JP2017151409A - Infrared transmission film, optical film, antireflection film, optical component, optical system and imaging device - Google Patents
Infrared transmission film, optical film, antireflection film, optical component, optical system and imaging device Download PDFInfo
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- 239000010408 film Substances 0.000 title claims abstract description 313
- 230000005540 biological transmission Effects 0.000 title claims abstract description 104
- 230000003287 optical effect Effects 0.000 title claims abstract description 70
- 239000012788 optical film Substances 0.000 title claims abstract description 25
- 238000003384 imaging method Methods 0.000 title claims description 24
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 143
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 143
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 51
- 230000008033 biological extinction Effects 0.000 claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 187
- 239000011787 zinc oxide Substances 0.000 claims description 93
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- 238000002834 transmittance Methods 0.000 description 10
- 238000007740 vapor deposition Methods 0.000 description 9
- 239000005083 Zinc sulfide Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
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- 239000005387 chalcogenide glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
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- 239000005751 Copper oxide Substances 0.000 description 4
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- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 4
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910017768 LaF 3 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910005866 GeSe Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 229910017835 Sb—Sn Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910018110 Se—Te Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001225 Ytterbium Chemical class 0.000 description 1
- IBGRYCCHEJZKTL-UHFFFAOYSA-N [Bi]=O.[Bi]=O Chemical compound [Bi]=O.[Bi]=O IBGRYCCHEJZKTL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical class [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 239000013077 target material Substances 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
本件発明は、赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置に関し、特に遠赤外線を利用する光学系に好適な赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置に関する。 The present invention relates to an infrared transmission film, an optical film, an antireflection film, an optical component, an optical system, and an imaging device, and particularly suitable for an optical system using far infrared rays, an infrared transmission film, an optical film, an antireflection film, an optical component, The present invention relates to an optical system and an imaging apparatus.
現在、監視用撮像装置、車載用撮像装置、或いは熱分布解析等の種々の用途で赤外線を使用する光学系が用いられている。これらの光学系として、中赤外波長域（２．５μｍ〜４μｍ）の光線を使用する中赤外光学系と、遠赤外波長域（８μｍ〜１４μｍ）の光線を使用する遠赤外線光学系とが一般に知られている。例えば、監視用撮像装置、車載用撮像装置などでは主に遠赤外線光学系が用いられている。これらの光学系を構成する赤外線透過レンズ等の光学部品は、可視光光学系を構成する光学部品と比較すると、入射光の透過率が低い。そのため、光学部品の入射面に反射防止膜を設け、入射光の透過光量を増加させ、表面反射による光量不足を防止することが特に重要になる。 At present, an optical system using infrared rays is used for various applications such as a monitoring imaging device, a vehicle-mounted imaging device, or a heat distribution analysis. As these optical systems, a mid-infrared optical system that uses light in the mid-infrared wavelength region (2.5 μm to 4 μm), and a far-infrared optical system that uses light in the far-infrared wavelength region (8 μm to 14 μm), Is generally known. For example, a far-infrared optical system is mainly used in an imaging device for monitoring, an on-vehicle imaging device, and the like. Optical components such as an infrared transmissive lens constituting these optical systems have lower incident light transmittance than optical components constituting a visible light optical system. For this reason, it is particularly important to provide an antireflection film on the incident surface of the optical component to increase the amount of incident light transmitted and to prevent a shortage of light due to surface reflection.
例えば、遠赤外線光学系に用いられる光学部品の反射防止膜として、例えば、特許文献１には、Ｓｉ基板上に、基板側から順にＧｅ膜、ＺｎＳ膜、Ｇｅ膜、ＺｎＳ膜、ＹＦ３膜を積層した５層構造の反射防止膜が開示されている。また、特許文献２には、カルコゲナイドガラス基板上に、ＢｉＯ２膜、ＹＦ３膜を基板側から順に積層した２層構造の反射防止膜が開示されている。これらの特許文献に開示されるように、反射防止膜を複数の赤外線透過膜を積層した多層構造とすることにより、広い波長域の光線に対して、波長域全域で低い反射率を達成することが容易になる。現在、遠赤外波長域で使用する反射防止膜の層構成材料として、特許文献１及び特許文献２に開示の材料を含む以下の材料が知られている。 For example, as an antireflection film for an optical component used in a far-infrared optical system, for example, in Patent Document 1, a Ge film, a ZnS film, a Ge film, a ZnS film, and a YF 3 film are sequentially formed on a Si substrate from the substrate side. An antireflection film having a laminated five-layer structure is disclosed. Patent Document 2 discloses an antireflection film having a two-layer structure in which a BiO 2 film and a YF 3 film are sequentially laminated on a chalcogenide glass substrate from the substrate side. As disclosed in these patent documents, the antireflection film has a multilayer structure in which a plurality of infrared transmission films are laminated, thereby achieving low reflectivity over the entire wavelength range for light in a wide wavelength range. Becomes easier. Currently, the following materials including the materials disclosed in Patent Document 1 and Patent Document 2 are known as the layer constituting materials of the antireflection film used in the far-infrared wavelength region.
高屈折率材料 ：Ｇｅ、Ｓｉ
低屈折率材料 ：ＹＦ３、ＹｂＦ３、ＮａＦ、ＮｄＦ３、ＬａＦ３、ＣａＦ２、ＳｒＦ２
中間屈折率材料：ＺｎＳ、ＺｎＳｅ、ＰｂＴｅ、Ｙ２Ｏ３、ＣｅＯ２、ＨｆＯ２
High refractive index material: Ge, Si
Low refractive index material: YF 3 , YbF 3 , NaF, NdF 3 , LaF 3 , CaF 2 , SrF 2
Intermediate refractive index material: ZnS, ZnSe, PbTe, Y 2 O 3 , CeO 2 , HfO 2
ところで、光学部品の表面に反射防止膜を設ける際には、電子線加熱や抵抗加熱により原料を加熱蒸着させる真空蒸着法が一般に採用されている。しかしながら、今後の赤外線光学系の需要の拡大を考慮すると、大量生産に適した生産効率のよい方法により反射防止膜を成膜することが求められる。 By the way, when an antireflection film is provided on the surface of an optical component, a vacuum deposition method is generally employed in which a raw material is heated and deposited by electron beam heating or resistance heating. However, in consideration of future demand for infrared optical systems, it is required to form an antireflection film by a method with high production efficiency suitable for mass production.
例えば、真空蒸着法よりも生産効率のよい成膜法としてマグネトロンスパッタリング法が挙げられる。しかしながら、上記低屈折率材料、すなわちフッ化物を原料として用いた場合、スパッタリング工程においてターゲット材料中のフッ素元素が損失する。そのため、化学量論的な組成の膜を得ることが困難であり、使用波長域の光線に対して透明な赤外線透過膜を得ることができない。上記中間屈折材料であるＺｎＳ、ＺｎＳｅ、ＰｂＴｅについても同様であり、これらの材料を用いてマグネトロンスパッタリング法により化学量論的な組成の膜を得ることは困難である。 For example, a magnetron sputtering method can be given as a film forming method with higher production efficiency than the vacuum evaporation method. However, when the low refractive index material, that is, fluoride is used as a raw material, the fluorine element in the target material is lost in the sputtering process. Therefore, it is difficult to obtain a film having a stoichiometric composition, and it is impossible to obtain an infrared transmission film that is transparent to light in the wavelength range of use. The same applies to the intermediate refractive materials ZnS, ZnSe, and PbTe, and it is difficult to obtain a film having a stoichiometric composition by the magnetron sputtering method using these materials.
一方、上記高屈折率材料であるＧｅ、Ｓｉは、マグネトロンスパッタリング法により成膜することができる。上述したように広い波長域の光線に対して波長域全域で低い反射率を達成するには、多層構造の光学膜とすることが求められる。 On the other hand, the high refractive index materials Ge and Si can be formed by a magnetron sputtering method. As described above, in order to achieve a low reflectance over the entire wavelength range with respect to light beams in a wide wavelength range, a multilayered optical film is required.
ここで、Ｇｅ又はＳｉに対して、フッ化物は屈折率が低すぎるため、Ｇｅ膜又はＳｉ膜に対してフッ化物膜を積層しても、良好な反射防止性能を得ることはできない。また、上述したとおり、マグネトロンスパッタリング法により所望の組成のフッ化物膜を成膜することは困難である。 Here, since the refractive index of fluoride is too low with respect to Ge or Si, even if a fluoride film is laminated on a Ge film or Si film, good antireflection performance cannot be obtained. Further, as described above, it is difficult to form a fluoride film having a desired composition by the magnetron sputtering method.
そこで、Ｇｅ膜又はＳｉ膜と、中間屈折率材料からなる膜とを交互に積層させる構成とすることが考えられる。しかしながら、上述のとおり、ＺｎＳ、ＺｎＳｅ、ＰｂＴｅはマグネトロンスパッタリング法により成膜することは困難である。また、これらの材料は毒性を有するため、その取り扱いには注意が必要である。さらに、これらの材料の環境に対する影響も懸念されることから使用量の低減が望まれる。一方、Ｙ２Ｏ３、ＣｅＯ２、ＨｆＯ２については、マグネトロンスパッタリング法により成膜することができ、且つ、毒性もない。しかしながら、他の材料と比較すると、遠赤外領域（８μｍ〜１４μｍ）の光線に対する透明度が低く、遠赤外線に対して透明な膜を得ることができない。 Therefore, it can be considered that the Ge film or the Si film and the film made of the intermediate refractive index material are alternately stacked. However, as described above, ZnS, ZnSe, and PbTe are difficult to form by magnetron sputtering. In addition, since these materials are toxic, they must be handled with care. Furthermore, since there are concerns about the environmental impact of these materials, it is desired to reduce the amount used. On the other hand, Y 2 O 3 , CeO 2 and HfO 2 can be formed by magnetron sputtering and have no toxicity. However, compared with other materials, the transparency to light in the far infrared region (8 μm to 14 μm) is low, and a film transparent to far infrared cannot be obtained.
さらに、監視用撮像装置、或いは車載用撮像装置等は屋外に設置されて使用されることが多い。光学膜はこれらの光学部品の表面に設けられるため、成膜面に対する密着性と共に、高い耐水性を有する必要がある。 Furthermore, a monitoring imaging device or a vehicle-mounted imaging device is often installed and used outdoors. Since the optical film is provided on the surface of these optical components, it is necessary to have high water resistance as well as adhesion to the film formation surface.
以上のことから、本件発明の課題は、成膜が容易であり、且つ、高い耐水性を有する新規な赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置を提供することにある。 In view of the above, an object of the present invention is to provide a novel infrared transmission film, optical film, antireflection film, optical component, optical system, and imaging device that are easy to form and have high water resistance. It is in.
本件発明の課題を解決するために、本件発明に係る赤外線透過膜は、酸化ビスマスと、８μｍ以上１４μｍ以下の波長域全域において消衰係数が０．４以下の金属酸化物とを含むことを特徴とする。 In order to solve the problems of the present invention, an infrared transmission film according to the present invention includes bismuth oxide and a metal oxide having an extinction coefficient of 0.4 or less over the entire wavelength region of 8 μm to 14 μm. And
また、本件発明に係る光学膜、反射防止膜、光学部品、光学系はそれぞれ上記本件発明に係る赤外線透過膜を備えたことを特徴とする。 The optical film, the antireflection film, the optical component, and the optical system according to the present invention each include the infrared transmission film according to the present invention.
さらに、本件発明に係る撮像装置は、上記本件発明に係る赤外線透過膜が設けられた光学面を含む光学系を備えたことを特徴とする。 Furthermore, an imaging apparatus according to the present invention includes an optical system including an optical surface provided with the infrared transmission film according to the present invention.
本件発明によれば、遠赤外線波長域で用いられる光学部品に設ける赤外線透過膜であって、成膜が容易であり、且つ、高い耐水性を有する新規な赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置を提供することができる。 According to the present invention, an infrared transmitting film provided on an optical component used in the far infrared wavelength region, which is easy to form and has high water resistance, a novel infrared transmitting film, optical film, and antireflection film An optical component, an optical system, and an imaging device can be provided.
以下、本件発明に係る赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置の実施の形態について説明する。 Hereinafter, embodiments of an infrared transmission film, an optical film, an antireflection film, an optical component, an optical system, and an imaging device according to the present invention will be described.
１．赤外線透過膜
まず、本件発明に係る赤外線透過膜の実施の形態を説明する。本件発明に係る赤外線透過膜は、酸化ビスマスと、８μｍ以上１４μｍ以下の波長域全域において消衰係数が０．４以下の金属酸化物とを含むことを特徴とする。
1. Infrared transmitting film First, an embodiment of an infrared transmitting film according to the present invention will be described. The infrared transmitting film according to the present invention includes bismuth oxide and a metal oxide having an extinction coefficient of 0.4 or less over the entire wavelength region of 8 μm to 14 μm.
１−１．酸化ビスマス
酸化ビスマスは、８μｍ以上１４μｍ以下の波長域全域、すなわち遠赤外波長域全域における消衰係数が０．０５未満であり、遠赤外線（８μｍ以上１４μｍ以下の波長の光線）に対する透明度が高い材料である。
1-1. Bismuth oxide Bismuth oxide has an extinction coefficient of less than 0.05 in the entire wavelength range of 8 μm or more and 14 μm or less, that is, the far infrared wavelength range, and has high transparency to far infrared rays (light having a wavelength of 8 μm or more and 14 μm or less). Material.
また、酸化ビスマスの遠赤外線に対する屈折率は、１．５以上２．８以下の範囲にあり、酸化ビスマスは遠赤外波長域における中屈折率材料である。従って、当該赤外透過膜は、反射防止膜の構成材料としても好適である。例えば、当該赤外透過膜と、遠赤外波長域において高い屈折率を有するＧｅ膜又はＳｉ膜等を交互に積層すること等により、遠赤外波長域全域において良好な反射防止性能を有する反射防止膜を得ることができる。 Further, the refractive index of bismuth oxide with respect to far infrared rays is in the range of 1.5 or more and 2.8 or less, and bismuth oxide is a medium refractive index material in the far infrared wavelength region. Therefore, the infrared transmission film is also suitable as a constituent material for the antireflection film. For example, by reflecting the infrared transmission film and a Ge film or Si film having a high refractive index in the far-infrared wavelength region alternately, a reflection having good antireflection performance in the entire far-infrared wavelength region. A prevention film can be obtained.
ところで、酸化ビスマスは結晶化しやすい材料である。真空蒸着法、スパッタリング法等の物理蒸着法により成膜した酸化ビスマスは多結晶構造を有する。そのため、結晶粒界には水等が含浸しやすく、酸化ビスマス膜は耐水性が低く、実用上必要な耐久性を満足することが困難である。そこで、本件発明者らは、酸化ビスマスと、所定の金属酸化物を添加物として含む膜とすることにより、耐水性を改善することができることを見出した。本件発明によれば、高い耐水性を実現することができる。以下、本件発明において酸化ビスマスと共に用いられる所定の金属酸化物について説明する。 By the way, bismuth oxide is a material that is easily crystallized. Bismuth oxide formed by physical vapor deposition such as vacuum vapor deposition or sputtering has a polycrystalline structure. For this reason, the crystal grain boundaries are easily impregnated with water, and the bismuth oxide film has low water resistance, making it difficult to satisfy practically required durability. Therefore, the present inventors have found that the water resistance can be improved by forming a film containing bismuth oxide and a predetermined metal oxide as additives. According to the present invention, high water resistance can be realized. Hereinafter, the predetermined metal oxide used with bismuth oxide in the present invention will be described.
１−２．金属酸化物
（１）消衰係数
当該金属酸化物は、遠赤外波長域全域における消衰係数が０．４以下であることが求められる。遠赤外波長域における消衰係数が０．４を超えると、遠赤外線に対する透明度が低下する。すなわち、当該赤外線透過膜における遠赤外線の透過率が低下するため、当該赤外線透過膜を光学膜として用いることが困難になる。
1-2. Metal oxide (1) extinction coefficient The said metal oxide is calculated | required that the extinction coefficient in the far-infrared wavelength range whole region is 0.4 or less. When the extinction coefficient in the far-infrared wavelength region exceeds 0.4, the transparency with respect to the far-infrared rays decreases. That is, since the far-infrared transmittance of the infrared transmission film is reduced, it is difficult to use the infrared transmission film as an optical film.
遠赤外波長域全域における消衰係数が０．４以下の金属酸化物として、例えば、酸化亜鉛（ＺｎＯ）、酸化ジルコニウム（ＺｒＯ２）、酸化クロム（Ｃｒ２Ｏ３）、酸化ハフニウム（ＨｆＯ２）、酸化イットリウム（Ｙ２Ｏ３）、酸化銅（ＣｕＯ）、酸化マグネシウム（ＭｇＯ）等を挙げることができる。酸化ビスマスと、これらの金属酸化物とを含む膜とすることにより、酸化ビスマス膜の遠赤外線に対する透過率を維持しつつ、酸化ビスマス膜の耐水性を改善することができる。 Examples of the metal oxide having an extinction coefficient of 0.4 or less in the entire far infrared wavelength region include, for example, zinc oxide (ZnO), zirconium oxide (ZrO 2 ), chromium oxide (Cr 2 O 3 ), hafnium oxide (HfO 2 ). ), Yttrium oxide (Y 2 O 3 ), copper oxide (CuO), magnesium oxide (MgO), and the like. By using a film containing bismuth oxide and these metal oxides, the water resistance of the bismuth oxide film can be improved while maintaining the transmittance of the bismuth oxide film with respect to far infrared rays.
ここで、使用波長域における当該赤外線透過膜の透明度をより高くするという観点から、添加物として用いる金属酸化物の消衰係数は、使用波長域全域において０．４未満であることが好ましく、０．２未満であることがより好ましく、０．１未満であることがさらに好ましい。当該赤外線透過膜の使用波長域に応じて、上記列挙した金属酸化物等の中から、適宜、適切な金属酸化物を選択することができる。なお、上記列挙した各金属酸化物の消衰係数を以下に示す。以下において、ｋ（８μｍ）は、波長が８μｍのときの消衰係数（ｋ）を表し、ｋ（１４μｍ）は、波長が１４μｍのときの消衰係数を表す。また、以下には酸化ビスマスの消衰係数も示す。 Here, from the viewpoint of further increasing the transparency of the infrared transmission film in the used wavelength range, the extinction coefficient of the metal oxide used as the additive is preferably less than 0.4 in the entire used wavelength range. Is more preferably less than .2 and even more preferably less than 0.1. An appropriate metal oxide can be appropriately selected from the metal oxides listed above according to the wavelength range of use of the infrared transmission film. In addition, the extinction coefficient of each metal oxide listed above is shown below. In the following, k (8 μm) represents the extinction coefficient (k) when the wavelength is 8 μm, and k (14 μm) represents the extinction coefficient when the wavelength is 14 μm. The extinction coefficient of bismuth oxide is also shown below.
酸化亜鉛： ｋ（８μｍ）＝０．００４ ｋ（１４μｍ）＝０．０３
酸化ジルコニウム：ｋ（８μｍ）＝０．０６ ｋ（１４μｍ）＝０．３５
酸化クロム： ｋ（８μｍ）＝０．００７ ｋ（１４μｍ）＝０．３７
酸化ハフニウム： ｋ（８μｍ）＝０．００６ ｋ（１４μｍ）＝０．４
酸化ビスマス： ｋ（８μｍ）＝０．００２ ｋ（１４μｍ）＝０．０２５
酸化イットリウム：ｋ（８μｍ）＝０．０００２７ ｋ（１４μｍ）＝０．０７８
酸化銅： ｋ（８μｍ）＝０．０００１ ｋ（１４μｍ）＝０．０４
酸化マグネシウム：ｋ（８μｍ）＝０．０００２５ ｋ（１４μｍ）＝０．０１４
Zinc oxide: k (8 μm) = 0.004 k (14 μm) = 0.03
Zirconium oxide: k (8 μm) = 0.06 k (14 μm) = 0.35
Chromium oxide: k (8 μm) = 0.007 k (14 μm) = 0.37
Hafnium oxide: k (8 μm) = 0.006 k (14 μm) = 0.4
Bismuth oxide: k (8 μm) = 0.002 k (14 μm) = 0.025
Yttrium oxide: k (8 μm) = 0.00027 k (14 μm) = 0.078
Copper oxide: k (8 μm) = 0.0001 k (14 μm) = 0.04
Magnesium oxide: k (8 μm) = 0.00025 k (14 μm) = 0.014
上記に示すように、酸化亜鉛、酸化イットリウム、酸化銅及び酸化マグネシウムの消衰係数は、酸化ジルコニウム、酸化クロム及び酸化ハフニウムと比較すると小さく、遠赤外波長域全域において０．１未満である。従って、遠赤外波長域全域において高い透明度を維持することができるという観点から、酸化ビスマスと共に、酸化亜鉛、酸化イットリウム、酸化銅及び酸化マグネシウムから成る群から選択される一種以上を用いることがより好ましい。このとき、これらの金属酸化物一種を用いてもよいし、一種以上を混合して用いてもよいのは勿論である。 As described above, the extinction coefficients of zinc oxide, yttrium oxide, copper oxide, and magnesium oxide are smaller than those of zirconium oxide, chromium oxide, and hafnium oxide, and are less than 0.1 in the far infrared wavelength region. Therefore, from the viewpoint that high transparency can be maintained in the entire far-infrared wavelength region, it is more preferable to use one or more selected from the group consisting of zinc oxide, yttrium oxide, copper oxide and magnesium oxide together with bismuth oxide. preferable. At this time, it is a matter of course that one kind of these metal oxides may be used, or one or more kinds may be mixed and used.
なお、酸化ビスマス膜の耐水性を改善するという観点のみからみれば、酸化タンタル（Ｔａ２Ｏ５）等の消衰係数が上記範囲外の金属酸化物を添加物として用いることもできる。酸化タンタルの消衰係数を以下に示す。しかしながら、酸化タンタルの消衰係数は下記のとおり大きく、当該酸化タンタルを酸化ビスマス膜に添加物として含有させると、遠赤外線に対する酸化ビスマス膜の透過率が低下し、光学膜として用いることが困難になる。
酸化タンタル： ｋ（８μｍ）＝０．０２８ ｋ（１４μｍ）＝０．７５
From the viewpoint of improving the water resistance of the bismuth oxide film, a metal oxide having an extinction coefficient outside the above range, such as tantalum oxide (Ta 2 O 5 ), can be used as an additive. The extinction coefficient of tantalum oxide is shown below. However, the extinction coefficient of tantalum oxide is large as follows, and when the tantalum oxide is added as an additive to the bismuth oxide film, the transmittance of the bismuth oxide film with respect to far infrared rays is reduced, making it difficult to use as an optical film. Become.
Tantalum oxide: k (8 μm) = 0.028 k (14 μm) = 0.75
（２）屈折率
また、当該金属酸化物の遠赤外線波長域内の光線に対する屈折率は０．８以上２．５以下であることが好ましい。酸化ビスマスの屈折率と同等の屈折率を有する金属酸化物を用いることにより、得られた赤外線透過膜の屈折率を酸化ビスマスと同様の屈折率とすることができる。なお、上記列挙した各金属酸化物の遠赤外線波長域における屈折率はいずれも０．８以上２．８以下の範囲内である。ここで、酸化ビスマスの屈折率を大きく変化させないという観点から、酸化ビスマスの屈折率とより同等屈折率の金属酸化物を用いることが好ましい。当該観点から、酸化ビスマスと、屈折率が１．０以上２．８以下の金属酸化物とを含む膜とすることがより好ましく、酸化ビスマスと、屈折率が１．５以上２．８以下の金属酸化物とを含む膜とすることがさらに好ましい。
(2) Refractive index Moreover, it is preferable that the refractive index with respect to the light ray in the far-infrared wavelength range of the said metal oxide is 0.8-2.5. By using a metal oxide having a refractive index equivalent to that of bismuth oxide, the refractive index of the obtained infrared transmission film can be made the same as that of bismuth oxide. In addition, the refractive index in the far-infrared wavelength region of each of the metal oxides listed above is in the range of 0.8 to 2.8. Here, from the viewpoint of not greatly changing the refractive index of bismuth oxide, it is preferable to use a metal oxide having a refractive index equivalent to that of bismuth oxide. From this viewpoint, it is more preferable to use a film containing bismuth oxide and a metal oxide having a refractive index of 1.0 to 2.8, and bismuth oxide and a refractive index of 1.5 to 2.8. More preferably, the film contains a metal oxide.
１−３．酸化亜鉛
ここで、上記列挙した各金属酸化物の中で、特に酸化亜鉛を用いることが好ましい。酸化亜鉛は、８μｍ以上１４μｍ以下の波長域全域、すなわち遠赤外波長域全域における消衰係数が０．００４と小さく、酸化イットリウム、酸化銅と比較すると、遠赤外線（８μｍ以上１４μｍ以下の波長の光線）に対する透明度がより高い。
1-3. Zinc oxide Here, it is particularly preferable to use zinc oxide among the metal oxides listed above. Zinc oxide has a small extinction coefficient of 0.004 over the entire wavelength range of 8 μm or more and 14 μm or less, that is, the far infrared wavelength range, and far infrared (having a wavelength of 8 μm or more and 14 μm or less) compared with yttrium oxide and copper oxide. (Transparency to light) is higher.
また、酸化亜鉛の遠赤外線に対する屈折率は、１．５以上２．５以下の範囲にあり、酸化亜鉛は遠赤外波長域における中屈折率材料である。従って、酸化亜鉛膜は、それ自体、酸化ビスマス膜と同様に、反射防止膜の構成材料としても好適である。例えば、当該赤外透過膜と、遠赤外波長域において高い屈折率を有するＧｅ膜又はＳｉ膜等を交互に積層すること等により、遠赤外波長域全域において良好な反射防止性能を有する反射防止膜を得ることができる。 Further, the refractive index of zinc oxide with respect to far infrared rays is in the range of 1.5 to 2.5, and zinc oxide is a medium refractive index material in the far infrared wavelength region. Therefore, the zinc oxide film itself is suitable as a constituent material of the antireflection film as well as the bismuth oxide film. For example, by reflecting the infrared transmission film and a Ge film or Si film having a high refractive index in the far-infrared wavelength region alternately, a reflection having good antireflection performance in the entire far-infrared wavelength region. A prevention film can be obtained.
ところで、酸化亜鉛も酸化ビスマスと同様に結晶化しやすい材料である。真空蒸着法、スパッタリング法等の物理蒸着法により成膜した酸化亜鉛膜は多結晶構造を有する。そのため、結晶粒界には水等が含浸しやすく、酸化亜鉛膜は耐水性が低く、実用上必要な耐久性を満足することが困難である。しかしながら、酸化ビスマスと酸化亜鉛とを含む膜、若しくは、酸化ビスマスと酸化亜鉛とからなる膜とすることにより、遠赤外波長全域において透明度が高く、且つ、高い耐水性を有する赤外線透過膜を実現することができる。
By the way, zinc oxide is a material that is easily crystallized, like bismuth oxide. A zinc oxide film formed by physical vapor deposition such as vacuum vapor deposition or sputtering has a polycrystalline structure. For this reason, the crystal grain boundary is easily impregnated with water or the like, and the zinc oxide film has low water resistance, and it is difficult to satisfy practically required durability. However, by using a film containing bismuth oxide and zinc oxide or a film made of bismuth oxide and zinc oxide, an infrared transmission film having high transparency and high water resistance in the entire far infrared wavelength range is realized. can do.
（３）含有量
次に、当該赤外線透過膜における酸化ビスマスの含有量と金属酸化物の含有量について説明する。当該赤外線透過膜は酸化ビスマスと上記金属酸化物とから構成されることが好ましく、不可避不純物を除いて、当該赤外線透過膜は酸化ビスマスと上記金属酸化物から実質なることが好ましい。このとき、酸化ビスマスは１０質量％以上９０質量％以下であることが好ましく、他の金属酸化物の含有量は９０質量％以下１０質量％以上であることが好ましい。但し、ここでいう他の金属酸化物の含有量とは、当該赤外線透過膜に含まれる酸化ビスマス以外の金属酸化物の総量をいう。すなわち、酸化ビスマス以外に複数の金属酸化物を用いる場合、その合計量をいうものとする。また、当該赤外線透過膜では、主成分を酸化ビスマス及び／又は酸化亜鉛とすることが好ましく、酸化ビスマス及び酸化亜鉛からなる遠赤外線透過膜とすることがより好ましい。酸化ビスマス及び酸化亜鉛は遠赤外波長域の光線に対して透明度の高い酸化ビスマス及び／又は酸化亜鉛を当該赤外線透過膜の主成分とすることにより、当該赤外線透過膜の遠赤外線に対する透明度を高く維持したまま、耐水性を改善することができる。上述したとおり、酸化ビスマス膜及び酸化亜鉛膜それ自体は耐水性が低いが、酸化ビスマスと酸化亜鉛の混合膜とすることにより、耐水性の高い遠赤外線透過膜を得ることができる。
(3) Content Next, the content of bismuth oxide and the content of metal oxide in the infrared transmission film will be described. The infrared transmission film is preferably composed of bismuth oxide and the metal oxide. Except for inevitable impurities, the infrared transmission film is preferably substantially composed of bismuth oxide and the metal oxide. At this time, it is preferable that bismuth oxide is 10 mass% or more and 90 mass% or less, and it is preferable that content of another metal oxide is 90 mass% or less and 10 mass% or more. However, the content of other metal oxides herein refers to the total amount of metal oxides other than bismuth oxide contained in the infrared transmission film. That is, when a plurality of metal oxides are used in addition to bismuth oxide, the total amount is used. In the infrared transmitting film, the main component is preferably bismuth oxide and / or zinc oxide, and more preferably a far infrared transmitting film made of bismuth oxide and zinc oxide. Bismuth oxide and zinc oxide have high transparency with respect to far infrared rays of the infrared transmission film by using bismuth oxide and / or zinc oxide having high transparency with respect to light in the far infrared wavelength region as the main component of the infrared transmission film. Water resistance can be improved while maintaining. As described above, the water resistance of the bismuth oxide film and the zinc oxide film itself is low, but by using a mixed film of bismuth oxide and zinc oxide, a far-infrared transmission film having high water resistance can be obtained.
（４）結晶構造
本件発明に係る赤外線透過膜は、酸化ビスマスの結晶粒界に上記金属酸化物が偏析したもの、又は、酸化ビスマス以外の他の金属酸化物の結晶粒界に酸化ビスマスが偏析したものであることが好ましい。特に、酸化ビスマスの結晶粒界に酸化亜鉛が偏析したもの、又は、酸化亜鉛の結晶粒界に酸化ビスマスが偏析したものであることが好ましい。酸化ビスマス（又は、酸化ビスマス以外の金属酸化物）の結晶粒界に偏析した他の金属酸化物（又は酸化ビスマス）によって、結晶粒界に水が含水されにくくなるため、当該赤外線透過膜の耐水性が良好になる。また、酸化ビスマス（又は他の金属酸化物）の結晶粒界に酸化ビスマス以外の金属酸化物（又は酸化ビスマス）が偏析していると、結晶成長が抑制され、結晶粒の肥大化が阻止され、その結果、結晶粒が微細になる。そのため、膜内の残留応力が小さくなる。このことも耐水性を高める要因の一つであると考えられる。また、微細な結晶構造を有するため、当該膜の機械的強度も高くなる。さらに、耐水性等も向上する。
(4) Crystal structure In the infrared transmitting film according to the present invention, the above-mentioned metal oxide is segregated at the crystal grain boundary of bismuth oxide, or bismuth oxide is segregated at the crystal grain boundary of other metal oxides other than bismuth oxide. It is preferable that In particular, it is preferable that zinc oxide is segregated at the crystal grain boundary of bismuth oxide or bismuth oxide is segregated at the crystal grain boundary of zinc oxide. The other metal oxide (or bismuth oxide) segregated at the crystal grain boundary of bismuth oxide (or metal oxide other than bismuth oxide) makes it difficult for water to be contained in the crystal grain boundary. Good. In addition, if a metal oxide (or bismuth oxide) other than bismuth oxide is segregated at the crystal grain boundary of bismuth oxide (or other metal oxide), crystal growth is suppressed and enlargement of the crystal grains is prevented. As a result, the crystal grains become fine. Therefore, the residual stress in the film is reduced. This is also considered to be one of the factors that increase water resistance. In addition, since the film has a fine crystal structure, the mechanical strength of the film is also increased. Furthermore, water resistance etc. improve.
すなわち、酸化ビスマス膜の耐水性を改善する上で、酸化ビスマス及び酸化亜鉛以外の金属酸化物は、酸化ビスマス（及び酸化亜鉛）の結晶粒の肥大化を阻止できる程度の量であることが好ましい。一方、酸化ビスマス以外の金属酸化物として酸化亜鉛を用いる場合、酸化ビスマスの含有量と酸化亜鉛の含有量は同量（５０質量％ずつ）であってもよい。 That is, in order to improve the water resistance of the bismuth oxide film, the amount of the metal oxide other than bismuth oxide and zinc oxide is preferably an amount that can prevent enlargement of crystal grains of bismuth oxide (and zinc oxide). . On the other hand, when zinc oxide is used as a metal oxide other than bismuth oxide, the content of bismuth oxide and the content of zinc oxide may be the same amount (50% by mass).
（５）膜密度
ここで、上述したとおり酸化ビスマスは他の金属酸化物と比較すると結晶化しやすい材料であるため、膜密度が低くなるという問題がある。一方、酸化ビスマス及び酸化ビスマス以外の上記金属酸化物を含む赤外線透過膜、特に、酸化ビスマスを１０質量％以上９０質量％以下含む赤外線透過膜は酸化ビスマス膜と比較すると膜密度を高くすることができ、基材と赤外線透過膜との密着性の向上することができ、且つ、高い耐久性を実現することができる。
(5) Film density Here, since bismuth oxide is a material that is easily crystallized as compared with other metal oxides as described above, there is a problem that the film density is lowered. On the other hand, an infrared transmitting film containing bismuth oxide and the above metal oxide other than bismuth oxide, particularly an infrared transmitting film containing bismuth oxide in an amount of 10% by mass to 90% by mass can increase the film density as compared with the bismuth oxide film. It is possible to improve the adhesion between the base material and the infrared transmission film and realize high durability.
ここで、下記式、すなわち、当該赤外線反射防止膜の膜密度を測定したときの実測値を、当該赤外線反射防止膜の理論膜密度で除することによって求めた値の百分率を相対膜密度と称する。 Here, the percentage of the value obtained by dividing the following formula, that is, the actual measurement value when the film density of the infrared antireflection film is measured by the theoretical film density of the infrared antireflection film is referred to as a relative film density. .
相対膜密度（％）＝（ 膜密度の実測値 ／ 理論膜密度 ）×１００ Relative film density (%) = (actual value of film density / theoretical film density) × 100
本件発明に係る赤外線透過膜の相対膜密度は、８０％以上であることが好ましい。上記計算式に従って求めた相対膜密度が８０％であると、基板と当該赤外線透過膜との密着性がよく、耐久性に優れた膜とすることができる。酸化ビスマスを１０質量％以上９０質量％以下含む赤外線透過膜であれば、相対膜密度８０％以上とすることができる。 The relative film density of the infrared transmission film according to the present invention is preferably 80% or more. When the relative film density obtained in accordance with the above calculation formula is 80%, the adhesion between the substrate and the infrared transmission film is good, and a film having excellent durability can be obtained. In the case of an infrared transmitting film containing 10% by mass or more and 90% by mass or less of bismuth oxide, the relative film density can be set to 80% or more.
（６）成膜方法
本件発明に係る赤外線透過膜を成膜するには、例えば、酸化ビスマスと酸化ビスマス以外の上記金属酸化物とを所定の含有比で含む焼結セラミックス等を出発原料として、真空蒸着法、スパッタリング法等の各種乾式成膜法により成膜することができる。いずれの方法でも、混合酸化物の焼結体を出発原料として用いることができる。
(6) Film formation method In order to form an infrared transmission film according to the present invention, for example, a sintered ceramic containing a metal oxide other than bismuth oxide and bismuth oxide in a predetermined content ratio is used as a starting material. The film can be formed by various dry film forming methods such as vacuum vapor deposition and sputtering. In any method, a mixed oxide sintered body can be used as a starting material.
各種乾式成膜法の中でも特に、マグネトロンスパッタリング法は簡便であり、真空蒸着法と比較したときの生産効率がよい。そのため、大量生産される光学部品に対して当該赤外線透過膜を成膜する際には、マグネトロンスパッタリング法を用いることが好ましい。この際、放電様式としては、直流電流、或いは高周波放電、或いは交流放電を採用することができる。 Among various dry film forming methods, the magnetron sputtering method is simple and has a high production efficiency when compared with the vacuum deposition method. For this reason, it is preferable to use a magnetron sputtering method when the infrared transmission film is formed on a mass-produced optical component. At this time, a direct current, a high frequency discharge, or an alternating current discharge can be adopted as a discharge mode.
赤外線透過膜をマグネトロンスパッタリング法により成膜する際には、金属ビスマスと、酸化ビスマス以外の金属酸化物を構成する金属とを所定の含有比で含む金属合金ターゲットを出発原料として用いることもできる。この金属合金ターゲットを用いて、酸素ガス雰囲気下で成膜することにより、酸化ビスマスと酸化ビスマス以外の他の金属酸化物とを所定の含有比で含む本件発明に係る赤外線透過膜を得ることができる。 When forming the infrared transmission film by magnetron sputtering, a metal alloy target containing metal bismuth and a metal constituting a metal oxide other than bismuth oxide in a predetermined content ratio can be used as a starting material. By using this metal alloy target to form a film in an oxygen gas atmosphere, an infrared transmission film according to the present invention containing bismuth oxide and a metal oxide other than bismuth oxide in a predetermined content ratio can be obtained. it can.
これらの物理蒸着法により、上記金属酸化物を含む酸化ビスマス膜を成膜すれば、上記金属酸化物は、酸化ビスマスと複合酸化物を形成することなく、酸化ビスマスの結晶粒界に偏析する。すなわち、結晶粒界に上記金属酸化物が偏析した酸化ビスマスの多結晶構造を有する赤外線透過膜が得られる。 When a bismuth oxide film containing the metal oxide is formed by these physical vapor deposition methods, the metal oxide is segregated at a crystal grain boundary of bismuth oxide without forming a composite oxide with bismuth oxide. That is, an infrared transmission film having a polycrystalline structure of bismuth oxide in which the metal oxide is segregated at the crystal grain boundary can be obtained.
なお、本件発明に係る赤外線透過膜は、乾式成膜法に限らず、化学的気相成長法、ゾルゲル法等の各種湿式成膜法により成膜することもできる。各成膜方法の中から、当該赤外線透過膜の用途や基材の材質等に応じて適宜、適切な成膜法を選択することができる。 The infrared transmission film according to the present invention is not limited to a dry film forming method, and can be formed by various wet film forming methods such as a chemical vapor deposition method and a sol-gel method. From each film forming method, an appropriate film forming method can be appropriately selected according to the use of the infrared transmission film, the material of the base material, and the like.
１−３．基材
本件発明に係る赤外線透過膜は、例えば、光学部品等の表面に設けられる。このとき、光学部品等の基材の材質は特に限定されるものではない。
1-3. Substrate The infrared transmission film according to the present invention is provided on the surface of an optical component, for example. At this time, the material of the base material such as an optical component is not particularly limited.
本件発明に係る赤外線透過膜は、遠赤外波長域の光線に対して透明なゲルマニウム（Ｇｅ）、シリコン（Ｓｉ）、セレン化亜鉛（ＺｎＳｅ）、硫化亜鉛（ＺｎＳ）と良好な密着性を有する。また、本件発明に係る赤外線透過膜は、ゲルマニウム、砒素（Ａｓ）、セレン（Ｓｅ）、硫黄（Ｓ）、アンチモン（Ｓｂ）、Ｇａ（ガリウム）等を成分とする各種のカルコゲナイドガラスと良好な密着性を有する。カルコゲナイドガラスの具体的な組成として、例えば、Ａｓ２Ｓｅ３、ＣｄＴｅ、ＰｂＴｅ、ＳｉＳｅ２、Ｇａ２Ｓ３、ＧｅＳｅ２、ＧｅＳ２、ＧｅＡｓ、ＣｄＳｅ、Ｇｅ−Ａｓ−Ｓｅ、Ｇｅ−Ｓｂ−Ｓ、Ｇｅ−Ｓｅ−Ｔｅ、Ｇｅ−Ｓｅ−Ｓｂ、Ｇｅ−Ｇａ−Ｓ、Ｇａ−Ｌａ−Ｓ、Ａｓ−Ｓ−Ｓｅ、Ａｓ−Ｓ−Ｔｅ、Ａｓ−Ｓｅ−Ｃｕ、Ｇｅ−Ｓｂ−Ｔｅ、Ｇａ−Ｇｅ−Ａｓ−Ｓ、Ｇｅ−Ａｓ−Ｇａ−Ｓｂ、Ａｓ−Ｓｅ−Ｓｂ−Ｓｎ、Ｇａ−Ｌａ−Ｓ−Ｃｅ、Ｇｅ−Ａｓ−Ｇａ−Ｓｅ、Ｇｅ−Ａｓ−Ｇａ−Ｓｂ−Ｓを挙げることができる。これらの材料からなる赤外線用光学レンズ等の各種赤外線光学部品を基材としたとき、本件発明に係る赤外線透過膜を赤外線光学部品の表面に直接設けることができ、良好な密着性を得ることができる。 The infrared transmission film according to the present invention has good adhesion to germanium (Ge), silicon (Si), zinc selenide (ZnSe), and zinc sulfide (ZnS) that are transparent to light in the far-infrared wavelength region. . In addition, the infrared transmission film according to the present invention has good adhesion to various chalcogenide glasses containing germanium, arsenic (As), selenium (Se), sulfur (S), antimony (Sb), Ga (gallium) and the like. Have sex. As a specific composition of chalcogenide glass, for example, As 2 Se 3 , CdTe, PbTe, SiSe 2 , Ga 2 S 3 , GeSe 2 , GeS 2 , GeAs, CdSe, Ge—As—Se, Ge—Sb—S, Ge-Se-Te, Ge-Se-Sb, Ge-Ga-S, Ga-La-S, As-S-Se, As-S-Te, As-Se-Cu, Ge-Sb-Te, Ga- Ge-As-S, Ge-As-Ga-Sb, As-Se-Sb-Sn, Ga-La-S-Ce, Ge-As-Ga-Se, Ge-As-Ga-Sb-S Can do. When various infrared optical components such as infrared optical lenses made of these materials are used as a base material, the infrared transmission film according to the present invention can be directly provided on the surface of the infrared optical component, and good adhesion can be obtained. it can.
２．光学膜
次に、本件発明に係る光学膜について説明する。本件発明において、光学膜とは反射防止膜や、エッジフィルター、バンドパスフィルターなどの光学フィルター等を意味する。本件発明に係る光学膜は一層の光学薄膜からなる単層膜であってもよいし、二層以上の光学薄膜が積層された多層膜であってもよい。いずれの場合であっても、本件発明に係る光学膜は、上述した本件発明に係る赤外線透過膜を備えるものとする。すなわち、当該光学膜は本件発明に係る赤外線透過膜からなる単層膜であってもよいし、少なくとも一層の赤外線透過膜を備える多層膜であってもよい。
2. Next, the optical film according to the present invention will be described. In the present invention, the optical film means an antireflection film, an optical filter such as an edge filter, a band pass filter, or the like. The optical film according to the present invention may be a single layer film composed of a single optical thin film, or a multilayer film in which two or more optical thin films are laminated. In any case, the optical film according to the present invention includes the above-described infrared transmission film according to the present invention. That is, the optical film may be a single layer film made of the infrared transmission film according to the present invention, or may be a multilayer film including at least one infrared transmission film.
本件発明に係る赤外線透過膜は、中間屈折率材料である酸化ビスマスと、酸化ビスマスと同等の屈折率を有する酸化亜鉛等の他の金属酸化物とを含む。また、当該赤外線透過膜は下記の高屈折率材料、或いは低屈折率材料との密着性も良好である。 The infrared transmitting film according to the present invention includes bismuth oxide which is an intermediate refractive index material and other metal oxides such as zinc oxide having a refractive index equivalent to that of bismuth oxide. In addition, the infrared transmission film has good adhesion to the following high refractive index material or low refractive index material.
高屈折率材料：Ｇｅ、Ｓｉ
低屈折率材料：ＹＦ３、ＹｂＦ３、ＮａＦ、ＮｄＦ３、ＬａＦ３、ＣａＦ２、ＳｒＦ２
High refractive index material: Ge, Si
Low refractive index materials: YF 3 , YbF 3 , NaF, NdF 3 , LaF 3 , CaF 2 , SrF 2
従って、当該赤外線透過膜を中間屈折率層として用い、適宜、上記材料からなる高屈折率層及び／又は低屈折率層と積層した任意の層構成の光学膜を得ることができる。 Accordingly, an optical film having an arbitrary layer structure in which the infrared transmission film is used as an intermediate refractive index layer and appropriately laminated with a high refractive index layer and / or a low refractive index layer made of the above material can be obtained.
３．反射防止膜
次に、本件発明に係る反射防止膜の実施の形態を説明する。本件発明に係る反射防止膜は、上記光学膜の一種であり、本件発明に係る赤外線透過膜を備えることを特徴とする。本件発明に係る反射防止膜は、上記赤外線透過膜一層からなる単層膜であってもよいが、上記高屈折率層及び／又は低屈折率層と積層した多層膜とすることがより好ましい。多層構造の反射防止膜とすることにより、各界面で生じる界面反射光により、光の干渉作用を利用して広い波長域において低い反射率を実現することが容易になる。
3. Next, an embodiment of the antireflection film according to the present invention will be described. The antireflection film according to the present invention is a kind of the above-described optical film, and includes the infrared transmission film according to the present invention. The antireflection film according to the present invention may be a single-layer film composed of one infrared transmission film, but more preferably a multilayer film laminated with the high refractive index layer and / or the low refractive index layer. By using an antireflection film having a multilayer structure, it becomes easy to realize a low reflectance in a wide wavelength region by utilizing the interference action of light by the interface reflected light generated at each interface.
４．光学部品
本件発明に係る光学部品は、本件発明に係る赤外線透過膜を備えることを特徴とする。光学部品としては、撮像装置又は投影装置の撮像光学系又は投影光学系などを構成する各種光学部品を挙げることができる。より具体的には、レンズ、プリズム（色分解プリズム、色合成プリズム等）、偏光ビームスプリッタ（ＰＢＳ）、カットフィルタ（長波長用、短波長用等）などを挙げることができる。特に、遠赤外波長域の光線を使用する遠赤外撮像光学系を構成する赤外線用レンズであることが好ましい。
4). Optical component The optical component which concerns on this invention is equipped with the infrared rays permeable film which concerns on this invention, It is characterized by the above-mentioned. Examples of the optical component include various optical components that constitute an imaging optical system or a projection optical system of the imaging device or the projection device. More specifically, a lens, a prism (color separation prism, color synthesis prism, etc.), a polarizing beam splitter (PBS), a cut filter (for long wavelength, for short wavelength, etc.) can be used. In particular, an infrared lens that constitutes a far-infrared imaging optical system that uses light rays in the far-infrared wavelength region is preferable.
５．光学系／撮像装置
本件発明に係る光学系は、本件発明に係る赤外線透過膜を備えることを特徴とする。当該光学系として、撮像光学系であることが好ましく、特に、遠赤外波長域の光線を使用する遠赤外撮像光学系であることが好ましい。例えば、監視用撮像装置、車載用撮像装置の光学系であることが好ましい。また、本件発明に係る撮像装置は、当該赤外線透過膜が設けられた光学面を含む光学系を備えることを特徴とし、これらの遠赤外線撮像光学系を備えた監視用撮像雄値、車載用撮像装置等であることが好ましい。
5. Optical System / Imaging Device An optical system according to the present invention includes the infrared transmission film according to the present invention. The optical system is preferably an imaging optical system, and particularly preferably a far infrared imaging optical system that uses light in the far infrared wavelength region. For example, an optical system of a monitoring imaging device or an in-vehicle imaging device is preferable. Moreover, the imaging device according to the present invention is characterized by including an optical system including an optical surface provided with the infrared transmission film, and the imaging male value for monitoring and the on-vehicle imaging provided with these far-infrared imaging optical systems. An apparatus or the like is preferable.
次に、実施例および比較例を示して本件発明を具体的に説明する。但し、本件発明は以下の実施例に限定されるものではない。 Next, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
実施例１では、マグネトロンスパッタリング法により基材の両面にそれぞれ酸化ビスマスと酸化亜鉛の混合膜を成膜した。以下、成膜の手順について具体的に説明する。 In Example 1, mixed films of bismuth oxide and zinc oxide were formed on both surfaces of the substrate by magnetron sputtering, respectively. Hereinafter, the procedure of film formation will be specifically described.
まず、マグネトロンスパッタリング装置に、成膜原料であるターゲットと、基材とを対向配置した。成膜原料としては、酸化亜鉛の焼結体ターゲットを用いた。このとき、当該ターゲット上に酸化ビスマスのタブレットの小片を均等に並べ、赤外線透過膜中の酸化ビスマスの含有量が４．０質量％になるようにした。基材として、カルコゲナイドガラス（湖北新華光信息材料有限公司製 ＩＲＧ２０６）を用いた。 First, the target which is a film-forming raw material, and the base material were arranged opposite to each other in a magnetron sputtering apparatus. A zinc oxide sintered compact target was used as a film forming material. At this time, small pieces of bismuth oxide tablets were arranged uniformly on the target so that the content of bismuth oxide in the infrared transmission film was 4.0% by mass. As the substrate, chalcogenide glass (IRG206 manufactured by Hubei Xinhua Guangxin Material Co., Ltd.) was used.
次に、装置内全体を真空に排気した。そして、装置内の圧力が３×１０−４Ｐａに到達した時点で、Ａｒガスを２０ＳＣＣＭ（ｓｔａｎｄａｒｄ ｃｃ／ｍｉｎ、１ａｔｍ（２５℃））流し、酸素ガスを５ＳＣＣＭ流した。この時の装置内の圧力が、０．３Ｐａになるように排気速度を調整した。 Next, the whole apparatus was evacuated. Then, when the pressure in the apparatus reached 3 × 10 −4 Pa, Ar gas was supplied at 20 SCCM (standard cc / min, 1 atm (25 ° C.)), and oxygen gas was supplied at 5 SCCM. The exhaust speed was adjusted so that the pressure in the apparatus at this time was 0.3 Pa.
その後、ターゲット表面に１３．５６ＭＨｚの高周波（約５００Ｗ）を印加し、ターゲットの前方で基材を回転させながら、基材の表面に酸化ビスマスを４質量％と酸化亜鉛９６質量％とを含む赤外線透過膜を成膜した。 Thereafter, a high frequency (about 500 W) of 13.56 MHz is applied to the target surface, and the base material is rotated in front of the target, and the infrared ray containing 4% by mass of bismuth oxide and 96% by mass of zinc oxide on the surface of the base material. A permeable membrane was formed.
実施例２では、赤外線透過膜中の酸化ビスマスの含有量が０．７質量％になるように酸化亜鉛焼結ターゲット上の酸化ビスマスの小片量を調整したことを除いては、実施例１と同様にして、酸化ビスマスを０．７質量％と酸化亜鉛９９．３質量％とを含む赤外線透過膜を成膜した。 Example 2 is the same as Example 1 except that the amount of small pieces of bismuth oxide on the zinc oxide sintered target was adjusted so that the content of bismuth oxide in the infrared transmission film was 0.7% by mass. Similarly, an infrared transmission film containing 0.7% by mass of bismuth oxide and 99.3% by mass of zinc oxide was formed.
実施例３では、酸化ビスマスの含有量が１４．７質量％の酸化亜鉛焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを１４．７質量％と酸化亜鉛８５．３質量％とを含む赤外線透過膜を成膜した。 In Example 3, 14.7% by mass of bismuth oxide and zinc oxide were obtained in the same manner as in Example 1 except that a zinc oxide sintered target having a bismuth oxide content of 14.7% by mass was used. An infrared transmission film containing 85.3 mass% was formed.
実施例４では、酸化ビスマスの含有量が４４．７質量％の酸化亜鉛焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを４４．７質量％と酸化亜鉛５５．３質量％とを含む赤外線透過膜を成膜した。 In Example 4, 44.7% by mass of bismuth oxide and zinc oxide were obtained in the same manner as in Example 1 except that a zinc oxide sintered target having a bismuth oxide content of 44.7% by mass was used. An infrared transmission film containing 55.3 mass% was formed.
実施例５では、酸化亜鉛の含有量が３０．０質量％の酸化ビスマス焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを７０．０質量％と酸化亜鉛３０．０質量％とを含む赤外線透過膜を成膜した。 In Example 5, 70.0% by mass of bismuth oxide and zinc oxide were obtained in the same manner as in Example 1 except that a sintered bismuth oxide target having a zinc oxide content of 30.0% by mass was used. An infrared transmission film containing 30.0% by mass was formed.
実施例６では、基板側から順にＧｅ膜、酸化ビスマスと酸化亜鉛膜とを含む赤外線透過膜を積層した反射防止膜を成膜した。Ｇｅ膜を成膜する際には、ゲルマニウムをターゲットとして用い、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を成膜する際には、酸化ビスマスの含有量が２質量％である酸化亜鉛の焼結体ターゲットを用いて、実施例１と同様にして各膜を成膜した。 In Example 6, an antireflection film was formed by laminating an infrared ray transmission film including a Ge film, bismuth oxide, and a zinc oxide film in this order from the substrate side. When forming a Ge film, germanium is used as a target, and when an infrared transmission film containing bismuth oxide and zinc oxide is formed, sintering of zinc oxide having a bismuth oxide content of 2 mass% is performed. Each film was formed in the same manner as in Example 1 using the combined target.
実施例７では、基板側から順にＧｅ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、Ｇｅ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を積層した。この際、赤外線透過膜を成膜する際に、酸化ビスマスの含有量が５質量％の酸化亜鉛焼結ターゲットを用い、酸化ビスマスの含有量が５質量％、酸化亜鉛の含有量が９５質量％になるようにしたことを除いて、実施例６と同様にして各膜を成膜した。 In Example 7, a Ge film, an infrared transmission film containing bismuth oxide and zinc oxide, and a Ge film, an infrared transmission film containing bismuth oxide and zinc oxide were stacked in this order from the substrate side. At this time, when forming the infrared transmission film, a zinc oxide sintered target having a bismuth oxide content of 5% by mass was used, the bismuth oxide content was 5% by mass, and the zinc oxide content was 95% by mass. Each film was formed in the same manner as in Example 6 except that the above was achieved.
実施例８では、実施例５と同様の方法で成膜した酸化ビスマスを３０質量％と酸化亜鉛７０質量％とを含む赤外線透過膜を用いた以外は、実施例６と同様にして、基板側から順にＧｅ膜、当該赤外線透過膜とが積層された反射防止膜を得た。 In Example 8, a substrate side was formed in the same manner as in Example 6 except that an infrared transmitting film containing 30% by mass of bismuth oxide and 70% by mass of zinc oxide formed by the same method as in Example 5 was used. The antireflection film in which the Ge film and the infrared transmission film were laminated in order was obtained.
実施例９では、成膜原料として、酸化ビスマスと酸化亜鉛とをそれぞれ５０質量％ずつ含む焼結体ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを５０．０質量％と酸化亜鉛５０．０質量％とを含む赤外線透過膜を成膜した。 In Example 9, as in Example 1, except that a sintered body target containing 50% by mass of bismuth oxide and zinc oxide was used as a film forming raw material, bismuth oxide was changed to 50.0%. An infrared transmission film containing 5% by mass and 50.0% by mass of zinc oxide was formed.
実施例１０では、酸化ビスマスの含有量が３８．０質量％である酸化亜鉛の焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを３８．０質量％と酸化亜鉛６２．０質量％とを含む赤外線透過膜を成膜した。 In Example 10, except that a sintered target of zinc oxide having a bismuth oxide content of 38.0% by mass was used, the bismuth oxide was 38.0% by mass in the same manner as in Example 1. An infrared transmission film containing 62.0% by mass of zinc oxide was formed.
実施例１１では、酸化亜鉛の含有量が３０．０質量％である酸化ビスマスの焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを７０．０質量％と酸化亜鉛３０．０質量％とを含む赤外線透過膜を成膜した。 In Example 11, bismuth oxide was 70.0% by mass in the same manner as in Example 1 except that a sintered target of bismuth oxide having a zinc oxide content of 30.0% by mass was used. An infrared transmission film containing 30.0% by mass of zinc oxide was formed.
実施例１２では、酸化亜鉛の含有量が１０質量％である酸化ビスマスの焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを９０質量％と酸化亜鉛１０質量％とを含む赤外線透過膜を成膜した。 In Example 12, 90% by mass of bismuth oxide and 10% by mass of zinc oxide were used in the same manner as in Example 1 except that a sintered target of bismuth oxide having a zinc oxide content of 10% by mass was used. % Infrared transparent film was formed.
実施例１３では、酸化ビスマスの含有量が８質量％である酸化亜鉛の焼結ターゲットを用いたことを除いては、実施例１と同様にして、酸化ビスマスを８質量％と酸化亜鉛を９２質量％とを含む赤外線透過膜を成膜した。 In Example 13, except that a sintered target of zinc oxide having a bismuth oxide content of 8% by mass was used, 8% by mass of bismuth oxide and 92% of zinc oxide were used in the same manner as in Example 1. An infrared transmission film containing 5% by mass was formed.
実施例１４では、実施例６と同様に、基板側から順にＧｅ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を積層した反射防止膜を成膜した。Ｇｅ膜を成膜する際には、ゲルマニウムをターゲットとして用い、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を成膜する際には、酸化ビスマスの含有量が３８質量％である酸化亜鉛の焼結体ターゲットを用いた以外は実施例１と同様にして、酸化ビスマスを３８質量％、酸化亜鉛を６２質量％含む赤外線透過膜を成膜した。 In Example 14, as in Example 6, an antireflection film was formed by laminating a Ge film and an infrared transmission film containing bismuth oxide and zinc oxide in this order from the substrate side. When forming a Ge film, germanium is used as a target, and when an infrared transmission film containing bismuth oxide and zinc oxide is formed, sintering of zinc oxide having a bismuth oxide content of 38% by mass is performed. An infrared transmission film containing 38% by mass of bismuth oxide and 62% by mass of zinc oxide was formed in the same manner as in Example 1 except that the combined target was used.
実施例１５では、基板側から順にＳｉ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を積層した反射防止膜を成膜した。Ｓｉ膜を成膜する際には、シリコンをターゲットとして用い、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜を成膜する際には、酸化ビスマスの含有量が３８質量％である酸化亜鉛の焼結体ターゲットを用いた以外は実施例１と同様にして、酸化ビスマスを３８質量％、酸化亜鉛を６２質量％含む赤外線透過膜を成膜した。 In Example 15, an antireflection film was formed by laminating an Si film, an infrared transmission film containing bismuth oxide and zinc oxide in this order from the substrate side. When forming an Si film, silicon is used as a target, and when an infrared transmission film containing bismuth oxide and zinc oxide is formed, sintering of zinc oxide having a bismuth oxide content of 38% by mass is performed. An infrared transmission film containing 38% by mass of bismuth oxide and 62% by mass of zinc oxide was formed in the same manner as in Example 1 except that the combined target was used.
実施例１６では、真空蒸着法により基材の両面にそれぞれ成膜原料である酸化ビスマスと酸化亜鉛を混合した真空蒸着材料を用いて、基材側から順に酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、フッ化イッテルビウム膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜との３層構造の積層膜を成膜した。以下、成膜の手順について具体的に説明する。 In Example 16, infrared transmission including bismuth oxide and zinc oxide in order from the substrate side using a vacuum deposition material in which bismuth oxide and zinc oxide, which are film forming raw materials, are mixed on both surfaces of the substrate by a vacuum deposition method. A laminated film having a three-layer structure including a film, an ytterbium fluoride film, and an infrared transmission film containing bismuth oxide and zinc oxide was formed. Hereinafter, the procedure of film formation will be specifically described.
まず、真空蒸着装置に、成膜原料である蒸着材料と、基材とを対向配置した。成膜原料としては、酸化ビスマスと酸化亜鉛を混合したタブレットとフッ化イッテルビウムの顆粒を用いた。基材として、カルコゲナイドガラス（湖北新華光信息材料有限公司製 ＩＲＧ２０６）を用いた。 First, a vapor deposition material, which is a film forming raw material, and a base material were arranged opposite to each other in a vacuum vapor deposition apparatus. As raw materials for the film formation, tablets mixed with bismuth oxide and zinc oxide and ytterbium fluoride granules were used. As the substrate, chalcogenide glass (IRG206 manufactured by Hubei Xinhua Guangxin Material Co., Ltd.) was used.
次に、装置内全体を真空に排気した。蒸着装置内で蒸着材料を加熱し、蒸発させて蒸着させた。蒸着材料を加熱蒸着する際、酸化ビスマスと酸化亜鉛を混合したタブレットについては、電子ビーム加熱により蒸着し、フッ化イッテルビウムの顆粒については抵抗加熱により蒸着した。 Next, the whole apparatus was evacuated. The vapor deposition material was heated and evaporated in a vapor deposition apparatus for vapor deposition. When the vapor deposition material was heated and vapor-deposited, tablets mixed with bismuth oxide and zinc oxide were vapor-deposited by electron beam heating, and granules of ytterbium fluoride were vapor-deposited by resistance heating.
酸化ビスマスと酸化亜鉛を混合したタブレットは、酸化ビスマスの含有量が９０質量％、酸化亜鉛の含有量が１０質量％になるようにした。 The tablet in which bismuth oxide and zinc oxide were mixed was adjusted so that the content of bismuth oxide was 90% by mass and the content of zinc oxide was 10% by mass.
実施例１７では、実施例１６と同様の方法で、基材側から順に酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、フッ化イッテルビウム膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、フッ化イッテルビウム膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜との５層構造の積層膜を成膜した。酸化ビスマスと酸化亜鉛とを含む赤外線透過膜は、実施例１１と同様にして、酸化ビスマスを９０質量％と酸化亜鉛１０質量％とを含む赤外線透過膜の各層を成膜した。 In Example 17, an infrared transmission film containing bismuth oxide and zinc oxide, an ytterbium fluoride film, an infrared transmission film containing bismuth oxide and zinc oxide in order from the substrate side in the same manner as in Example 16, fluoride film A laminated film having a five-layer structure of an ytterbium film and an infrared transmitting film containing bismuth oxide and zinc oxide was formed. The infrared transmission film containing bismuth oxide and zinc oxide was formed in the same manner as in Example 11 by forming each layer of an infrared transmission film containing 90% by mass of bismuth oxide and 10% by mass of zinc oxide.
実施例１８では、実施例１６と同様の方法で、基材側から順にＧｅ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、Ｇｅ膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜、フッ化イッテルビウム膜、酸化ビスマスと酸化亜鉛とを含む赤外線透過膜との６層構造の積層膜を成膜した。ゲルマニウムは、ゲルマニウムの顆粒を用いて、電子ビーム加熱により蒸着した。酸化ビスマスと酸化亜鉛とを含む赤外線透過膜は、実施例１１と同様にして、酸化ビスマスを９０質量％と酸化亜鉛１０質量％とを含む赤外線透過膜の各層を成膜した。 In Example 18, in the same manner as in Example 16, a Ge film, an infrared transmission film containing bismuth oxide and zinc oxide, a Ge film, an infrared transmission film containing bismuth oxide and zinc oxide, and a fluorine film in this order from the substrate side. A laminated film having a six-layer structure of an ytterbium oxide film and an infrared transmitting film containing bismuth oxide and zinc oxide was formed. Germanium was deposited by electron beam heating using germanium granules. The infrared transmission film containing bismuth oxide and zinc oxide was formed in the same manner as in Example 11 by forming each layer of an infrared transmission film containing 90% by mass of bismuth oxide and 10% by mass of zinc oxide.
［比較例１］
比較例１では、出発原料として酸化亜鉛の焼結体ターゲットのみを用いた以外は、実施例１と同様にして酸化亜鉛膜を成膜した。すなわち、比較例１では酸化ビスマスを含まない酸化亜鉛膜を成膜した。
[Comparative Example 1]
In Comparative Example 1, a zinc oxide film was formed in the same manner as in Example 1 except that only a zinc oxide sintered compact target was used as a starting material. That is, in Comparative Example 1, a zinc oxide film not containing bismuth oxide was formed.
［比較例２］
比較例２では、出発原料として酸化ビスマスの焼結ターゲットを用いた以外は、実施例１と同様にして成膜し、酸化ビスマス膜を得た。すなわち、比較例２では他の金属酸化物を含まない酸化亜鉛膜を成膜した。
[Comparative Example 2]
In Comparative Example 2, a bismuth oxide film was obtained in the same manner as in Example 1 except that a bismuth oxide sintered target was used as a starting material. That is, in Comparative Example 2, a zinc oxide film containing no other metal oxide was formed.
［評価］
実施例１〜実施例１８、比較例１及び比較例２で成膜した各膜の膜厚、組成、遠赤外線に対する平均透過率をそれぞれ測定すると共に、耐水試験を行った。また、一部の試料についてテープ試験を行うと共に、相対膜密度を求めた。
[Evaluation]
While measuring the film thickness of each film | membrane formed in Example 1- Example 18, Comparative Example 1 and Comparative Example 2, the average transmittance | permeability with respect to a far infrared ray, the water resistance test was done. In addition, a tape test was performed on some samples and the relative film density was determined.
（膜厚）
各膜の膜厚を触針式段差計で測定した。結果を表１〜表３に示す。なお、表１〜表３に示す膜厚は、各膜の実際の膜厚であって、いわゆる光学膜厚ではない。
(Film thickness)
The film thickness of each film was measured with a stylus type step gauge. The results are shown in Tables 1 to 3. The film thicknesses shown in Tables 1 to 3 are actual film thicknesses of the respective films, and are not so-called optical film thicknesses.
（組成）
各膜の組成をＩＣＰ（誘導結合プラズマ発光分光分析法）で分析した。結果を表１〜表３に示す。
(composition)
The composition of each film was analyzed by ICP (inductively coupled plasma emission spectroscopy). The results are shown in Tables 1 to 3.
（平均透過率）
各実施例及び比較例で得た試料の波長範囲８μｍ〜１２μｍ及び波長範囲８μｍ〜１４μｍにおける平均透過率をパーキンエルマー社製のＦＴ−ＩＲ Ｓｐｅｃｔｒｕｍ １００ Ｏｐｔｉｃａを用いて測定した。なお、各試料とは、基板の両面にそれぞれの膜を備えたものをいう（以下、同じ）。結果を表１〜表３に示す。
(Average transmittance)
The average transmittance | permeability in wavelength range 8micrometer-12micrometer and wavelength range 8micrometer-14micrometer of the sample obtained by each Example and the comparative example was measured using FT-IR Spectrum 100 Optica by Perkin Elmer. In addition, each sample means what provided each film | membrane on both surfaces of the board | substrate (hereinafter, the same). The results are shown in Tables 1 to 3.
（耐水試験）
各実施例及び比較例で得た試料を純水に浸漬した。そして、試料を純水に浸漬してから２４時間が経過した時点で観察を終了した。結果を表１〜表３に示す。但し、表１〜表３には、耐水試験の結果を「○」、「×」で示している。ここで、「○」は、試料を純水に浸漬してから２４時間が経過しても基材と膜との密着が良好であり、膜剥がれ等が一切生じなかったことを意味する。また、「×」は試料を純水に浸漬してから２４時間が経過するまでの間に、基材から膜が浮いたり、膜が剥がれたりなど、基材と膜との密着性低下が観察されたことを意味する。
(Water resistance test)
Samples obtained in each example and comparative example were immersed in pure water. And observation was complete | finished when 24 hours passed since the sample was immersed in the pure water. The results are shown in Tables 1 to 3. However, in Tables 1 to 3, the results of the water resistance test are indicated by “◯” and “×”. Here, “◯” means that the adhesion between the substrate and the film was good and no film peeling occurred even after 24 hours had passed since the sample was immersed in pure water. In addition, “×” indicates a decrease in the adhesion between the substrate and the film, such as the film floating or peeling off from the substrate until 24 hours have passed since the sample was immersed in pure water. Means that
（テープ試験）ＭＩＬ−Ｃ−４８４９７Ａ ｐａｒａ４．５．３．１
実施例９〜実施例１８と、比較例１及び比較例２で得た試料について、耐水試験後にテープ試験を行い、基材と被膜の密着性を評価した。結果を表１〜表３に示す。但し、表１〜表３には、テープ試験の結果を「○」、「×」で示している。ここで、「○」は、試料にテープを貼り付けて引き剥がしても基材と被膜との密着が良好であり、膜剥がれ等が一切生じなかったことを意味する。また、「×」は試料にテープを貼り付けて引き剥がした時に、基材から膜が浮いたり、膜が剥がれたりなど、基材と被膜との密着性低下が観察されたことを意味する。
(Tape test) MIL-C-48497A para4.5.3.1
The samples obtained in Examples 9 to 18 and Comparative Examples 1 and 2 were subjected to a tape test after the water resistance test to evaluate the adhesion between the substrate and the coating. The results are shown in Tables 1 to 3. However, in Tables 1 to 3, the results of the tape test are indicated by “◯” and “×”. Here, “◯” means that the adhesion between the substrate and the film was good even when the tape was applied to the sample and peeled off, and no film peeling occurred. In addition, “x” means that when the tape was applied to the sample and peeled off, a decrease in adhesion between the substrate and the coating was observed, such as the film floating from the substrate or the film peeling off.
（膜密度）
実施例９〜実施例１８と、比較例１及び比較例２で得た試料について、当該赤外線反射防止膜の膜密度をＸ線反射率法（ＸＲＲ）により測定した。この際、ＸＲＲ測定用サンプルとして、膜厚１５０ｎｍに成膜したものを用いた。膜厚１５０ｎｍ程度のサンプルを用いることにより、Ｓｉウェーハ上の測定感度が良好になるためである。得られた実測値を各試料についての理論膜密度で除した値の百分率を求め、相対膜密度とした。その結果を表１〜表３に示す。また、実施例９と実施例１３の試料について、その理論膜密度と平均膜密度を表４に示す。
(Film density)
For the samples obtained in Examples 9 to 18 and Comparative Examples 1 and 2, the film density of the infrared antireflection film was measured by the X-ray reflectance method (XRR). At this time, a sample having a film thickness of 150 nm was used as a sample for XRR measurement. This is because the measurement sensitivity on the Si wafer is improved by using a sample having a thickness of about 150 nm. The percentage of the value obtained by dividing the obtained actual measurement value by the theoretical film density for each sample was determined and used as the relative film density. The results are shown in Tables 1 to 3. Table 4 shows the theoretical film density and average film density of the samples of Example 9 and Example 13.
（外観観察）
実施例９、実施例１３の試料について、当該赤外線反射防止膜の表面を走査型電子顕微鏡（ＪＳＭ−６５００Ｆ（日本電子株式会社製））を用いて倍率１万倍で観察した。各試料についてのＳＥＭ画像を図１及び図２に示す。
(Appearance observation)
About the sample of Example 9 and Example 13, the surface of the said infrared rays antireflection film was observed at a magnification of 10,000 times using a scanning electron microscope (JSM-6500F (manufactured by JEOL Ltd.)). SEM images for each sample are shown in FIGS.
表１及び表２に示すように、実施例１〜実施例１８の試料はいずれも耐水試験の結果が良好であり、各試料を純水に浸漬してから２４時間が経過しても、基板からの膜剥がれが一切生じなかった。一方、比較例１の試料は酸化亜鉛からなる赤外線透過膜を備える。表２に示すように純水に当該試料を水に浸漬して２４時間経過後には基板から完全に膜が剥離した状態となった。従って、酸化ビスマスを一切含まない酸化亜鉛膜と比較すると、酸化ビスマスと酸化亜鉛の混合膜は耐水性が良好であることが確認された。 As shown in Table 1 and Table 2, the samples of Examples 1 to 18 all have good results of the water resistance test, and even if 24 hours have passed since each sample was immersed in pure water, the substrate There was no film peeling from the film. On the other hand, the sample of Comparative Example 1 includes an infrared transmission film made of zinc oxide. As shown in Table 2, the sample was immersed in pure water and after 24 hours, the film was completely peeled from the substrate. Therefore, it was confirmed that the mixed film of bismuth oxide and zinc oxide has good water resistance as compared with the zinc oxide film containing no bismuth oxide.
また、テープ試験を実施した実施例９〜実施例１８の試料のうち、実施例９〜実施例１２及び実施例１４〜実施例１８の試料は、膜の剥がれは観察されず、結果は良好であった。一方、実施例１３の試料及び比較例２の試料は、耐水試験後のテープ試験では膜が剥離した状態となった。実施例１３の試料は、酸化ビスマスの含有量が８質量％であり、他の試料と比較すると酸化ビスマスの含有量が低い。また、比較例２の試料は酸化亜鉛を含まない。 In addition, among the samples of Examples 9 to 18 in which the tape test was performed, the samples of Examples 9 to 12 and Examples 14 to 18 were not observed to peel off, and the results were good. there were. On the other hand, the sample of Example 13 and the sample of Comparative Example 2 were in a state where the film was peeled off in the tape test after the water resistance test. The sample of Example 13 has a bismuth oxide content of 8% by mass, and the bismuth oxide content is lower than that of the other samples. Further, the sample of Comparative Example 2 does not contain zinc oxide.
ここで、表１及、表２及び表４に示すように、実施例９〜実施例１２及び実施例１４〜実施例１８の試料において、各赤外線透過膜の相対膜密度は８０．０％以上、より具体的には８５．０％以上であるのに対して、実施例１３の試料の相対膜密度は８０．０％未満である。同様に比較例１及び比較例２の試料の相対膜密度も８０．０％未満である。また、図１及び図２から、実施例９の赤外線透過膜は、実施例１３の赤外線透過膜よりも微細な結晶粒からなり、膜密度が向上していることがＳＥＭ画像からも確認された。酸化ビスマスと酸化亜鉛の混合比を変化させることにより、相対膜密度が変化することが確認され、酸化ビスマスと他の金属酸化物（酸化亜鉛）とからなる赤外線透過膜において、酸化ビスマスの含有量を１０質量％以上９０質量％以下とすることにより、酸化ビスマス膜（又は酸化亜鉛膜）の耐水性及び密着性を著しく向上することができることが確認された。 Here, as shown in Table 1, Table 2, and Table 4, in the samples of Examples 9 to 12 and Examples 14 to 18, the relative film density of each infrared transmission film was 80.0% or more. More specifically, it is 85.0% or more, whereas the relative film density of the sample of Example 13 is less than 80.0%. Similarly, the relative film density of the samples of Comparative Example 1 and Comparative Example 2 is also less than 80.0%. Further, from FIG. 1 and FIG. 2, it was confirmed from the SEM image that the infrared transmission film of Example 9 was composed of finer crystal grains than the infrared transmission film of Example 13, and the film density was improved. . By changing the mixing ratio of bismuth oxide and zinc oxide, it was confirmed that the relative film density was changed, and the content of bismuth oxide in the infrared transmitting film composed of bismuth oxide and other metal oxides (zinc oxide) was confirmed. It was confirmed that the water resistance and adhesiveness of the bismuth oxide film (or zinc oxide film) can be remarkably improved by setting the content of 10 mass% or more and 90 mass% or less.
さらに、表１及び表２に示すように、実施例１〜実施例１８の試料は、波長範囲８μｍ〜１２μｍにおける平均透過率が８３％以上を示し、これらの波長範囲の光線に対して高い透明度を示す。従って、実施例１〜実施例１８で成膜した本件発明に係る赤外線透過膜は光学膜として好適に用いることができる。 Furthermore, as shown in Table 1 and Table 2, the samples of Examples 1 to 18 have an average transmittance of 83% or more in the wavelength range of 8 μm to 12 μm, and are highly transparent to light in these wavelength ranges. Indicates. Therefore, the infrared transmission film according to the present invention formed in Examples 1 to 18 can be suitably used as an optical film.
一方、表３に示すように、比較例１の試料の波長範囲８μｍ〜１２μｍにおける平均透過率が９０％以上を示し、光学膜として好適な光学特性を備える。しかしながら、上述したとおり、耐水性及び密着性が低いため、実用上必要とされる耐久性を満足することができない。また、比較例２の試料は波長範囲８μｍ〜１２μｍにおける平均透過率が８１％となり、遠赤外線に対する透明度が低いため、光学膜として用いることが困難である。 On the other hand, as shown in Table 3, the average transmittance of the sample of Comparative Example 1 in the wavelength range of 8 μm to 12 μm is 90% or more, and has optical characteristics suitable as an optical film. However, as described above, since water resistance and adhesion are low, durability required for practical use cannot be satisfied. In addition, the sample of Comparative Example 2 has an average transmittance of 81% in the wavelength range of 8 μm to 12 μm, and has low transparency with respect to far infrared rays, so that it is difficult to use as an optical film.
本件発明によれば、成膜が容易であり、且つ、耐水性等の実用上十分な耐久性を有する新規な赤外線透過膜、及び当該赤外線透過膜を備えた光学膜、反射防止膜、光学部品、光学系及び撮像装置を提供することができる。 According to the present invention, a novel infrared transmission film that is easy to form and has practically sufficient durability such as water resistance, and an optical film, an antireflection film, and an optical component provided with the infrared transmission film An optical system and an imaging device can be provided.
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