be arrange
- the master 1 has a structure in which the macro uneven structure 12 and the micro uneven structure 13 are superimposed on the surface of the base material 11. Therefore, the optical body 4 to which the uneven structure of the master 1 is transferred has a surface shape in which the macro uneven structure 41 and the micro uneven structure 42 are superimposed (see FIG. 15). Thereby, the optical body 4 can have both the anti-glare function by the macro uneven structure 12 and the antireflection function by the micro uneven structure 13.
- a base material resist layer 15 is formed (film formation) on the base material 11.
- a base-material main body is produced. That is, in this example, the substrate body is composed of the substrate 11 and the substrate resist layer 15.
- the micro concavo-convex structure 15 ⁇ / b> B that is the first micro concavo-convex structure is formed on the base resist layer 15.
- the resist material constituting the base resist layer 15 is not particularly limited, and may be either an organic resist material or an inorganic resist material. Examples of the organic resist material include novolak resists and chemically amplified resists.
- the inorganic resist material examples include metal oxides containing one or more transition metals such as tungsten (W) or molybdenum (Mo).
- the base material resist layer 15 is preferably formed of a thermal reaction resist containing a metal oxide.
- the base resist layer 15 may be formed on the base 11 by using spin coating, slit coating, dip coating, spray coating, screen printing, or the like. Moreover, when using an inorganic resist material for the base material resist layer 15, the base material resist layer 15 may be formed by using a sputtering method.
- a latent image 15 ⁇ / b> A is formed on the base resist layer 15 by exposing a part of the base resist layer 15 with an exposure apparatus 200 (see FIG. 13). Specifically, the exposure apparatus 200 modulates the laser beam 20 and irradiates the substrate resist layer 15 with the laser beam 20. As a result, a part of the base resist layer 15 irradiated with the laser beam 20 is modified, so that a latent image 15A corresponding to the micro uneven structure 13 can be formed on the base resist layer 15.
- the latent image 15A is formed on the base resist layer 15 with an average period equal to or shorter than the visible light wavelength.
- the base resist layer 15 is developed by dropping a developer onto the base resist layer 15 on which the latent image 15A is formed.
- the micro uneven structure 15 ⁇ / b> B first micro uneven structure
- the substrate resist layer 15 is a positive resist
- the exposed portion exposed by the laser beam 20 that is, the portion where the latent image 15A is formed
- the micro concavo-convex structure 15B is formed in which the exposed portion is a concave portion and the unexposed portion is a convex portion.
- the base resist layer 15 is a negative resist
- the exposed portion exposed by the laser beam 20 has a lower dissolution rate in the developer than the unexposed portion. Removed.
- the micro concavo-convex structure 15B is formed in which the exposed part is a convex part and the unexposed part is a concave part.
- an inorganic resist layer 17 is formed (deposited) on the micro uneven structure 15B (that is, on the base resist layer 15) so as to embed the micro uneven structure 15B.
- the inorganic resist material constituting the inorganic resist layer 17 include a metal oxide containing one or more transition metals such as SiO 2 , Si, DLC (Diamond Like Carbon), W, Mo, W, or Mo. Etc.
- the inorganic resist layer 17 is formed on the micro concavo-convex structure 15B by a sputtering method or a CVD method (chemical vapor deposition method).
- the inorganic resist layer 17 is formed in a state where the micro uneven structure 15B of the base resist layer 15 is left. The reason is as follows.
- the aspect ratio of the micro concavo-convex structure is a value obtained by dividing the distance between the convex portions or the concave portions (for example, the distance P2 shown in FIG. 2) by the height of the convex portions or the depth of the concave portions.
- the inorganic resist layer 17 is formed in a state where the micro uneven structure 15B of the base resist layer 15 is left. Even when the inorganic resist layer 17 is formed after the micro uneven structure 14 is formed on the base material 11, the micro uneven structure 13 having a desired aspect ratio is formed according to the second modification described later. can do. The second modification will be described later.
- the inorganic resist material constituting the inorganic resist layer 17 is selected so that the etching rate of the inorganic resist layer 17 is different from the etching rate of the base material resist layer 15.
- the inorganic resist layer 17 and the base material resist layer 15 are etched at the same time, if the etching rates of both are the same, they are etched equally. In this case, the micro uneven structure 13 cannot be formed on the surface of the substrate 11.
- the base resist layer 15 is made of a metal oxide such as tungsten oxide
- the inorganic resist layer 17 may be made of SiO 2 , Si or the like.
- the thickness of the inorganic resist layer 17 is not particularly limited, but may be 500 to 1500 nm, for example.
- this inventor tried omitting the inorganic resist layer 17 and forming the organic resist layer 19 mentioned later on the micro uneven
- the micro uneven structure 13 was not formed on the substrate 11.
- the organic resist material 191 has some adverse effects on the base resist layer 15 and the base 11.
- the inorganic resist layer 17 was interposed between the micro concavo-convex structure 15B and the organic resist layer 19 (in this embodiment), the micro concavo-convex structure 13 could be formed on the substrate 11.
- an organic resist layer 19 is formed on the inorganic resist layer 17 as shown in FIG.
- the organic resist layer 19 includes an organic resist material 191 and filler particles 192 dispersed in the organic resist material 191.
- the organic resist layer 19 is formed on the inorganic resist layer 17 by using, for example, spin coating, slit coating, dip coating, spray coating, or screen printing.
- the spray coating method is particularly preferable because the thin organic resist layer 19 can be formed uniformly and continuously.
- the spray coater used in the spray coating method may be any spray coater as long as it is a general spray coater. For example, a needle type spray coater may be used.
- the organic resist material 191 is not particularly limited, and examples thereof include novolak resists and chemically amplified resists.
- the filler particles 192 are made of a material whose etching rate is different from that of the organic resist material 191. That is, in this embodiment, the macro uneven structure 19 ⁇ / b> A is formed on the surface of the organic resist layer 19 by utilizing the difference between the etching rate of the filler particles 192 and the etching rate of the organic resist material 191.
- the etching rate of the organic resist material 191 and the filler particles 192 is specifically an etching rate for a macro uneven structure forming gas described later.
- the etching rate of the filler particles 192 is preferably higher than the etching rate of the organic resist material 191.
- the contents of this embodiment will be described on the assumption that the etching rate of the filler particles 192 is higher than the etching rate of the organic resist material 191.
- the etching rate of the filler particles 192 may be different from the etching rate of the organic resist material 191.
- materials that can be selected as the material of the filler particles 192 include various acrylic resins, carbon particles, and hollow silica.
- the average particle diameter of the filler particles 192 is larger than the visible light wavelength.
- the average particle diameter of the filler particles 192 is, for example, a value obtained by arithmetically averaging the sphere equivalent diameters (diameters) of the filler particles 192.
- a laser diffraction particle size distribution measuring device a microscope, an SEM (scanning electron microscope), and the like. Can be measured.
- the organic resist layer 19 is etched by an etching gas (macro uneven structure forming gas).
- the filler particles 192 are etched at a higher etching rate than the organic resist material 191. Therefore, as the etching of the organic resist layer 19 proceeds, the interface between the filler particles 192 and the organic resist material 191 disposed below the filler particles 192 is formed on the surface of the organic resist layer 19 as shown in FIG. An uneven structure substantially matching the shape is formed. Thereafter, the organic resist layer 19 is etched while maintaining this uneven structure.
- the concavo-convex structure is the macro concavo-convex structure 19A. That is, the macro uneven structure 19 ⁇ / b> A can be formed in the organic resist layer 19 by setting the etching rate and average particle diameter of the filler particles 192 as described above.
- the average period of the macro uneven structure 19 ⁇ / b> A can be adjusted to a desired value by adjusting the average particle diameter of the filler particles 192 and the concentration in the organic resist layer 19.
- the average period can be increased by increasing the average particle diameter of the filler particles 192.
- the average period can be reduced by increasing the concentration of the filler particles 192.
- the arithmetic average roughness of the macro uneven structure 19A can be adjusted to a desired value by adjusting the ratio of the etching rate of the organic resist material 191 and the etching rate of the filler particles 192. That is, the closer the etching rate is, the smaller the arithmetic average roughness is (that is, the macro uneven structure 19A is almost flat), and the longer the etching rate is, the larger the arithmetic average roughness is.
- the average particle diameter of the filler particles 192 is not particularly limited as long as it is larger than the visible light wavelength, but is preferably 2 to 15 ⁇ m, and more preferably 6 to 10 ⁇ m. This is because by setting the average particle size of the filler particles 192 to a value within such a range, the antiglare function of the optical body 4 can be further enhanced, and glare of the optical body 4 can be suppressed.
- the average particle size of the filler particles 192 when the average particle size of the filler particles 192 is less than 2 ⁇ m, the macro uneven structure 12 may not be formed on the surface of the substrate 11.
- the layer thickness of the organic resist layer 19 becomes very large. That is, the organic resist layer 19 needs to be at least 1/3 or more of the filler particles 192. Therefore, when the average particle diameter of the filler particles 192 exceeds 15 ⁇ m, the layer thickness of the organic resist layer 19 becomes very large. And when the organic resist layer 19 becomes thick in this way, etching takes a lot of time and labor. If the average particle size of the filler particles 192 exceeds 15 ⁇ m, the filler particles 192 may settle in the organic resist layer 19 due to their own weight.
- the organic resist layer 19 is substantially separated into an upper layer made of the organic resist material 191 and a lower layer made of the filler particles 192.
- the macro uneven structure of the inorganic resist layer 17 is obtained by using the ratio (in other words, the difference) between the etching rate of the organic resist material 191 and the etching rate of the inorganic resist layer 17. Adjust the arithmetic average roughness of 17A.
- the arithmetic average roughness of the macro uneven structure 17A increases.
- the filler particles 192 settle, the organic resist material 191 hardly exists on the inorganic resist layer 17. Therefore, it becomes almost impossible to use the difference between the etching rates of the two. As a result, it becomes very difficult to adjust the arithmetic average roughness of the macro uneven structure 17A.
- the content of the filler particles 192 is not particularly limited as long as the above effect is realized, but it is preferably at a concentration at which the filler particles 192 are distributed at least over the entire surface of the inorganic resist layer 17. Specifically, the content of the filler particles 192 is preferably suppressed to a mass within twice the solid content mass of the organic resist material 192. If the content of the filler particles 192 is larger than this, it becomes difficult to form the organic resist layer 19 uniformly on the inorganic resist layer 17, and as a result, the possibility that the filler particles 192 fall off from the inorganic resist layer 17 increases.
- the thickness of the organic resist layer 19 is not particularly limited as long as it is 1/3 or more of the average particle diameter of the filler particles 192. However, if it exceeds twice, for example, the filler particles 192 are not easily deposited at the time of etching, and the process time may be increased. There is sex. For this reason, the thickness of the organic resist layer 19 is preferably not more than twice the average particle diameter of the filler particles 192.
- the organic resist layer 19, the inorganic resist layer 17, the base resist layer 15, and the base 11 are sequentially etched.
- the etching of the present embodiment is preferably dry etching having vertical anisotropy, for example, reactive ion etching (RIE).
- RIE reactive ion etching
- the macro uneven structure and the micro uneven structure formed in each resist layer are transferred to another resist layer.
- the organic resist layer 19 is etched by isotropic etching such as wet etching, the micro uneven structure 13 may not be formed on the substrate 11.
- etching gas contains any 1 or more types of atoms selected from the group which consists of a carbon atom, a fluorine atom, an oxygen atom, and a hydrogen atom.
- the etching gas may be a fluorocarbon gas such as CHF 3 , CH 2 F 2 , CF 4 , C 2 F 8 , and C 3 F 8, and the fluorocarbon gas may be O 2 gas, H 2.
- a gas or an additive gas such as Ar gas may be added.
- the specific composition of the etching gas may be appropriately selected depending on the resist to be etched. Details will be described later.
- the macro concavo-convex structure 12 and the micro concavo-convex structure 13 are superimposed on the base 11 and the first etching for transferring the macro concavo-convex structure 19A formed on the organic resist layer 19 to the inorganic resist layer 17. It is divided into the second etching to be formed.
- first etching In the first etching, first, the organic resist layer 19 is etched.
- An etching gas used in the first etching (hereinafter also referred to as “macro uneven structure forming gas”) includes a first etching gas and a second etching gas.
- the etching rate of the organic resist material 191 with respect to the first etching gas is higher than the etching rate of the inorganic resist layer 17 with respect to the first etching gas.
- the etching rate of the organic resist material 191 with respect to the second etching gas is lower than the etching rate of the inorganic resist layer 17 with respect to the second etching gas.
- the first etching gas is, for example, O 2 gas
- the second etching gas is, for example, fluorocarbon gas.
- a macro uneven structure 19A is formed on the surface of the organic resist layer 19 as shown in FIG.
- the shape of the macro uneven structure 19 ⁇ / b> A varies every time the macro uneven structure forming gas etches the filler particles 192. Then, the shape of the macro uneven structure 19A becomes constant when all the filler particles 192 are etched. Thereafter, the organic resist layer 19 is etched while maintaining the shape of the macro uneven structure 19A.
- the first etching is continued.
- the macro uneven structure 19A is transferred to the inorganic resist layer 17 as shown in FIG. That is, the macro uneven structure 17 ⁇ / b> A is formed on the surface of the inorganic resist layer 17.
- the first etching is finished.
- the macro uneven structure forming gas is a mixed gas of the first etching gas and the second etching gas having the above-described characteristics. For this reason, the etching rate of the organic resist material 191 for the macro uneven structure forming gas is different from the etching rate of the inorganic resist layer 17 for the macro uneven structure forming gas. That is, the selection ratio of the macro uneven structure forming gas is different.
- the selection ratio of the macro uneven structure forming gas is a value obtained by dividing the etching rate of the organic resist material 191 with respect to the macro uneven structure forming gas by the etching rate of the inorganic resist layer 17 with respect to the macro uneven structure forming gas. . Therefore, the shape of the macro uneven structure 17A does not completely match the macro uneven structure 19A. Specifically, the arithmetic average roughness of the macro uneven structure 17A is different from the arithmetic average roughness of the macro uneven structure 19A.
- the arithmetic average roughness of the macro uneven structure 17A can be adjusted by adjusting the selection ratio of the macro uneven structure forming gas.
- adjusting the selection ratio of the macro uneven structure forming gas for example, adjusting the mixing ratio of the first etching gas and the second etching gas can be mentioned.
- the mixing ratio of the first etching gas is increased, the selection ratio of the macro uneven structure forming gas is increased (that is, the etching rate of the inorganic resist layer 17 is decreased and the etching rate of the organic resist material 191 is increased). Increase).
- the arithmetic average roughness of the macro uneven structure 17A decreases. That is, the macro uneven structure 17A becomes shallow.
- the selection ratio of the macro uneven structure forming gas is decreased (that is, the etching rate of the inorganic resist layer 17 is increased and the etching rate of the organic resist material 191 is increased). Decrease). For this reason, the arithmetic average roughness of the macro uneven structure 17A increases. That is, the macro uneven structure 17A is deepened.
- the selection ratio of the macro uneven structure forming gas can be adjusted by adjusting the mixing ratio of the first etching gas and the second etching gas.
- the arithmetic average roughness of the macro uneven structure 17A can be adjusted.
- the selection ratio of the macro uneven structure forming gas can also be adjusted by adjusting the combination of the organic resist material 191 and the inorganic resist material constituting the inorganic resist layer 17.
- the average period of the macro uneven structure 17A substantially matches the average period of the macro uneven structure 19A.
- the average period of the macro uneven structure 17A can be adjusted by adjusting the average particle diameter and concentration of the filler particles 192, and the selection ratio of the macro uneven structure forming gas can be adjusted.
- the arithmetic average roughness of the macro uneven structure 17A can be adjusted. Therefore, the macro uneven structure 17A having a desired average period and arithmetic average roughness can be formed.
- the first etching may be repeatedly performed before the second etching is performed. By repeating the first etching, the average period of the macro uneven structure 17A can be increased, and the arithmetic average roughness can be decreased.
- the inorganic resist layer 17 is etched.
- the etching gas used in the second etching (hereinafter also referred to as “overlapping structure forming gas”) is not particularly limited as long as it can etch the inorganic resist layer 17, the base material resist layer 15, and the base material 11.
- the superposition structure forming gas may be a mixed gas of one or two or more kinds of fluorocarbon gases when the substrate 11 is quartz glass. Examples of the fluorocarbon gas include CHF 3 , CH 2 F 2 , CF 4 , C 2 F 8 , and C 3 F 8 .
- the superposition structure forming gas may be a gas obtained by adding an additive gas such as H 2 gas or Ar gas to these fluorocarbon gases.
- the superposition structure forming gas may further contain O 2 gas, but since O 2 gas is more isotropic than other gases, the concentration of O 2 gas is preferably as low as possible.
- O 2 gas is included in the macro uneven structure forming gas.
- only a relatively large unevenness of the macro uneven structure 17A is formed on the inorganic resist layer 17, so there is no particular problem even if the macro uneven structure forming gas has some isotropic property. .
- the inorganic resist layer 17 is etched while maintaining the shape of the macro uneven structure 17A.
- the superposition structure forming gas reaches the base resist layer 15.
- the inorganic resist layer 17 and the base material resist layer 15 that is, the convex portion of the micro concavo-convex structure 15B) existing in the concave portion of the micro concavo-convex structure 15B are etched by the overlapping structure forming gas.
- the overlapping structure forming gas reaches the substrate 11.
- the convex portion of the micro concavo-convex structure 15B is ahead of the inorganic resist layer 17 existing in the concave portion of the micro concavo-convex structure 15B. Disappear. Therefore, in this case, the base material 11 is etched from the portion where the convex portions of the micro uneven structure 15B existed. As the second etching progresses, the inorganic resist layer 17 present in the recesses of the micro concavo-convex structure 15B also disappears completely. Thereafter, the entire surface of the substrate 11 is etched. Thereby, the micro uneven structure 13 having the inverted shape of the micro uneven structure 15 ⁇ / b> B is formed on the surface of the substrate 11.
- the etching rate of the base resist layer 15 is lower than the etching rate of the inorganic resist layer 17, the inorganic resist layer 17 present in the concave portion of the micro uneven structure 15B disappears before the convex portion of the micro uneven structure 15B.
- the base material 11 is etched from the portion where the concave portion of the micro uneven structure 15B was present.
- the convex portions of the micro concavo-convex structure 15B disappear completely. Thereafter, the entire surface of the substrate 11 is etched.
- the micro uneven structure 13 having the same arrangement pattern (uneven arrangement pattern) as the micro uneven structure 15 ⁇ / b> B is formed on the surface of the substrate 11.
- the macro uneven structure 17 A of the inorganic resist layer 17 is also transferred to the base material 11.
- the second etching is finished.
- the macro uneven structure 12 and the micro uneven structure 13 are formed so as to overlap each other on the surface of the substrate 11. That is, the master 1 is produced.
- the shape of the macro uneven structure 12 substantially matches the macro uneven structure 17A.
- the etching rate of the inorganic resist layer 17 with respect to the overlapping structure forming gas and the etching rate of the substrate 11 with respect to the overlapping structure forming gas Is different. That is, the selection ratio of the superposition structure forming gas is different.
- the selection ratio of the superposed structure forming gas is a value obtained by dividing the etching rate of the inorganic resist layer 17 with respect to the superposed structure forming gas by the etching rate of the base material 11 with respect to the superposed structure forming gas. Therefore, the shape of the macro uneven structure 12 does not completely match the macro uneven structure 17A. Specifically, the arithmetic average roughness of the macro uneven structure 12 is different from the arithmetic average roughness of the macro uneven structure 17A.
- the arithmetic average roughness of the macro uneven structure 12 can be adjusted by changing the selection ratio of the superposition structure forming gas.
- a method for changing the selection ratio of the superposition structure forming gas for example, a combination of the inorganic resist material constituting the inorganic resist layer 17 and the material of the base material 11 may be changed.
- the etching rate of the inorganic resist layer 17 increases and the etching rate of the base material 11 decreases, so that the arithmetic average roughness of the macro uneven structure 12 decreases. That is, the macro uneven structure 12 becomes shallow.
- the selective ratio of the superposition structure forming gas decreases, the etching rate of the inorganic resist layer 17 decreases and the etching rate of the substrate 11 increases, so that the arithmetic average roughness of the macro uneven structure 12 increases. That is, the macro uneven structure 12 is deepened.
- the selection ratio of the superposition structure forming gas can be adjusted by changing the combination of the inorganic resist material constituting the inorganic resist layer 17 and the material of the base material 11.
- the arithmetic average roughness of the macro uneven structure 12 can be adjusted.
- the macro uneven structure 12 is further adjusted by adjusting the selection ratio of the superposition structure forming gas. Can be set to a desired value.
- the average period of the macro uneven structure 12 substantially matches the average period of the macro uneven structure 17A.
- the average period of the macro uneven structure 12 can be adjusted by adjusting the average particle size and concentration of the filler particles 192, and the selection ratio of the macro uneven structure forming gas and the formation of the superposed structure
- the arithmetic average roughness of the macro uneven structure 12 can be adjusted by adjusting the selection ratio of the working gas. Therefore, the macro uneven structure 12 having a desired average period and arithmetic average roughness can be formed.
- the inorganic resist layer 17 has a two-layer structure. That is, in the first modified example, the inorganic resist layer 17 includes the first inorganic resist layer 171 formed on the micro uneven structure 15B and the second inorganic resist formed on the first inorganic resist layer 171. Layer 172. Each inorganic resist layer 171 and 172 is formed by the same method as in the second step described above.
- Examples of the inorganic resist material constituting the first inorganic resist layer 171 and the second inorganic resist layer 172 include one kind of SiO 2 , Si, DLC (Diamond Like Carbon), W, Mo, W, or Mo, or Examples thereof include metal oxides containing two or more transition metals.
- the first inorganic resist layer 171 and the second inorganic resist layer 172 are made of inorganic resist materials that are different from each other (specifically, the etching rates are different). Furthermore, the etching rate of the second inorganic resist layer 172 is different from the etching rate of the base material resist layer 15. All other steps are the same as those described above.
- the arithmetic average roughness of the macro uneven structure 17A can be adjusted by the selection ratio of the macro uneven structure forming gas.
- the selection ratio of the macro uneven structure forming gas can be adjusted by a combination of the organic resist material and the inorganic resist material constituting the inorganic resist layer 17. Therefore, when the inorganic resist layer 17 and the base resist layer 15 are made of the same inorganic resist material, the arithmetic average roughness of the macro uneven structure 17A may be a desired value. However, if the inorganic resist layer 17 is a single layer and is formed of the same inorganic resist material as the base resist layer 15, the micro uneven structure 13 cannot be formed.
- the selection ratio of the macro uneven structure forming gas is determined by the combination of the organic resist material and the inorganic resist material in the portion of the inorganic resist layer 17 in contact with the organic resist layer 19.
- the portion in contact with the organic resist layer 19, that is, the second inorganic resist layer 172 is formed of the same inorganic resist material as the base material resist layer 15, and the first inorganic resist layer 171 is used as the base material. It can be formed of an inorganic resist material different from the resist layer 15. That is, according to the first modification, the material selectivity of the second inorganic resist layer 172 can be increased.
- the layer thickness ratio between the first inorganic resist layer 171 and the second inorganic resist layer 172 is not particularly limited, but depends on the etching rate between the first inorganic resist layer 171 and the second orientation resist layer 172. It only has to be set. For example, the layer thickness of the layer having a high etching rate may be set in proportion to the etching rate ratio with the layer having a low etching rate.
- a base resist layer 15 is formed on the base 11, and a micro uneven structure 15B (third micro uneven structure) is formed on the base resist layer 15.
- the base resist layer 15 and the base 11 are etched by the same method as the second etching described above.
- the micro uneven structure 14 (first micro uneven structure) shown in FIG. 12 is formed on the surface of the substrate 11. Therefore, in the second modification, the base material 11 constitutes the base material body.
- the micro uneven structure 14 has the same arrangement pattern (uneven arrangement pattern) as the micro uneven structure 15B.
- an inorganic resist layer 17 having a two-layer structure is formed on the micro uneven structure 14.
- the 1st inorganic resist layer 171 is a resist layer for forming the micro uneven structure 13 in the base material 11, and is comprised by DLC.
- the second inorganic resist layer 172 is composed of the same inorganic resist material (except for DLC) as in the first modification. Thereafter, the same processing as described above is performed.
- the exposure apparatus 200 is an apparatus that exposes the base resist layer 15.
- the exposure apparatus 200 includes a laser light source 201, a first mirror 203, a photodiode (PD) 205, a deflection optical system, a control mechanism 230, a second mirror 213, a moving optical table 220, and a spindle motor. 225 and a turntable 227.
- the base material 11 is mounted on the turntable 227 and can rotate.
- the laser light source 201 is a light source that emits laser light 20, and is, for example, a solid-state laser or a semiconductor laser.
- the wavelength of the laser light 20 emitted from the laser light source 201 is not particularly limited, but may be, for example, a blue light band wavelength of 400 nm to 500 nm.
- the spot diameter of the laser beam 20 (the diameter of the spot irradiated on the resist layer) may be smaller than the diameter of the opening surface of the concave portion of the micro concavo-convex structure 15B, for example, about 200 nm.
- the laser light 20 emitted from the laser light source 201 is controlled by the control mechanism 230.
- the laser light 20 emitted from the laser light source 201 travels straight in a parallel beam, is reflected by the first mirror 203, and is guided to the deflection optical system.
- the first mirror 203 is composed of a polarization beam splitter, and has a function of reflecting one of the polarization components and transmitting the other of the polarization components.
- the polarization component transmitted through the first mirror 203 is received by the photodiode 205 and subjected to photoelectric conversion.
- the light reception signal photoelectrically converted by the photodiode 205 is input to the laser light source 201, and the laser light source 201 performs phase modulation of the laser light 20 based on the input light reception signal.
- the deflection optical system includes a condenser lens 207, an electro-optic deflector (EOD) 209, and a collimator lens 211.
- EOD electro-optic deflector
- the laser beam 20 is condensed on the electro-optic deflection element 209 by the condenser lens 207.
- the electro-optic deflection element 209 is an element that can control the irradiation position of the laser light 20.
- the exposure apparatus 200 can also change the irradiation position of the laser beam 20 guided onto the moving optical table 220 by the electro-optic deflection element 209. After the irradiation position of the laser light 20 is adjusted by the electro-optic deflection element 209, the laser light 20 is converted into a parallel beam again by the collimator lens 211.
- the laser beam 20 emitted from the deflection optical system is reflected by the second mirror 213 and guided horizontally and parallel onto the moving optical table 220.
- the moving optical table 220 includes a beam expander (BEX) 221 and an objective lens 223.
- the laser light 20 guided to the moving optical table 220 is shaped into a desired beam shape by the beam expander 221, and then irradiated to the base material resist layer 15 formed on the base material 11 through the objective lens 223. Is done. Further, the moving optical table 220 moves by one feed pitch (track pitch) in the arrow R direction (feed pitch direction) every time the substrate 11 rotates once.
- the base material 11 On the turntable 227, the base material 11 is installed.
- the spindle motor 225 rotates the substrate 11 by rotating the turntable 227.
- the control mechanism 230 includes a formatter 231 and a driver 233, and controls the irradiation of the laser light 20.
- the formatter 231 generates a modulation signal that controls the irradiation of the laser light 20, and the driver 233 controls the laser light source 201 based on the modulation signal generated by the formatter 231. Thereby, irradiation of the laser beam 20 onto the substrate 11 is controlled.
- the formatter 231 generates a control signal for irradiating the substrate resist layer 15 with the laser beam 20 based on an input image on which an arbitrary pattern to be drawn on the substrate resist layer 15 is drawn. Specifically, first, the formatter 231 acquires an input image on which an arbitrary pattern to be drawn on the base material resist layer 15 is drawn. The input image is an image corresponding to a developed view of the outer peripheral surface of the base resist layer 15 that is cut out in the axial direction and extended to one plane. Next, the formatter 231 divides the input image into small areas of a predetermined size (for example, in a grid pattern), and determines whether each small area includes a drawing pattern.
- a predetermined size for example, in a grid pattern
- the formatter 231 generates a control signal that controls to irradiate the laser light 20 to each small region determined to include a drawing pattern. Further, the driver 233 controls the output of the laser light source 201 based on the control signal generated by the formatter 231. Thereby, irradiation of the laser beam 20 to the base material resist layer 15 is controlled.
- the optical body 4 can be manufactured by a roll-to-roll type transfer device 300 using the master 1.
- the optical body 4 is produced using a photocurable resin.
- the transfer device 300 includes a master 1, a base material supply roll 301, a winding roll 302, guide rolls 303 and 304, a nip roll 305, a peeling roll 306, a coating device 307, and a light source 309.
- the base material supply roll 301 is a roll in which the long base film 3 is wound in a roll shape
- the winding roll 302 is a roll that winds up the optical body 4.
- the guide rolls 303 and 304 are rolls that transport the base film 3.
- the nip roll 305 is a roll for bringing the base film 3 on which the uncured resin layer 310 is laminated, that is, the transfer film 3 a into close contact with the master 1.
- the peeling roll 306 is a roll for peeling the base film 3 on which the cured resin layer 310 a is laminated, that is, the optical body 4 from the master 1.
- the coating device 307 includes coating means such as a coater, and applies an uncured photocurable resin composition to the base film 3 to form an uncured resin layer 310.
- the coating device 307 may be, for example, a gravure coater, a wire bar coater, or a die coater.
- the light source 309 is a light source that emits light having a wavelength capable of curing the photocurable resin composition, and may be, for example, an ultraviolet lamp.
- the photo-curable resin composition is a resin that is hardened due to a decrease in fluidity when irradiated with light having a predetermined wavelength.
- the photocurable resin composition may be an ultraviolet curable resin such as an acrylic resin.
- the photocurable resin composition may contain an initiator, a filler, a functional additive, a solvent, an inorganic material, a pigment, an antistatic agent, a sensitizing dye, or the like, if necessary.
- the base film 3 is continuously sent from the base material supply roll 301 through the guide roll 303. In addition, you may change the base material supply roll 301 into the base material supply roll 301 of another lot in the middle of sending out.
- An uncured photocurable resin composition is applied to the sent base film 3 by the coating device 307, and the uncured resin layer 310 is laminated on the base film 3. Thereby, the to-be-transferred film 3a is produced.
- the transferred film 3 a is brought into close contact with the master 1 by the nip roll 305.
- the light source 309 cures the uncured resin layer 310 by irradiating light to the uncured resin layer 310 that is in close contact with the master 1.
- the arrangement pattern of the macro uneven structure 12 and the micro uneven structure 13 formed on the outer peripheral surface of the master 1 is transferred to the uncured resin layer 310. That is, the cured resin layer 310a in which the inverted pattern of the macro uneven structure 12 and the micro uneven structure 13 is formed is formed.
- the light source 309 may irradiate light obliquely with respect to the concave portion 422 (see FIG. 15) of the micro uneven structure 42. In this case, only a part of the recess 422 is cured.
- the base film 3 on which the cured resin layer 310 a is laminated, that is, the optical body 4 is peeled from the master 1 by the peeling roll 306. Next, the optical body 4 is taken up by the take-up roll 302 via the guide roll 304.
- the transfer film 3a is conveyed by roll-to-roll, while the peripheral surface shape of the master 1 is transferred to the transfer film 3a. Thereby, the optical body 4 is produced.
- the coating device 307 and the light source 309 become unnecessary.
- the base film 3 is a thermoplastic resin film, and a heating device is disposed upstream of the master 1. The base film 3 is heated and softened by this heating device, and then the base film 3 is pressed against the master 1. Thereby, the arrangement pattern of the macro uneven structure 12 and the micro uneven structure 13 formed on the peripheral surface of the master 1 is transferred to the base film 3.
- the base film 3 may be a film made of a resin other than the thermoplastic resin, and the base film 3 and the thermoplastic resin film may be laminated. In this case, the laminated film is pressed against the master 1 after being heated by the heating device.
- the transfer device 300 can continuously produce a transfer product, that is, the optical body 4 to which the array pattern of the macro uneven structure 12 and the micro uneven structure 13 formed on the master 1 is transferred.
- the macro uneven structure 12 formed on the peripheral surface of the master 1 has a desired average period and arithmetic average roughness. Therefore, the macro uneven structure 41 (see FIG. 15) formed on the optical body 4 has a desired average period and arithmetic average roughness.
- FIG. 15 shows the configuration of the optical body 4 manufactured by the above manufacturing method.
- the optical body 4 has, for example, a film shape, and includes a macro uneven structure 41 formed on the surface thereof, and a micro uneven structure 42 superimposed on the macro uneven structure 41.
- the macro uneven structure 41 has a convex portion 411 and a concave portion 412.
- the shape of the macro uneven structure 41 is an inverted shape of the macro uneven structure 12 of the master 1.
- the micro concavo-convex structure 42 has a convex portion 421 and a concave portion 422.
- the shape of the micro uneven structure 42 is an inverted shape of the micro uneven structure 13 of the master 1.
- the optical body 4 according to the present embodiment can realize a high antiglare function by the macro uneven structure 41 and can realize a high antireflection function by the micro uneven structure 13. Therefore, in order to improve the antiglare function of the optical body 4, it is not necessary to mix a separate scatterer into the optical body 4. Therefore, according to this embodiment, the optical body 4 having a high antiglare function and an antireflection function can be produced stably at low cost.
- the arithmetic average roughness of the optical body 4 is the arithmetic average roughness of the superimposed structure of the macro uneven structure 41 and the micro uneven structure 42.
- the arithmetic average roughness of the macro uneven structure 41 substantially matches the arithmetic average roughness of the macro uneven structure 12 of the master 1. Further, in the present embodiment, when the master 1 is manufactured, only the shape of the macro uneven structure 12 can be arbitrarily changed while keeping the arrangement pattern of the micro uneven structure 13 constant.
- optical bodies 4 in which the arrangement pattern of the micro concavo-convex structure 42 is constant and the arithmetic average roughness of the superimposed structure is different.
- arithmetic average roughness of the optical body 4 means “arithmetic average roughness of the superposed structure of the optical body 4” unless otherwise specified.
- the average period of the optical body 4 is the average period of the macro uneven structure 41.
- the average period and arithmetic average roughness of the optical body 4 can be set to desired values. And when this inventor examined in detail about the average period and arithmetic mean roughness of the optical body 4, they discovered that there exists a close correlation between these and the haze value of the optical body 4.
- FIG. An example of the correlation between the average period and arithmetic average roughness of the optical body 4 and the haze value of the optical body 4 is shown in FIG.
- the vertical axis represents the haze value (%) of the optical body 4.
- Point A shows the correlation between Ra / Rsm and haze value. Incidentally, the correlation indicated by the point A is obtained by an example described later.
- the optical body 4 having a desired haze value can be stably produced.
- an optical body having a high haze value could not be stably produced. That is, even a conventional technique can produce an optical body with a high haze value by polishing the optical body. However, there was a lot of quality variation and it was not practical. In this embodiment, an optical body having a high haze value can be stably produced.
- optical bodies The optical body 4 produced by this embodiment can be applied to various uses.
- the optical body 4 can be used as an antireflection film such as a display device or an optical element, or an antiglare film.
- the optical body 4 is not limited to these applications, and can be applied to any field where antireflection and antiglare are required.
- the master 1 and the optical body 4 according to the above embodiment will be described in detail with reference to examples and comparative examples.
- the Example shown below is one example of conditions for showing the feasibility and effect of the master 1 and the optical body 4 according to the above embodiment, and the master 1 and the optical body 4 of the present invention are the following examples. It is not limited to.
- the optical body 4 was manufactured by the following steps. (Example 1) A substrate 11 made of cylindrical quartz glass was prepared, and a substrate resist layer 15 made of tungsten oxide was formed on the surface of the substrate 11 by sputtering. The layer thickness of the base resist layer 15 was 50 nm. Subsequently, the substrate resist layer was irradiated with laser light from the exposure apparatus 200 shown in FIG. 13, thereby forming a latent image 15 ⁇ / b> A having a staggered arrangement pattern on the substrate resist layer 15.
- the setting values of the exposure apparatus 200 relating to the pitch of the latent image 15A are a dot pitch of 230 nm and a track pitch of 153 nm.
- an alkaline developer (NMD3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped on the base resist layer 15 to remove the exposed portion (the portion where the latent image 15A was formed). That is, development processing was performed. Thereby, the micro uneven structure 15 ⁇ / b> B was formed on the base resist layer 15.
- an inorganic resist layer 17 made of SiO 2 was formed on the micro concavo-convex structure 15B by sputtering.
- the inorganic resist layer 17 was a single layer, and the layer thickness was 1000 nm.
- the etching rate for the superposed structure forming gas (composition will be described later) of the inorganic resist layer 17 is different from the etching rate for the superposed structure forming gas of the base resist layer 15.
- the ratio between the etching rate of the base resist layer 15 and the etching rate of the inorganic resist layer 17 was 1/3.
- both etching rates were measured by etching the single layer of the inorganic resist layer 17 and the single layer of the base-material resist layer 15 on the conditions of the 2nd etching mentioned later.
- P4210 manufactured by AZ Electronic Materials was prepared as the organic resist material 191
- acrylic particles SE010T manufactured by Negami Kogyo Co., Ltd.
- the filler particles 192 were prepared as the filler particles 192.
- the average particle diameter of the acrylic particles was measured with a microscope, the average particle diameter was 10 ⁇ m.
- an organic resist composition was prepared by mixing the organic resist material 191 and the filler particles 192 in a weight ratio of 70:30. And this dispersion liquid for spray coating was produced by mixing this organic resist composition and PGM (propylene glycol monomethyl ether) which is a solvent by weight ratio of 1:20.
- PGM propylene glycol monomethyl ether
- the dispersion liquid for spray coating was sprayed onto the inorganic resist layer 17 to form an organic resist layer 19 having a layer thickness of 10 to 15 ⁇ m.
- the layer thickness of the organic resist layer 19 takes various values within the plane of the organic resist layer 19, and any layer thickness is within the above range. That is, in Example 1, the organic resist layer 19 was formed on the inorganic resist layer 17 by spray coating.
- PGM which is a solvent volatilizes in spraying and standing in the air.
- the macro uneven structure forming gas used for the first etching was a gas in which CF 4 gas and O 2 gas were mixed at a flow rate ratio (sccm ratio) of 2:28.
- the output of the reactive ion etching apparatus was 200 W, and the gas pressure was 0.5 Pa.
- the etching rate ratio was 1 to 2.
- the selectivity of the macro uneven structure forming gas was 25/1.
- the selection ratio was calculated by the following method. That is, a single layer of the organic resist material 191 and a single layer of SiO 2 were etched under the above etching conditions, and the etching rates of both were measured. Then, the selection ratio was calculated by dividing the etching rate of the organic resist material 191 by the etching rate of the inorganic resist layer 17.
- a second etching was performed using a reactive ion etching apparatus.
- the overlapping structure forming gas used for the second etching was a gas in which CHF 3 gas and CF 4 gas were mixed at a flow rate ratio (sccm ratio) of 27: 3.
- the output of the reactive ion etching apparatus was 200 W, the gas pressure was 0.5 Pa, and the etching time was 2 hours.
- the master 1 according to Example 1 was manufactured through the above steps.
- the selection ratio of the superposition structure forming gas was 1/3.
- the selection ratio was calculated by the following method. That is, the base material 11 and the single layer of SiO 2 were etched under the above etching conditions, and the etching rates of both were measured. Then, the selection ratio was calculated by dividing the etching rate of the organic resist material 191 by the etching rate of the inorganic resist layer 17.
- the optical body 4 was produced using the transfer apparatus 300 shown in FIG.
- the base film 3 was a polyethylene terephthalate film, and the photocurable resin composition was an acrylic resin acrylate.
- the uncured resin layer 310 was cured by irradiating the uncured resin layer 310 with 1000 mJ / cm 2 of ultraviolet rays.
- the optical body 4 was produced through the above steps.
- the arithmetic mean roughness and average period of the optical body 4 were measured using Surfcorder ET200 by Kosaka Laboratory.
- the measurement conditions were a speed of 100 ⁇ m / sec and a measuring force of 100 ⁇ N.
- the dot pitch of the micro concavo-convex structure 42 of the optical body 4 was 270 nm
- the track pitch was 153 nm
- the depth was about 500 to 600 nm.
- Example 2 The same processing as in Example 1 was performed except that the second etching was performed after the first etching was performed twice.
- the second first etching was performed under the same conditions as the first first etching.
- the dispersion liquid for spray coating was sprayed on the inorganic resist layer 17 under the same spray conditions (spray pressure, spray time, etc.) as the first etching for the first time.
- the arithmetic average roughness and average period of the optical body 4 were measured by the same method as in Example 1, the arithmetic average roughness was 0.112 ⁇ m and the average period was 11.8 ⁇ m. Therefore, Ra / Rsm was 0.009.
- the average period of the optical body 4 can be increased and the arithmetic average roughness can be decreased. Therefore, by repeating the first etching, the average period of the macro uneven structure 17A can be increased and the arithmetic average roughness can be decreased. Further, the dot pitch, track pitch, and depth of the micro concavo-convex structure 42 of the optical body 4 were approximately the same as those in Example 1. These values were confirmed by SEM.
- Example 3 In Example 3, the same processing as in Example 1 was performed, except that the average particle diameter of the filler particles 192 was 6 ⁇ m, the inorganic resist layer 17 was made into a two-layer structure, and the composition of the macro uneven structure forming gas was changed. . Specifically, in Example 3, the first inorganic resist layer 171 made of SiO 2 was formed on the micro concavo-convex structure 15B by sputtering. The thickness of the first inorganic resist layer 171 was 200 nm. Next, a second inorganic resist layer 172 made of tungsten oxide was formed on the first inorganic resist layer 171 by sputtering. The layer thickness of the second inorganic resist layer 172 was 500 nm. Therefore, Example 3 corresponds to the first modification.
- Example 1 a dispersion for spray coating was prepared in the same manner as in Example 1 except that acrylic particles having an average particle diameter of 6 ⁇ m (SE006T manufactured by Negami Kogyo Co., Ltd.) were used.
- the spray coating dispersion was sprayed onto the second inorganic resist layer 172 in the same manner as in Example 1 to form the organic resist layer 19 on the second inorganic resist layer 172.
- the macro uneven structure forming gas was a gas in which CF 4 gas and O 2 gas were mixed at a flow rate ratio (sccm ratio) of 5:25.
- sccm ratio flow rate ratio
- the arithmetic average roughness and average period of the macro uneven structure 41 formed on the optical body 4 were measured by the same method as in Example 1, the arithmetic average roughness was 0.311 ⁇ m and the average period was 6.69 ⁇ m. . Therefore, Ra / Rsm was 0.046.
- the dot pitch, track pitch, and depth of the micro concavo-convex structure 42 of the optical body 4 were approximately the same as those in Example 1. These values were confirmed by SEM.
- Example 4 the optical body 4 was produced by performing the following processing. That is, first, the micro uneven structure 15 ⁇ / b> B was formed on the substrate 11 by the same process as in Example 1. Subsequently, the base material resist layer 15 and the base material 11 were etched using a reactive ion etching apparatus.
- the etching gas was a gas in which CHF 3 gas and CF 4 gas were mixed at a flow rate ratio (sccm ratio) of 27: 3.
- the output of the reactive ion etching apparatus was 150 W, the gas pressure was 0.5 Pa, and the etching time was 1 hour.
- the micro uneven structure 14 was formed on the substrate 11.
- a first inorganic resist layer 171 made of DLC was formed on the micro uneven structure 14 by a CVD method.
- the thickness of the first inorganic resist layer 171 was 150 nm.
- a second inorganic resist layer 172 made of tungsten oxide was formed on the first inorganic resist layer 171 by sputtering.
- the layer thickness of the second inorganic resist layer 172 was 800 nm.
- the ratio of the etching rate for the superposed structure forming gas of DLC and the etching rate for the superposed structure forming gas of the substrate 11 was 1/3. These etching rates are values measured by the same method as described above.
- an organic resist layer 19 was formed on the second inorganic resist layer 172 by the same method as in Example 1.
- the optical body 4 was produced by performing the process similar to Example 1.
- FIG. 1 When the arithmetic average roughness and average period of the optical body 4 were measured by the same method as in Example 1, the arithmetic average roughness was 0.12 to 0.15 ⁇ m, and the average period was 11 to 15 ⁇ m.
- the arithmetic average roughness and the average period varied slightly depending on the measurement position of the optical body 4. Further, the dot pitch, track pitch, and depth of the micro concavo-convex structure 42 of the optical body 4 were approximately the same as those in Example 1. These values were confirmed by SEM.
- FIGS. 17A to 17C show that the planar structure of the optical body 4 produced in Example 2.
- the results are shown in FIGS. 17A to 17C.
- 17A is 500 times
- FIG. 17B is 5000 times
- FIG. 17C is 50000 times.
- FIG. 17A shows that the macro uneven structure 12 is formed on the base material 11.
- the substantially circular structures distributed in FIG. 17A are the macro uneven structures 12.
- FIG. 17B it was confirmed that the micro uneven structure 13 was formed on the same surface as the macro uneven structure 12.
- FIG. 17C it was confirmed more clearly that the micro uneven structure 13 was formed on the same surface as the macro uneven structure 12.
- the diffuse reflection spectrum of the optical body 4 was measured.
- the optical system used for the measurement of a diffuse reflection spectral spectrum will be described.
- the light 72A from the light source 71 is reflected by the spherical mirror 73 and then irradiated to the sample 77 provided in the integrating sphere 75.
- the reflected light 72B from the sample 77 is detected after multiple reflection in the integrating sphere 75 and homogenization.
- the diffuse reflection spectrum was measured using a spectrophotometer V550 manufactured by JASCO Corporation and an absolute reflectometer ARV474S.
- Example 4 A diffuse reflection spectrum is shown in FIG. In Example 4, a spectrum similar to that in Examples 1 and 2 was obtained. As can be seen from FIG. 19, the optical bodies according to Examples 1 to 4 have a low diffuse reflectance over the entire visible light band, and can sufficiently prevent diffuse reflection. Thus, in this embodiment, even if the haze value is as high as about 20% or more, the diffuse reflectance can be made 2% or less.
- Example 3 the haze value is smaller in diffuse reflectance in the entire visible light band than in the other examples. Since the macro uneven structure 12 of Example 3 has a large level difference of each unevenness (arithmetic average roughness Ra) compared to the macro uneven structure 12 of other Examples 1 and 2, when forming the micro uneven structure 13 In addition, the etching state is partially different. Therefore, the micro uneven structure 13 has a partially different shape depending on the shape of the macro uneven structure 12. For this reason, in Example 3, it is estimated that reflection can be suppressed in a wider wavelength range.
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Abstract
Description
[1.1.原盤の構造]
まず、図1~図3を参照して、本実施形態に係る原盤1の構成について説明する。図1は原盤1の外観例を示す斜視図であり、図2は原盤1の表面形状を模式的に示す断面図であり、図3は原盤の表面形状を模式的に示す平面図である。なお、図2は、原盤1の中心軸を通り、かつ中心軸に平行な平面で原盤1を切断することで得られる断面図である。図3の左右方向は原盤1の円周方向に一致し、上下方向は原盤1の軸方向に一致する。図1に示すように、原盤1は、例えば、ナノインプリント法で使用される原盤であり、円筒形状となっている。原盤1は円柱形状であっても、他の形状(例えば平板状)であってもよい。ただし、原盤1が円柱または円筒形状である場合、ロールツーロール方式によって原盤1の凹凸構造を樹脂基材等にシームレスで転写することができる。これにより、原盤1の凹凸構造が転写された光学体4(図15参照)を高い生産効率で作製することができる。このような観点からは、原盤1の形状は、円筒形状または円柱形状であることが好ましい。なお、本実施形態に係る原盤1により凹凸構造が転写された光学体4は、例えば、反射防止フィルム等として使用される。なお、図1では、後述するマクロ凹凸構造12及びミクロ凹凸構造13のうち、ミクロ凹凸構造13のみ示した。実際は、基材11の表面には、マクロ凹凸構造12及びミクロ凹凸構造13が重畳して形成されている。
次に、図4~図10を参照して、原盤の製造方法の一例について説明する。
(第1のステップ)
まず、図4に示すように、例えば、基材11上に、基材レジスト層15を形成(成膜)する。これにより、基材本体を作製する。すなわち、本例では、基材本体は、基材11と、基材レジスト層15とで構成される。そして、基材レジスト層15に第1のミクロ凹凸構造であるミクロ凹凸構造15Bを形成する。ここで、基材レジスト層15を構成するレジスト材は特に制限されず、有機レジスト材及び無機レジスト材のいずれであってもよい。有機レジスト材としては、例えば、ノボラック系レジスト、または化学増幅型レジストなどが挙げられる。また、無機レジスト材としては、例えば、タングステン(W)またはモリブデン(Mo)などの1種または2種以上の遷移金属を含む金属酸化物等が挙げられる。ただし、熱反応リソグラフィを行うためには、基材レジスト層15は、金属酸化物を含む熱反応型レジストで形成されることが好ましい。
次に、図7に示すように、ミクロ凹凸構造15Bを包埋するように、ミクロ凹凸構造15B上に(すなわち基材レジスト層15上に)無機レジスト層17を形成(成膜)する。無機レジスト層17を構成する無機レジスト材としては、例えば、SiO2、Si、DLC(Diamond Like Carbon)、W、Mo、WまたはMoなどの1種または2種以上の遷移金属を含む金属酸化物などが挙げられる。無機レジスト層17は、スパッタ法あるいはCVD法(化学蒸着法)等によってミクロ凹凸構造15B上に形成される。このように、本実施形態では、基材レジスト層15のミクロ凹凸構造15Bを残した状態で無機レジスト層17を形成する。この理由は以下の通りである。
続いて、図8に示すように、無機レジスト層17上に有機レジスト層19を形成する。ここで、有機レジスト層19は、有機レジスト材191と、有機レジスト材191中に分散したフィラー粒子192とを含む。有機レジスト層19は、例えば、スピンコーティング、スリットコーティング、ディップコーティング、スプレーコーティング、またはスクリーン印刷等を用いることで無機レジスト層17上に形成される。これらのうち、スプレーコーティング法は、薄厚の有機レジスト層19を均一かつ連続的に形成できることから、特に好ましい。スプレーコーティング法に使用されるスプレーコータは、一般的なスプレーコータであれば、どのようなスプレーコータであってもよい。例えば、ニードルタイプのスプレーコータを用いて行ってもよい。
第4のステップでは、有機レジスト層19、無機レジスト層17、基材レジスト層15、及び基材11を順次エッチングする。ここで、本実施形態のエッチングは、垂直異方性を有するドライエッチングであることが好ましく、例えば、反応性イオンエッチング(Reactive Ion Etching:RIE)であることが好ましい。これにより、各レジスト層に形成されたマクロ凹凸構造、ミクロ凹凸構造が他のレジスト層に転写されるからである。例えばウェットエッチング等の等方性を有するエッチングにより有機レジスト層19をエッチングした場合、基材11にミクロ凹凸構造13が形成されない可能性がある。
第1のエッチングでは、まず、有機レジスト層19をエッチングする。第1のエッチングで使用されるエッチングガス(以下、「マクロ凹凸構造形成用ガス」とも称する)は、第1のエッチングガスと、第2のエッチングガスとを含む。ここで、有機レジスト材191の第1のエッチングガスに対するエッチングレートは、無機レジスト層17の第1のエッチングガスに対するエッチングレートよりも高い。また、有機レジスト材191の第2のエッチングガスに対するエッチングレートは、無機レジスト層17の第2のエッチングガスに対するエッチングレートよりも低い。第1のエッチングガスは、例えばO2ガスであり、第2のエッチングガスは、例えばフッ化炭素ガスである。
第2のエッチングでは、まず、無機レジスト層17をエッチングする。第2のエッチングで使用されるエッチングガス(以下、「重畳構造形成用ガス」とも称する)は、無機レジスト層17、基材レジスト層15、及び基材11をエッチングできるものであれば特に制限されない。例えば、重畳構造形成用ガスは、基材11が石英ガラスである場合、1または2種類以上のフッ化炭素ガスの混合ガスであってもよい。フッ化炭素ガスとしては、例えば、CHF3、CH2F2、CF4、C2F8、およびC3F8などが挙げられる。重畳構造形成用ガスは、これらのフッ化炭素ガスにH2ガス、またはArガス等の添加ガスを添加したものであってもよい。なお、重畳構造形成用ガスには、O2ガスをさらに含めても良いが、O2ガスは他のガスに比べて等方性が大きいので、O2ガスの濃度はなるべく低いことが好ましい。なお、第1のエッチングでは、マクロ凹凸構造形成用ガスにO2ガスを含める。しかし、第1のエッチングでは、無機レジスト層17にマクロ凹凸構造17Aという比較的大きな凹凸を形成するだけなので、マクロ凹凸構造形成用ガスが多少の等方性を有していても特に問題はない。
次に、図11を参照して、原盤の製造方法の第1の変形例について説明する。図11に示すように、第1の変形例では、無機レジスト層17を2層構造とする。すなわち、第1の変形例では、無機レジスト層17は、ミクロ凹凸構造15B上に形成される第1の無機レジスト層171と、第1の無機レジスト層171上に形成される第2の無機レジスト層172とで構成される。各無機レジスト層171、172は、上述した第2のステップと同様の方法によって形成される。
次に、図4~図6、図12を参照して、原盤の製造方法の第2の変形例を説明する。第2の変形例では、第1のステップ及び第2のステップが異なる。
次に、図13に基づいて、露光装置200の構成について説明する。露光装置200は、基材レジスト層15を露光する装置である。露光装置200は、レーザ光源201と、第1ミラー203と、フォトダイオード(Photodiode:PD)205と、偏向光学系と、制御機構230と、第2ミラー213と、移動光学テーブル220と、スピンドルモータ225と、ターンテーブル227とを備える。また、基材11は、ターンテーブル227上に載置され、回転することができるようになっている。
次に、図14を参照して、原盤1を用いた光学体4の製造方法の一例について説明する。光学体4は、原盤1を用いたロールツーロール方式の転写装置300によって製造可能である。図14に示す転写装置300では、光硬化性樹脂を用いて光学体4を作製する。
[4.1.光学体の全体構成]
図15に、上記の製造方法によって作製された光学体4の構成を示す。光学体4は、例えばフィルム形状であり、その表面に形成されたマクロ凹凸構造41と、マクロ凹凸構造41上に重畳されたミクロ凹凸構造42とを備える。
光学体4の算術平均粗さは、マクロ凹凸構造41とミクロ凹凸構造42との重畳構造の算術平均粗さとなる。ここで、本実施形態では、マクロ凹凸構造41の算術平均粗さは、原盤1のマクロ凹凸構造12の算術平均粗さに略一致する。さらに、本実施形態では、原盤1を作製するに際し、ミクロ凹凸構造13の配列パターンを一定としたまま、マクロ凹凸構造12の形状だけを任意に変えることができる。したがって、本実施形態では、ミクロ凹凸構造42の配列パターンが一定で、重畳構造の算術平均粗さが異なる様々な光学体4を作製することができる。以下、「光学体4の算術平均粗さ」は、特に断りのない限り、「光学体4の重畳構造の算術平均粗さ」を意味するものとする。一方、光学体4の平均周期は、マクロ凹凸構造41の平均周期となる。
上述したように、本実施形態によれば、光学体4の平均周期及び算術平均粗さを所望の値とすることができる。そして、本発明者は、光学体4の平均周期及び算術平均粗さについて詳細に検討したところ、これらと光学体4のヘイズ値との間に密接な相関があることを見出した。光学体4の平均周期及び算術平均粗さと光学体4のヘイズ値との相関の一例を図16に示す。図16の横軸は光学体4の算術平均粗さ(=Ra)を平均周期(=Rsm)で除算した値(=Ra/Rsm)を示す。縦軸は、光学体4のヘイズ値(%)を示す。
本実施形態によって作製された光学体4は、様々な用途に適用可能である。例えば、光学体4は、表示装置や光学素子等の反射防止フィルム、アンチグレアフィルムとして使用することができる。光学体4は、これらの用途に限られず、反射防止及び防眩が要求される分野であれば適用可能である。
以下の工程により、光学体4を製造した。
(実施例1)
円筒形状の石英ガラスからなる基材11を用意し、スパッタ法により基材11の表面に酸化タングステンからなる基材レジスト層15を形成した。基材レジスト層15の層厚は50nmとした。ついで、図13に示す露光装置200から基材レジスト層にレーザ光を照射することで、基材レジスト層15に千鳥状の配列パターンの潜像15Aを形成した。ここで、潜像15Aのピッチに関する露光装置200の設定値は、ドットピッチ230nm、トラックピッチ153nmとした。
第1のエッチングを2回行ってから第2のエッチングを行った他は、実施例1と同様の処理を行った。なお、2回目の第1のエッチングは、1回目の第1のエッチングと同じ条件で行われた。例えば、1回目の第1のエッチングと同じ噴霧条件(噴霧圧、噴霧時間等)でスプレーコーティング用分散液を無機レジスト層17に噴霧した。光学体4の算術平均粗さ及び平均周期を実施例1と同様の方法によって測定したところ、算術平均粗さは0.112μm、平均周期は11.8μmであった。したがって、Ra/Rsmは0.009であった。また、第1のエッチングを繰り返して行うことで、光学体4の平均周期を大きく、算術平均粗さを小さくすることができることがわかった。したがって、第1のエッチングを繰り返して行うことで、マクロ凹凸構造17Aの平均周期を大きく、算術平均粗さを小さくすることができることになる。また、光学体4のミクロ凹凸構造42のドットピッチ、トラックピッチ、深さは実施例1と同程度であった。これらの値はSEMにより確認した。
実施例3では、フィラー粒子192の平均粒径を6μmとし、無機レジスト層17を2層構造とし、マクロ凹凸構造形成用ガスの組成を変えた他は、実施例1と同様の処理を行った。具体的には、実施例3では、ミクロ凹凸構造15B上にスパッタ法によりSiO2からなる第1の無機レジスト層171を形成した。第1の無機レジスト層171の層厚は200nmとした。ついで、第1の無機レジスト層171上にスパッタ法により酸化タングステンからなる第2の無機レジスト層172を形成した。第2の無機レジスト層172の層厚は500nmとした。したがって、実施例3は第1の変形例に対応する。
実施例4では、以下の処理を行うことで光学体4を作製した。すなわち、まず、実施例1と同様の処理により、基材11上にミクロ凹凸構造15Bを形成した。ついで、反応性イオンエッチング装置を用いて、基材レジスト層15及び基材11をエッチングした。ここで、エッチングガスは、CHF3ガスとCF4ガスとを27:3の流量比(sccm比)で混合したガスとした。また、反応性イオンエッチング装置の出力を150Wとし、ガス圧を0.5Paとし、エッチング時間を1時間とした。以上の工程により、基材11にミクロ凹凸構造14を形成した。
(光学体の算術平均粗さ及び平均周期とヘイズ値との関係)
上記各実施例で作製された光学体4のヘイズ値を、村上色彩技術研究所製のヘイズメータHM-150を用いて測定した。そして、Ra/Rsmとヘイズ値との組み合わせを示す点を横軸がRa/Rsm、縦軸がヘイズ値(%)となるxy平面にプロットした。この結果を図16に示す。図16の点Aは、Ra/Rsmとヘイズ値との相関を示す。
まず、実施例2で作製した光学体4の平面構造をSEMで観察した。その結果を図17A~図17Cに示す。図17Aの倍率は500倍、図17Bの倍率は5000倍、図17Cの倍率は50000倍である。図17Aによれば、基材11上にマクロ凹凸構造12が形成されていることがわかる。なお、図17A中に分布している略円形状の構造体がマクロ凹凸構造12である。また、図17Bには極めて微細であるがマクロ凹凸構造12と同一面にミクロ凹凸構造13が形成されていることが確認できた。図17Cではミクロ凹凸構造13がマクロ凹凸構造12と同一面に形成されていることがより明確に確認できた。
各実施例で作製された光学体4の反射防止機能を評価するために、光学体4の拡散反射分光スペクトルを測定した。まず、図18に基づいて、拡散反射分光スペクトルの測定に使用される光学系を説明する。拡散分光スペクトルの測定では、光源71からの光72Aは、球面ミラー73にて反射された後、積分球75内に備えられた試料77に照射される。試料77からの反射光72Bは、積分球75内で多重反射して均質化した後、検出される。拡散反射分光スペクトルの測定は、具体的には、日本分光社製の分光光度計V550、および絶対反射率測定器ARV474Sを用いて行った。拡散反射分光スペクトルを図19に示す。なお、実施例4では、実施例1、2と同程度のスペクトルが得られた。図19から明らかな通り、実施例1~4に係る光学体は、可視光帯域の全域にわたって拡散反射率が低く、拡散反射を十分に防止可能であることがわかる。このように、本実施例では、ヘイズ値が20%程度あるいはそれ以上という高い値になっても、拡散反射率2%以下にすることができる。
4 光学体
41 マクロ凹凸構造
411 凸部
412 凹部
42 ミクロ凹凸構造
421 凸部
422 凹部
11 基材
12 マクロ凹凸構造
121 凸部
122 凹部
13 ミクロ凹凸構造
131 凸部
132 凹部
14 ミクロ凹凸構造
15 基材レジスト層
15B ミクロ凹凸構造
17 無機レジスト層
171 第1の無機レジスト層
172 第2の無機レジスト層
19 有機レジスト層
191 有機レジスト材
192 フィラー粒子
Claims (11)
- 凹凸の平均周期が可視光波長以下である第1のミクロ凹凸構造を、少なくとも基材を含む基材本体の表面に形成する第1のステップと、
前記第1のミクロ凹凸構造上に無機レジスト層を形成する第2のステップと、
有機レジスト材及び前記有機レジスト材中に分散したフィラー粒子を含む有機レジスト層を前記無機レジスト層上に形成する第3のステップと、
前記有機レジスト層及び前記無機レジスト層をエッチングすることで、凹凸の平均周期が可視光波長より大きいマクロ凹凸構造と、凹凸の平均周期が可視光波長以下である第2のミクロ凹凸構造とを前記基材の表面に重畳して形成する第4のステップと、を含み、
前記フィラー粒子の平均粒径は可視光波長よりも大きく、
前記フィラー粒子のエッチングレートは、前記有機レジスト材のエッチングレートと異なる、原盤の製造方法。 - 前記フィラー粒子のエッチングレートは、前記有機レジスト材のエッチングレートより高い、請求項1記載の原盤の製造方法。
- 前記フィラー粒子の平均粒径は2~15μmである、請求項1または2に記載の原盤の製造方法。
- 前記第4のステップでは、前記有機レジスト層および前記無機レジスト層をドライエッチングによりエッチングし、
前記有機レジスト層をドライエッチングする際に使用されるエッチングガスは、前記無機レジスト層をドライエッチングする際に使用されるエッチングガスと異なる、請求項1~3の何れか1項に記載の原盤の製造方法。 - 前記有機レジスト層をドライエッチングする際に使用されるエッチングガスは、第1のエッチングガスと第2のエッチングガスとを含み、
前記有機レジスト材の前記第1のエッチングガスに対するエッチングレートは、前記無機レジスト層の前記第1のエッチングガスに対するエッチングレートよりも高く、
前記有機レジスト材の前記第2のエッチングガスに対するエッチングレートは、前記無機レジスト層の前記第2のエッチングガスに対するエッチングレートよりも低い、請求項4記載の原盤の製造方法。 - 前記ドライエッチングに使用されるエッチングガスは、炭素原子、フッ素原子、酸素原子および水素原子からなる群から選択される1種以上の原子を含む、請求項4または5に記載の原盤の製造方法。
- 前記第1のステップは、
前記基材の表面に基材レジスト層を形成することで、前記基材本体を作製するステップと、
前記基材レジスト層に前記第1のミクロ凹凸構造を形成するステップと、を含み、
前記基材レジスト層のエッチングレートは、前記無機レジスト層のエッチングレートと異なる、請求項1~6のいずれか1項に記載の原盤の製造方法。 - 前記基材本体は、前記基材で構成され、
前記第1のステップは、
前記基材の表面に基材レジスト層を形成するステップと、
前記第1のミクロ凹凸構造と同じ配列パターンを有する第3のミクロ凹凸構造を前記基材レジスト層に形成するステップと、
前記基材レジスト層をエッチングすることで、前記基材の表面に前記第1のミクロ凹凸構造を形成するステップと、を含む、請求項1~6のいずれか1項に記載の原盤の製造方法。 - 前記第2のステップは、前記第1のミクロ凹凸構造上に第1の無機レジスト層を形成するステップと、
前記第1の無機レジスト層上に第2の無機レジスト層を形成するステップと、を含む、請求項1~8のいずれか1項に記載の原盤の製造方法。 - 請求項1~9のいずれか1項に記載の原盤の製造方法により製造された原盤。
- 請求項10記載の原盤に形成された前記マクロ凹凸構造及び前記第2のミクロ凹凸構造が転写された、光学体。
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