JPH0720302A - Infrared anti-reflection film and formation thereof - Google Patents
Infrared anti-reflection film and formation thereofInfo
- Publication number
- JPH0720302A JPH0720302A JP5163402A JP16340293A JPH0720302A JP H0720302 A JPH0720302 A JP H0720302A JP 5163402 A JP5163402 A JP 5163402A JP 16340293 A JP16340293 A JP 16340293A JP H0720302 A JPH0720302 A JP H0720302A
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- Prior art keywords
- layer
- antireflection film
- silicon substrate
- silicon
- substrate
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は光学部品の反射防止膜に
関するものであり、特に赤外用光学材料として使用され
るシリコン基板の赤外反射防止膜とその形成方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film for optical parts, and more particularly to an infrared antireflection film for a silicon substrate used as an infrared optical material and a method for forming the same.
【０００２】[0002]
【従来の技術】従来、赤外用光学材料としてはシリコン
（Ｓｉ）がよく知られている。しかしながら、シリコン
は屈折率が通常の光学用ガラスに比べて高い（約３．
３）ために反射が高く（１面当たり約２８％）、光学部
品として使用するには反射防止膜が不可欠である。2. Description of the Related Art Silicon (Si) has been well known as an infrared optical material. However, the refractive index of silicon is higher than that of ordinary optical glass (about 3.
3), the reflection is high (about 28% per surface), and an antireflection film is indispensable for use as an optical component.
【０００３】以下、図面を参照しながら従来のシリコン
基板に対する赤外反射防止膜とその形成方法について説
明する。A conventional infrared antireflection film for a silicon substrate and a method for forming the same will be described below with reference to the drawings.
【０００４】単層の反射防止膜としては硫化亜鉛（Ｚｎ
Ｓ）からなるものが一般的であり、その断面構造を図５
に示す。図５において、５１はシリコン（Ｓｉ）の基
板、５２は硫化亜鉛層である。反射防止膜の光学的膜厚
はλ／４（λは反射防止波長域の中心波長）であり、通
常真空蒸着法によって形成される。前記の硫化亜鉛層５
２からなる単層反射防止膜は、基板５１との密着性およ
び耐湿性が低いので、それらを向上するために蒸着時に
シリコン基板５１を加熱したり、蒸着前に基板５１にイ
オンボンバードの処理を行ったりする。As a single-layer antireflection film, zinc sulfide (Zn
S) is generally used, and its sectional structure is shown in FIG.
Shown in. In FIG. 5, reference numeral 51 is a silicon (Si) substrate, and 52 is a zinc sulfide layer. The optical film thickness of the antireflection film is λ / 4 (λ is the center wavelength of the antireflection wavelength region), and is usually formed by a vacuum vapor deposition method. The zinc sulfide layer 5
Since the single-layer antireflection film consisting of 2 has low adhesion and moisture resistance to the substrate 51, in order to improve them, the silicon substrate 51 is heated during vapor deposition, or the substrate 51 is subjected to ion bombardment treatment before vapor deposition. I will go.
【０００５】また、反射防止膜を多層化することもあ
り、例えば２層反射防止膜については基板側から数えて
第１層がチタン酸化物層、第２層が硫化亜鉛層のものが
提案されている（例えば特開昭５６−１０６２０２号公
報）。In some cases, the antireflection film may be multi-layered. For example, regarding a two-layer antireflection film, it is proposed that the first layer is a titanium oxide layer and the second layer is a zinc sulfide layer, counted from the substrate side. (For example, JP-A-56-106202).
【０００６】[0006]
【発明が解決しようとする課題】前述したように、赤外
用反射防止膜の材料として硫化亜鉛（ＺｎＳ）がよく用
いられるが、この硫化亜鉛（ＺｎＳ）は約１０００℃以
上に加熱すると昇華によって蒸発し、比較的容易に薄膜
を形成することができる。As described above, zinc sulfide (ZnS) is often used as a material for the antireflection coating for infrared rays. This zinc sulfide (ZnS) evaporates by sublimation when heated above 1000 ° C. However, a thin film can be formed relatively easily.
【０００７】しかしながら室温の基板面に蒸着したＺｎ
Ｓ膜は、基板との密着性が弱く湿度に弱い。これを解決
するために基板温度を１５０℃程度に加熱して蒸着する
方法が採用されるが、この方法は可視域用の比較的膜厚
の薄い（約０．２μｍぐらいまで）ものにはある程度有
効ではあるが、赤外域の反射防止膜として膜厚が１μｍ
前後あるようなものでは、基板との密着性および耐湿性
向上の効果は小さく、膜にクラックが発生し、その結果
光学特性が劣化することもあり改善の効果は小さい。However, Zn deposited on the substrate surface at room temperature
The S film has weak adhesion to the substrate and is weak against humidity. In order to solve this, a method of heating the substrate temperature to about 150 ° C. and vapor deposition is adopted, but this method has some extent for a relatively thin film for visible region (up to about 0.2 μm). Effective, but with a thickness of 1 μm as an antireflection film in the infrared region
If there is such a situation, the effect of improving the adhesion to the substrate and the moisture resistance is small, and cracks may occur in the film, resulting in deterioration of the optical characteristics, and the effect of the improvement is small.
【０００８】また、イオンボンバードの処理をおこなっ
たものについてもその改善の効果は小さい。さらに、チ
タン酸化物層、硫化亜鉛層からなる２層反射防止膜はＺ
ｎＳの耐湿性は向上されるが、これも近赤外域までの比
較的薄い膜厚に相当するものまでであり、この反射防止
膜においてもチタン酸化物層とシリコン基板との密着性
は優れたものではない。Further, the effect of improving the ion bombardment treatment is also small. Furthermore, a two-layer antireflection film consisting of a titanium oxide layer and a zinc sulfide layer is Z
Although the moisture resistance of nS is improved, this is up to a thickness corresponding to a relatively thin film thickness in the near infrared region, and the adhesion between the titanium oxide layer and the silicon substrate is excellent even in this antireflection film. Not a thing.
【０００９】以上のように従来の赤外反射防止膜には、
シリコン基板との密着性が悪い、耐湿性に劣る、光学特
性の安定性に欠けるという課題を有していた。As described above, the conventional infrared antireflection film has
There were problems such as poor adhesion with a silicon substrate, poor moisture resistance, and lack of stability in optical characteristics.
【００１０】本発明は上記従来の課題を解決するもの
で、シリコン基板に対しての密着性および耐久性および
光学特性に優れた赤外反射防止膜とその形成方法を提供
することを目的とする。The present invention solves the above-mentioned conventional problems, and an object of the present invention is to provide an infrared antireflection film excellent in adhesion to a silicon substrate, durability and optical characteristics, and a method for forming the same. .
【００１１】[0011]
【課題を解決するための手段】この目的を達成するため
に、本発明の赤外反射防止膜は、シリコン基板表面に形
成する２層構造の赤外反射防止膜であって、基板側から
数えて第１層目はシリコン改質層であり、第２層目は硫
化亜鉛層である赤外反射防止膜である。To achieve this object, the infrared antireflection film of the present invention is an infrared antireflection film having a two-layer structure formed on the surface of a silicon substrate and counted from the substrate side. The first layer is a silicon modified layer, and the second layer is a zinc sulfide layer which is an infrared antireflection film.
【００１２】また、本発明の赤外反射防止膜は、シリコ
ン基板表面に形成する２層構造の赤外反射防止膜であっ
て、基板側から数えて第１層目はシリコン改質層であ
り、第２層目は酸化物誘電体層である赤外反射防止膜で
ある。The infrared antireflection film of the present invention is a two-layer structure infrared antireflection film formed on the surface of a silicon substrate, and the first layer counted from the substrate side is a silicon modified layer. The second layer is an infrared antireflection film which is an oxide dielectric layer.
【００１３】また、本発明の赤外反射防止膜は、シリコ
ン基板表面に形成する３層構造の赤外反射防止膜であっ
て、基板側から数えて第１層目はシリコン改質層であ
り、第２層目は酸化物誘電体層であり、第３層目は硫化
亜鉛層である赤外反射防止膜である。The infrared antireflection film of the invention is a three-layer infrared antireflection film formed on the surface of a silicon substrate, and the first layer counted from the substrate side is a silicon modified layer. The second layer is an oxide dielectric layer, and the third layer is a zinc sulfide layer, which is an infrared antireflection film.
【００１４】これらの反射防止膜は、イオンビームの照
射によってシリコン基板表面に改質層を形成し、しかる
後、電子ビームをシリコン基板に照射しながら硫化亜鉛
の層を形成することによって得ることができる。These antireflection films can be obtained by forming a modified layer on the surface of a silicon substrate by irradiation with an ion beam, and then forming a zinc sulfide layer while irradiating the silicon substrate with an electron beam. it can.
【００１５】また、イオンビームの照射によってシリコ
ン基板表面に改質層を形成した後その上に酸化物誘電体
層を形成し、しかる後に、電子ビームをシリコン基板に
照射しながら硫化亜鉛層を形成することによって得るこ
とができる。Further, a modified layer is formed on the surface of the silicon substrate by irradiation with an ion beam, and then an oxide dielectric layer is formed on the modified layer. Thereafter, a zinc sulfide layer is formed while irradiating the silicon substrate with an electron beam. Can be obtained by doing.
【００１６】また、イオンビームの照射によってシリコ
ン基板表面に改質層を形成した後その上にイオンビーム
を照射しながら酸化物誘電体層を形成し、しかる後に、
電子ビームをシリコン基板に照射しながら硫化亜鉛層を
形成することによって得ることができる。Further, after forming a modified layer on the surface of the silicon substrate by irradiating with an ion beam, an oxide dielectric layer is formed thereon while irradiating with an ion beam, and thereafter,
It can be obtained by forming a zinc sulfide layer while irradiating a silicon substrate with an electron beam.
【００１７】[0017]
【作用】上記構成によれば本発明の赤外反射防止膜は次
の作用を有する。According to the above structure, the infrared antireflection film of the present invention has the following functions.
【００１８】本発明の赤外反射防止膜の構成は２層また
は３層構造のものであるが、基板側から数えて第１層を
イオンビーム照射によるシリコン改質層とすることによ
って、従来であれば密着性が悪かった反射防止膜の材料
をその上に密着性よく形成することができる。The structure of the infrared antireflection film of the present invention has a two-layer or three-layer structure. However, the first layer, counted from the substrate side, is a silicon modified layer formed by ion beam irradiation. If so, the material of the antireflection film having poor adhesion can be formed thereon with good adhesion.
【００１９】それはシリコン基板にイオンビームを照射
することによって、まずシリコン基板の最表面の酸化層
がエッチング除去され、除去後の表面酸化層を数十Å
（オングストローム）の深さで一部のシリコン−酸素の
結合を破断し活性化した層（改質層）が形成される。こ
の方法によって形成された改質層の上に、硫化亜鉛層あ
るいは酸化物誘電体層を形成すると、極めて基板との密
着性のよい膜が形成されることを見い出した。By irradiating the silicon substrate with an ion beam, the oxide layer on the outermost surface of the silicon substrate is first etched and removed, and the surface oxide layer after removal is tens of liters.
At a depth of (angstrom), a part of silicon-oxygen bonds are broken and an activated layer (modified layer) is formed. It has been found that when a zinc sulfide layer or an oxide dielectric layer is formed on the modified layer formed by this method, a film having excellent adhesion to the substrate is formed.
【００２０】そして、改質層の上に硫化亜鉛層を形成す
る際、電子ビームをシリコン基板に照射しながら硫化亜
鉛の層を形成することによって緻密な硫化亜鉛膜が得ら
れ、基板との密着性および耐久性に優れた赤外用反射防
止膜を得ることができる。Then, when forming the zinc sulfide layer on the modified layer, a dense zinc sulfide film is obtained by forming the zinc sulfide layer while irradiating the silicon substrate with the electron beam, so that a close contact with the substrate is obtained. It is possible to obtain an infrared antireflection film having excellent properties and durability.
【００２１】また、改質層の上に酸化物誘電体層を形成
し、しかる後に、電子ビームをシリコン基板に照射しな
がら硫化亜鉛層を形成することによって緻密な硫化亜鉛
膜が得られ、基板との密着性および耐久性に優れた赤外
用反射防止膜を得ることができる。A dense zinc sulfide film can be obtained by forming an oxide dielectric layer on the modified layer and then forming a zinc sulfide layer while irradiating the silicon substrate with an electron beam. It is possible to obtain an infrared antireflection film having excellent adhesion and durability.
【００２２】また、改質層の上に酸化物誘電体層を形成
する際、イオンビームを照射しながら酸化物誘電体を蒸
着することによって、緻密で内部応力が緩和された酸化
物誘電体層が形成でき、さらに前記酸化物誘電体層の上
に硫化亜鉛層を形成する際、電子ビームをシリコン基板
に照射しながら硫化亜鉛層を形成するすることによって
緻密な硫化亜鉛膜が得られ、基板との密着性および耐久
性に優れた赤外用反射防止膜を得ることができる。When the oxide dielectric layer is formed on the modified layer, the oxide dielectric is vapor-deposited while being irradiated with an ion beam, so that the oxide dielectric layer is dense and the internal stress is relaxed. A fine zinc sulfide film is obtained by forming the zinc sulfide layer while irradiating the silicon substrate with an electron beam when forming the zinc sulfide layer on the oxide dielectric layer. It is possible to obtain an infrared antireflection film having excellent adhesion and durability.
【００２３】[0023]
（実施例１）以下本発明の実施例について、図面を参照
しながら説明する。(Embodiment 1) An embodiment of the present invention will be described below with reference to the drawings.
【００２４】図１に本発明の第１の実施例（実施例１）
の赤外反射防止膜の構成（断面図）を示す。図１におい
て、１１はシリコン（Ｓｉ）の基板、１２はシリコン基
板１１の表面を改質することにより形成されたシリコン
改質層、１３は硫化亜鉛層である。FIG. 1 shows a first embodiment (first embodiment) of the present invention.
2 shows the structure (cross-sectional view) of the infrared antireflection film of FIG. In FIG. 1, 11 is a silicon (Si) substrate, 12 is a silicon modified layer formed by modifying the surface of the silicon substrate 11, and 13 is a zinc sulfide layer.
【００２５】各層の形成条件は以下の通りである。シリ
コン改質層の形成は、イオンビームのガス種にアルゴン
を使用し、加速電圧１．５ｋＶで、シリコン基板上の電
流密度を５０〜６０μＡ／ｃｍ2 の範囲でシリコン基板
表面をイオンビームで照射して、約５０Åの厚さの改質
層を形成した。The conditions for forming each layer are as follows. The silicon modified layer is formed by using argon as a gas species of the ion beam, irradiating the silicon substrate surface with the ion beam at an acceleration voltage of 1.5 kV and a current density on the silicon substrate in the range of 50 to 60 μA / cm 2. As a result, a modified layer having a thickness of about 50Å was formed.
【００２６】次に光学的膜厚λ／４（λ＝７０００ｎ
ｍ）の厚さの硫化亜鉛層１３を、蒸着速度約６〜８Å／
ｓｅｃでシリコン改質層１２上に、電子ビームを電流密
度４〜６μＡ／ｃｍ2 で照射しながら形成した。Next, the optical film thickness λ / 4 (λ = 7000n)
m) the zinc sulfide layer 13 having a thickness of about 6 to 8Å /
It was formed on the silicon reforming layer 12 for sec while irradiating with an electron beam at a current density of 4 to 6 μA / cm 2 .
【００２７】本実施例の反射防止膜の分光反射特性（１
面当たり）を、図４において特性曲線ａで示す。比較の
ため反射防止膜なしの特性を曲線ｄで示した。図からわ
かるように中心波長（λ＝７０００ｎｍ）で反射率は５
％以下であり、赤外反射防止膜として優れた特性が得ら
れた。Spectral reflection characteristics of the antireflection film of this embodiment (1
(Per surface) is shown by the characteristic curve a in FIG. For comparison, a characteristic without an antireflection film is shown by a curve d. As can be seen from the figure, the reflectance is 5 at the central wavelength (λ = 7000 nm).
% Or less, and excellent characteristics as an infrared antireflection film were obtained.
【００２８】本実施例の赤外反射防止膜の基板との密着
性および耐久性を確認するために次の項目の試験を行っ
た。 （ａ）剥離試験：温度４０℃、相対湿度８５％の高温・
高湿雰囲気中に１６８時間放置した後、粘着テープをシ
リコン基板表面に密着し、引きはがす。 （ｂ）高温試験：温度８０℃の雰囲気中に２５０時間放
置する。 （ｃ）低温試験：温度−２０℃の雰囲気中に２５０時間
放置する。 （ｄ）熱衝撃試験：温度−３０℃、８０℃の低温・高温
雰囲気中に交互に３０分間ずつ放置を約２４時間くり返
す。 （ｅ）高温・高湿試験：温度６０℃、相対湿度９０％の
高温・高湿雰囲気中に１６８時間放置する。 （ｆ）硫化水素ガス試験：硫化水素濃度３ｐｐｍ、温度
４０℃の雰囲気中に２４時間放置する。 （ｇ）亜硫酸ガス試験：亜硫酸ガス濃度１０ｐｐｍ、温
度４０℃の雰囲気中に２４時間放置する。In order to confirm the adhesion and durability of the infrared antireflection film of this example with the substrate, the following tests were conducted. (A) Peeling test: high temperature of 40 ° C. and relative humidity of 85%
After standing in a high humidity atmosphere for 168 hours, the adhesive tape is adhered to the surface of the silicon substrate and peeled off. (B) High temperature test: left in an atmosphere at a temperature of 80 ° C. for 250 hours. (C) Low temperature test: left in an atmosphere at a temperature of −20 ° C. for 250 hours. (D) Thermal shock test: The sample is left to stand in a low temperature / high temperature atmosphere at temperatures of −30 ° C. and 80 ° C. for 30 minutes alternately for about 24 hours. (E) High-temperature / high-humidity test: left in a high-temperature / high-humidity atmosphere having a temperature of 60 ° C. and a relative humidity of 90% for 168 hours. (F) Hydrogen sulfide gas test: Leave for 24 hours in an atmosphere having a hydrogen sulfide concentration of 3 ppm and a temperature of 40 ° C. (G) Sulfurous acid gas test: It is left for 24 hours in an atmosphere having a sulfurous acid gas concentration of 10 ppm and a temperature of 40 ° C.
【００２９】試験結果は（表１）に示す通りである。The test results are shown in (Table 1).
【００３０】[0030]
【表１】 [Table 1]
【００３１】（表１）からわかるように本実施例の赤外
反射防止膜は基板との密着性および耐久性に優れてい
る。As can be seen from (Table 1), the infrared antireflection film of this example is excellent in adhesion to the substrate and durability.
【００３２】（実施例２）図２に本発明の第２の実施例
（実施例２）の赤外反射防止膜の構成（断面図）を示
す。図２において、２１はシリコン（Ｓｉ）の基板、２
２はシリコン改質層、２３は二酸化チタン層である。(Embodiment 2) FIG. 2 shows the structure (cross-sectional view) of an infrared antireflection film according to the second embodiment (Embodiment 2) of the present invention. In FIG. 2, reference numeral 21 denotes a silicon (Si) substrate, 2
2 is a silicon modified layer, and 23 is a titanium dioxide layer.
【００３３】各層の形成条件は以下の通りである。イオ
ンビームの改質層の形成については、実施例１と同様で
あり、シリコン基板表面に約５０Åの厚さの改質層を形
成した。次に光学的膜厚λ／４（λ＝５０００ｎｍ）の
厚さの二酸化チタンを、蒸着速度約４〜５Å／ｓｅｃで
形成した。二酸化チタン形成時には、シリコン基板にア
ルゴンイオンビームを加速電圧０．５ＫＶ、イオン電流
密度１０〜２０μＡ／ｃｍ2 で照射した。The conditions for forming each layer are as follows. The ion beam modified layer was formed in the same manner as in Example 1, and a modified layer having a thickness of about 50 Å was formed on the surface of the silicon substrate. Next, titanium dioxide having an optical film thickness of λ / 4 (λ = 5000 nm) was formed at a vapor deposition rate of about 4 to 5Å / sec. During the formation of titanium dioxide, a silicon substrate was irradiated with an argon ion beam at an acceleration voltage of 0.5 KV and an ion current density of 10 to 20 μA / cm 2 .
【００３４】本実施例の反射防止膜の分光反射特性（１
面当たり）を図４において曲線ｂで示す。中心波長（λ
＝５０００ｎｍ）で反射率は５％以下であり、赤外反射
防止膜として優れた特性が得られた。Spectral reflection characteristics of the antireflection film of this embodiment (1
(Per surface) is shown by the curve b in FIG. Center wavelength (λ
= 5000 nm), the reflectance was 5% or less, and excellent properties as an infrared antireflection film were obtained.
【００３５】本実施例の赤外反射防止膜の基板との密着
性および耐久性を確認するために次の項目の試験を行っ
た。 （ａ）剥離試験：温度４０℃、相対湿度８５％の高温・
高湿雰囲気中に５００時間放置した後、粘着テープをシ
リコン基板表面に密着し、引きはがす。 （ｂ）高温試験：温度８０℃の雰囲気中に５００時間放
置する。 （ｃ）低温試験：温度−２０℃の雰囲気中に５００時間
放置する。 （ｄ）熱衝撃試験：温度−３０℃、８０℃の低温・高温
雰囲気中に交互に３０分間ずつ放置を約９６時間くり返
す。 （ｅ）高温・高湿試験：温度６０℃、相対湿度９０％の
高温・高湿雰囲気中に５００時間放置する。 （ｆ）硫化水素ガス試験：硫化水素濃度３ｐｐｍ、温度
４０℃の雰囲気中に９６時間放置する。 （ｇ）亜硫酸ガス試験：亜硫酸ガス濃度１０ｐｐｍ、温
度４０℃の雰囲気中に９６時間放置する。In order to confirm the adhesion and durability of the infrared antireflection film of this example to the substrate, the following tests were conducted. (A) Peeling test: high temperature of 40 ° C. and relative humidity of 85%
After leaving in a high humidity atmosphere for 500 hours, the adhesive tape is adhered to the surface of the silicon substrate and peeled off. (B) High temperature test: left in an atmosphere at a temperature of 80 ° C. for 500 hours. (C) Low temperature test: left in an atmosphere at a temperature of −20 ° C. for 500 hours. (D) Thermal shock test: Alternately left for 30 minutes in a low temperature / high temperature atmosphere at temperatures of -30 ° C and 80 ° C for about 96 hours. (E) High temperature / high humidity test: Leave for 500 hours in a high temperature / high humidity atmosphere having a temperature of 60 ° C. and a relative humidity of 90%. (F) Hydrogen sulfide gas test: Leave for 96 hours in an atmosphere having a hydrogen sulfide concentration of 3 ppm and a temperature of 40 ° C. (G) Sulfurous acid gas test: left in an atmosphere having a sulfurous acid gas concentration of 10 ppm and a temperature of 40 ° C. for 96 hours.
【００３６】試験結果は（表２）に示す通りである。The test results are shown in (Table 2).
【００３７】[0037]
【表２】 [Table 2]
【００３８】（表２）からわかるように本実施例の赤外
反射防止膜は基板との密着性および耐久性に優れてい
る。As can be seen from (Table 2), the infrared antireflection film of this example is excellent in adhesion to the substrate and durability.
【００３９】（実施例３）図３に本発明の第３の実施例
（実施例３）の赤外反射防止膜の構成（断面図）を示
す。図３において、３１はシリコン（Ｓｉ）の基板、３
２はシリコン改質層、３３は二酸化チタン層、３４は硫
化亜鉛層である。(Embodiment 3) FIG. 3 shows a structure (cross-sectional view) of an infrared antireflection film according to a third embodiment (Embodiment 3) of the present invention. In FIG. 3, 31 is a substrate of silicon (Si), 3
2 is a silicon modified layer, 33 is a titanium dioxide layer, and 34 is a zinc sulfide layer.
【００４０】各層の形成条件は以下の通りである。イオ
ンビームの改質層の形成については、実施例１と同様で
あり、シリコン基板表面に約８０Åの厚さの改質層を形
成した。次に光学的膜厚約２００Åの厚さの二酸化チタ
ンを、蒸着速度約４〜５Å／ｓｅｃで形成した。次に硫
化亜鉛を光学的膜厚が二酸化チタン層と合わせてλ／４
（λ＝６０００ｎｍ）の厚さになるように蒸着速度約６
〜８Å／ｓｅｃで形成した。なお、二酸化チタンの薄膜
形成時には実施例２の場合と同じ条件でイオンビームを
シリコン基板に照射しながら形成し、硫化亜鉛の薄膜形
成時には実施例１の場合と同じ条件で電子ビームをシリ
コン基板に照射しながら形成した。The conditions for forming each layer are as follows. The ion beam modified layer was formed in the same manner as in Example 1, and a modified layer having a thickness of about 80 Å was formed on the surface of the silicon substrate. Next, titanium dioxide having an optical film thickness of about 200Å was formed at a deposition rate of about 4 to 5Å / sec. Next, zinc sulfide is added to the titanium dioxide layer with an optical film thickness of λ / 4.
The deposition rate is about 6 so that the thickness is (λ = 6000 nm).
It was formed at ~ 8Å / sec. When the titanium dioxide thin film was formed, the silicon substrate was irradiated with an ion beam under the same conditions as in Example 2, and when the zinc sulfide thin film was formed, an electron beam was applied to the silicon substrate under the same conditions as in Example 1. It was formed while irradiating.
【００４１】本実施例の反射防止膜の分光反射特性（１
面当たり）を図４において曲線ｃで示す。図からわかる
ように中心波長（λ＝６０００ｎｍ）で反射率は５％以
下であり、赤外反射防止膜として優れた特性が得られ
た。Spectral reflection characteristics of the antireflection film of this embodiment (1
(Per surface) is shown by the curve c in FIG. As can be seen from the figure, the reflectance was 5% or less at the central wavelength (λ = 6000 nm), and excellent characteristics as an infrared antireflection film were obtained.
【００４２】本実施例の赤外反射防止膜の基板との密着
性および耐久性を確認するために次の項目の試験を行っ
た。 （ａ）剥離試験：温度４０℃、相対湿度８５％の高温・
高湿雰囲気中に２５０時間放置した後、粘着テープをシ
リコン基板表面に密着し、引きはがす。 （ｂ）高温試験：温度８０℃の雰囲気中に２５０時間放
置する。 （ｃ）低温試験：温度−２０℃の雰囲気中に２５０時間
放置する。 （ｄ）熱衝撃試験：温度−３０℃、８０℃の低温・高温
雰囲気中に交互に３０分間ずつ放置を約２４時間くり返
す。 （ｅ）高温・高湿試験：温度６０℃、相対湿度９０％の
高温・高湿雰囲気中に１６８時間放置する。 （ｆ）硫化水素ガス試験：硫化水素濃度３ｐｐｍ、温度
４０℃の雰囲気中に２４時間放置する。 （ｇ）亜硫酸ガス試験：亜硫酸ガス濃度１０ｐｐｍ、温
度４０℃の雰囲気中に２４時間放置する。In order to confirm the adhesion and durability of the infrared antireflection film of this example with the substrate, the following tests were conducted. (A) Peeling test: high temperature of 40 ° C. and relative humidity of 85%
After leaving in a high humidity atmosphere for 250 hours, the adhesive tape is adhered to the surface of the silicon substrate and peeled off. (B) High temperature test: left in an atmosphere at a temperature of 80 ° C. for 250 hours. (C) Low temperature test: left in an atmosphere at a temperature of −20 ° C. for 250 hours. (D) Thermal shock test: The sample is left to stand in a low temperature / high temperature atmosphere at temperatures of −30 ° C. and 80 ° C. for 30 minutes alternately for about 24 hours. (E) High-temperature / high-humidity test: left in a high-temperature / high-humidity atmosphere having a temperature of 60 ° C. and a relative humidity of 90% for 168 hours. (F) Hydrogen sulfide gas test: Leave for 24 hours in an atmosphere having a hydrogen sulfide concentration of 3 ppm and a temperature of 40 ° C. (G) Sulfurous acid gas test: It is left for 24 hours in an atmosphere having a sulfurous acid gas concentration of 10 ppm and a temperature of 40 ° C.
【００４３】試験結果は（表３）に示す通りである。The test results are shown in (Table 3).
【００４４】[0044]
【表３】 [Table 3]
【００４５】（表３）からわかるように本発明の赤外反
射防止膜は基板との密着性および耐久性に優れている。
シリコン改質層と硫化亜鉛層の間に二酸化チタン層を設
けることにより実施例１より基板との密着性が向上し
た。また、この波長領域では硫化亜鉛と二酸化チタンの
屈折率はほぼ同じであり、約百Å程度の膜厚であれば波
長約１１０００ｎｍ（１１μｍ）までは二酸化チタンの
吸収は無視できる。As can be seen from (Table 3), the infrared antireflection film of the present invention has excellent adhesion to the substrate and durability.
By providing the titanium dioxide layer between the silicon modified layer and the zinc sulfide layer, the adhesion to the substrate was improved as compared with Example 1. Further, in this wavelength region, zinc sulfide and titanium dioxide have almost the same refractive index, and absorption of titanium dioxide is negligible up to a wavelength of about 11000 nm (11 μm) if the film thickness is about 100 Å.
【００４６】[0046]
【発明の効果】以上のように本発明によれば、シリコン
基板表面に、シリコン改質層と硫化亜鉛層からなる層を
形成して赤外反射防止膜となすので基板との密着性およ
び耐久性に優れた赤外反射防止膜を実現することができ
る。As described above, according to the present invention, a layer composed of a silicon modified layer and a zinc sulfide layer is formed on the surface of a silicon substrate to form an infrared anti-reflection film, so that the adhesion and durability to the substrate are improved. It is possible to realize an infrared antireflection film having excellent properties.
【００４７】また、使用波長域で透明であれば酸化物誘
電体を硫化亜鉛に代わって使用することができる。前記
実施例では酸化物誘電体として二酸化チタンを使用した
が、二酸化ジルコニウム、酸化鉛等も使用できる。If it is transparent in the used wavelength range, the oxide dielectric can be used in place of zinc sulfide. Titanium dioxide was used as the oxide dielectric in the above embodiments, but zirconium dioxide, lead oxide, etc. can also be used.
【００４８】また、シリコン改質層と硫化亜鉛層の間に
酸化物誘電体層を設けることにより、基板との密着性を
向上させることができる。シリコン改質層は基板にイオ
ンビームを照射することによって形成できる。硫化亜鉛
膜層の形成時には電子ビームを基板に照射しながら形成
することにより、また、酸化物誘電体膜層の形成時には
イオンビームを照射しながら形成することにより緻密な
膜が得られる。Further, by providing an oxide dielectric layer between the silicon modified layer and the zinc sulfide layer, the adhesion with the substrate can be improved. The silicon modified layer can be formed by irradiating the substrate with an ion beam. A dense film can be obtained by forming the zinc sulfide film layer while irradiating the substrate with an electron beam and by forming the oxide dielectric film layer while irradiating with the ion beam.
【図１】本発明の実施例１の赤外反射防止膜の構成を示
す断面図FIG. 1 is a cross-sectional view showing the structure of an infrared antireflection film of Example 1 of the present invention.
【図２】本発明の実施例２の赤外反射防止膜の構成を示
す断面図FIG. 2 is a cross-sectional view showing the structure of an infrared antireflection film of Example 2 of the present invention.
【図３】本発明の実施例３の赤外反射防止膜の構成を示
す断面図FIG. 3 is a sectional view showing the structure of an infrared antireflection film of Example 3 of the present invention.
【図４】本発明の実施例の光学特性図FIG. 4 is an optical characteristic diagram of an example of the present invention.
【図５】従来の赤外反射防止膜の構成図FIG. 5 is a configuration diagram of a conventional infrared antireflection film.
１１、２１、３１、５１ シリコン基板 １２、２２、３２ シリコン改質層 １３、２４、５２ 硫化亜鉛層 ２３、３３ 二酸化チタン層 11, 21, 31, 51 Silicon substrate 12, 22, 32 Silicon modified layer 13, 24, 52 Zinc sulfide layer 23, 33 Titanium dioxide layer
Claims (6)
外反射防止膜であって、基板側から数えて第１層目はシ
リコン改質層であり、第２層目は硫化亜鉛層である赤外
反射防止膜。1. An infrared antireflection film having a two-layer structure formed on the surface of a silicon substrate, wherein the first layer is a silicon modified layer and the second layer is a zinc sulfide layer when counted from the substrate side. An infrared antireflection film.
外反射防止膜であって、基板側から数えて第１層目はシ
リコン改質層であり、第２層目は酸化物誘電体層である
赤外反射防止膜。2. An infrared antireflection film having a two-layer structure formed on the surface of a silicon substrate, wherein the first layer is a silicon modified layer and the second layer is an oxide dielectric when counted from the substrate side. Infrared antireflection film that is a layer.
外反射防止膜であって、基板側から数えて第１層目はシ
リコン改質層であり、第２層目は酸化物誘電体層であ
り、第３層目は硫化亜鉛層である赤外反射防止膜。3. An infrared antireflection film having a three-layer structure formed on the surface of a silicon substrate, wherein the first layer counted from the substrate side is a silicon modified layer and the second layer is an oxide dielectric. The third layer is an infrared antireflection film which is a zinc sulfide layer.
表面に改質層を形成し、その後、電子ビームをシリコン
基板に照射しながら硫化亜鉛の層を形成する赤外反射防
止膜の形成方法。4. A method for forming an infrared antireflection film, which comprises forming a modified layer on the surface of a silicon substrate by irradiating an ion beam and then forming a zinc sulfide layer while irradiating the silicon substrate with an electron beam.
表面に改質層を形成し、その後、イオンビームをシリコ
ン基板に照射しながら酸化物誘電体層を形成する赤外反
射防止膜の形成方法。5. A method for forming an infrared antireflection film, which comprises forming a modified layer on the surface of a silicon substrate by irradiation with an ion beam, and then forming an oxide dielectric layer while irradiating the silicon substrate with the ion beam.
表面に改質層を形成し、その後、イオンビームをシリコ
ン基板に照射しながら酸化物誘電体層を形成し、その
後、電子ビームをシリコン基板に照射しながら硫化亜鉛
層を形成する赤外反射防止膜の形成方法。6. A modified layer is formed on the surface of a silicon substrate by irradiation with an ion beam, and then an oxide dielectric layer is formed while irradiating the silicon substrate with the ion beam, and then the silicon substrate is irradiated with an electron beam. While forming a zinc sulfide layer, a method for forming an infrared antireflection film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05163402A JP3136845B2 (en) | 1993-07-01 | 1993-07-01 | Infrared antireflection film and method of forming the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05163402A JP3136845B2 (en) | 1993-07-01 | 1993-07-01 | Infrared antireflection film and method of forming the same |
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| Publication Number | Publication Date |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017223914A (en) * | 2016-06-17 | 2017-12-21 | 株式会社ニデック | Silicon substrate with infrared functional film |
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