JP5148839B2 - Antireflection film for infrared light - Google Patents
Antireflection film for infrared light Download PDFInfo
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- JP5148839B2 JP5148839B2 JP2006125464A JP2006125464A JP5148839B2 JP 5148839 B2 JP5148839 B2 JP 5148839B2 JP 2006125464 A JP2006125464 A JP 2006125464A JP 2006125464 A JP2006125464 A JP 2006125464A JP 5148839 B2 JP5148839 B2 JP 5148839B2
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- 239000010408 film Substances 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 40
- 239000005083 Zinc sulfide Substances 0.000 claims description 32
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 32
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052732 germanium Inorganic materials 0.000 claims description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- 230000005540 biological transmission Effects 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229940105963 yttrium fluoride Drugs 0.000 claims description 10
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 claims description 10
- 239000012788 optical film Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 60
- 238000002834 transmittance Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
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Description
本発明は、例えば非接触放射温度計測や人体検知等の用途に用いられる熱型赤外線センサの窓材や光学フィルタなどのように、６〜１２μｍ波長領域の中赤外光を利用する光学機器の反射防止のために使用される赤外光用反射防止膜に関する。 The present invention relates to an optical device that uses mid-infrared light in the 6 to 12 μm wavelength region, such as a window material or an optical filter of a thermal infrared sensor used for non-contact radiation temperature measurement or human body detection. The present invention relates to an antireflection film for infrared light used for antireflection.
この種の反射防止膜のうち、基板上に単一の膜を形成してなる単層構造の反射防止膜の場合は、基板の屈折率（以下、ｎで表わす）の平方根（√ｎ）と等しい屈折率を持つ膜を形成することにより、ある波長の一点で反射率を０％にすることが可能である。例えば、基板がシリコン基板である場合、シリコン（Ｓｉ）の屈折率は、ｎ＝３．４であるから、反射率の低減を図るためには、√（３．４）＝１．８４の屈折率を持つ膜を形成することが必要であり、それに近い屈折率を有する膜材料としては、酸化ケイ素（ＳｉＯ、その屈折率ｎ＝１．８）が相当する。しかし、このＳｉＯ単層をＳｉ基板上に形成した反射防止膜は、５μｍ以下の波長領域で高い透過率が得られるものの、６μｍ以上の波長領域ではＳｉＯ中の不純物による吸収が多く、高い透過率を得ることができず、６〜１２μｍ波長領域の中赤外光を利用する光学機器の反射防止膜としては全く実用に供し得ない。 In this type of antireflection film, in the case of an antireflection film having a single-layer structure formed by forming a single film on the substrate, the square root (√n) of the refractive index of the substrate (hereinafter referred to as n) and By forming a film having an equal refractive index, the reflectance can be reduced to 0% at a certain wavelength. For example, when the substrate is a silicon substrate, the refractive index of silicon (Si) is n = 3.4. Therefore, in order to reduce the reflectance, the refraction of √ (3.4) = 1.84 It is necessary to form a film having a refractive index, and silicon oxide (SiO, its refractive index n = 1.8) corresponds to a film material having a refractive index close to that. However, the antireflection film in which the SiO single layer is formed on the Si substrate can obtain high transmittance in the wavelength region of 5 μm or less, but in the wavelength region of 6 μm or more, there is much absorption due to impurities in SiO, and high transmittance. And cannot be practically used as an antireflection film for an optical device using mid-infrared light in the 6 to 12 μm wavelength region.
また、Ｓｉ基板を用いる赤外光用反射防止膜として、前記酸化ケイ素（ＳｉＯ）に代えて、硫化亜鉛（ＺｎＳ、ｎ＝２．３）を用い、このＺｎＳ層上に該硫化亜鉛の屈折率（ｎ＝２．３）の平方根、即ち、√（２．３）＝１．５１に近い屈折率を有する材料層、例えばＢａＦ2 やＰｂＦ2 （共に、ｎ＝１．４）等の低屈折率材料を積層して多層構造としたものが考えられるが、これら各層を反射防止に必要な厚膜に成膜すると、多結晶性が顕著になり、粒界面での光の散乱によって高い透過率を得ることが技術的に難しい。さらに、厚膜多層構造であるために、基板を含む下地との密着性にも問題があり、短期間の使用で剥離が生じるなど実用に供し得ない。 Further, instead of silicon oxide (SiO), zinc sulfide (ZnS, n = 2.3) is used as an antireflection film for infrared light using a Si substrate, and the refractive index of the zinc sulfide is formed on the ZnS layer. Low refraction such as a square root of (n = 2.3), that is, a material layer having a refractive index close to √ (2.3) = 1.51, such as BaF 2 or PbF 2 (both n = 1.4). Multi-layered materials can be used to form a multilayer structure. However, when these layers are formed in a thick film necessary for antireflection, polycrystallinity becomes prominent, and light transmittance at the grain interface causes high transmittance. It is technically difficult to get. Furthermore, since it is a thick film multilayer structure, there is also a problem with the adhesion to the substrate including the substrate, and it cannot be put to practical use because it peels off after a short period of use.
上述のようなＳｉ基板を用いる赤外光用反射防止膜では単層構造、多層構造のいずれの場合も６〜１２μｍ波長領域で実用に十分に供し得るだけの透過特性、反射特性が得られない。この点に鑑みて、従来、基板として６〜１２μｍ波長領域で不純物吸収が少ないゲルマニウム（Ｇｅ）基板を用い、このＧｅ基板上に、ＺｎＳ層、Ｇｅ層、ＺｎＳ層及びフッ化イットリウム（ＹＦ3 ）層を基板側から順に積層して、６〜１２μｍ波長領域で高い透過率が得られるように構成した反射防止膜が提案されている（例えば、特許文献１参照）。 In the antireflection film for infrared light using the Si substrate as described above, transmission characteristics and reflection characteristics sufficient for practical use in the wavelength range of 6 to 12 μm cannot be obtained in either a single layer structure or a multilayer structure. . In view of this point, conventionally, a germanium (Ge) substrate that absorbs less impurities in the 6 to 12 μm wavelength region is used as the substrate, and a ZnS layer, a Ge layer, a ZnS layer, and yttrium fluoride (YF 3 ) are formed on the Ge substrate. An antireflection film has been proposed in which layers are stacked in order from the substrate side so that high transmittance can be obtained in a wavelength range of 6 to 12 μm (see, for example, Patent Document 1).
上記特許文献１に示した従来の赤外光用反射防止膜は、基板から最も外側の最終層、つまり、光が最初に入射する層に、中赤外光領域での屈折率がｎ＝１．５という低屈折率のＹＦ3 層を用いていることにより、反射防止膜面の３〜１５μｍ波長領域での平均透過率を９０％以上と高くすることが可能である。反面、Ｇｅ基板はＳｉ基板に比べて、１０倍以上もコスト高であり、そのため、全体コストの安価な光学機器への適用は実際問題として困難である。また、最終層に低屈折率のＹＦ3層を用いた従来の赤外光用反射防止膜は、高い平均透過率が得られるものの、図２の点線で示すように、９μｍ前後の波長領域に透過率が急激かつ局所的に低下する、いわゆる、リップルが発生し、実用範囲において平坦な透過特性が得られないという難点があった。
The conventional anti-reflection film for infrared light shown in
本発明は上述の実情に鑑みてなされたもので、その目的は、コスト的に安価な割に不純物吸収があるシリコン基板を用いながらも、６〜１２μｍ波長領域の全範囲に亘って高く、かつ、リップルのない平坦な透過特性を得ることができる赤外光用反射防止膜を提供することにある。 The present invention has been made in view of the above-mentioned circumstances, and its purpose is high over the entire range of the 6 to 12 μm wavelength region while using a silicon substrate having impurity absorption for a low cost. Another object of the present invention is to provide an antireflection film for infrared light capable of obtaining flat transmission characteristics free from ripples.
上記目的を達成するために、本発明に係る赤外光用反射防止膜は、シリコン基板に複数の薄膜が積層状態に形成されてなる赤外光用反射防止膜であって、前記シリコン基板の少なくとも一方の面に、ゲルマニウム層、硫化亜鉛層、ゲルマニウム層、硫化亜鉛層及び他の層よりも低屈折率のフッ化イットリウム層を前記シリコン基板側から順に積層し、これら計五つの各層それぞれの光学膜厚を６〜１２μｍ付近の赤外波長領域で９０％以上の透過特性となるように設定した多層構造で構成されていることを特徴としている。
In order to achieve the above object, an antireflection film for infrared light according to the present invention is an antireflection film for infrared light in which a plurality of thin films are formed in a laminated state on a silicon substrate. on at least one side, germanium layer, zinc sulfide layer, a germanium layer, laminating a yttrium fluoride layer of lower refractive index than the zinc sulfide layer and other layers in this order from the silicon substrate side, these total five or each layer Each optical film thickness is constituted by a multilayer structure in which transmission characteristics of 90% or more are set in an infrared wavelength region near 6 to 12 μm.
上記構成の本発明によれば、基板として、材料コスト的に非常に安価なＳｉ基板を用いて反射防止膜全体（製品）のコスト低減を図り、経済的な見地から光学機器への適用範囲を広く確保しながら、Ｓｉ基板中の不純物による吸収が現れない６〜１２μｍ付近の赤外波長領域において重点的に透過率が高くなるように最も外側に低屈折率のフッ化イットリウム層を配した多層構造とすることによって、実用的な中赤外波長領域の全範囲に亘って透過率が９０％以上と高く、かつ、リップルのない平坦な透過特性、反射特性を得ることができる。また、反射率が小さくなるので、該反射防止膜をセンサへの導光路に設置して用いることで、迷光の影響を低減できるという効果も奏する。 According to the present invention configured as described above, the cost of the entire antireflection film (product) is reduced by using a Si substrate that is very inexpensive in terms of material cost. Multilayer with a low refractive index yttrium fluoride layer arranged on the outermost side so as to increase the transmittance preferentially in the infrared wavelength region near 6 to 12 μm where absorption by impurities in the Si substrate does not appear while ensuring a wide range by the structure, practical in transmittance over the entire range of the infrared wavelength region as high as 90% or more, and a flat transmission characteristic without ripple, it is possible to obtain a reflection characteristic. In addition, since the reflectance is reduced, the effect of stray light can be reduced by using the antireflection film in a light guide path to the sensor.
特に、本発明に係る赤外光用反射防止膜において、上記のような高い透過特性を得るための前記ゲルマニウム層、硫化亜鉛層、ゲルマニウム層、硫化亜鉛層及びフッ化イットリウム層の各光学膜厚を、請求項２に記載のように、Ｇｅ：１．７９μｍ、ＺｎＳ:２．５０μｍ、Ｇｅ：０．９３μｍ、ＺｎＳ：６．００μｍ及びＹＦ3 ：５．３８μｍに設定することにより、全体を薄膜にして基板との密着性を良好に保ちつつ、図２の実線に示すように、６〜１２μｍ付近の赤外波長領域において、平均透過率が９５〜９８％でリップルのない平坦な透過特性を確実に得ることができる。 In particular, in the antireflection film for infrared light according to the present invention, the optical film thicknesses of the germanium layer, zinc sulfide layer, germanium layer, zinc sulfide layer, and yttrium fluoride layer for obtaining the high transmission characteristics as described above. Is set to Ge: 1.79 μm, ZnS: 2.50 μm, Ge: 0.93 μm, ZnS: 6.00 μm and YF 3 : 5.38 μm. As shown by the solid line in FIG. 2, while maintaining good adhesion to the substrate, in the infrared wavelength region near 6 to 12 μm, the average transmittance is 95 to 98% and flat transmission characteristics without ripples. You can definitely get it.
また、本発明に係る赤外光用反射防止膜において、前記シリコン基板の他の面には、ロングパスフィルタまたはショートパスフィルタなどのエッジフィルタや、バンドパスフィルタを形成してもよく、また、請求項３に記載のように、前記したと同一のゲルマニウム層、硫化亜鉛層、ゲルマニウム層、硫化亜鉛層及びフッ化イットリウム層を形成して所定波長領域の中赤外光の透過特性を持たせてもよい。 In the antireflection film for infrared light according to the present invention, an edge filter such as a long pass filter or a short pass filter, or a band pass filter may be formed on the other surface of the silicon substrate. As described in Item 3, the same germanium layer, zinc sulfide layer, germanium layer, zinc sulfide layer, and yttrium fluoride layer as those described above are formed to provide the mid-infrared light transmission characteristics in a predetermined wavelength region. Also good.
以下、本発明の実施の形態を、図面を参照しながら説明する。
図１は、本発明に係る赤外光用反射防止膜の多層膜構造を示す概略縦断面図であり、同図において、１はシリコン（Ｓｉ）基板であり、このＳｉ基板１は１ｍｍの厚さを有し、その一方の面上に、第１ゲルマニウム（Ｇｅ）層２、第１硫化亜鉛（ＺｎＳ）層３、第２Ｇｅ層４、第２ＺｎＳ層５及びフッ化イットリウム（ＹＦ3 ）層６を、前記Ｓｉ基板１側から順に積層してなる。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic longitudinal sectional view showing a multilayer structure of an antireflection film for infrared light according to the present invention. In FIG. 1, 1 is a silicon (Si) substrate, and this
前記第１Ｇｅ層２、第１ＺｎＳ層３、第２Ｇｅ層４、第２ＺｎＳ層５及びＹＦ3 層６それぞれの光学膜厚は、Ｇｅ：１．７９μｍ、ＺｎＳ:２．５０μｍ、Ｇｅ：０．９３μｍ、ＺｎＳ：６．００μｍ及びＹＦ3：５．３８μｍで、６〜１２μｍ付近の赤外波長領域で９０％以上の透過特性となるように設定されている。
ここで、実際には、各層の屈折率は成膜条件により多少変化するとともに、屈折率の波長分散によって広い波長範囲で一様な値にならないが、上述したような各層それぞれの光学膜厚は、各層材料の波長１０μｍ付近の屈折率を、Ｇｅ＝４．２５、ＺｎＳ＝２．３、ＹＦ3 ＝１．５とみなして設定している。
The optical thicknesses of the
Here, in practice, the refractive index of each layer varies somewhat depending on the film formation conditions, and does not become a uniform value in a wide wavelength range due to the wavelength dispersion of the refractive index. However, the optical film thickness of each layer as described above is The refractive index of each layer material around the wavelength of 10 μm is set assuming that Ge = 4.25, ZnS = 2.3, and YF 3 = 1.5.
なお、各層２〜６の形成手段としては、真空蒸着、イオンプレーティング、スパッタリング等の真空薄膜堆積方法が用いられる。また、最外側のＹＦ3 層６の外側の屈折率は空気の屈折率（ｎ＝１．０）とみなしている。 In addition, as a formation means of each layer 2-6, vacuum thin film deposition methods, such as vacuum evaporation, ion plating, and sputtering, are used. The outer refractive index of the outermost YF 3 layer 6 is regarded as the refractive index of air (n = 1.0).
上記のように、Ｓｉ基板１中の不純物による吸収が現れない６〜１２μｍ付近の赤外波長領域を重点的に透過率が高くなるように、最も外側に低屈折率のＹＦ3 層６を配した多層構造とすることによって、基板として材料コストの非常に安価なＳｉ基板１を用い、かつ、反射防止機能を発揮する各層の膜厚も薄くして膜全体（製品）のコスト低減を図り、光学機器への適用範囲を経済的見地からも広く確保しながら、図２の実線に示すように、６〜１５μｍの広い赤外波長領域に亘って９０％以上の高い透過率で、特に、６〜１２μｍ付近の赤外波長領域においては平均透過率が９５〜９８％で、かつ、リップルのほとんどない平坦な透過特性、反射特性を得ることができる。
As described above, the YF 3 layer 6 having a low refractive index is arranged on the outermost side so that the transmittance is increased mainly in the infrared wavelength region in the vicinity of 6 to 12 μm where absorption due to impurities in the
図３は、上記した赤外光用反射防止膜において、最外側のＹＦ3 層６を真空蒸着によりその光学膜厚が５．３８μｍとなるように比較的厚膜に成膜する場合に用いられる真空蒸着装置の概要構成図である。該真空蒸着装置は、蒸着炉１０内の上部に、前記第１Ｇｅ層２、第１ＺｎＳ層３、第２Ｇｅ層４、第２ＺｎＳ層５を積層形成したＳｉ基板１（以下、Ｓｉ基板１等という）を下向き状態に支持するホルダ１１と、このホルダ１１に支持されたＳｉ基板１等を輻射加熱するヒータ１２とが配置されているとともに、蒸着炉１０内の下部に、ＹＦ3を充填したハース（ルツボ）１３に電子銃１４から放射される電子ビームを照射させてハース１３を加熱しＹＦ3 を蒸発させる電子銃加熱源１５とが配置されて構成されている。
FIG. 3 is used when the outermost YF 3 layer 6 in the above-described antireflection film for infrared light is formed into a relatively thick film by vacuum deposition so that its optical film thickness becomes 5.38 μm. It is a schematic block diagram of a vacuum evaporation system. The vacuum deposition apparatus includes an Si substrate 1 (hereinafter referred to as
次に、上記のような構成の真空蒸着装置を用いてＳｉ基板１等の最外側に、ＹＦ3 を真空蒸着して所定の光学膜厚のＹＦ3 層６を成膜する方法について説明する。
まず、Ｓｉ基板１等をホルダ１１にセットした上で、ヒータ１２を作動させてＳｉ基板１等を１００℃以下、詳しくは、６０℃以上１００℃以下に加熱し、その加熱温度を維持しつつ、電子銃加熱源１５の電子銃１４から放射される電子ビームをハース１３に照射して該ハース１３を加熱することにより、ハース１３に充填されているＹＦ3 を蒸発させて１〜１５Å／ｓｅｃ．の速度で成膜を開始する。
Next, a method for forming a YF 3 layer 6 having a predetermined optical film thickness by vacuum-depositing YF 3 on the outermost side of the
First, after setting the
このように蒸着温度を１００℃以下とすることにより、密着強度が大きく、膜剥離の生じないＹＦ3 層６を確実に成膜することができる。 Thus, by setting the vapor deposition temperature to 100 ° C. or less, the YF 3 layer 6 having high adhesion strength and no film peeling can be reliably formed.
１ Ｓｉ基板
２ 第１ゲルマニウム（Ｇｅ）層
３ 第１硫化亜鉛（ＺｎＳ）層
４ 第２Ｇｅ層
５ 第２ＺｎＳ層
６ フッ化イットリウム（ＹＦ3 ）層
DESCRIPTION OF
Claims (3)
前記シリコン基板の少なくとも一方の面に、ゲルマニウム層、硫化亜鉛層、ゲルマニウム層、硫化亜鉛層及び他の層よりも低屈折率のフッ化イットリウム層を前記シリコン基板側から順に積層し、これら計五つの各層それぞれの光学膜厚を６〜１２μｍ付近の赤外波長領域で９０％以上の透過特性となるように設定した多層構造で構成されていることを特徴とする赤外光用反射防止膜。 An antireflection film for infrared light, in which a plurality of thin films are formed in a laminated state on a silicon substrate,
On at least one surface of the silicon substrate, germanium layer, laminated zinc sulfide layer, a germanium layer, a yttrium fluoride layer having a low refractive index from the silicon substrate side of the zinc sulfide layer and other layers in this order, these Anti-reflection for infrared light, characterized in that it has a multilayer structure in which the optical film thickness of each of the five layers in total is set to have a transmission characteristic of 90% or more in the infrared wavelength region near 6-12 μm film.
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| CN101863152B (en) * | 2010-05-07 | 2012-04-25 | 中国人民解放军63983部队 | Infrared radiation inhibiting material with nano periodic structure and method for preparing same |
| CN106443841B (en) * | 2016-11-14 | 2018-10-26 | 天津津航技术物理研究所 | A kind of ultralow residual reflectance ZnS substrates long wave antireflection film |
| JP6739628B2 (en) * | 2017-03-28 | 2020-08-12 | 富士フイルム株式会社 | High refractive index film and optical interference film |
| KR102342322B1 (en) * | 2017-07-21 | 2021-12-23 | 한국광기술원 | Infrared optical lens equipped with ta-C and yttrium oxide thin film |
| JP7172024B2 (en) * | 2017-09-12 | 2022-11-16 | 日本電気硝子株式会社 | Chalcogenide glass material |
| CN110146948B (en) * | 2018-11-26 | 2021-05-11 | 上海欧菲尔光电技术有限公司 | Silicon substrate long-wave pass infrared filter and preparation method thereof |
| CN112859208B (en) * | 2021-02-20 | 2022-05-17 | 无锡奥夫特光学技术有限公司 | Infrared window anti-reflection protective film |
| CN114774847B (en) * | 2022-04-20 | 2024-01-23 | 湖北久之洋红外系统股份有限公司 | Preparation method of low-stress protection anti-reflection film of large-size infrared optical element |
| CN116577850B (en) * | 2023-03-31 | 2024-07-02 | 云南驰宏国际锗业有限公司 | Infrared germanium window sheet of HD film with wave band of 8-12um |
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