WO2014061236A1 - 反射防止膜を備えた光学部材およびその製造方法 - Google Patents

反射防止膜を備えた光学部材およびその製造方法 Download PDF

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WO2014061236A1
WO2014061236A1 PCT/JP2013/006048 JP2013006048W WO2014061236A1 WO 2014061236 A1 WO2014061236 A1 WO 2014061236A1 JP 2013006048 W JP2013006048 W JP 2013006048W WO 2014061236 A1 WO2014061236 A1 WO 2014061236A1
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layer
optical member
transparent
thin film
refractive index
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French (fr)
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WO2014061236A9 (ja
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慎一郎 園田
真也 白田
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Fujifilm Corp
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Fujifilm Corp
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C03C2218/322—Oxidation

Definitions

  • the present invention relates to an optical member and a manufacturing method thereof, and more particularly to an optical member having an antireflection film on the surface thereof and a manufacturing method thereof.
  • an antireflection structure (antireflection film) is provided on the light incident surface in order to reduce the loss of transmitted light due to surface reflection.
  • an antireflection structure for example, a dielectric multilayer film, a fine concavo-convex structure having a pitch shorter than the wavelength of visible light, and the like are known (Patent Documents 1 and 2, etc.).
  • the fine concavo-convex structure provided on the lens surface has a gradient refractive index that gradually approaches the refractive index of air from the refractive index of the lens, relieves the refractive index difference between the lens and air, and reflects incident light. It has a function to prevent.
  • Patent Document 1 discloses a configuration in which a fine uneven layer is formed on a base material via a transparent thin film layer.
  • the fine uneven layer is mainly composed of alumina
  • the transparent thin film layer is a layer containing at least one of zirconia, silica, titania, and zinc oxide.
  • the concavo-convex layer and the transparent thin film layer under the concavo-convex layer are subjected to warm water treatment on a multi-component film formed using a coating solution containing at least one compound of zirconia, silica, titania, and zinc oxide and an aluminum compound. Is obtained.
  • Patent Document 2 discloses a configuration in which a fine concavo-convex layer mainly composed of alumina is formed on a substrate via Al 2 O 3 and SiO 2 .
  • a method for growing boehmite which is a hydroxide of aluminum, on a permeable substrate
  • a method of steam treatment or hot water treatment of an alumina film formed by a vacuum film formation method or a sol-gel method is disclosed.
  • Patent Document 1 describes that the fine uneven film thickness can be controlled to 0.005 to 5.0 ⁇ m and the transparent layer thickness can be controlled to 0.01 to 10 ⁇ m.
  • Patent Document 1 it is assumed that a multi-component film is formed by the sol-gel method, but the sol-gel method has a problem that productivity is low because batch processing cannot be performed.
  • Patent Document 2 it is described that Al 2 O 3 is deposited in a thickness of 80 nm and SiO 3 is deposited in a thickness of 100 nm on a substrate in sequence, and then a fine uneven film 300 nm mainly composed of alumina is formed. As described above, a specific method for forming an uneven thin film is not disclosed.
  • the layer structure of Patent Document 2 further includes a layer made of a material (for example, TiO 2 ) having a higher refractive index than Al 2 O 3 .
  • a material for example, TiO 2
  • at least three kinds of materials Al 2 O 3 , SiO 2 , TiO 2
  • the number of deposition hearts or targets required for film formation is required, which is a very complicated manufacturing method.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an optical member including an antireflection film that can be produced more easily and with a small number of materials, and a method for manufacturing the same.
  • the optical member of the present invention is an optical member provided with an antireflection film comprising, in this order, a transparent thin film layer and a transparent fine uneven layer mainly composed of alumina hydrate on the surface of a transparent substrate.
  • the transparent thin film layer has a refractive index between the refractive index of the transparent substrate and the refractive index of the fine uneven layer
  • the transparent thin film layer includes at least a nitride layer or an oxynitride layer.
  • the “main component” is defined as the largest component of the weight% among the components of the chemical structure contained in the site.
  • corrugated layer are made into the average refractive index of each layer.
  • the transparent thin film layer is provided with a plurality of nitride layers and / or oxynitride layers of the same type, and the nitrogen content of the transparent base layer side of the plurality of layers is more than the nitrogen content of the fine uneven layer side layer. It is also preferable that there are many.
  • the same species means that the species (metal, nonmetal, alloy, etc.) that are nitrided or oxynitrided are common.
  • the same kind of nitride layer and / or oxynitride layer is, for example, SiN and / or SiON if the nitrided species is Si, and if the nitrided species is Al, If AlN and / or AlON and the nitrided species is SiAl, then SiAlN and / or SiAlON.
  • “providing a plurality of nitride layers and / or oxynitride layers” may include only a plurality of nitride layers, or may include only a plurality of oxynitride layers. Alternatively, a plurality of layers including a nitride layer and an oxynitride layer may be provided.
  • the nitride layer is made of SiN, AlN or SiAlN;
  • the oxynitride layer is preferably made of SiON, AlON or SiAlON.
  • the transparent thin film layer includes a flat layer mainly composed of hydrated alumina on the fine uneven surface side.
  • the thickness of the fine uneven layer can be 150 nm or less.
  • the thickness of the transparent thin film layer at the center of the curved surface is preferably 274 nm or more.
  • the transparent thin film layer can be formed by reactive sputtering.
  • the method for producing an optical member of the present invention comprises an optical member comprising an antireflection film comprising a transparent thin film layer and a transparent fine irregular layer mainly composed of alumina hydrate in this order on the surface of a transparent substrate.
  • a manufacturing method of On the transparent substrate at least one of a nitride layer and an oxynitride layer, and an alumina layer are sequentially formed by reactive sputtering, A transparent substrate on which at least one of a nitride layer or an oxynitride layer and an alumina layer are formed is treated with warm water.
  • the optical member of the present invention is provided with a transparent thin film layer and a transparent fine uneven layer mainly composed of alumina hydrate in this order on the surface of the transparent substrate, and the refractive index of the transparent substrate and the fine uneven layer
  • the transparent thin film layer having a refractive index between the refractive index includes at least a nitride layer or an oxynitride layer. By using a nitride, a refractive index layer higher than that of an oxide can be obtained. The choice of the layer provided between the transparent substrate and the fine uneven layer can be greatly increased.
  • the refractive index is changed by changing the amount of nitridation using vapor deposition that is possible from a batch with high productivity. Since the rate can be adjusted, it can be manufactured with a small number of material types.
  • Sectional schematic diagram which shows schematic structure of the optical member of 1st Embodiment.
  • Cross-sectional schematic diagram showing a schematic configuration of the optical member of design change example 2 Sectional schematic diagram which shows schematic structure of the optical member of 2nd Embodiment.
  • FIG. 1 shows the SiO 2 film thickness dependence of the reflectance sum
  • the optical element of Comparative Example 1 illustrates the wavelength dependence of the reflectance in the case of SiO 2 film thickness 100nm
  • FIG. 1 is a schematic cross-sectional view showing the configuration of the optical member 1 according to the first embodiment of the present invention.
  • the optical member 1 according to the first embodiment has an antireflection film comprising a transparent thin film layer 15 and a transparent fine uneven layer 18 mainly composed of an alumina hydrate in this order on the surface of a transparent substrate 10.
  • 19 is an optical member.
  • the transparent thin film layer 15 includes a nitride layer 11, oxynitride layers 12 and 13, and a transparent flat layer 14 mainly composed of alumina hydrate.
  • the transparent thin film layer 15 has a refractive index between the refractive index of the transparent substrate 10 and the refractive index of the fine concavo-convex layer 12, the refractive index n 0 of the transparent substrate 10, and the refraction of the nitride layer 11.
  • n 1 the refractive index n 2 of the oxynitride layer 12, the refractive index n 3 of the oxynitride layer 13, the refractive index n 4 of the flat layer 14, the relationship between the refractive index n 5 of the uneven layer, n 0> n 1> n 2> n 3> n 4> is n 5, the transparent thin film layer, refractive index gradually toward the air from the transparent substrate such as a lens has a structure to decrease.
  • Refractive index n 5 of the uneven layer in the above equation is the average refractive index of the entire uneven layer.
  • the transparent substrate side is increased by increasing the nitrogen content toward the transparent substrate 10 side. It can have a large refractive index.
  • the transparent thin film layer 15 has a four-layer structure in the present embodiment, but may be a single layer or any number of two or more layers. What is necessary is just to arrange
  • the transparent thin film layer 15 is composed of one nitride layer or oxynitride layer 16 and a flat layer 14 mainly composed of alumina hydrate, like the optical member 2 of the design modification shown in FIG.
  • a layer structure may be used, or a single layer made of a nitride layer or an oxynitride layer may be used like the optical member 3 of another design modification example shown in FIG.
  • the nitride include Si, Al, or SiAl nitride, that is, SiN, AlN, or SiAlN.
  • Specific examples of the oxynitride include Si, Al, or SiAl oxynitride, that is, SiON, AlON, or SiAlON.
  • the nitride and oxynitride of each substance have a higher refractive index as the nitrogen content increases.
  • the same kind of nitride layer and / or oxynitride layer is, for example, a nitride layer and / or oxynitride layer of Si, Al or SiAl.
  • the Si nitride layer and / or the oxynitride layer is only SiN, SiON, or SiN and SiON layers. Even if only SiN is used, a plurality of nitrogen contents are changed. What is necessary is just to provide a layer.
  • the refractive index can be changed only by changing the nitrogen content.
  • Alumina hydrate is boehmite (expressed as Al 2 O 3 .H 2 O or AlOOH), which is alumina monohydrate, and Bayerlite (Al, which is alumina trihydrate (aluminum hydroxide)). 2 O 3 .3H 2 O or Al (OH) 3 .
  • the fine concavo-convex layer 18 containing alumina hydrate as a main component is transparent, and as shown in FIG. 1 and the like, the size (vertical angle size) and the direction are various, but a substantially sawtooth cross section. have.
  • the period (average pitch) of the fine concavo-convex layer 18 is sufficiently smaller than the shortest wavelength in the use wavelength range that is the wavelength range of incident light.
  • the pitch is the distance between the apexes of the most adjacent convex portions across the concave portion, and the depth is the distance from the convex vertex to the bottom of the adjacent concave portion.
  • the period of fine irregularities is on the order of several tens of nm to several hundreds of nm.
  • corrugated layer) t1 from a convex part top to the bottom part of an adjacent recessed part is 150 nm or less.
  • the fine concavo-convex layer 18 has a structure that becomes sparse as the distance from the base material increases (the width of the void corresponding to the concave portion increases and the width of the convex portion decreases), and the refractive index decreases as the distance from the base material increases. Become.
  • the average pitch of the unevenness is obtained by taking a surface image of the fine unevenness structure with an SEM (scanning electron microscope), binarizing the image, and calculating by statistical processing.
  • the film thickness of the concavo-convex layer is obtained by taking a cross-sectional image of the fine concavo-convex layer and processing the image.
  • the fine concavo-convex layer can be formed by performing hot water treatment after film formation of alumina or aluminum, and batch processing is possible for film formation of alumina and aluminum, and productivity can be improved. It is preferable to use a vapor phase growth method such as an evaporation method or a sputtering method. According to the study by the present inventors, when vapor deposition or sputtering is used, it can be formed by performing hot water treatment after forming a predetermined thickness of aluminum, but even if the thickness of the aluminum to be formed is changed, it is fine. The thickness of the concavo-convex layer can only be up to about 150 nm, and the thickness of the concavo-convex layer cannot be thicker than this. ) Was formed.
  • FIG. 4 is an SEM image in plan view of the produced fine uneven layer
  • FIG. 5 is an SEM image in cross-sectional view. As shown in FIG. 4, a fine uneven layer is formed on the surface, and a flat layer is formed between the substrate and the uneven layer.
  • FIG. 6 shows the results of investigating the relationship between the thickness of the fine uneven layer and the flat layer and the thickness of Al before immersion when the thickness of Al to be formed is changed and the same hot water treatment is performed.
  • FIG. 6 shows a case where Al is deposited and heated to be boehmite, but similar data was obtained when Al 2 O 3 was heated to boehmite instead of Al. Similar data was obtained when Al was deposited by vapor deposition instead of sputtering.
  • the refractive index nd of the flat layer takes a constant value of 1.26 and has a thickness of about 80 nm.
  • the uneven layer has an effective refractive index that decreases in the direction away from the substrate, has a thickness of 150 nm, and a total film thickness of 230 nm.
  • FIG. 8A and 8B are diagrams described in the 123rd Micro-Optics Research Society, MICROOPTICS NEWS Vol. 30, No. 1, P49, and are reference diagrams showing the dependency of the refractive index on the height of the fine concavo-convex structure.
  • the fine uneven layer obtained by the hot water treatment has a thickness of 150 nm or less.
  • a transparent thin film layer having a refractive index between the refractive index between the concave-convex microstructure and the substrate is provided.
  • the transparent thin film layer including the above-described Al or Si nitride layer or oxynitride layer is formed using a vapor phase method such as a reactive sputtering method or a vapor deposition method
  • a vapor phase method such as a reactive sputtering method or a vapor deposition method
  • the number of sputter targets or the number of vapor deposition hearts can be greatly suppressed.
  • the reactive sputtering method is used, layers of various refractive indexes can be formed by using two targets of Si and Al and adjusting the flow rate ratio of N 2 and O 2 as a reaction gas. It can be very easily formed.
  • FIG. 9 is a schematic cross-sectional view showing the configuration of the optical member 4 according to the second embodiment of the present invention.
  • the optical member 4 includes a meniscus lens having a curved surface as the transparent base material 20, a transparent thin film layer 25 on the concave surface, and a transparent fine uneven layer mainly composed of alumina hydrate.
  • An antireflection film 29 having 28 in this order is provided.
  • the transparent thin film layer 25 includes a nitride layer or oxynitride layer 26 and a flat layer 24 mainly composed of alumina hydrate from the base material 20 side.
  • the transparent thin film layer 25 may include a plurality of oxide layers or oxynitride layers, and the details of this case are the same as those in the first embodiment.
  • the curved surface of the transparent substrate 20 is particularly preferably such that the angle ⁇ formed by the normals at both ends of the curved surface when the curved surface as the effective optical surface of the lens is cut out exceeds 90 °.
  • FIG. 10 is a diagram for explaining a film forming angle ⁇ when a thin film layer is formed on the curved surface of the concave meniscus lens. It is assumed that an evaporation source or a sputtering target is disposed on the normal line A with respect to the center O of the lens so as to face the lens during film formation. Here, it is assumed that the vapor deposition source and the sputter target are point sources.
  • An angle formed between the normal A and the normal at each position P on the lens surface is defined as a film formation angle ⁇ .
  • the film formation angle ⁇ at the lens surface center position O is 0 °
  • the film formation angle ⁇ at the end position of the curved surface is the maximum film formation angle ⁇ Max .
  • twice the maximum film forming angle ⁇ Max is ⁇ .
  • the number of incident particles on each surface position is proportional to cos ⁇ with respect to the film forming angle ⁇ during vapor deposition or sputtering. That is, the film thickness is small in the peripheral portion compared to the center position of the lens.
  • the thickness of the transparent thin film layer at the center of the transparent substrate is 274 nm or more. Is preferable in order to obtain a sufficient antireflection effect.
  • the total thickness needs to be 424 nm at ⁇ 0 °, and since the fine uneven layer is 150 nm or less, the transparent thin film layer is 274 nm or more Will be required. Further, in order to secure a layer thickness of 300 nm at ⁇ 85 °, the total thickness needs to be 3442 nm at ⁇ 0 °, and since the fine uneven layer is 150 nm or less, the transparent thin film layer requires 3292 nm or more.
  • the film thickness is the film thickness at the center of the thickest lens.
  • ECR electron cyclotron resonance
  • the uppermost Al 2 O 3 film was immersed in boiling water for 5 minutes after film formation and was subjected to hot water treatment.
  • the reflectance of this lens was measured with a spectrophotometer FE-3000 manufactured by Otsuka Electronics. The results are shown in FIG. As shown in FIG. 13, in the optical member of this example, a low reflectance of 1% or less can be realized over a wavelength range of 400 to 800 nm.
  • the results are shown in FIG. As shown in FIG. 14, the total reflectance was small when the SiO 2 film thickness was around 100 nm. However, as shown in FIG. 15, the spectral spectrum when the film thickness of SiO 2 is 100 nm, the optical member of this configuration has a reflectance with respect to light in the 520 to 780 nm wavelength region exceeding 1.0%.

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  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Surface Treatment Of Glass (AREA)
PCT/JP2013/006048 2012-10-17 2013-10-10 反射防止膜を備えた光学部材およびその製造方法 Ceased WO2014061236A1 (ja)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016136262A1 (ja) * 2015-02-27 2016-09-01 富士フイルム株式会社 反射防止膜およびその製造方法、並びに光学部材
WO2016136261A1 (ja) * 2015-02-27 2016-09-01 富士フイルム株式会社 反射防止膜および光学部材
JP6850401B1 (ja) * 2019-07-22 2021-03-31 日本碍子株式会社 接合体および弾性波素子

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9366784B2 (en) 2013-05-07 2016-06-14 Corning Incorporated Low-color scratch-resistant articles with a multilayer optical film
US9110230B2 (en) 2013-05-07 2015-08-18 Corning Incorporated Scratch-resistant articles with retained optical properties
JP6396003B2 (ja) * 2013-06-03 2018-09-26 富士フイルム株式会社 反射防止膜を備えた光学部材
US11267973B2 (en) 2014-05-12 2022-03-08 Corning Incorporated Durable anti-reflective articles
US9335444B2 (en) * 2014-05-12 2016-05-10 Corning Incorporated Durable and scratch-resistant anti-reflective articles
US9790593B2 (en) 2014-08-01 2017-10-17 Corning Incorporated Scratch-resistant materials and articles including the same
CN106574985B (zh) 2014-08-25 2019-02-26 富士胶片株式会社 防反射膜及具备防反射膜的光学部件
JP6362105B2 (ja) * 2014-08-27 2018-07-25 キヤノン株式会社 反射防止膜を有する光学素子、光学系、光学機器
CN106574986B (zh) * 2014-08-27 2019-02-22 富士胶片株式会社 具备防反射膜的光学部件及其制造方法
CN107430214B (zh) * 2015-03-31 2019-08-06 富士胶片株式会社 防反射膜及其制造方法
EP3300520B1 (en) 2015-09-14 2020-11-25 Corning Incorporated High light transmission and scratch-resistant anti-reflective articles
WO2019187416A1 (ja) * 2018-03-29 2019-10-03 富士フイルム株式会社 反射防止膜および光学部材
JP7228028B2 (ja) 2018-08-17 2023-02-22 コーニング インコーポレイテッド 薄い耐久性の反射防止構造を有する無機酸化物物品
JP2021162728A (ja) * 2020-03-31 2021-10-11 デクセリアルズ株式会社 光学体、光学体の製造方法及び光学デバイス
US12147009B2 (en) 2020-07-09 2024-11-19 Corning Incorporated Textured region to reduce specular reflectance including a low refractive index substrate with higher elevated surfaces and lower elevated surfaces and a high refractive index material disposed on the lower elevated surfaces
US11714212B1 (en) * 2020-09-14 2023-08-01 Apple Inc. Conformal optical coatings for non-planar substrates
US12379524B2 (en) 2021-09-01 2025-08-05 Largan Precision Co., Ltd. Optical imaging lens assembly comprising a gradient refractive coating having a plurality of holes, imaging apparatus and electronic device
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CN118915201A (zh) * 2024-10-10 2024-11-08 宁波舜宇车载光学技术有限公司 光学元件及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006259711A (ja) * 2005-02-18 2006-09-28 Canon Inc 光学用透明部材及びそれを用いた光学系
JP2010169914A (ja) * 2009-01-23 2010-08-05 Seiko Epson Corp プロジェクター
JP2011090225A (ja) * 2009-10-23 2011-05-06 Canon Inc 光学部材、及びその製造方法
JP2012073590A (ja) * 2010-08-31 2012-04-12 Canon Inc 光学部材、その製造方法及び光学系
JP2012132044A (ja) * 2010-12-20 2012-07-12 Central Glass Co Ltd 酸窒化ケイ素膜の形成方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001281415A (ja) * 2000-03-31 2001-10-10 Sony Corp 反射防止フィルタ及びその製造方法
KR100708640B1 (ko) * 2001-02-07 2007-04-18 삼성에스디아이 주식회사 광학적 전기적 특성을 지닌 기능성 박막
US6589658B1 (en) * 2001-11-29 2003-07-08 Guardian Industries Corp. Coated article with anti-reflective layer(s) system
JP2007017668A (ja) * 2005-07-07 2007-01-25 Konica Minolta Holdings Inc 光学フィルム
JP2007248562A (ja) * 2006-03-14 2007-09-27 Shincron:Kk 光学物品およびその製造方法
JP2010169918A (ja) * 2009-01-23 2010-08-05 Alps Electric Co Ltd 光学素子アレイ及びその製造方法
JP2010271533A (ja) * 2009-05-21 2010-12-02 Canon Inc 光学素子及びそれを有する光学系
JP5647924B2 (ja) * 2011-03-18 2015-01-07 富士フイルム株式会社 光学部材の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006259711A (ja) * 2005-02-18 2006-09-28 Canon Inc 光学用透明部材及びそれを用いた光学系
JP2010169914A (ja) * 2009-01-23 2010-08-05 Seiko Epson Corp プロジェクター
JP2011090225A (ja) * 2009-10-23 2011-05-06 Canon Inc 光学部材、及びその製造方法
JP2012073590A (ja) * 2010-08-31 2012-04-12 Canon Inc 光学部材、その製造方法及び光学系
JP2012132044A (ja) * 2010-12-20 2012-07-12 Central Glass Co Ltd 酸窒化ケイ素膜の形成方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016136262A1 (ja) * 2015-02-27 2016-09-01 富士フイルム株式会社 反射防止膜およびその製造方法、並びに光学部材
WO2016136261A1 (ja) * 2015-02-27 2016-09-01 富士フイルム株式会社 反射防止膜および光学部材
JPWO2016136262A1 (ja) * 2015-02-27 2017-11-30 富士フイルム株式会社 反射防止膜およびその製造方法、並びに光学部材
JPWO2016136261A1 (ja) * 2015-02-27 2017-12-14 富士フイルム株式会社 反射防止膜および光学部材
US10518501B2 (en) 2015-02-27 2019-12-31 Fujifilm Corporation Antireflection film and optical member
US10564323B2 (en) 2015-02-27 2020-02-18 Fujifilm Corporation Antireflection film and method of producing the same, and optical member
JP6850401B1 (ja) * 2019-07-22 2021-03-31 日本碍子株式会社 接合体および弾性波素子
US12166465B2 (en) 2019-07-22 2024-12-10 Ngk Insulators, Ltd. Bonded body and acoustic wave element

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