JPH10339802A - Optical thin film - Google Patents
Optical thin filmInfo
- Publication number
- JPH10339802A JPH10339802A JP10141792A JP14179298A JPH10339802A JP H10339802 A JPH10339802 A JP H10339802A JP 10141792 A JP10141792 A JP 10141792A JP 14179298 A JP14179298 A JP 14179298A JP H10339802 A JPH10339802 A JP H10339802A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- refractive index
- optical thin
- film
- optical
- 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.)
- Pending
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- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反射防止膜等として用
いられる光学薄膜に関し、特にプラスチックレンズ上へ
の形成に好適な光学薄膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical thin film used as an antireflection film or the like, and more particularly to an optical thin film suitable for forming on a plastic lens.
【０００２】[0002]
【従来の技術】従来、光学部品の反射防止膜としては、
屈折率が低く、可視域での吸収が少ないＭｇＦ2膜が汎
用されている。このＭｇＦ2膜は、ガラスからなる光学
部品用の反射防止膜として真空蒸着法により実用化さ
れ、今日までに至っている。しかし、真空蒸着法により
ＭｇＦ2膜を形成する場合、蒸着時及び蒸着後に高温
（２００〜４００℃）で加熱しなければ、光学的及び機
械的性能を十分に満足させることはできない。従って、
光学部品がプラスチックからなる場合、熱変形等の理由
から、強靱なＭｇＦ2膜を形成することは非常に困難で
ある。このため、現在のところＭｇＦ2膜はプラスチッ
クレンズ等には実用化されていないのが実情である。2. Description of the Related Art Conventionally, as an antireflection film for optical parts,
MgF 2 films having a low refractive index and low absorption in the visible region are widely used. This MgF 2 film has been put to practical use by a vacuum deposition method as an antireflection film for optical components made of glass, and has been used up to the present. However, when the MgF 2 film is formed by the vacuum deposition method, the optical and mechanical performances cannot be sufficiently satisfied unless heated at a high temperature (200 to 400 ° C.) during and after the deposition. Therefore,
When the optical component is made of plastic, it is very difficult to form a tough MgF 2 film due to thermal deformation and the like. Therefore, at present, the MgF 2 film is not practically used for plastic lenses and the like.
【０００３】光学薄膜を常温で形成する試みとしては、
Ｈｏｌｌａｎｄらが、”Ｌ Ｍａｒｔｉｎｕ，Ｈ Ｂｉ
ｅｄｅｒｍａｎ ａｎｄ Ｌ Ｈｏｌｌａｎｄ，Ｖａｃ
ｕｕｍ／ｖｏｌ．３５／ｎｕｍｂｅｒ １２／ｐ５３１
〜５３５／１９８５”（文献１）の中でスパッタリング
による方法について記載している。Ｈｏｌｌａｎｄら
は、この文献の中で、「１）スパッタリングガスとして
Ａｒガスを使って作成した膜ではＭｇＦ2蒸着膜と同等
の低い屈折率（ｎ＝１．３８〜１．４２）が得られる。
２）スパッタリングで形成したＭｇＦ2膜で可視域での
吸収が生じるのは、プラズマ中のＦ-イオンが基板ホル
ダ側に励起される負のプラズマポテンシャルにより反発
するため、薄膜内に取り込まれるＦ重量が不足すること
と、プラズマ中での水の解離により励起されたＯ- イオ
ンとＭｇ+ イオンとの酸化反応により形成されるＭｇＯ
による。」と述べている。Attempts to form an optical thin film at room temperature include:
Holland et al., “L Martinu, H Bi
ederman and L Holland, Vac
um / vol. 35 / number 12 / p531
535/1985 "(Reference 1) describes a method by sputtering. Holland et al. Disclose in this reference that" 1) MgF 2 deposited film is used for a film formed using Ar gas as a sputtering gas. A low refractive index (n = 1.38 to 1.42) equivalent to the above is obtained.
2) The absorption in the visible region of the MgF 2 film formed by sputtering occurs because F − ions in the plasma are repelled by the negative plasma potential excited to the substrate holder side, and thus the F weight taken in the thin film. Formed by the oxidation reaction between O − ions and Mg + ions excited by the dissociation of water in the plasma
by. "It has said.
【０００４】しかし、本発明者らが上記のＨｏｌｌａｎ
ｄらの文献に基づいて、スパッタリングによってＭｇＦ
２膜を作成したところ、Ａｒガスを用いても低屈折率の
薄膜は得られなかった。また、基板ホルダ側にＲＦのバ
イアスをかけてＭｇＦ2膜を作成し、光学特性を検討し
たが、基板側のプラズマポテンシャルが負電位であるか
否かとということと、薄膜の光学特性の間にＨｏｌｌａ
ｎｄらが述べているような関係は認められなかった。[0004] However, the present inventors have proposed the above Hollan.
d, et al., the sputtering of MgF
When two films were formed, a thin film having a low refractive index was not obtained even when Ar gas was used. In addition, an RF bias was applied to the substrate holder to form an MgF 2 film, and the optical characteristics were examined. Holla
The relationship described by nd et al. was not observed.
【０００５】この他、ＭｇＦ2膜を高温処理せずに作成
する方法としては、ＩＡＤ法（Ｉｏｎ ａｓｓｉｓｔｅ
ｄ ｄｅｐｏｓｉｔｉｏｎ）が考えられる。しかし、こ
のＩＡＤ法は、分子容を大きくする（イオン半径の大き
いイオンを導入して配位数を高め、充填率を高くする）
方法であるため、得られたＭｇＦ2膜の屈折率は蒸着膜
に比べて高くなってしまう。In addition, as a method of forming an MgF 2 film without performing high-temperature treatment, an IAD method (Ion associate) is used.
d deposition). However, this IAD method increases the molecular volume (introduces ions having a large ionic radius to increase the coordination number and increase the packing ratio).
Because of this method, the refractive index of the obtained MgF 2 film is higher than that of the deposited film.
【０００６】更に、ＩＡＤ法でＭｇＦ2膜を作成する場
合、機械的性能を上げるためには、かなり高いイオン電
流密度を必要とするため、イオン損傷による膜の内部応
力の変化に対する影響が大きく、光学特性の経時的安定
性に問題点がある。また、プラスチックレンズ用の低屈
折率膜としては、二酸化ケイ素（ＳｉＯ2）が用いられ
ることがあるが、ＳｉＯ2の屈折率はｎ＝１．４７程度
と高く、反射率が高くなってしまう。Furthermore, when an MgF 2 film is formed by the IAD method, a considerably high ion current density is required in order to improve the mechanical performance, and therefore, the change in the internal stress of the film due to ion damage is greatly affected. There is a problem in stability over time of optical characteristics. Further, silicon dioxide (SiO 2 ) is sometimes used as a low refractive index film for a plastic lens, but the refractive index of SiO 2 is as high as about n = 1.47, and the reflectance is high.
【０００７】[0007]
【課題を解決するための手段】本発明者は、蒸着法によ
るＭｇＦ2膜と同等以上の光学特性及び機械特性を有
し、かつ、高温処理が不要で、プラスチックレンズ等に
も支障なく用いることのできる新規な光学薄膜を得るべ
く、鋭意研究の結果、偶然にもこれまで文献等に報告の
ない硬いフッ化マグネシウム系光学薄膜を初めて成膜す
ることに成功し、本発明を成すに至った。SUMMARY OF THE INVENTION The present inventor has determined that the present invention has an optical property and a mechanical property equal to or higher than that of a MgF 2 film formed by a vapor deposition method, does not require high-temperature treatment, and can be used for a plastic lens without any trouble. As a result of earnest research, a hard magnesium fluoride-based optical thin film that has not been reported in the literature has been successfully formed for the first time, and the present invention has been achieved. .
【０００８】即ち本発明は、「ヌープ硬度が溶融石英と
略同じであることを特徴とするフッ化マグネシウム系光
学薄膜」を提供することにある。このような光学薄膜
は、これまで知られておらず、新規物質である。本発明
の光学薄膜の光学特性の経時安定性を向上させるために
は、無機化合物中のＳｉ濃度を３〜１０ｗｔ％とすると
良い。この際の各元素の好ましい原子比の範囲は次のよ
うである。That is, an object of the present invention is to provide a "magnesium fluoride optical thin film characterized in that the Knoop hardness is substantially the same as that of fused quartz." Such an optical thin film has not been known so far and is a novel substance. In order to improve the stability over time of the optical characteristics of the optical thin film of the present invention, the concentration of Si in the inorganic compound is preferably set to 3 to 10% by weight. At this time, the preferable range of the atomic ratio of each element is as follows.
【０００９】 Ｆ／Ｍｇ＝（１．３／１）〜（１．６／１） Ｏ／Ｍｇ＝（０．４／１）〜（０．７／１） Ｓｉ／Ｍｇ＝（０．１／１）〜（０．３／１） Ｓｉを添加する場合、ＭｇＦ2とＳｉをプラズマ中で反
応させる方法、具体的にはスパッタリング等によって作
成することができる。スパッタリングの条件は、求める
光学的特性等に応じて適宜設定されるものであるが、例
えば、ＭｇＦ2とＳｉをターゲットとし、スパッタリン
グガスとしてＡｒとＯ２を用いて、バックグランド圧力
を１．１×１０-3Ｐａ程度、スパッタリンガス圧６×１
０-1Ｐａ程度とすると良い。F / Mg = (1.3 / 1) to (1.6 / 1) O / Mg = (0.4 / 1) to (0.7 / 1) Si / Mg = (0.1 / 1) to (0.3 / 1) When Si is added, it can be prepared by a method of reacting MgF 2 and Si in plasma, specifically, by sputtering or the like. The sputtering conditions are appropriately set according to the optical characteristics to be obtained. For example, the background pressure is set to 1.1 × with MgF 2 and Si as targets, Ar and O 2 as sputtering gases. About 10 -3 Pa, sputtering gas pressure 6 × 1
It is good to be about 0 -1 Pa.
【００１０】[0010]
【作用】本発明の光学薄膜は屈折率が低く、低くなる理
由としては、薄膜を構成する無機化合物の分子屈折の変
化が考えられる。本発明は、屈折率が低くなる方法とし
て、分子屈折を変化させるため（結合角を小さくす
る）、スパッタリング中の酸素イオンによる分子容の変
化を抑制でき、ＩＡＤ法による膜のように屈折率が高く
ならず（酸素イオンが取り込まれて分子容が大きくなる
と屈折率が高くなる）、ＭｇＦ2 蒸着膜と同等の屈折率
を得ることができる。The optical thin film of the present invention has a low refractive index, which may be attributable to a change in the molecular refraction of the inorganic compound constituting the thin film. In the present invention, as a method of lowering the refractive index, since the molecular refraction is changed (the bonding angle is reduced), the change in the molecular volume due to oxygen ions during sputtering can be suppressed, and the refractive index can be reduced as in a film obtained by the IAD method. The refractive index does not increase (the refractive index increases as the molecular volume increases due to the incorporation of oxygen ions), and a refractive index equivalent to that of the MgF 2 deposited film can be obtained.
【００１１】次に、本発明の光学薄膜の光学特性の経時
安定性について述べる。光学薄膜をを反射防止膜等とし
て用いるにあたって、屈折率を低い一定の値に保つ必要
がある場合、薄膜中のＳｉ濃度を調整することで屈折率
の経時変化を抑えることができる。本発明者らの検討結
果によれば（具体的なデータは実施例で説明）、薄膜中
のＳｉ濃度が低い場合、Ｓｉ濃度が高すぎる場合に比べ
てＳｉＯX の割合が低下してＳｉ−Ｆ2結合の割合が高
くなる。具体的には、Ｓｉ濃度を３〜１０ｗｔ％程度と
することで、屈折率の経時安定性が向上する。この理由
は、Ｓｉ濃度が低い場合、より結合エネルギーの高いＳ
ｉ−Ｆの結合が促進されることにより、Ｓｉのダングリ
ングボンドの不動態化が行なわれるものと推測される。Next, the stability with time of the optical characteristics of the optical thin film of the present invention will be described. When using an optical thin film as an anti-reflection film or the like and it is necessary to keep the refractive index at a low and constant value, the change in the refractive index with time can be suppressed by adjusting the Si concentration in the thin film. According to the study results of the present inventors (specific data will be described in Examples), when the Si concentration in the thin film is low, the ratio of SiO x is reduced as compared with the case where the Si concentration is too high. The proportion of F 2 bonds increases. Specifically, by setting the Si concentration to about 3 to 10 wt%, the stability over time of the refractive index is improved. The reason for this is that when the Si concentration is low, S
It is presumed that passivation of dangling bonds of Si is performed by promoting the bonding of i-F.
【００１２】[0012]
【実施例】本発明の光学薄膜の機械的性能を検討した結
果を以下に示す。試料としては、基板は全て青板ガラス
を用い、基板を２７０℃にして蒸着法でＭｇＦ2膜を形
成したもの、常温でＭｇＦ2蒸着膜を形成したもの、ス
パッタリングにより本発明の光学薄膜を形成したものを
用意した。密着性については、４〜５ｋｇ／ｃｍ2での
セロハンテープテストによる引き剥がしテストを行な
い、耐溶剤性については、薄膜表面をシルボン紙にアセ
トンをしみこませて十数回強く拭いた。また、耐擦傷性
については、＃００００のスチールウールを使って荷重
８００ｇをかけ、往復５０回／３０秒こすることを行な
った。これらの試験の結果は次のようになった。EXAMPLES The results of studying the mechanical performance of the optical thin film of the present invention are shown below. As a sample, the substrate was all blue plate glass, the substrate was formed at 270 ° C. to form an MgF 2 film by vapor deposition, the MgF 2 vapor deposited film was formed at room temperature, and the optical thin film of the present invention was formed by sputtering. I prepared something. For the adhesion, a peeling test was carried out by a cellophane tape test at 4 to 5 kg / cm 2 , and for the solvent resistance, the thin film surface was soaked with acetone in silbon paper and wiped ten or more times. Regarding the abrasion resistance, a load of 800 g was applied using # 0000 steel wool, and rubbing was performed 50 times / 30 seconds. The results of these tests were as follows.
【００１３】[0013]
【表１】 [Table 1]
【００１４】また、本発明光学薄膜（常温作成）と蒸着
ＭｇＦ2膜（２７０℃加熱）とのヌープ硬度を比較した
結果を図１に示す。ヌープ硬度の測定は、明石製作所製
のマイクロビッカース硬度計ＭＶＫ−Ｇ３５００ＡＴを
用いて行い、負荷を１０ｇ，１５ｇ，２５ｇとした。基
板は両者共ホウケイ酸ガラス（青板）を使用した。その
他の比較例として青板単体と溶融石英板の測定結果も併
せて記載した。図１から、本発明の薄膜は、蒸着ＭｇＦ
2膜（２７０℃加熱）よりもヌープ硬度が高く、溶融石
英とほぼ同程度の硬度を持つことがわかる。FIG. 1 shows the results of comparison of the Knoop hardness between the optical thin film of the present invention (prepared at room temperature) and the deposited MgF 2 film (heated to 270 ° C.). The Knoop hardness was measured using a micro Vickers hardness meter MVK-G3500AT manufactured by Akashi Seisakusho, and the load was set to 10 g, 15 g, and 25 g. Both substrates used borosilicate glass (blue plate). As other comparative examples, measurement results of a blue plate alone and a fused quartz plate are also described. From FIG. 1, it can be seen that the thin film of the present invention has
It can be seen that the Knoop hardness is higher than that of the two films (heated at 270 ° C.), and the hardness is almost the same as that of fused quartz.
【００１５】[0015]
【発明の効果】以上のように、本発明の光学薄膜は、結
晶構造が緻密であり、低屈折率で、かつヌープ硬度が溶
融石英と略同程度であるために、従来の光学薄膜に比べ
て耐擦傷性や機械的強度が優れた光学薄膜が得られる。
また従来、溶融石英で製造していた光学物品に代えて、
本発明の光学薄膜を形成した物品を代用することも可能
であることから、低コストで効率よく溶融石英と同程度
の硬度を有する光学物品が得られる。As described above, the optical thin film of the present invention has a dense crystal structure, a low refractive index, and a Knoop hardness which is almost the same as that of fused silica, and therefore is smaller than that of the conventional optical thin film. Thus, an optical thin film having excellent scratch resistance and mechanical strength can be obtained.
Conventionally, instead of optical articles made of fused quartz,
Since the article formed with the optical thin film of the present invention can be substituted, an optical article having the same hardness as fused quartz can be obtained efficiently at low cost.
【図１】負荷を変えたときのヌーブ硬度変化を示す図で
ある。FIG. 1 is a diagram showing a change in the Nuev hardness when a load is changed.
Claims (1)
ことを特徴とするフッ化マグネシウム系光学薄膜。1. A magnesium fluoride optical thin film having a Knoop hardness substantially equal to that of fused quartz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10141792A JPH10339802A (en) | 1998-05-22 | 1998-05-22 | Optical thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10141792A JPH10339802A (en) | 1998-05-22 | 1998-05-22 | Optical thin film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02414523A Division JP3079580B2 (en) | 1990-12-25 | 1990-12-25 | Thin film for optical component, optical component having the same, and method of manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10339802A true JPH10339802A (en) | 1998-12-22 |
Family
ID=15300265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10141792A Pending JPH10339802A (en) | 1998-05-22 | 1998-05-22 | Optical thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10339802A (en) |
-
1998
- 1998-05-22 JP JP10141792A patent/JPH10339802A/en active Pending
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