JPH06331809A - Metallic mirror and its production - Google Patents
Metallic mirror and its productionInfo
- Publication number
- JPH06331809A JPH06331809A JP5145703A JP14570393A JPH06331809A JP H06331809 A JPH06331809 A JP H06331809A JP 5145703 A JP5145703 A JP 5145703A JP 14570393 A JP14570393 A JP 14570393A JP H06331809 A JPH06331809 A JP H06331809A
- Authority
- JP
- Japan
- Prior art keywords
- film
- protective film
- substrate
- reflective film
- metal mirror
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Optical Elements Other Than Lenses (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カメラ、複写機、プリ
ンタ等の光学機械に用いられる金属ミラーおよびその製
造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 a metal mirror used in an optical machine such as a camera, a copying machine and a printer, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来、カメラ、複写機、プリンタ等の光
学機械に用いられる金属ミラーは、プラスチック等で作
られた基体の表面にＡｌ，Ｃｕ，Ａｕ，Ａｇ等の高反射
率を有する金属の反射膜を成膜し、その上に誘電体材料
の保護膜や増反射膜を設けたものが一般的である。特
に、Ａｌ等の腐蝕しやすい金属からなる反射膜は、時間
とともに反射率が低下する性質（以下、「経時的劣化特
性」という。）や膜強度および耐薬品性が低い点を補う
ために、酸化処理による酸化層の形成あるいはＳｉＯ2
やＳｉＯの保護膜を積層するなどの工夫がなされてお
り、例えば以下の例が公知である。2. Description of the Related Art Conventionally, a metal mirror used in an optical machine such as a camera, a copying machine or a printer is made of a metal such as Al, Cu, Au, Ag having a high reflectance on the surface of a substrate made of plastic or the like. Generally, a reflective film is formed, and a protective film of a dielectric material and a reflection increasing film are provided on the reflective film. In particular, a reflective film made of a metal such as Al that easily corrodes has a property of decreasing the reflectance with time (hereinafter referred to as “degradation property over time”), a film strength and a low chemical resistance. Formation of oxide layer by oxidation treatment or SiO 2
A device such as laminating a protective film of SiO 2 or SiO has been made, and the following examples are known.
【０００３】１）プラスチック基体の表面に真空蒸着等
によってＡｌ，Ａｕ，Ａｇ，Ｎｉ，Ｃｒ等の反射膜を蒸
着し、その上に膜厚３〜８ｎｍのＳｉＯの保護膜を設け
る（特開昭５６−１１０９０４号公報参照）。1) A reflective film of Al, Au, Ag, Ni, Cr or the like is vapor-deposited on the surface of a plastic substrate by vacuum vapor deposition or the like, and a protective film of SiO having a thickness of 3 to 8 nm is provided thereon (Japanese Patent Laid-Open Publication No. Sho. 56-110904).
【０００４】２）透明基体の表面にＡｌの反射膜を成膜
し、次いでＳｉＯ2 膜とＴｉＯ2 膜からなる増反射膜を
加熱することなく積層したうえで大気中で加熱してＡｌ
の反射膜の表面を酸化させる（特開昭５８−４３４０２
号公報参照）。2) An Al reflection film is formed on the surface of a transparent substrate, and then a reflection enhancing film consisting of a SiO 2 film and a TiO 2 film is laminated without heating and then heated in the atmosphere to form an Al film.
The surface of the reflective film of JP-A-58-43402
(See the official gazette).
【０００５】３）基体の表面にＡｌの反射膜を成膜し、
酸素ガスの雰囲気中でＡｌの反射膜の表面を酸化させた
うえで、ＳｉＯ2 膜と、ＴｉＯ2 膜からなる増反射膜を
設ける（特開昭５８−５５９０１号公報参照）。3) Form a reflective film of Al on the surface of the substrate,
The surface of the Al reflection film is oxidized in an atmosphere of oxygen gas, and then a reflection enhancing film composed of a SiO 2 film and a TiO 2 film is provided (see Japanese Patent Laid-Open No. 58-59001).
【０００６】４）Ａｌの反射膜の表面を酸化させて１０
ｎｍ〜２０ｎｍのＡｌ2 Ｏ3 層を形成し、その上にＳｉ
Ｏ2 の保護膜を設ける（特開昭５８−７２１０６号公報
参照）。4) 10 by oxidizing the surface of the Al reflection film
nm to 20 nm Al 2 O 3 layer is formed, and Si is formed thereon.
A protective film of O 2 is provided (see Japanese Patent Laid-Open No. 58-72106).
【０００７】５）基体の表面にＡｌの反射膜を蒸着した
のち、光学膜厚０．０３λ0 〜０．１５λ0 （λ0 は設
計波長）の珪素酸化物あるいはフッ化マグネシウムの保
護膜を設ける（特開平２−５０１０４号公報参照）。5) After depositing a reflective film of Al on the surface of the substrate, a protective film of silicon oxide or magnesium fluoride having an optical film thickness of 0.03λ 0 to 0.15λ 0 (λ 0 is a design wavelength) is provided. (See Japanese Patent Application Laid-Open No. 2-50104).
【０００８】６）合成樹脂の基体の表面にＳｉＯの保護
膜を設け、その上に反射膜を蒸着したのち、さらに膜厚
０．０５〜１．０μｍのＳｉＯの保護膜を設ける（特開
平４−２３５５０２号公報参照）。6) An SiO protective film is provided on the surface of a synthetic resin substrate, a reflective film is vapor-deposited on the SiO protective film, and then an SiO protective film having a thickness of 0.05 to 1.0 μm is further provided (Japanese Patent Laid-Open Publication No. 4 (1999) -1999). -235502 gazette).
【０００９】７）合成樹脂裏面反射鏡において、基板側
から珪素酸化物の保護膜、Ａｌ反射膜、膜厚１０〜１０
０ｎｍのＳｉＯ2 の保護膜を積層する（特開平４−２４
０８０２号公報参照）。7) In a synthetic resin rear surface reflecting mirror, a silicon oxide protective film, an Al reflecting film, and a film thickness of 10 to 10 are provided from the substrate side.
A 0 nm SiO 2 protective film is laminated (JP-A-4-24).
0802).
【００１０】[0010]
【発明が解決しようとする課題】しかしながら上記従来
の技術によれば、ＳｉＯ2 やＳｉＯ等を主成分とする保
護膜のみでは水分の透過を完全に防ぐことができないた
めに反射膜の経時的劣化特性の改善が充分ではない。ま
た、反射膜の表面を酸化する方法は、酸化する工程が複
雑であったり、反射膜の反射率が初めから低いという難
点があった。すなわち、１）の方法は単にＳｉＯの保護
膜を設けただけであるため、水分の透過によるＡｌの反
射膜の経時的劣化特性を充分に改質できず、２）ないし
４）の方法は、Ａｌの反射膜の表面に水分に対して高い
不透過性を有するＡｌの酸化膜を形成させることで経時
的劣化特性を改質するものであるが、Ａｌの反射膜の表
面を酸化するために加熱またはプラズマ処理を必要とし
たり、あるいはＡｌの反射膜の表面を酸化するために酸
素を導入したのちに保護膜の成膜のために再び成膜室を
減圧する工程を要し、生産性が低いうえに、基体の材料
が限定されたり、プラズマ処理によるダメージや汚染等
のおそれもある。５）の方法は珪素酸化物やフッ化マグ
ネシウムの保護膜の膜厚を薄くすることによってＡｌの
反射膜との境界面にＡｌの酸化膜を形成させるものであ
り、２）ないし４）の方法と同じく経時的劣化特性の改
質は充分であるが、保護膜の膜厚が設計波長（６５０ｎ
ｍ）から算出すると１３〜６５ｎｍであり、このために
反射率が初めから低いという難点がある。また、６）お
よび７）の方法は珪素酸化物の保護膜のみでは水分に対
する不透過性が充分ではないために、時間がたつとＡｌ
の反射膜の腐蝕が進み反射率が低下する。However, according to the above-mentioned conventional technique, the permeation of moisture cannot be completely prevented only by the protective film containing SiO 2 or SiO as a main component, so that the reflective film is deteriorated with time. The characteristics are not sufficiently improved. Further, the method of oxidizing the surface of the reflective film has a drawback that the oxidation process is complicated and the reflectance of the reflective film is low from the beginning. That is, since the method 1) is merely provided with a protective film of SiO, the deterioration characteristics of the Al reflective film over time due to the transmission of moisture cannot be sufficiently modified, and the methods 2) to 4) are The deterioration property over time is modified by forming an Al oxide film having a high impermeability to water on the surface of the Al reflection film. However, in order to oxidize the surface of the Al reflection film, Heat or plasma treatment is required, or oxygen is introduced to oxidize the surface of the Al reflection film, and then a step of depressurizing the film formation chamber again for film formation of the protective film is required. In addition to being low, the material of the substrate is limited, and there is a risk of damage and contamination due to plasma treatment. The method 5) is to form an Al oxide film on the interface with the Al reflection film by reducing the thickness of the protective film of silicon oxide or magnesium fluoride. As with the above, modification of the deterioration characteristics with time is sufficient, but the thickness of the protective film is set to the design wavelength (650 n
It is 13 to 65 nm when calculated from m), and therefore there is a drawback that the reflectance is low from the beginning. Further, in the methods 6) and 7), since the impermeability to moisture is not sufficient only with the protective film of silicon oxide, Al may be used with time.
Corrosion of the reflective film of 1) progresses and the reflectance decreases.
【００１１】本発明は、上記従来の技術の有する問題点
に鑑みてなされたものであり、極めて高い反射率を有
し、該反射率が時間とともに低下するおそれがないうえ
に、製造工程が簡単で安価である金属ミラーおよびその
製造方法を提供することを目的とするものである。The present invention has been made in view of the above problems of the prior art, has an extremely high reflectance, there is no fear that the reflectance will decrease with time, and the manufacturing process is simple. It is an object of the present invention to provide a metal mirror which is inexpensive and inexpensive and a method for manufacturing the same.
【００１２】[0012]
【課題を解決するための手段】上記の目的を達成するた
めに本発明の金属ミラーは、基体の表面に成膜された金
属の反射膜と、該反射膜の表面に積層された膜厚０．１
から１０ｎｍの範囲の保護膜を有し、前記反射膜の表面
が酸化されていることを特徴とする。In order to achieve the above object, the metal mirror of the present invention has a metal reflective film formed on the surface of a substrate and a film thickness of 0 laminated on the surface of the reflective film. .1
From 10 nm to 10 nm, and the surface of the reflection film is oxidized.
【００１３】また本発明の方法は、減圧された成膜室で
基体の表面に金属の反射膜を成膜する工程と、前記反射
膜の表面に０．１から１０ｎｍの範囲の膜厚と所定のパ
ッキング密度を有する保護膜を成膜する工程と、成膜後
から前記成膜室に酸素を導入して前記反射膜の表面を酸
化させる工程からなることを特徴とする。Further, the method of the present invention comprises the step of forming a metal reflection film on the surface of the substrate in a reduced pressure film formation chamber, and a film thickness in the range of 0.1 to 10 nm and a predetermined thickness on the surface of the reflection film. And a step of forming a protective film having a packing density of 1 and a step of oxidizing oxygen on the surface of the reflective film by introducing oxygen into the film forming chamber after the film formation.
【００１４】[0014]
【作用】上記金属ミラーによれば、反射膜の表面が酸化
されて水分を透過しない酸化層が形成されているため、
反射膜の腐蝕を防ぐことができる。また、保護膜の膜厚
が０．１から１０ｎｍの範囲であるため、反射膜の表面
硬度を向上させるには充分であり、しかも反射膜の反射
率が保護膜によって大幅に損なわれるおそれがない。保
護膜の膜厚が０．１ｎｍより小さい場合は強度が不十分
であり、保護膜の膜厚が１０ｎｍより大きい場合は反射
率が低下する。また、保護膜の膜厚が薄いため、これを
透過する酸素によって速やかに反射膜の表面を酸化させ
ることができ、従って、酸化層が形成される前に水分が
反射膜に侵入するのを防ぐことができる。その結果、酸
化膜が形成される前に水分が侵入し反射膜の腐蝕が進む
おそれもない。また、保護膜を成膜後に成膜室に酸素を
導入し、反射膜の表面を酸化させたうえでそのまま大気
に開放できるため、製造工程が簡単である。According to the metal mirror described above, since the surface of the reflective film is oxidized to form an oxide layer that does not allow water to pass through,
Corrosion of the reflective film can be prevented. Further, since the thickness of the protective film is in the range of 0.1 to 10 nm, it is sufficient to improve the surface hardness of the reflective film, and the reflectance of the reflective film is not significantly impaired by the protective film. . If the thickness of the protective film is smaller than 0.1 nm, the strength is insufficient, and if the thickness of the protective film is larger than 10 nm, the reflectance decreases. Further, since the thickness of the protective film is thin, the surface of the reflective film can be quickly oxidized by oxygen that permeates the protective film, thus preventing moisture from entering the reflective film before the oxide layer is formed. be able to. As a result, there is no risk that moisture will enter before the oxide film is formed and the reflection film will be corroded. Further, after the protective film is formed, oxygen can be introduced into the film forming chamber to oxidize the surface of the reflective film and then directly open to the atmosphere, so that the manufacturing process is simple.
【００１５】また、上記方法によれば、保護膜の成膜中
にパッキング密度が所定の値になるように堆積速度を制
御し、保護膜の成膜後に成膜室に酸素を導入する。パッ
キング密度を０．６ないし０．９に制御することで反射
膜の表面を極めて迅速に酸化することができる。この
後、成膜室をそのまま大気に解放し、製品を取りだすこ
とができる。According to the above method, the deposition rate is controlled so that the packing density becomes a predetermined value during the formation of the protective film, and oxygen is introduced into the film forming chamber after the protective film is formed. By controlling the packing density to 0.6 to 0.9, the surface of the reflective film can be oxidized very quickly. After that, the film formation chamber can be directly opened to the atmosphere and the product can be taken out.
【００１６】[0016]
【実施例】本発明の実施例を図面に基づいて説明する。Embodiments of the present invention will be described with reference to the drawings.
【００１７】第１実施例 図１は、第１実施例に用いる蒸着装置を示すもので、該
蒸着装置は、排気口１ａを有する成膜室である真空槽１
と、これに酸素ガス等の反応ガスを導入するための反応
ガス導入ライン１ｂと、真空槽１内において図示しない
回転装置によって回転される傘形の基板ホルダ２と、こ
れに保持された基体である基板Ｗに向かってそれぞれ蒸
気を発生させる第１および第２の蒸発源３，４と、基板
Ｗに蒸着される薄膜の堆積速度をモニタする水晶センサ
からなる膜厚モニタ５を有する。なお、第１の蒸発源３
は電子銃によって加熱されてＡｌの蒸気を発生し、第２
の蒸発源４は抵抗加熱によって加熱されて珪素酸化物Ｓ
ｉＯx （１＜ｘ＜２）（以下、「不飽和珪素酸化物」と
いう。）の蒸気を発生する。また、排気口１ａは図示し
ない真空ポンプおよび大気導入ライン１ｃに交互に接続
される。First Embodiment FIG. 1 shows a vapor deposition apparatus used in the first embodiment. The vapor deposition apparatus is a vacuum chamber 1 which is a film forming chamber having an exhaust port 1a.
A reaction gas introduction line 1b for introducing a reaction gas such as oxygen gas, an umbrella-shaped substrate holder 2 rotated by a rotation device (not shown) in the vacuum chamber 1, and a substrate held by the substrate holder 2. It has first and second evaporation sources 3 and 4 for respectively generating vapor toward a certain substrate W, and a film thickness monitor 5 composed of a quartz sensor for monitoring a deposition rate of a thin film deposited on the substrate W. The first evaporation source 3
Is heated by an electron gun to generate Al vapor,
Of the silicon oxide S
The vapor of iO x (1 <x <2) (hereinafter referred to as “unsaturated silicon oxide”) is generated. Further, the exhaust ports 1a are alternately connected to a vacuum pump (not shown) and the air introduction line 1c.
【００１８】第１実施例の金属ミラーは以下のように製
作される。The metal mirror of the first embodiment is manufactured as follows.
【００１９】ポリカーボネート製の基板Ｗを基板ホルダ
２へ装着して真空槽１を１×１０-3Ｐａ以下の圧力に排
気したのち、反応ガス導入ライン１ｂから酸素ガスを導
入して１×１０-2Ｐａの圧力に調整し、この真空度で第
２の蒸発源４を加熱して膜厚８５ｎｍの不飽和珪素酸化
物のアンダーコートを成膜し、次いで、１×１０-3Ｐａ
の真空度で第１の蒸発源３を加熱して膜厚１００ｎｍの
Ａｌの反射膜を積層し、続いて、前述と同様に酸素ガス
を導入して１．５×１０-2Ｐａの真空度に調整し、この
真空度で第２の蒸発源４を加熱して膜厚５ｎｍの不飽和
珪素酸化物の保護膜を積層した。これらのアンダーコー
ト、反射膜および保護膜の蒸着はすべて基板Ｗを加熱す
ることなく連続的に行われ、保護膜の堆積速度は膜厚モ
ニタ５でモニタし、ほぼ０．５ｎｍ／秒に制御された。
保護膜の成膜後、反応ガス導入ライン１ｂから酸素ガス
を導入し、真空槽１の圧力を約１００Ｐａまで上昇させ
たうえで大気導入ライン１ｃを開放し、空気を導入し
た。なお、前述の堆積速度で成膜された保護膜のパッキ
ング密度は０．８８以下であり、また、屈折率は４００
ｎｍの波長でほぼ１．４８であった。After a substrate W made of polycarbonate is mounted on the substrate holder 2 and the vacuum chamber 1 is evacuated to a pressure of 1 × 10 −3 Pa or less, oxygen gas is introduced from the reaction gas introduction line 1b to 1 × 10 −. The pressure was adjusted to 2 Pa, the second evaporation source 4 was heated at this degree of vacuum to form an unsaturated silicon oxide undercoat having a film thickness of 85 nm, and then 1 × 10 −3 Pa
The first evaporation source 3 is heated at a vacuum degree of 1 to stack a reflective film of Al having a film thickness of 100 nm, and then oxygen gas is introduced in the same manner as described above to obtain a vacuum degree of 1.5 × 10 -2 Pa. Then, the second evaporation source 4 was heated at this degree of vacuum to stack a protective film of unsaturated silicon oxide having a film thickness of 5 nm. Deposition of these undercoat, reflection film and protective film is all performed continuously without heating the substrate W, and the deposition rate of the protective film is monitored by the film thickness monitor 5 and controlled to about 0.5 nm / sec. It was
After forming the protective film, oxygen gas was introduced from the reaction gas introduction line 1b, the pressure in the vacuum chamber 1 was increased to about 100 Pa, the atmosphere introduction line 1c was opened, and air was introduced. The packing density of the protective film formed at the above-described deposition rate is 0.88 or less, and the refractive index is 400.
It was approximately 1.48 at a wavelength of nm.
【００２０】図２は本実施例の金属ミラーの入射角４５
度における分光反射率を示すグラフである。この図から
解るように、本実施例の金属ミラーの製造直後の反射率
（以下、「初期反射率」という。）は波長４００ｎｍに
おいて極めて高くかつ広い波長領域において均一であ
る。また後述する製造直後の品質評価テスト（以下、
「初期評価テスト」という。）の結果、本実施例の金属
ミラーは、製造直後の状態において外観、耐薬品性、耐
環境性のすべてにおいて良好であり、また、外観および
反射率の経時的変化を評価する品質評価テスト（以下、
「経時評価テスト」という。）の結果、外観および反射
率のいずれも大きく変化するおそれがないことが判明し
た。FIG. 2 shows the incident angle 45 of the metal mirror of this embodiment.
It is a graph which shows the spectral reflectance in degrees. As can be seen from this figure, the reflectance of the metal mirror of this example immediately after its production (hereinafter referred to as “initial reflectance”) is extremely high at a wavelength of 400 nm and uniform in a wide wavelength range. In addition, the quality evaluation test immediately after manufacturing (described below,
It is called "initial evaluation test". ), The metal mirror of this example has good appearance, chemical resistance, and environmental resistance in the state immediately after manufacturing, and a quality evaluation test for evaluating changes over time in appearance and reflectance ( Less than,
It is called "evaluation test over time". As a result, it was found that neither the appearance nor the reflectance is significantly changed.
【００２１】なお、パッキング密度とは、真空槽で成膜
された薄膜の単位体積当りの質量とこれを大気中に取り
だしたときの同薄膜の質量との比で表わされるものであ
り、予め、真空槽の膜厚モニタによる堆積速度とパッキ
ング密度の関係を調べておき、前述のように、成膜中の
堆積速度を制御することでパッキング密度を所定の値に
制御するのが一般的である。The packing density is represented by the ratio of the mass per unit volume of the thin film formed in the vacuum chamber to the mass of the thin film when it is taken out into the atmosphere, and is previously set. Generally, the relationship between the deposition rate and the packing density is checked by a film thickness monitor in a vacuum chamber, and as described above, the packing rate is generally controlled by controlling the deposition rate during film formation. .
【００２２】次に実験によれば、保護膜の膜厚が０．１
から１０ｎｍの範囲でパッキング密度が０．６ないし
０．９であれば、酸素の浸透が極めて迅速に行われ、真
空槽の残留水分が保護膜を通って反射膜の表面に到達す
る前に、該表面が酸化されて水分に対して不透過性を有
する酸化層が形成されることが判明した。また、保護膜
が珪素の酸化物、窒化物あるいは炭化物で作られていれ
ば、これらは水分との親和性がよいために水分を吸収
し、水分が反射膜の表面に到達するのを防ぐのに役立
つ。なお、これらが不飽和化合物であればより一層水分
との親和性が増す。さらに、前記アンダーコート、反射
膜および保護膜の成膜はすべて基板を加熱することなく
行われるのが望ましい。その理由は、加熱によって真空
槽内の残留水分が活性化して反射膜と結合しやすくなる
からである。Next, according to experiments, the thickness of the protective film was 0.1.
If the packing density is 0.6 to 0.9 in the range from 10 nm to 10 nm, the penetration of oxygen is extremely rapid, and the residual water in the vacuum chamber passes through the protective film and reaches the surface of the reflective film. It was found that the surface was oxidized to form an oxide layer impermeable to moisture. If the protective film is made of silicon oxide, nitride, or carbide, they have a good affinity with water and therefore absorb water, preventing water from reaching the surface of the reflective film. To help. If these are unsaturated compounds, the affinity for water is further increased. Further, it is desirable that the undercoat, the reflective film and the protective film are all formed without heating the substrate. The reason is that the residual water in the vacuum chamber is activated by heating and is easily bonded to the reflective film.
【００２３】次に比較のために以下の金属ミラーを製作
した。Next, the following metal mirrors were manufactured for comparison.
【００２４】第１比較例 保護膜の膜厚をほぼ１５ｎｍにするとともに保護膜の成
膜後直ちに大気導入ライン１ｃを開放して空気を導入し
た以外は、すべて第１実施例と同様の方法でアンダーコ
ートと反射膜と保護膜を成膜した。初期評価テストの結
果、初期反射率がやや劣り、加えて、経時評価テストの
結果、反射率の低下が著しいうえに反射膜の腐蝕による
数μ程度の斑点が現れる等、外観の劣化もみられた。First Comparative Example All were the same as in the first example except that the thickness of the protective film was set to about 15 nm and the air introduction line 1c was opened immediately after the protective film was formed to introduce air. An undercoat, a reflective film and a protective film were formed. As a result of the initial evaluation test, the initial reflectance was slightly inferior.In addition, the deterioration of the appearance such as a few μ spots due to the corrosion of the reflective film was observed in addition to the significant deterioration of the reflectance as a result of the evaluation test with time. .
【００２５】第２比較例 保護膜の膜厚をほぼ５ｎｍにするとともにその成膜中に
酸素ガスを導入することなく、真空槽内の圧力を１×１
０-3Ｐａに調整し、また成膜後直ちに空気を導入した以
外すべて第１実施例と同様の方法で金属ミラーを製作し
た。保護膜の屈折率はほぼ１．８、パッキング密度はほ
ぼ０．９６であった。初期評価テストの結果は良好であ
ったが、経時評価テストの結果、Ａｌの反射膜の腐蝕の
ために斑点状のクモリが発生し、外観および反射率の劣
化が著しいことが判明した。この理由は、保護膜のパッ
キング密度が高いために反射膜の酸化が遅く、水分が侵
入したためと推測される。Second Comparative Example The thickness of the protective film was set to about 5 nm and the pressure in the vacuum chamber was set to 1 × 1 without introducing oxygen gas during the film formation.
A metal mirror was manufactured in the same manner as in Example 1 except that the pressure was adjusted to 0 -3 Pa and air was introduced immediately after the film formation. The protective film had a refractive index of about 1.8 and a packing density of about 0.96. The results of the initial evaluation test were good, but the results of the time-dependent evaluation test revealed that spot-like cloud was generated due to corrosion of the Al reflection film, and the appearance and reflectance were significantly deteriorated. It is presumed that the reason is that the protective film has a high packing density, so the oxidation of the reflective film is slow and the moisture invades.
【００２６】第３比較例 保護膜の材料をＳｉＯ2 、膜厚を約５ｎｍにするととも
にその成膜中に酸素ガスを導入することなく、真空槽内
の圧力を１×１０-3Ｐａに調整し、また成膜後直ちに空
気を導入した以外すべて第１実施例と同様の方法で金属
ミラーを製作した。保護膜の屈折率はほぼ１．４５、パ
ッキング密度はほぼ０．９４であった。初期評価テスト
の結果は良好であったが経時評価テストの結果、Ａｌの
反射膜の腐蝕によるクモリが発生し、外観および反射率
の劣化が著しいことが判明した。この理由は、保護膜の
材料が飽和酸化物のＳｉＯ2 であるうえにパッキング密
度が高いために反射膜の酸化が遅く、水分が侵入したた
めと考えられる。Third Comparative Example SiO 2 was used as the material for the protective film, the film thickness was set to about 5 nm, and the pressure in the vacuum chamber was adjusted to 1 × 10 −3 Pa without introducing oxygen gas during the film formation. In addition, a metal mirror was manufactured in the same manner as in Example 1 except that air was introduced immediately after the film formation. The protective film had a refractive index of about 1.45 and a packing density of about 0.94. The result of the initial evaluation test was good, but the result of the time-dependent evaluation test revealed that clouding occurred due to corrosion of the Al reflection film, and the appearance and reflectance were significantly deteriorated. It is considered that the reason for this is that the protective film is made of SiO 2 which is a saturated oxide, and the packing density is high, so that the oxidation of the reflective film is slow and moisture penetrates.
【００２７】第４比較例 保護膜の膜厚の成膜中に真空槽の圧力を１×１０-2Ｐａ
に調整した以外は第１実施例と同様の方法で金属ミラー
を製作した。保護膜の屈折率は４００ｎｍの波長で約
１．５５、パッキング密度は０．８８以下であった。初
期評価テストおよび経時評価テストの結果は第１実施例
とほぼ同様であったが、反射率の経時的劣化がやや大き
いという欠点がある。保護膜の屈折率が１．５０を越え
ていることが原因であると見られる。Fourth Comparative Example The pressure in the vacuum chamber was set to 1 × 10 -2 Pa during the film formation of the protective film.
A metal mirror was manufactured in the same manner as in the first embodiment except that the adjustment was made to 1. The protective film had a refractive index of about 1.55 at a wavelength of 400 nm and a packing density of 0.88 or less. The results of the initial evaluation test and the evaluation test with time were almost the same as those of the first embodiment, but there was a drawback that the deterioration of the reflectance with time was rather large. It seems that the cause is that the refractive index of the protective film exceeds 1.50.
【００２８】第２実施例 第１実施例の膜厚５ｎｍの不飽和珪素酸化物の保護膜に
替えて、膜厚５ｎｍの不飽和珪素窒化物ＳｉＮx の保護
膜を有する金属ミラーを製作した。アンダーコートと反
射膜の成膜方法は第１実施例と同様であり、保護膜は、
真空槽内に酸素ガスを導入して１．５×１０-2Ｐａの真
空度に調整し、蒸発材料を電子銃によって加熱気化させ
て成膜し、その後酸素ガスを導入して真空槽の圧力を１
０2 Ｐａまで上昇させたうえで大気開放を行った。保護
膜の屈折率は４００ｎｍの波長で約２．０５、パッキン
グ密度は０．８６以下であった。初期評価テストおよび
経時評価テストの結果はすべて第１実施例と同様に良好
であった。Second Example A metal mirror having a 5 nm thick protective film of unsaturated silicon nitride SiN x was produced in place of the 5 nm thick protective film of unsaturated silicon oxide of the first example. The method of forming the undercoat and the reflective film is the same as in the first embodiment, and the protective film is
Oxygen gas was introduced into the vacuum chamber to adjust the degree of vacuum to 1.5 × 10 -2 Pa, the evaporation material was heated and vaporized by an electron gun to form a film, and then oxygen gas was introduced to the pressure of the vacuum chamber. 1
After raising the pressure to 0 2 Pa, the atmosphere was released. The refractive index of the protective film was about 2.05 at a wavelength of 400 nm, and the packing density was 0.86 or less. The results of the initial evaluation test and the aging evaluation test were all good as in the first embodiment.
【００２９】第３実施例 第１実施例の膜厚５ｎｍの不飽和珪素酸化物の保護膜に
替えて、膜厚５ｎｍの不飽和珪素炭化物ＳｉＣの保護膜
を有する金属ミラーを製作した。アンダーコートと反射
膜の成膜方法は第１実施例と同様であり、保護膜は、真
空槽内に酸素ガスを導入して１．５×１０-2Ｐａの真空
度に調整し、蒸発材料を電子銃によって加熱気化させて
成膜し、その後酸素ガスを導入して１０2 Ｐａまで昇圧
させたうえで大気開放を行った。保護膜の屈折率は４０
０ｎｍの波長で約２．０７、パッキング密度は０．８５
以下であった。初期評価テストおよび経時評価テストの
結果は良好であった。Third Example A metal mirror having a 5 nm-thick unsaturated silicon carbide SiC protective film in place of the 5 nm-thick unsaturated silicon oxide protective film of the first example was manufactured. The method of forming the undercoat and the reflective film is the same as that of the first embodiment, and the protective film is prepared by introducing oxygen gas into the vacuum chamber to adjust the vacuum degree to 1.5 × 10 −2 Pa and evaporating material. Was heated and vaporized by an electron gun to form a film, after which oxygen gas was introduced to raise the pressure to 10 2 Pa and then the atmosphere was opened. Refractive index of protective film is 40
About 2.07 at 0 nm wavelength, packing density 0.85
It was below. The results of the initial evaluation test and the aging evaluation test were good.
【００３０】次に、ポリカーボネート基板に替えて、Ｂ
Ｋ７光学用ガラスの基板、アクリル樹脂の基板、ポリオ
レフィン樹脂の基板を用いて第１実施例と同様の金属ミ
ラーを製作し、それぞれについて初期評価テストおよび
経時評価テストを行った。ＢＫ７光学用ガラスの基板を
用いた金属ミラーを第４実施例、アクリル樹脂の基板を
用いたものを第５実施例、ポリオレフィン樹脂の基板を
用いたものを第６実施例として、第１ないし第６実施例
の金属ミラーおよび第１ないし第４の比較例の金属ミラ
ーについて行った初期評価テストおよび経時評価テスト
の結果を表１に示す。Next, in place of the polycarbonate substrate, B
Using the K7 optical glass substrate, the acrylic resin substrate, and the polyolefin resin substrate, the same metal mirrors as those in the first embodiment were manufactured, and the initial evaluation test and the time-dependent evaluation test were performed for each. The metal mirror using the BK7 optical glass substrate is the fourth embodiment, the one using the acrylic resin substrate is the fifth embodiment, and the one using the polyolefin resin substrate is the sixth embodiment. Table 1 shows the results of the initial evaluation test and the aging evaluation test performed on the metal mirrors of the sixth example and the metal mirrors of the first to fourth comparative examples.
【００３１】[0031]
【表１】 なお、外観の評価は、目視によるクモリ、膜ワレ、膜ハ
ガレ等の異常の有無を調べることによって行い、耐薬品
性は、アルコールとフロンソルブの混合液に浸したシル
ボン紙を用いて５００ｇ／ｃｍ2 の荷重で１０往復した
ときの外観の異常を調べたものであり、耐環境性は−３
０度から６０度までの温度変化を１０工程連続して繰返
したときの外観の異常を調べたものである。経時評価テ
ストは、温度６０度、湿度９０％の環境で５００時間経
過後に外観の異常および反射率を調べたものである。[Table 1] The appearance was evaluated by visually inspecting for abnormalities such as spiders, film cracks, and film peeling. The chemical resistance was 500 g / cm 2 using sillbon paper dipped in a mixture of alcohol and CFC. Was examined for abnormal appearance after 10 reciprocations under the load of, and the environmental resistance was -3.
This is an examination of abnormalities in appearance when the temperature change from 0 to 60 degrees was repeated 10 steps in succession. The aging evaluation test is to examine abnormalities in appearance and reflectance after 500 hours have passed in an environment of a temperature of 60 degrees and a humidity of 90%.
【００３２】[0032]
【発明の効果】本発明は、上述のように構成されている
ので、以下に記載するような効果を奏する。Since the present invention is configured as described above, it has the following effects.
【００３３】極めて高い反射率を有し、該反射率が時間
とともに低下するおそれがないうえに、製造工程が簡単
で安価である金属ミラーを実現できる。It is possible to realize a metal mirror which has an extremely high reflectance, there is no fear that the reflectance will decrease with time, and the manufacturing process is simple and inexpensive.
【図１】第１実施例の金属ミラーを製作するための蒸着
装置を説明する説明図である。FIG. 1 is an explanatory diagram illustrating a vapor deposition device for manufacturing a metal mirror according to a first embodiment.
【図２】第１実施例の金属ミラーの反射率特性を示すグ
ラフである。FIG. 2 is a graph showing reflectance characteristics of the metal mirror of the first embodiment.
１ 真空槽 １ｂ 反応ガス導入ライン ２ 基板ホルダ ３ 第１の蒸発源 ４ 第２の蒸発源 ５ 膜厚モニタ 1 vacuum tank 1b reaction gas introduction line 2 substrate holder 3 first evaporation source 4 second evaporation source 5 film thickness monitor
Claims (7)
と、該反射膜の表面に積層された膜厚０．１から１０ｎ
ｍの範囲の保護膜を有し、前記反射膜の表面が酸化され
ていることを特徴とする金属ミラー。1. A metal reflective film formed on the surface of a substrate, and a film thickness of 0.1 to 10 n laminated on the surface of the reflective film.
A metal mirror having a protective film in the range of m, wherein the surface of the reflective film is oxidized.
項１記載の金属ミラー。2. The metal mirror according to claim 1, wherein the metal is Al.
素窒化物、不飽和珪素炭化物およびこれらのうちの少く
とも２つからなる混合物のうちのいずれか１つで作られ
ていることを特徴とする請求項１または２記載の金属ミ
ラー。3. The protective film is made of any one of unsaturated silicon oxides, unsaturated silicon nitrides, unsaturated silicon carbides and mixtures of at least two of these. The metal mirror according to claim 1 or 2, characterized in that.
屈折率が１．５以下の不飽和珪素酸化物で作られている
ことを特徴とする請求項１または２記載の金属ミラー。4. The metal mirror according to claim 1, wherein the protective film is made of unsaturated silicon oxide having a refractive index of 1.5 or less for light having a wavelength of 400 nm.
反射膜を成膜する工程と、前記反射膜の表面に０．１か
ら１０ｎｍの範囲の膜厚と所定のパッキング密度を有す
る保護膜を成膜する工程と、成膜後から前記成膜室に酸
素を導入して前記反射膜の表面を酸化させる工程からな
る金属ミラーの製造方法。5. A step of forming a metal reflective film on the surface of a substrate in a depressurized film forming chamber, and having a film thickness in the range of 0.1 to 10 nm and a predetermined packing density on the surface of the reflective film. A method for manufacturing a metal mirror, comprising a step of forming a protective film and a step of oxidizing the surface of the reflective film by introducing oxygen into the film forming chamber after the film is formed.
あることを特徴とする請求項５記載の金属ミラーの製造
方法。6. The method of manufacturing a metal mirror according to claim 5, wherein the packing density is 0.6 to 0.9.
連続的に行われることを特徴とする請求項５または６記
載の金属ミラーの製造方法。7. The method for producing a metal mirror according to claim 5, wherein all steps are continuously performed without heating the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14570393A JP3320148B2 (en) | 1993-05-25 | 1993-05-25 | Manufacturing method of metal mirror |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14570393A JP3320148B2 (en) | 1993-05-25 | 1993-05-25 | Manufacturing method of metal mirror |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06331809A true JPH06331809A (en) | 1994-12-02 |
| JP3320148B2 JP3320148B2 (en) | 2002-09-03 |
Family
ID=15391167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14570393A Expired - Fee Related JP3320148B2 (en) | 1993-05-25 | 1993-05-25 | Manufacturing method of metal mirror |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3320148B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112734A (en) * | 1997-06-19 | 1999-01-19 | Mitsui Chem Inc | Thin metallic film, and optical recording medium using same |
| JP2007271312A (en) * | 2006-03-30 | 2007-10-18 | Nikon Corp | Surface inspection device |
-
1993
- 1993-05-25 JP JP14570393A patent/JP3320148B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1112734A (en) * | 1997-06-19 | 1999-01-19 | Mitsui Chem Inc | Thin metallic film, and optical recording medium using same |
| JP2007271312A (en) * | 2006-03-30 | 2007-10-18 | Nikon Corp | Surface inspection device |
| JP4635939B2 (en) * | 2006-03-30 | 2011-02-23 | 株式会社ニコン | Surface inspection device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3320148B2 (en) | 2002-09-03 |
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