JP2015064419A - Reflection suppressing film and reflection suppressing member - Google Patents

Reflection suppressing film and reflection suppressing member Download PDF

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JP2015064419A
JP2015064419A JP2013196953A JP2013196953A JP2015064419A JP 2015064419 A JP2015064419 A JP 2015064419A JP 2013196953 A JP2013196953 A JP 2013196953A JP 2013196953 A JP2013196953 A JP 2013196953A JP 2015064419 A JP2015064419 A JP 2015064419A
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refractive index
index layer
layer
low refractive
reflection
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悦二 福井
Etsuji Fukui
悦二 福井
今村　努
Tsutomu Imamura
努 今村
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Nippon Electric Glass Co Ltd
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    • 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

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Abstract

PROBLEM TO BE SOLVED: To provide a reflection suppressing film with a wide reflection suppressing wavelength region.SOLUTION: A reflection suppressing film 11 comprises a high refractive index layer 12H with a relatively high refractive index and a low refractive index layer 12L with a relatively low refractive index. The high refractive index layer 12H and the low refractive index layer 12L are alternately stacked so that an outermost layer is a low refractive index layer 12L1. The reflection suppressing film 11 further comprises an intermediate refractive index layer 12M. The intermediate refractive index layer 12M is positioned between the low refractive index layer 12L1 forming the outermost layer and a high refractive index layer 12H1 positioned next. The intermediate refractive index layer 12M has a refractive index which is higher than the refractive index of the low refractive index layer 12L1 forming the outermost layer and lower than the refractive index of the high refractive index layer 12H1 positioned next.

Description

本発明は、反射抑制膜及び反射抑制部材に関する。   The present invention relates to a reflection suppressing film and a reflection suppressing member.

従来、表面反射を抑制する反射抑制膜が種々の光学部材に設けられている。例えば、広い波長域において反射を抑制し得る反射抑制膜として、相対的に屈折率が高い高屈折率層と、相対的に屈折率が低い低屈折率層とを交互に積層した誘電体多層膜が知られている。このような誘電体多層膜において、反射が抑制される波長域（反射抑制波長域）を広くするためには、積層数を多くする必要がある。しかしながら、膜応力の問題で、積層数を多くするには限界がある。また、積層数が多いと、膜設計が困難になるばかりか、成膜に要する時間、コスト等も高くなるという問題も生じる。従って、積層数を多くすることなく反射が抑制される波長域を広げる手段が求められている。   Conventionally, a reflection suppressing film that suppresses surface reflection is provided on various optical members. For example, a dielectric multilayer film in which a high refractive index layer having a relatively high refractive index and a low refractive index layer having a relatively low refractive index are alternately laminated as a reflection suppressing film capable of suppressing reflection in a wide wavelength range It has been known. In such a dielectric multilayer film, it is necessary to increase the number of stacked layers in order to widen the wavelength range where reflection is suppressed (reflection suppression wavelength range). However, there is a limit to increasing the number of layers due to film stress. In addition, when the number of stacked layers is large, not only film design becomes difficult, but also the time and cost required for film formation increase. Therefore, there is a demand for means for expanding the wavelength range in which reflection is suppressed without increasing the number of stacked layers.

例えば、特許文献１では、高屈折率層と低屈折率層とが交互に積層された多層膜であって、そのうちの１層を中間屈折率層とした多層膜において、中間屈折率層の物質として、ＹＢＦ３，ＤＹＦ３，ＨｏＦ３，ＥｕＦ３，ＥｒＦ３のいずれかを使用した反射抑制膜が提案されている。具体的には、特許文献１には、基板側から、高屈折率層、低屈折率層、高屈折率層、低屈折率層、中間屈折率層、低屈折率層、高屈折率層がこの順番で積層されてなる反射抑制膜が記載されている。特許文献１には、このような反射抑制膜では、反射抑制帯域を８０ｎｍ以上確保できる旨が記載されている。 For example, in Patent Document 1, a multilayer film in which a high refractive index layer and a low refractive index layer are alternately stacked, and one of the layers is an intermediate refractive index layer. For example, a reflection suppressing film using any one of YBF 3 , DYF 3 , HoF 3 , EuF 3 , and ErF 3 has been proposed. Specifically, Patent Document 1 includes a high refractive index layer, a low refractive index layer, a high refractive index layer, a low refractive index layer, an intermediate refractive index layer, a low refractive index layer, and a high refractive index layer from the substrate side. A reflection suppressing film formed by laminating in this order is described. Patent Document 1 describes that such a reflection suppression film can secure a reflection suppression band of 80 nm or more.

特開平７−２４４２０５号公報Japanese Patent Laid-Open No. 7-244205

反射抑制膜の反射抑制波長域をより広くしたいという要望がある。   There is a desire to make the reflection suppression wavelength region of the reflection suppression film wider.

本発明の主な目的は、広い反射抑制波長域を有する反射抑制膜を提供することにある。   A main object of the present invention is to provide a reflection suppressing film having a wide reflection suppressing wavelength region.

本発明に係る反射抑制膜は、基材の上に形成された反射抑制膜である。本発明に係る反射抑制膜は、相対的に高い屈折率を有する高屈折率層と、相対的に低い屈折率を有する低屈折率層とを備える。高屈折率層と低屈折率層とが、最外層が低屈折率層となるように交互に積層されている。本発明に係る反射抑制膜は、中間屈折率層をさらに備える。中間屈折率層は、最外層を構成している低屈折率層と、次に位置する高屈折率層との間に配されている。中間屈折率層は、最外層を構成している低屈折率層の屈折率よりも高く、次に位置する高屈折率層の屈折率よりも低い屈折率を有する。   The antireflection film according to the present invention is an antireflection film formed on a substrate. The antireflection film according to the present invention includes a high refractive index layer having a relatively high refractive index and a low refractive index layer having a relatively low refractive index. High refractive index layers and low refractive index layers are alternately laminated so that the outermost layer is a low refractive index layer. The antireflection film according to the present invention further includes an intermediate refractive index layer. The intermediate refractive index layer is disposed between the low refractive index layer constituting the outermost layer and the next high refractive index layer. The intermediate refractive index layer has a refractive index higher than the refractive index of the low refractive index layer constituting the outermost layer and lower than the refractive index of the next high refractive index layer.

中間屈折率層は、屈折率が低屈折率層側から高屈折率層側に向けて漸増している屈折率傾斜層であってもよい。   The intermediate refractive index layer may be a refractive index gradient layer whose refractive index gradually increases from the low refractive index layer side to the high refractive index layer side.

中間屈折率層は、最外層を構成している低屈折率層と、次に位置する高屈折率層との間にのみ配されていることが好ましい。   The intermediate refractive index layer is preferably disposed only between the low refractive index layer constituting the outermost layer and the next high refractive index layer.

中間屈折率層は、隣接する高屈折率層に含まれる金属と、隣接する低屈折率層に含まれる金属との両方を含むことが好ましい。   The intermediate refractive index layer preferably includes both a metal contained in the adjacent high refractive index layer and a metal contained in the adjacent low refractive index layer.

中間屈折率層の厚みが、最外層を構成している低屈折率層の厚み以下であることが好ましい。   The thickness of the intermediate refractive index layer is preferably not more than the thickness of the low refractive index layer constituting the outermost layer.

中間屈折率層は、隣接する低屈折率層の屈折率の１．１１倍以上であって、隣接する高屈折率層の屈折率の０．９６倍以下の屈折率を有する部分を含むことが好ましい。   The intermediate refractive index layer may include a portion having a refractive index that is not less than 1.11 times the refractive index of the adjacent low refractive index layer and not more than 0.96 times the refractive index of the adjacent high refractive index layer. preferable.

本発明に係る反射抑制膜の層数が７以下であることが好ましい。   The number of layers of the antireflection film according to the present invention is preferably 7 or less.

本発明に係る反射抑制部材は、基材と、基材の上に設けられた反射抑制膜とを備えている。反射抑制膜は、相対的に高い屈折率を有する高屈折率層と、相対的に低い屈折率を有する低屈折率層とを備える。高屈折率層と低屈折率層とが、最外層が低屈折率層となるように交互に積層されている。反射抑制膜は、中間屈折率層をさらに備える。中間屈折率層は、最外層を構成している低屈折率層と、次に位置する高屈折率層との間に配されている。中間屈折率層は、最外層を構成している低屈折率層の屈折率よりも高く、次に位置する高屈折率層の屈折率よりも低い屈折率を有する。   The reflection suppressing member according to the present invention includes a base material and a reflection suppressing film provided on the base material. The antireflection film includes a high refractive index layer having a relatively high refractive index and a low refractive index layer having a relatively low refractive index. High refractive index layers and low refractive index layers are alternately laminated so that the outermost layer is a low refractive index layer. The antireflection film further includes an intermediate refractive index layer. The intermediate refractive index layer is disposed between the low refractive index layer constituting the outermost layer and the next high refractive index layer. The intermediate refractive index layer has a refractive index higher than the refractive index of the low refractive index layer constituting the outermost layer and lower than the refractive index of the next high refractive index layer.

本発明によれば、広い反射抑制波長域を有する反射抑制膜を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the reflection suppression film | membrane which has a wide reflection suppression wavelength range can be provided.

本発明の一実施形態に係る反射抑制部材の模式的断面図である。It is typical sectional drawing of the reflection suppression member which concerns on one Embodiment of this invention. 実施例１に係る反射抑制膜の反射率と、比較例１に係る反射抑制膜の反射率とを表すグラフである。6 is a graph showing the reflectance of a reflection suppression film according to Example 1 and the reflectance of a reflection suppression film according to Comparative Example 1. 比較例１に係る反射抑制膜の反射率と、比較例２に係る反射抑制膜の反射率とを表すグラフである。5 is a graph showing the reflectance of a reflection suppression film according to Comparative Example 1 and the reflectance of a reflection suppression film according to Comparative Example 2. 比較例１に係る反射抑制膜の反射率と、比較例３に係る反射抑制膜の反射率とを表すグラフである。5 is a graph showing the reflectance of a reflection suppression film according to Comparative Example 1 and the reflectance of a reflection suppression film according to Comparative Example 3. 実施例１に係る反射抑制膜の反射率と、実施例２に係る反射抑制膜の反射率と、実施例３に係る反射抑制膜の反射率とを表すグラフである。6 is a graph showing the reflectance of a reflection suppression film according to Example 1, the reflectance of a reflection suppression film according to Example 2, and the reflectance of a reflection suppression film according to Example 3. 実施例４に係る反射抑制膜の反射率と、実施例５に係る反射抑制膜の反射率と、実施例６に係る反射抑制膜の反射率とを表すグラフである。14 is a graph showing the reflectance of a reflection suppression film according to Example 4, the reflectance of a reflection suppression film according to Example 5, and the reflectance of a reflection suppression film according to Example 6. 実施例７に係る反射抑制膜の反射率と、実施例８に係る反射抑制膜の反射率と、実施例９に係る反射抑制膜の反射率と、実施例１０に係る反射抑制膜の反射率と、実施例１１に係る反射抑制膜の反射率と、実施例１２に係る反射抑制膜の反射率とを表すグラフである。The reflectance of the antireflection film according to Example 7, the reflectance of the antireflection film according to Example 8, the reflectance of the antireflection film according to Example 9, and the reflectance of the antireflection film according to Example 10. 14 is a graph showing the reflectance of the reflection suppression film according to Example 11 and the reflectance of the reflection suppression film according to Example 12.

以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。   Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

図１は、本実施形態に係る反射抑制部材１の模式的断面図である。反射抑制部材１は、例えば、電荷結合素子（Ｃｈａｒｇｅ Ｃｏｕｐｌｅｄ Ｄｅｖｉｃｅ：ＣＣＤ）などの撮像素子の前方に配され、撮像素子への光の到達率を向上させるものであってもよい。また、反射抑制部材１は、例えば、レンズ、プリズム、フィルター等の、光の反射を抑制する以外の光学特性を有する光学部品であってもよい。   FIG. 1 is a schematic cross-sectional view of a reflection suppressing member 1 according to this embodiment. The reflection suppressing member 1 may be disposed in front of an imaging device such as a charge coupled device (CCD), for example, and may improve the arrival rate of light to the imaging device. Further, the reflection suppressing member 1 may be an optical component having optical characteristics other than suppressing light reflection, such as a lens, a prism, and a filter.

反射抑制部材１は、基材１０を備える。基材１０は、特に限定されない。基材１０は、反射抑制部材１に要求される特性等に応じて適宜選択することができる。基材１０は、例えば、ガラス材、樹脂材、セラミック材等であってもよい。基材１０は、透光性を有していてもよいし、透光性を有していなくてもよい。基材１０の形状も特に限定されない。基材１０は、例えば、板状、プリズム状、レンズ状、立方体状、角柱状、円柱状等であってもよい。   The reflection suppressing member 1 includes a base material 10. The substrate 10 is not particularly limited. The base material 10 can be appropriately selected according to the characteristics required for the reflection suppressing member 1. The base material 10 may be a glass material, a resin material, a ceramic material, or the like, for example. The base material 10 may have translucency or may not have translucency. The shape of the substrate 10 is not particularly limited. The substrate 10 may be, for example, a plate shape, a prism shape, a lens shape, a cubic shape, a prismatic shape, a cylindrical shape, or the like.

基材１０の上には、反射抑制膜１１が設けられている。反射抑制膜１１は、基材１０の表面における光の反射率を低減させる。反射抑制膜１１が基材１０の表面における光の反射率をゼロにするものである必要は必ずしもない。   On the base material 10, the antireflection film 11 is provided. The antireflection film 11 reduces the reflectance of light on the surface of the substrate 10. The reflection suppression film 11 is not necessarily required to make the light reflectance on the surface of the substrate 10 zero.

反射抑制膜１１は、複数の層の積層体により構成されている。反射抑制膜１１の層数は、特に限定されないが、例えば、４〜７であることが好ましく、４〜６であることがより好ましく、４〜５であることがさらに好ましい。   The antireflection film 11 is composed of a laminate of a plurality of layers. Although the number of layers of the reflection suppression film | membrane 11 is not specifically limited, For example, it is preferable that it is 4-7, it is more preferable that it is 4-6, and it is further more preferable that it is 4-5.

反射抑制膜１１は、相対的に屈折率が高い高屈折率層１２Ｈと、相対的に屈折率が低い低屈折率層１２Ｌとを有する。反射抑制膜１１においては、高屈折率層１２Ｈと低屈折率層１２Ｌとが交互に積層されている。反射抑制膜１１の最外層、すなわち、基材１０から最も離れた位置に位置している層は、低屈折率層１２Ｌ１により構成されている。   The reflection suppression film 11 includes a high refractive index layer 12H having a relatively high refractive index and a low refractive index layer 12L having a relatively low refractive index. In the reflection suppressing film 11, high refractive index layers 12H and low refractive index layers 12L are alternately stacked. The outermost layer of the reflection suppressing film 11, that is, the layer located at the position farthest from the substrate 10 is configured by the low refractive index layer 12 </ b> L <b> 1.

反射抑制膜１１の最外層を構成している低屈折率層１２Ｌ１と、低屈折率層１２Ｌ１の次に位置する高屈折率層１２Ｈ１との間には、中間屈折率層１２Ｍが配されている。中間屈折率層１２Ｍの屈折率は、低屈折率層１２Ｌ１の屈折率よりも高く、高屈折率層１２Ｈ１の屈折率よりも低い。このような中間屈折率層１２Ｍを設けることにより、反射抑制膜１１の層数をそれほど多くすることなく、反射抑制膜１１の反射を抑制できる波長域（反射抑制波長域）を広くすることができる。   An intermediate refractive index layer 12M is disposed between the low refractive index layer 12L1 constituting the outermost layer of the reflection suppressing film 11 and the high refractive index layer 12H1 positioned next to the low refractive index layer 12L1. . The refractive index of the intermediate refractive index layer 12M is higher than the refractive index of the low refractive index layer 12L1, and lower than the refractive index of the high refractive index layer 12H1. By providing such an intermediate refractive index layer 12M, the wavelength region (reflection suppression wavelength region) in which reflection of the reflection suppression film 11 can be suppressed can be widened without increasing the number of layers of the reflection suppression film 11 so much. .

なお、中間屈折率層１２Ｍは、厚み方向において屈折率が実質的に変化しない層であってもよいし、厚み方向において屈折率が変化する層であってもよい。例えば、中間屈折率層１２Ｍは、屈折率が低屈折率層１２Ｌ１側から高屈折率層１２Ｈ側に向けて漸増している屈折率傾斜層であってもよい。   The intermediate refractive index layer 12M may be a layer whose refractive index does not substantially change in the thickness direction, or may be a layer whose refractive index changes in the thickness direction. For example, the intermediate refractive index layer 12M may be a refractive index gradient layer whose refractive index gradually increases from the low refractive index layer 12L1 side toward the high refractive index layer 12H side.

高屈折率層１２Ｈは、例えば、酸化ニオブ、酸化チタン、酸化ランタン、酸化イットリウム、酸化タングステン、酸化タンタル等のうちの少なくとも一種により構成することができる。   The high refractive index layer 12H can be composed of, for example, at least one of niobium oxide, titanium oxide, lanthanum oxide, yttrium oxide, tungsten oxide, tantalum oxide, and the like.

低屈折率層１２Ｌは、例えば、酸化ケイ素、酸化ガリウム、フッ化マグネシウム、フッ化ナトリウム、フッ化アルミニウム、フッ化リチウム、フッ化カルシウム等のうちの少なくとも一種により構成することができる。   The low refractive index layer 12L can be composed of, for example, at least one of silicon oxide, gallium oxide, magnesium fluoride, sodium fluoride, aluminum fluoride, lithium fluoride, calcium fluoride, and the like.

中間屈折率層１２Ｍは、例えば、高屈折率層１２Ｈ１に含まれる金属と、低屈折率層１２Ｌ１に含まれる金属との両方を含んでいてもよいし、含んでいなくてもよい。   For example, the intermediate refractive index layer 12M may or may not include both the metal included in the high refractive index layer 12H1 and the metal included in the low refractive index layer 12L1.

中間屈折率層１２Ｍの厚みは、低屈折率層１２Ｌ１の厚み以下であることが好ましく、低屈折率層１２Ｌ１の厚みの０．４５倍以下であることがより好ましく、０．３５倍以下であることがさらに好ましい。中間屈折率層１２Ｍの厚みは、１０ｎｍ〜３０ｎｍであることが好ましく、１０ｎｍ〜２５ｎｍであることがより好ましく、１５ｎｍ〜２５ｎｍであることがさらに好ましい。   The thickness of the intermediate refractive index layer 12M is preferably not more than the thickness of the low refractive index layer 12L1, more preferably not more than 0.45 times the thickness of the low refractive index layer 12L1, and not more than 0.35 times. More preferably. The thickness of the intermediate refractive index layer 12M is preferably 10 nm to 30 nm, more preferably 10 nm to 25 nm, and further preferably 15 nm to 25 nm.

中間屈折率層１２Ｍの屈折率が厚み方向に実質的に均一である場合は、中間屈折率層１２Ｍの屈折率は、低屈折率層１２Ｌ１の屈折率の１．１１倍〜高屈折率層１２Ｈ１の０．９６倍であることが好ましく、低屈折率層１２Ｌ１の屈折率の１．１７倍〜高屈折率層１２Ｈ１の０．９２倍であることがより好ましく、低屈折率層１２Ｌ１の屈折率の１．２３倍〜高屈折率層１２Ｈ１の０．８８倍であることがさらに好ましい。   When the refractive index of the intermediate refractive index layer 12M is substantially uniform in the thickness direction, the refractive index of the intermediate refractive index layer 12M is 1.11 times the refractive index of the low refractive index layer 12L1 to the high refractive index layer 12H1. 0.96 times, preferably 1.17 times the refractive index of the low refractive index layer 12L1 to 0.92 times the high refractive index layer 12H1, and the refractive index of the low refractive index layer 12L1. It is more preferable that it is 1.23 times as high as 0.88 times that of the high refractive index layer 12H1.

以下、低屈折率層からなる第１層（最外層）と、高屈折率層からなる第３層との間に、中間屈折率層からなる第２層を設けることにより反射抑制波長域を広げることができることについて具体例に基づいて詳細に説明する。   Hereinafter, by providing a second layer made of an intermediate refractive index layer between a first layer (outermost layer) made of a low refractive index layer and a third layer made of a high refractive index layer, the reflection suppression wavelength region is widened. This will be described in detail based on a specific example.

図２に、実施例１に係る反射抑制膜の反射率と、比較例１に係る反射抑制膜の反射率とを表すグラフである。   FIG. 2 is a graph showing the reflectance of the reflection suppression film according to Example 1 and the reflectance of the reflection suppression film according to Comparative Example 1.

実施例１に係る反射抑制膜の膜構成と、比較例１に係る反射抑制膜の膜構成とは、下記の表１及び表２に示す通りである。表１に示される通り、実施例１では、低屈折率層からなる第１層（最外層）と、高屈折率層からなる第３層との間に、中間屈折率層からなる第２層が設けられている。一方、比較例１では、表２に示される通り、低屈折率層からなる第１層（最外層）の次に、中間屈折率層が設けられておらず、高屈折率層からなる第２層が設けられている。   The film configuration of the antireflection film according to Example 1 and the film configuration of the antireflection film according to Comparative Example 1 are as shown in Table 1 and Table 2 below. As shown in Table 1, in Example 1, the second layer made of an intermediate refractive index layer is provided between the first layer (outermost layer) made of a low refractive index layer and the third layer made of a high refractive index layer. Is provided. On the other hand, in Comparative Example 1, as shown in Table 2, the intermediate refractive index layer is not provided next to the first layer (outermost layer) made of the low refractive index layer, and the second layer made of the high refractive index layer. A layer is provided.

Figure 2015064419
Figure 2015064419

Figure 2015064419
Figure 2015064419

図２に示すグラフから、低屈折率層からなる第１層（最外層）と、高屈折率層からなる第３層との間に、中間屈折率層からなる第２層を設けることにより、反射抑制波長域を広くできることが分かる。例えば、反射率が０．４％
以下の波長域の広さは、比較例１では、２６５．３ｎｍであったのに対して、実施例１では、２８０．１ｎｍであった。 From the graph shown in FIG. 2, by providing a second layer consisting of an intermediate refractive index layer between a first layer consisting of a low refractive index layer (outermost layer) and a third layer consisting of a high refractive index layer, It can be seen that the reflection suppression wavelength region can be widened. For example, the reflectance is 0.4%
The width of the following wavelength region was 265.3 nm in Comparative Example 1, whereas it was 280.1 nm in Example 1.

また、図２に示される結果から、中間屈折率層を設けた実施例１の方が、比較例１よりも反射抑制波長域における反射率の変動を小さくすることができる。よって、中間屈折率層を設けることにより、反射抑制膜の製造が容易になるというメリットも得られる。   Further, from the results shown in FIG. 2, the variation in reflectance in the reflection suppression wavelength region can be made smaller in Example 1 in which the intermediate refractive index layer is provided than in Comparative Example 1. Therefore, by providing the intermediate refractive index layer, it is possible to obtain an advantage that the production of the reflection suppressing film becomes easy.

図２に示すように、中間屈折率層を設けない比較例１の方が、中間屈折率層を設けた実施例１よりも最低反射率は低い。このため、従来は、最外層を構成している低屈折率層と、次の高屈折率層との間に中間屈折率層を設けることにより、光学特性を向上させるという発想は当業者にはなかった。本発明者は、鋭意研究した結果、最外層を構成している低屈折率層と、次の高屈折率層との間に中間屈折率層を設けることにより、最低反射率が高くなる場合があるものの、反射抑制波長域を拡大できることを初めて見出した。その結果、本発明者らは、最外層を構成している低屈折率層と、次の高屈折率層との間に中間屈折率層を設ける構成に想到した。   As shown in FIG. 2, the minimum reflectance is lower in Comparative Example 1 in which the intermediate refractive index layer is not provided than in Example 1 in which the intermediate refractive index layer is provided. For this reason, the conventional idea of improving the optical characteristics by providing an intermediate refractive index layer between the low refractive index layer constituting the outermost layer and the next high refractive index layer is known to those skilled in the art. There wasn't. As a result of diligent research, the present inventors have found that the lowest reflectance may be increased by providing an intermediate refractive index layer between the low refractive index layer constituting the outermost layer and the next high refractive index layer. However, for the first time, it was found that the reflection suppression wavelength range can be expanded. As a result, the present inventors have conceived a configuration in which an intermediate refractive index layer is provided between the low refractive index layer constituting the outermost layer and the next high refractive index layer.

図３は、比較例１に係る反射抑制膜の反射率と、比較例２に係る反射抑制膜の反射率とを表すグラフである。図４は、比較例１に係る反射抑制膜の反射率と、比較例３に係る反射抑制膜の反射率とを表すグラフである。   FIG. 3 is a graph showing the reflectance of the reflection suppression film according to Comparative Example 1 and the reflectance of the reflection suppression film according to Comparative Example 2. FIG. 4 is a graph showing the reflectance of the reflection suppression film according to Comparative Example 1 and the reflectance of the reflection suppression film according to Comparative Example 3.

表３に比較例２に係る反射抑制膜の膜構成を示す。表４に比較例３に係る反射抑制膜の膜構成を示す。   Table 3 shows the film configuration of the antireflection film according to Comparative Example 2. Table 4 shows the film configuration of the antireflection film according to Comparative Example 3.

Figure 2015064419
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Figure 2015064419
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表３及び表４に示す通り、比較例２，３に係る反射抑制膜も、実施例１に係る反射抑制膜と同様に、中間屈折率層を有する。しかしながら、比較例２，３では、中間屈折率層が、低屈折率層からなる第１層（最外層）と、高屈折率層からなる第３層との間に設けられていない。図３及び図４に示すように、このような比較例２，３係る反射抑制膜は、中間屈折率層を有さない比較例１に係る反射抑制膜と、反射抑制波長域が実質的に等しい。この結果から、反射抑制波長域を広げるためには、少なくとも、中間屈折率層を低屈折率層からなる第１層（最外層）と、高屈折率層からなる第３層との間に設ける必要があることが分かる。反射抑制膜１１の層数の増大を抑制しつつ、反射抑制波長域を広げる観点からは、中間屈折率層１２Ｍを、最外層を構成している低屈折率層１２Ｌ１と、次に位置する高屈折率層１２Ｈ１との間のみに配することが好ましい。もっとも、本発明においては、他の場所に、さらなる中間屈折率層が設けられていてもよい。   As shown in Tables 3 and 4, the antireflection film according to Comparative Examples 2 and 3 also has an intermediate refractive index layer, like the antireflection film according to Example 1. However, in Comparative Examples 2 and 3, the intermediate refractive index layer is not provided between the first layer (outermost layer) made of the low refractive index layer and the third layer made of the high refractive index layer. As shown in FIG. 3 and FIG. 4, such a reflection suppressing film according to Comparative Examples 2 and 3 has substantially the same reflection suppressing wavelength region as that of the reflection suppressing film according to Comparative Example 1 having no intermediate refractive index layer. equal. From this result, in order to widen the reflection suppression wavelength region, at least the intermediate refractive index layer is provided between the first layer (outermost layer) composed of the low refractive index layer and the third layer composed of the high refractive index layer. I understand that it is necessary. From the viewpoint of expanding the reflection suppression wavelength region while suppressing an increase in the number of layers of the reflection suppression film 11, the intermediate refractive index layer 12M is arranged next to the low refractive index layer 12L1 constituting the outermost layer and the high refractive index layer 12L1. It is preferable to dispose only between the refractive index layer 12H1. However, in the present invention, a further intermediate refractive index layer may be provided in another place.

図５は、実施例１に係る反射抑制膜の反射率と、実施例２に係る反射抑制膜の反射率と、実施例３に係る反射抑制膜の反射率とを表すグラフである。図６は、実施例４に係る反射抑制膜の反射率と、実施例５に係る反射抑制膜の反射率と、実施例６に係る反射抑制膜の反射率とを表すグラフである。   FIG. 5 is a graph showing the reflectance of the reflection suppression film according to Example 1, the reflectance of the reflection suppression film according to Example 2, and the reflectance of the reflection suppression film according to Example 3. FIG. 6 is a graph illustrating the reflectance of the reflection suppression film according to Example 4, the reflectance of the reflection suppression film according to Example 5, and the reflectance of the reflection suppression film according to Example 6.

表５に実施例２に係る反射抑制膜の膜構成を示す。表６に実施例３に係る反射抑制膜の膜構成を示す。表７に実施例４に係る反射抑制膜の膜構成を示す。表８に実施例５に係る反射抑制膜の膜構成を示す。表９に実施例６に係る反射抑制膜の膜構成を示す。   Table 5 shows the film configuration of the antireflection coating according to Example 2. Table 6 shows the film configuration of the antireflection coating according to Example 3. Table 7 shows the film configuration of the antireflection coating according to Example 4. Table 8 shows the film configuration of the reflection suppressing film according to Example 5. Table 9 shows the film configuration of the antireflection film according to Example 6.

Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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実施例１〜３に係る反射抑制膜は、第２層のみに中間屈折率層を有する点において共通しており、その中間屈折率層の厚みが相互に異なる。実施例４〜６に係る反射抑制膜は、第２，第４，第６層に中間屈折率層を有する点において共通しており、その中間屈折率層の厚みが相互に異なる。   The antireflection films according to Examples 1 to 3 are common in that only the second layer has an intermediate refractive index layer, and the thicknesses of the intermediate refractive index layers are different from each other. The antireflection films according to Examples 4 to 6 are common in that the second, fourth, and sixth layers have intermediate refractive index layers, and the thicknesses of the intermediate refractive index layers are different from each other.

図６に示す結果から、第２，第４，第６層に中間屈折率層を設けた場合は、中間屈折率層の厚みが１ｎｍずれただけでも大きく反射抑制特性が変化する。それに対して、第２層にのみ中間屈折率層を設けた場合は、中間屈折率層の厚みが変化しても反射抑制特性が変化しにくい。従って、第２層にのみ中間屈折率層を設けることにより、反射抑制膜を安定した反射抑制特性で製造することが容易になる。   From the results shown in FIG. 6, when the intermediate refractive index layers are provided in the second, fourth, and sixth layers, the reflection suppression characteristics change greatly even when the thickness of the intermediate refractive index layer is shifted by 1 nm. On the other hand, when the intermediate refractive index layer is provided only in the second layer, even if the thickness of the intermediate refractive index layer changes, the reflection suppression characteristics are unlikely to change. Therefore, by providing the intermediate refractive index layer only in the second layer, it becomes easy to manufacture the antireflection film with stable antireflection characteristics.

図７は、実施例７に係る反射抑制膜の反射率と、実施例８に係る反射抑制膜の反射率と、実施例９に係る反射抑制膜の反射率と、実施例１０に係る反射抑制膜の反射率と、実施例１１に係る反射抑制膜の反射率と、実施例１２に係る反射抑制膜の反射率とを表すグラフである。表１０に実施例７に係る反射抑制膜の膜構成を示す。表１１に実施例８に係る反射抑制膜の膜構成を示す。表１２に実施例９に係る反射抑制膜の膜構成を示す。表１３に実施例１０に係る反射抑制膜の膜構成を示す。表１４に実施例１１に係る反射抑制膜の膜構成を示す。表１５に実施例１２に係る反射抑制膜の膜構成を示す。   7 shows the reflectance of the reflection suppression film according to Example 7, the reflectance of the reflection suppression film according to Example 8, the reflectance of the reflection suppression film according to Example 9, and the reflection suppression according to Example 10. 14 is a graph showing the reflectance of a film, the reflectance of a reflection suppressing film according to Example 11, and the reflectance of a reflection suppressing film according to Example 12. Table 10 shows the film configuration of the antireflection coating according to Example 7. Table 11 shows the film configuration of the antireflection film according to Example 8. Table 12 shows the film configuration of the reflection suppressing film according to Example 9. Table 13 shows the film configuration of the antireflection film according to Example 10. Table 14 shows the film configuration of the antireflection film according to Example 11. Table 15 shows the film configuration of the antireflection coating according to Example 12.

Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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Figure 2015064419
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実施例７〜１２に係る反射抑制膜は、第２層に中間屈折率層を有する点において共通している。実施例７〜１２では、中間屈折率層の厚みが相互に異なる。他の層の厚みは、反射率が最低となるように微調整しているため、実施例７〜１２において異なる場合がある。   The antireflection films according to Examples 7 to 12 are common in that the second layer has an intermediate refractive index layer. In Examples 7 to 12, the thicknesses of the intermediate refractive index layers are different from each other. Since the thicknesses of the other layers are finely adjusted so that the reflectance is minimized, the thicknesses of Examples 7 to 12 may be different.

図７に示す結果から、第２層を構成している中間屈折率層の厚みが大きくなるほど反射抑制波長域が広くなるものの、最低反射率は高くなる傾向にあることが分かる。   From the results shown in FIG. 7, it can be seen that the minimum reflectance is likely to increase although the reflection suppression wavelength region becomes wider as the thickness of the intermediate refractive index layer constituting the second layer increases.

１：反射抑制部材
１０：基材
１１：反射抑制膜
１２Ｈ：高屈折率層
１２Ｌ：低屈折率層
１２Ｍ：中間屈折率層
1: Antireflection member 10: Base material 11: Antireflection film 12H: High refractive index layer 12L: Low refractive index layer 12M: Intermediate refractive index layer

Claims (8)

基材の上に形成された反射抑制膜であって、
相対的に高い屈折率を有する高屈折率層と、
相対的に低い屈折率を有する低屈折率層と、
を備え、
前記高屈折率層と前記低屈折率層とが、最外層が前記低屈折率層となるように交互に積層されており、
前記最外層を構成している低屈折率層と、次に位置する前記高屈折率層との間に配されており、前記最外層を構成している低屈折率層の屈折率よりも高く、前記次に位置する高屈折率層の屈折率よりも低い屈折率を有する中間屈折率層をさらに備える、反射抑制膜。 An antireflection film formed on a substrate,
A high refractive index layer having a relatively high refractive index;
A low refractive index layer having a relatively low refractive index;
With
The high refractive index layer and the low refractive index layer are alternately laminated so that the outermost layer is the low refractive index layer,
It is arranged between the low refractive index layer constituting the outermost layer and the high refractive index layer located next, and is higher than the refractive index of the low refractive index layer constituting the outermost layer. The antireflection film further comprises an intermediate refractive index layer having a refractive index lower than that of the next higher refractive index layer. 前記中間屈折率層は、屈折率が前記低屈折率層側から前記高屈折率層側に向けて漸増している屈折率傾斜層である、請求項１に記載の反射抑制膜。   2. The antireflection film according to claim 1, wherein the intermediate refractive index layer is a gradient refractive index layer whose refractive index gradually increases from the low refractive index layer side toward the high refractive index layer side. 前記中間屈折率層は、前記最外層を構成している低屈折率層と、次に位置する前記高屈折率層との間にのみ配されている、請求項１又は２に記載の反射抑制膜。   The reflection suppression according to claim 1 or 2, wherein the intermediate refractive index layer is disposed only between a low refractive index layer constituting the outermost layer and the high refractive index layer positioned next. film. 前記中間屈折率層は、隣接する前記高屈折率層に含まれる金属と、隣接する前記低屈折率層に含まれる金属との両方を含む、請求項１〜３のいずれか一項に記載の反射抑制膜。   The said intermediate | middle refractive index layer contains both the metal contained in the said adjacent high refractive index layer, and the metal contained in the adjacent said low refractive index layer, It is any one of Claims 1-3. Antireflection film. 前記中間屈折率層の厚みが、前記最外層を構成している低屈折率層の厚み以下である、請求項１〜４のいずれか一項に記載の反射抑制膜。   The reflection suppression film according to any one of claims 1 to 4, wherein a thickness of the intermediate refractive index layer is equal to or less than a thickness of a low refractive index layer constituting the outermost layer. 前記中間屈折率層は、隣接する前記低屈折率層の屈折率の１．１１倍以上であって、隣接する前記高屈折率層の屈折率の０．９６倍以下の屈折率を有する部分を含む、請求項１〜５のいずれか一項に記載の反射抑制膜。   The intermediate refractive index layer includes a portion having a refractive index of 1.11 times or more of the refractive index of the adjacent low refractive index layer and 0.96 times or less of the refractive index of the adjacent high refractive index layer. The reflection suppression film | membrane as described in any one of Claims 1-5 containing. 層数が７以下である、請求項１〜６のいずれか一項に記載の反射抑制膜。   The antireflection film according to any one of claims 1 to 6, wherein the number of layers is 7 or less. 基材と、
前記基材の上に設けられた反射抑制膜と、
を備える反射抑制部材であって、
前記反射抑制膜は、
相対的に高い屈折率を有する高屈折率層と、
相対的に低い屈折率を有する低屈折率層と、
を備え、
前記高屈折率層と前記低屈折率層とが、前記反射抑制膜の最外層が前記低屈折率層となるように交互に積層されており、
前記反射抑制膜は、前記最外層を構成している低屈折率層と、次に位置する前記高屈折率層との間に配されており、前記最外層を構成している低屈折率層の屈折率よりも高く、前記次に位置する高屈折率層の屈折率よりも低い屈折率を有する中間屈折率層をさらに備える、反射抑制部材。 A substrate;
An antireflection film provided on the substrate;
A reflection suppressing member comprising:
The antireflection film is
A high refractive index layer having a relatively high refractive index;
A low refractive index layer having a relatively low refractive index;
With
The high refractive index layer and the low refractive index layer are alternately laminated so that the outermost layer of the reflection suppressing film becomes the low refractive index layer,
The antireflection film is disposed between the low refractive index layer constituting the outermost layer and the high refractive index layer positioned next, and the low refractive index layer constituting the outermost layer. A reflection suppressing member further comprising an intermediate refractive index layer having a refractive index higher than that of the second refractive index and lower than that of the next high refractive index layer.
JP2013196953A 2013-09-24 2013-09-24 Reflection suppressing film and reflection suppressing member Pending JP2015064419A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109856707A (en) * 2019-02-26 2019-06-07 江西凤凰光学科技有限公司 A kind of anti-reflection film of broadband ultra-low reflectance

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JP2001192822A (en) * 2000-01-07 2001-07-17 Nippon Sheet Glass Co Ltd Film deposition method, and article obtained by the same
JP4120932B2 (en) * 2003-03-24 2008-07-16 日本ゼオン株式会社 Laminated body and optical member
JP4380752B2 (en) * 2007-09-11 2009-12-09 凸版印刷株式会社 Method for manufacturing antireflection laminate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109856707A (en) * 2019-02-26 2019-06-07 江西凤凰光学科技有限公司 A kind of anti-reflection film of broadband ultra-low reflectance

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