JPH0925562A - Thin anitireflection multilater coating film, formation of the same coating film and film forming device therefor - Google Patents
Thin anitireflection multilater coating film, formation of the same coating film and film forming device thereforInfo
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- JPH0925562A JPH0925562A JP17359995A JP17359995A JPH0925562A JP H0925562 A JPH0925562 A JP H0925562A JP 17359995 A JP17359995 A JP 17359995A JP 17359995 A JP17359995 A JP 17359995A JP H0925562 A JPH0925562 A JP H0925562A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本願発明は、眼鏡レンズ等の光学
機器や部品に適用される反射防止多層膜、およびその成
膜方法並びにその成膜装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection multilayer film applied to optical instruments and parts such as spectacle lenses, a film forming method thereof, and a film forming apparatus thereof.
【０００２】[0002]
【従来の技術】従来、眼鏡レンズの両面或いは片面に低
屈折率と高屈折率の誘電体材料を交互に成膜し、レンズ
の内側では反射による視認性の低下を防止すると共にそ
の外側では光の反射を防止することが行われている。ま
た、最近では、ＶＤＴ作業における外光の映り込み防止
のために、表面に直接反射防止膜を成膜したディスプレ
ーや、ＰＥＴ（ポリエチレンテレフタレート）やＰＭＭ
Ａ（ポリメチルメタアクリレート）等のフィルム状の高
分子基板上に反射防止膜を成膜してこれをディスプレー
上に貼着け或いは前面に設置したものが市販されてい
る。2. Description of the Related Art Conventionally, dielectric materials having a low refractive index and a high refractive index are alternately formed on both surfaces or one surface of a spectacle lens so as to prevent a decrease in visibility due to reflection inside the lens and to prevent light from being outside the lens. To prevent the reflection of. Further, recently, in order to prevent reflection of external light in VDT work, a display having a direct antireflection film formed on the surface thereof, PET (polyethylene terephthalate), or PMM.
An antireflection film is formed on a film-like polymer substrate such as A (polymethylmethacrylate), and the film is attached to the display or placed on the front surface, which is commercially available.
【０００３】眼鏡レンズへの反射防止膜の成膜は、Ｓｉ
Ｏ2 、ＴｉＯ2 、ＭｇＦ等を成膜の出発材料とし、電子
ビーム蒸着法により成膜が行われている。また、ディス
プレー等の大画面に反射防止の機能を持たせる場合に
は、フッ酸等によるエッチング処理によって表面を凹凸
にして表面反射光を低下させるという方法や、画面にス
プレー塗布後に焼き付けでＳｉＯ2 等の反射防止膜を形
成するという方法も実施されている。The formation of the antireflection film on the spectacle lens is made of Si.
Film formation is performed by an electron beam evaporation method using O 2 , TiO 2 , MgF or the like as a starting material for film formation. When a large screen such as a display is provided with an antireflection function, a method of making the surface uneven by etching with hydrofluoric acid or the like to reduce the reflected light on the surface, or baking after spraying the screen with SiO 2 There is also practiced a method of forming an antireflection film such as.
【０００４】しかし、最近では成膜時の膜厚制御が容易
であるために、大面積により高品位の反射防止膜を制御
性よく成膜可能であるスパッタリング法が注目されてい
る。スパッタリング法の中でも、生産性の観点と、フィ
ルム上にも低温で成膜が可能というプロセス実行上の観
点から、高速で低温成膜を実現し得る反応性ＤＣマグネ
トロンスパッタ法が製法上の主流を占めつつある。However, recently, since the film thickness can be easily controlled during the film formation, a sputtering method is attracting attention because it can form a high-quality antireflection film in a large area with good controllability. Among the sputtering methods, the reactive DC magnetron sputtering method, which enables high-speed low-temperature film formation, is the mainstream in the manufacturing process from the viewpoint of productivity and the process execution that allows film formation on a film at low temperature. It is occupying.
【０００５】従来の反射防止膜の多層膜の構成は、図１
の（Ａ）（Ｂ）に示す如くであり、図１の（Ａ）の各層
は、単元素の酸化物で、ガラスやＰＥＴ、ＰＭＭＡ等の
透明基板ａ上に、高屈折率のＴｉＯ2 膜の層ｂと低屈折
率のＳｉＯ2 膜の層ｃとが交互に設計値に見合った膜厚
で４層に積層されている。また、図１の（Ｂ）の多層膜
は、透明基板ａ上の第１層ｄがＩＴＯ膜で、他の３層は
（Ａ）の場合と同じ高屈折率と低屈折率の層ｂ、ｃが交
互に積層されたもので、第１層ｄに導電性を持たせるこ
とによって電磁シールドを兼備させたものである。The structure of a conventional multi-layered antireflection film is shown in FIG.
(A) and (B) of FIG. 1, each layer of (A) of FIG. 1 is an oxide of a single element and is formed of a high refractive index TiO 2 film on a transparent substrate a such as glass, PET or PMMA. The layer b and the layer c of the SiO 2 film having a low refractive index are alternately laminated in four layers with a film thickness corresponding to the design value. Further, in the multilayer film of FIG. 1B, the first layer d on the transparent substrate a is an ITO film, and the other three layers have the same high refractive index and low refractive index layer b as in (A), c is laminated alternately, and the first layer d is also made to have conductivity to serve also as an electromagnetic shield.
【０００６】また、こうした多層膜を成膜する装置の構
成の１例は図２に示す如くであり、仕込み・取出しチャ
ンバーｅと成膜チャンバーｆが仕切りバルブｇを介して
接続した２室構成を有し、該成膜チャンバーｆ内には、
Ｔｉなどの高屈折率膜を成膜するためのターゲットを設
けたカソードｈ1，ｈ2と、ＢもしくはＰドープしたＳｉ
などの低屈折率膜の成膜用のターゲットを設けたカソー
ドｉ1，ｉ2が交互に配置され、成膜中にガス導入系ｊ、
ｊからＡｒガスとＯ2 ガスとを夫々導入し、反応性成膜
によって酸化膜を透明基板ａに形成する。基板ａは、ト
レイｌに取付けられて回転制御されたロール等の基板搬
送手段ｏにより搬送される。尚、夫々のカソードｈ、ｉ
には、ＤＣスパッタリングを行う際の異常放電を制御す
るためのパルス発生ユニットｍを介して直流電源ｎが接
続される。ｐは真空ポンプに接続された排気系である。An example of the construction of an apparatus for depositing such a multi-layer film is as shown in FIG. 2, in which a loading / unloading chamber e and a deposition chamber f are connected via a partition valve g. In the film forming chamber f,
Cathodes h 1 and h 2 provided with targets for forming a high refractive index film such as Ti, and B or P-doped Si
Such as cathodes i 1 and i 2 provided with targets for forming a low refractive index film are alternately arranged, and a gas introduction system j during film formation,
Ar gas and O 2 gas are introduced from j, respectively, and an oxide film is formed on the transparent substrate a by reactive film formation. The substrate a is carried by a substrate carrying means o such as a roll which is attached to the tray 1 and whose rotation is controlled. In addition, each cathode h, i
Is connected to a DC power supply n via a pulse generation unit m for controlling abnormal discharge during DC sputtering. p is an exhaust system connected to a vacuum pump.
【０００７】図２の装置により基板ａに反射防止多層膜
を成膜する場合、仕込み・取出しチャンバーｅ内にガラ
ス、ＰＥＴ或いはＰＭＭＡ等のシート状の基板ａをトレ
イｌに取付け、仕切りバルブｇを介して搬送手段ｏによ
り該トレイｌと共に基板ａを予め排気系ｐにより１０-5
Torr台まで排気したのちスパッタリングガスＡｒと反応
性ガスＯ2 を所定流量流してガス圧力を１０-3Torr台に
維持した成膜チャンバーｆ内へ搬送する。そして各カソ
ードｈ、ｉに電源ｎから通電してスパッタ放電を発生さ
せ、基板ａが各カソードｈ、ｉの前方を通過するとき、
基板ａ上に夫々のカソードの放電パワーと基板搬送速度
に見合った、設計膜厚の酸化膜が図１のように多層に形
成され、る。表１にこの場合の成膜条件の諸元を示し
た。When the antireflection multilayer film is formed on the substrate a by the apparatus shown in FIG. 2, a sheet-like substrate a such as glass, PET or PMMA is attached to the tray 1 in the loading / unloading chamber e, and the partition valve g is set. the air exhaust system p substrate a with the tray l by conveying means o through 10-5
After evacuating to the Torr level, the sputtering gas Ar and the reactive gas O 2 are flown at a predetermined flow rate and transported into the film forming chamber f where the gas pressure is maintained at the 10 −3 Torr level. When the cathodes h and i are energized from the power source n to generate sputter discharge and the substrate a passes in front of the cathodes h and i,
On the substrate a, an oxide film having a designed film thickness corresponding to the discharge power of each cathode and the substrate transport speed is formed in multiple layers as shown in FIG. Table 1 shows the specifications of the film forming conditions in this case.
【０００８】[0008]
【表１】 [Table 1]
【０００９】[0009]
【発明が解決しようとする課題】反射防止膜は、通常、
外光に直接曝されるものであり、人の手や外界の埃等の
不純物に触れるため、定期的にその汚れを拭き取る等の
メンテナンス作業が要求される。こうした場合、その拭
き取り作業時や不慮に鋭角的なものが触れると膜上に傷
が発生し、膜本来の反射防止機能が損なわれてしまう。
従来の反射防止膜の各層は、５００g/cm2 程度の擦傷硬
度しかなく、実用上、強度が不十分である欠点があっ
た。従来の反射防止膜を構成する各単層膜ＴｉＯ2 、Ｓ
ｉＯ2 、Ａｌ2 Ｏ3 、Ｔａ2 Ｏ5 、ＭｇＯ、ＺｒＯ2 の
擦傷硬度を図３に示した。擦傷硬度は、０番のスチール
ウール１cm2 あたりに定荷重を加え、２cm/secの引っか
き速度で膜表面を５回ランビングしたのち、肉眼にて１
cm幅当たりに１本以上の擦傷痕を生じるときの最低荷重
で表わしている。The antireflection film is usually composed of
Since it is directly exposed to external light and comes into contact with human hands and impurities such as dust in the external environment, maintenance work such as periodically wiping off the dirt is required. In such a case, scratches are generated on the film during the wiping operation or when an object with an acute angle is inadvertently touched, and the original antireflection function of the film is impaired.
Each layer of the conventional antireflection film has a scratch hardness of about 500 g / cm 2 and has a defect that the strength is insufficient in practical use. Conventional single-layer films TiO 2 , S constituting the antireflection film
The scratch hardness of iO 2 , Al 2 O 3 , Ta 2 O 5 , MgO and ZrO 2 is shown in FIG. The scratch hardness was 1 with the naked eye after a constant load was applied to 1 cm 2 of No. 0 steel wool and the film surface was rubbed 5 times at a scratch rate of 2 cm / sec.
It represents the minimum load when one or more scratch marks are produced per cm width.
【００１０】また、従来より反応性ＤＣスパッタリング
法でＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒ等の単元素材
料を出発材料としてＡｒとＯ2 ガスを導入しながらスパ
ッタを行うと、成膜したＴｉＯ2 、ＳｉＯ2 、Ｔａ2 Ｏ
5 、ＭｇＯ、ＺｒＯ2 などの単元素の酸化物は、酸化物
生成の過程で膜中に格子欠陥を多く含むため、構造的に
膜が脆くなることが知られている。従って、反応性ＤＣ
スパッタリング法で成膜した反射防止膜は、密度が粗く
脆いという欠点も持つ。Further, a film was formed by a conventional reactive DC sputtering method using a single element material such as Ti, Si, Al, Ta, Mg and Zr as a starting material while introducing Ar and O 2 gas. TiO 2 , SiO 2 , Ta 2 O
It is known that oxides of single elements such as 5 , MgO and ZrO 2 have many lattice defects in the film during the oxide formation process, and thus the film becomes structurally brittle. Therefore, reactive DC
The antireflection film formed by the sputtering method also has a defect that the density is rough and brittle.
【００１１】本発明は、実用レベル上十分な擦傷硬度を
有する緻密な反射防止膜を提供すること、およびこの反
射防止膜を製造する方法並びに装置を提供することを目
的とするものである。It is an object of the present invention to provide a dense antireflection film having a sufficient scratch hardness on a practical level, and a method and an apparatus for producing the antireflection film.
【００１２】[0012]
【課題を解決するための手段】本発明では、基板上に屈
折率の異なった材料の薄膜が複数層に積層した多層薄膜
の反射防止膜に於いて、該多層薄膜のうちの少なくとも
１層の薄膜をＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのい
ずれかの元素の酸化物が２種以上混入している薄膜とす
ることにより、十分な擦傷硬度を有する緻密な反射防止
膜を得るようにした。この反射防止多層膜は、成膜チャ
ンバー内に反応性ガスとスパッタリングガスを同時に導
入しながら、Ｔｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのい
ずれかの元素から成るターゲットをＤＣマグネトロンス
パッタ法によりスパッタして、該ターゲットの前方を移
動する基板上に屈折率の異なった材料の薄膜を順次に積
層することにより多層薄膜の反射防止膜を成膜する方法
に於いて、該多層薄膜の少なくとも１層の薄膜を、該タ
ーゲットとしてＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒの
いずれかの元素を２種以上混入させた合金ターゲットを
使用すると共に反応性ガスとして酸素を含むガスを使用
してＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのいずれかの
元素の酸化物が２種以上混入した薄膜に成膜する方法に
より製作できる。また、排気系を備えた成膜チャンバー
と、該成膜チャンバー内に配設された複数個のＤＣスパ
ッタリングカソードと、各カソードに設けられるターゲ
ットと、基板を各ターゲットの前方を通過させる基板搬
送手段と、該成膜チャンバー内へ反応性ガスとスパッタ
リングガスとを導入するガス導入系とから成る成膜装置
であって、該ガス導入系から反応性ガスとスパッタリン
グガスを成膜チャンバー内へ導入すると共に該基板上に
各ターゲットの材料の薄膜を多層に形成する装置に於い
て、該ターゲットのうちの少なくとも１つをＴｉ、Ｓ
ｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのいずれかの元素を２種以
上混合した合金ターゲットとすることにより、該反射防
止多層膜を１個の装置で成膜できる。According to the present invention, there is provided an antireflection film of a multilayer thin film in which a plurality of thin films of materials having different refractive indexes are laminated on a substrate, and at least one of the multilayer thin films is provided. By using a thin film in which two or more kinds of oxides of any elements of Ti, Si, Al, Ta, Mg, and Zr are mixed, a dense antireflection film having sufficient scratch hardness can be obtained. did. This antireflection multilayer film is formed by sputtering a target made of any one of Ti, Si, Al, Ta, Mg, and Zr by a DC magnetron sputtering method while simultaneously introducing a reactive gas and a sputtering gas into the film forming chamber. Then, a method of forming an antireflection film of a multilayer thin film by sequentially laminating thin films of materials having different refractive indexes on a substrate moving in front of the target, wherein at least one layer of the multilayer thin film is formed. Of the thin film of Ti, Si, Al, Ta, Mg, using an alloy target in which two or more elements of any one of Zr are mixed as the target and using a gas containing oxygen as a reactive gas, Ti, It can be manufactured by a method of forming a thin film in which two or more kinds of oxides of any one of Si, Al, Ta, Mg and Zr are mixed. Further, a film forming chamber provided with an exhaust system, a plurality of DC sputtering cathodes arranged in the film forming chamber, a target provided on each cathode, and a substrate transfer means for passing a substrate in front of each target. And a gas introducing system for introducing a reactive gas and a sputtering gas into the film forming chamber, wherein the reactive gas and the sputtering gas are introduced into the film forming chamber from the gas introducing system. In addition, in an apparatus for forming a thin film of the material of each target in multiple layers on the substrate, at least one of the targets is Ti, S
The antireflection multilayer film can be formed by one apparatus by using an alloy target in which two or more elements selected from i, Al, Ta, Mg, and Zr are mixed.
【００１３】[0013]
【作用】複数のＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒ等
のターゲットをＤＣマグネトロンスパッタしてその前方
を移動する基板へ多層の薄膜を成膜し、その際、Ｏ2 ガ
スを導入することで該基板には各ターゲット材料の酸化
物の多層膜が形成されるが、該ターゲットの少なくとも
１つにＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのいずれか
の元素を２種以上混合した合金ターゲット、例えばＴｉ
−Ａｌのターゲットを使用して該合金組成の酸化物の膜
を成膜することにより、格子欠陥が酸化物により補われ
構造的に非常に緻密で硬く擦傷硬度の大きい多層膜が得
られる。また、該合金組成の酸化物の膜の屈折率は、各
組成の酸化物の化学量論組成の屈折率の間をその組成比
率に比例してほぼ直線的に変化するので、その組成比を
変化させて任意の屈折率の薄膜が得られ、膜の発色性を
自在に調節できる。Operation: A plurality of targets of Ti, Si, Al, Ta, Mg, Zr, etc. are sputtered by DC magnetron to form a multi-layered thin film on a substrate moving in front of it, and at that time, O 2 gas is introduced. Then, a multilayer film of oxides of each target material is formed on the substrate. An alloy in which at least one of the targets is mixed with two or more elements of any one of Ti, Si, Al, Ta, Mg and Zr Target, eg Ti
By forming a film of an oxide having the alloy composition using a target of -Al, a lattice defect is compensated by the oxide to obtain a multilayer film which is structurally very dense and hard and has a large scratch hardness. Further, the refractive index of the oxide film of the alloy composition changes approximately linearly between the stoichiometric compositions of the oxides of the respective compositions in proportion to the composition ratio. By changing it, a thin film having an arbitrary refractive index can be obtained, and the coloring property of the film can be freely adjusted.
【００１４】[0014]
【発明の実施の形態】本発明の実施例を図面に基づき説
明すると、図４は本発明の反射防止多層膜を成膜する装
置の１例を示し、同図に於いて符号１は仕込み・取出し
チャンバーで、その内部のトレイ２にガラスやＰＥＴ或
いはＰＭＭＡ等のシートの基板３が設置される。該トレ
イ２は、開閉自在の仕切バルブ４を介して成膜チャンバ
ー５へ正逆回転するローラー等の適当な搬送手段６によ
り搬送される。該成膜チャンバー５内にはＤＣマグネト
ロンスパッタを行うために直流電源７へ異常放電防止用
パルスユニット８を介して成膜層数に応じた例えば４基
のマグネトロンカソード９が設けられ、各カソード９に
Ｔｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのいずれかの元素
から成るターゲット１０を取付け、これらの少なくとも
１つのターゲット１０をこれらの元素を２種以上混入し
た合金ターゲットとした。図示の例は、４個のターゲッ
ト１０を全てＡｌ合金ターゲットとしたもので、ターゲ
ット１０ａ、１０ｃをＴｉ−Ａｌ1at%の合金とし、ター
ゲット１０ｂ、１０ｄをＳｉ−Ａｌ1a t%の合金とした。
１１は酸素ガス等の反応性ガスを導入するガス導入系、
１２はＡｒガスのスパッタガスを導入するガス導入系、
１３は真空ポンプに接続された排気口である。カソード
９は公知の構造を有し、板面にターゲット１０をボンデ
ィング等により取付け、その背面に設けた永久磁石等の
磁石により該ターゲット１０のスパッタ面上にマグネト
ロン放電用の磁界が形成される。BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described with reference to the drawings. FIG. 4 shows an example of an apparatus for forming an antireflection multilayer film of the present invention. In FIG. In the take-out chamber, a substrate 3 of a sheet of glass, PET, PMMA or the like is placed on a tray 2 inside the take-out chamber. The tray 2 is conveyed to the film forming chamber 5 through a partition valve 4 which can be opened and closed by a suitable conveying means 6 such as a roller which rotates forward and backward. In the film forming chamber 5, for example, four magnetron cathodes 9 corresponding to the number of film forming layers are provided to the DC power supply 7 through the abnormal discharge preventing pulse unit 8 for performing DC magnetron sputtering. A target 10 made of any one element of Ti, Si, Al, Ta, Mg, and Zr was attached to, and at least one of these targets 10 was used as an alloy target in which two or more kinds of these elements were mixed. In the illustrated example, all four targets 10 are Al alloy targets, the targets 10a and 10c are Ti-Al 1at% alloys, and the targets 10b and 10d are Si-Al 1at % alloys.
11 is a gas introduction system for introducing a reactive gas such as oxygen gas,
12 is a gas introduction system for introducing a sputtering gas of Ar gas,
Reference numeral 13 is an exhaust port connected to a vacuum pump. The cathode 9 has a known structure. A target 10 is attached to the plate surface by bonding or the like, and a magnet such as a permanent magnet provided on the back surface thereof forms a magnetic field for magnetron discharge on the sputtering surface of the target 10.
【００１５】該成膜チャンバー５内を１０-5Torr台にま
で排気し、スパッタリングガスＡｒと反応性ガスＯ2 を
所定流量流してガス圧力を１０-3Torr台に維持し、電源
７を通電して該成膜チャンバー５内のカソード９にマグ
ネトロン放電を発生させる。そしてトレイ２による搬送
で基板３が各ターゲット１０上を通過するとき、該基板
３上に各ターゲット１０の材料の酸化薄膜が１層ずつ成
膜され、通過し終わると、該基板３上に多層の反射防止
膜が形成される。該カソード９に投入されるスパッタ電
力の大きさと、基板３の搬送速度を調節することで、該
酸化薄膜の膜厚を設計膜厚とすることができる。該基板
３をソーダガラスとし、ターゲット９が上記組成である
とき、該成膜装置を次表２の諸元の成膜条件で成膜する
と、基板３上に、（Ｔｉ−Ａｌ1at%）ＯX 膜、（Ｓｉ−
Ａｌ1at%）ＯX 膜、（Ｔｉ−Ａｌ1at%）ＯX 膜、（Ｓｉ
−Ａｌ1at%）ＯX 膜、が、夫々１２０Å、３６０Å、１
１５０Å、９１０Åの厚さで積層した図５に示す４層構
造の反射防止多層薄膜が得られる。The inside of the film forming chamber 5 is evacuated to the level of 10 -5 Torr, the sputtering gas Ar and the reactive gas O 2 are flown at a predetermined flow rate to maintain the gas pressure at the level of 10 -3 Torr, and the power supply 7 is energized. Then, a magnetron discharge is generated at the cathode 9 in the film forming chamber 5. When the substrate 3 is conveyed by the tray 2 and passes over each target 10, an oxide thin film of the material of each target 10 is formed on the substrate 3 one layer at a time. The antireflection film is formed. By adjusting the magnitude of the sputtering power applied to the cathode 9 and the transport speed of the substrate 3, the film thickness of the oxide thin film can be made the designed film thickness. When the substrate 3 is made of soda glass and the target 9 has the above composition, a film is formed by the film forming apparatus under the film forming conditions of the following Table 2, the (Ti-Al 1at% ) O 2 is formed on the substrate 3. X film, (Si-
Al 1at% ) O X film, (Ti-Al 1at% ) O X film, (Si
-Al 1at%) O X film, but each 120 Å, 360 Å, 1
The antireflection multilayer thin film having a four-layer structure shown in FIG. 5 is obtained, which is laminated with a thickness of 150Å and 910Å.
【００１６】[0016]
【表２】 [Table 2]
【００１７】図５の反射防止多層薄膜の反射率特性およ
び透過率特性を調べたところ、図６および図７の結果と
なった。これによれば、４５０nm〜５５０nmの可視域で
反射率０．１％以下、透過率９４％以上を示し、良好な
反射防止特性が得られていることが分かる。また、その
擦傷硬度は、図８の点Ａで示したように、１５００g/cm
2 を示し、点Ｇで示した前記従来の反射防止多層薄膜の
擦傷硬度の約３倍の硬度が得られた。When the reflectance characteristics and transmittance characteristics of the antireflection multilayer thin film of FIG. 5 were examined, the results shown in FIGS. 6 and 7 were obtained. According to this, the reflectance is 0.1% or less and the transmittance is 94% or more in the visible region of 450 nm to 550 nm, which shows that good antireflection characteristics are obtained. The scratch hardness is 1500 g / cm, as shown by point A in FIG.
2 was obtained, and the hardness was about 3 times the scratch hardness of the conventional antireflection multilayer thin film shown by the point G.
【００１８】また、図５の膜の第１層目のみをＩＴＯ膜
とし、或いは図５の第１層目乃至第４層目のいずれか１
層以外をＴｉＯ、ＳｉＯとして反射防止多層薄膜を成膜
したが、これらの場合の擦傷硬度は、図８の点Ｂ〜Ｆで
示したように、１０００g/cm2 の荷重硬度となり、従来
の反射防止多層薄膜よりも十分な硬度が得られた。Further, only the first layer of the film of FIG. 5 is an ITO film, or any one of the first to fourth layers of FIG.
The antireflection multilayer thin film was formed by using TiO and SiO other than the layers, and the scratch hardness in these cases was 1000 g / cm 2 of load hardness as shown by points B to F in FIG. Sufficient hardness was obtained compared to the prevention multilayer film.
【００１９】Ｔｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒのい
ずれかの２種以上の元素からなる合金ターゲットを出発
材料としてＡｒ＋Ｏ2 ガスを導入しながら反応性ＤＣス
パッタにより成膜した２元素以上の酸化物は、各々の金
属元素の酸化物の格子定数が異なるため、格子欠陥を互
いの酸化物が補い、構造的に緻密で非常に硬い膜である
ことが見出された。１例としてＴｉに、Ｓｉ、Ａｌ、Ｔ
ａ、Ｍｇ、Ｚｒを比率を変えて混入した膜の擦傷硬度
を、図９に示した。これによれば、Ｔｉ1at%乃至Ｔｉ
99at% の範囲で混合した場合の擦傷硬度は、１５００g/
cm2 以上の荷重を加えても擦傷痕が発生せず、従来の単
元素の酸化物の膜よりも約３倍の硬度を持つことが分か
る。また、この１例の膜の屈折率は、図１０に示したよ
うに、夫々の化学量論組成の酸化物が有する屈折率の間
を組成比率に比例してほぼ直線的に変化し、１ａｔ％程
度のＴｉ混入量では、屈折率の変化がわずかであり、例
えば、Ｔｉ−Ｓｉ1at%の酸化物では、屈折率の変化がＴ
ｉＯ2 の２．６からわずか−０．０１１５変化するだけ
で、膜設計上何等問題が生じることがない。さらに、組
成比を変化させることによって、任意の屈折率を有する
酸化物膜が得られ、また膜の発色の自在性があるので、
膜設計上大きな利点となる。Two or more elements are formed by reactive DC sputtering while introducing Ar + O 2 gas using an alloy target composed of two or more elements of Ti, Si, Al, Ta, Mg and Zr as a starting material. It has been found that the oxides are structurally dense and very hard films because the oxides of the respective metal elements have different lattice constants, so that the oxides of the oxides complement each other. As an example, Ti, Si, Al, T
FIG. 9 shows the scratch hardness of the film in which a, Mg, and Zr were mixed in different ratios. According to this, Ti 1at% to Ti
The scratch hardness when mixed in the range of 99 at% is 1500 g /
It can be seen that even if a load of cm 2 or more is applied, no scratch mark is generated, and the hardness is about 3 times that of the conventional single-element oxide film. In addition, the refractive index of the film of this example changes substantially linearly between the refractive indexes of the oxides of the respective stoichiometric compositions in proportion to the composition ratio, as shown in FIG. %, The change in the refractive index is slight. For example, in the case of an oxide of Ti—Si 1 at% , the change in the refractive index is T.
Only a slight change of -0.0115 from 2.6 of iO 2 does not cause any problem in the film design. Furthermore, by changing the composition ratio, an oxide film having an arbitrary refractive index can be obtained, and since the film can be colored freely,
This is a great advantage in membrane design.
【００２０】以上の傾向は、前記の元素の組合わせ以外
の組合わせにおいても、全く同様の結果が見られた。With respect to the above tendency, the same results were observed in combinations other than the above-mentioned combinations of elements.
【００２１】尚、本発明では、２元素のターゲット材を
酸素ガスにより酸化物の膜を成膜したが、ＳｉＯＮのよ
うに可視域で９４％以上の透過率をもつものであれば、
反応性ガスとしてＯ2 の一部をＮ2 、Ｎ2 Ｏ、ＮＨ3 等
の窒化系ガスで置換し、酸化物と窒化物の混合物として
も、２元素酸化物と同様の効果を発揮させることができ
る。また、Ｏ2 の一部をＣＯ2 、ＣＯ、ＣＦ4 、ＣＨ4
等、カーボンを含んだガスで置換してもよい。In the present invention, an oxide film is formed by using a two-element target material with oxygen gas. However, as long as it has a transmittance of 94% or more in the visible region, such as SiON,
A part of O 2 as a reactive gas is replaced with a nitriding gas such as N 2 , N 2 O, NH 3 and the like, and a mixture of an oxide and a nitride exhibits the same effect as a two-element oxide. You can Further, a part of O 2 is CO 2 , CO, CF 4 , CH 4
Etc., it may be replaced with a gas containing carbon.
【００２２】また、図４の基板の仕込みと取出しを共通
のチャンバーとしたインターバック形式の成膜装置を、
仕込みチャンバーと取出しチャンバーを個別に備える３
室以上のチャンバー構成のインライン形式の装置として
もよい。さらに、ＰＥＴ、ＰＭＭＡ等の長尺巻物状の基
板に成膜を行うロールコーター形式のスパッタ装置、或
いは枚葉装置として用いられるマルチチャンバー形式の
スパッタ装置も適用可能である。In addition, an interback type film forming apparatus having a common chamber for loading and unloading the substrate of FIG.
Separate preparation chamber and extraction chamber 3
An in-line type device having a chamber configuration of more than one chamber may be used. Further, a roll coater type sputtering apparatus for forming a film on a long scroll substrate such as PET or PMMA, or a multi-chamber type sputtering apparatus used as a single-wafer apparatus is also applicable.
【００２３】[0023]
【実施例】図４に示す装置に於いて、５００mm×８５０
mmのソーダガラスの基板を仕込み・取出しチャンバー内
のトレイに用意し、成膜チャンバー内を１０-5Torrに排
気したのち、ガス導入系からＡｒガスを１０００SCCMと
Ｏ2 ガスを２４０SCCM流し、ガス圧を１０-3Torr台に維
持しながら、該成膜チャンバー内の各マグネトロンカソ
ードに直流電源から通電した。各カソードは５インチ×
４０インチの寸法の各ターゲットが設けられており、タ
ーゲット１０ａ、１０ｃはＴｉ−Ａｌ1at%、ターゲット
１０ｂ、１０ｄはＳｉ−Ａｌ1at%で、ターゲット１０ａ
には電源から５Kwを投入し、１０ｂには２Kw、１０ｃに
は２０Kw、１０ｄには１０Kwを夫々投入し、トレイを５
００mm/minの速度で移動させて基板上に図５に示す４層
の反射防止多層膜をＤＣマグネトロンスパッタで成膜し
た。第１層の（Ｔｉ−Ａｌ1at%）ＯX 膜の膜厚は１２０
Å、第２層の（Ｓｉ−Ａｌ1at%）ＯX 膜の膜厚は３６０
Å、第３層の（Ｔｉ−Ａｌ1at%）ＯX 膜の膜厚は１１５
０Å、第４層の（Ｓｉ−Ａｌ1at%）ＯX 膜の膜厚は９１
０Åであった。EXAMPLE In the apparatus shown in FIG. 4, 500 mm × 850
mm soda glass substrate is prepared in a tray inside the loading / unloading chamber, the film forming chamber is evacuated to 10 -5 Torr, then 1000 SCCM of Ar gas and 240 SCCM of O 2 gas are flown from the gas introduction system to set the gas pressure. Was maintained on the order of 10 −3 Torr, each magnetron cathode in the film forming chamber was energized from a DC power supply. Each cathode is 5 inches x
Each target having a size of 40 inches is provided, the targets 10a and 10c are Ti-Al 1at% , the targets 10b and 10d are Si-Al 1at% , and the target 10a is provided.
5Kw from the power source, 2kw into 10b, 20kw into 10c, 10kw into 10d, and 5 trays.
The 4-layer antireflection multilayer film shown in FIG. 5 was formed on the substrate by moving it at a speed of 00 mm / min by DC magnetron sputtering. The film thickness of the first layer of (Ti-Al 1at%) O X film 120
Å, the thickness of the second layer of the (Si-Al 1at%) O X film 360
Å, the thickness of the (Ti—Al 1at% ) O X film of the third layer is 115
0Å, the thickness of the (Si—Al 1at % ) O X film of the fourth layer is 91.
It was 0 °.
【００２４】この多層膜の擦傷硬度を、前記のように０
番のスチールウール１cm2 あたりに定荷重を加え、２cm
/secの引っかき速度で膜表面を５回ランビングしたの
ち、肉眼にて１cm幅当たりに１本以上の擦傷痕を生じる
ときの最低荷重で測定したところ、１５００g/cm2 であ
った。またその反射率と透過率は４５０nm〜５５０nmの
可視域で夫々０．１％以下と９４％以上で、良好な反射
防止特性が得られた。The scratch hardness of this multilayer film is 0 as described above.
A constant load is applied to 1 cm 2 of # 2 steel wool and 2 cm
The surface of the film was rubbed 5 times at a scratching speed of / sec, and then it was measured with the naked eye at the minimum load at which one or more scratch marks were produced per 1 cm width, and it was 1500 g / cm 2 . The reflectance and the transmittance were 0.1% or less and 94% or more, respectively, in the visible region of 450 nm to 550 nm, and good antireflection characteristics were obtained.
【００２５】[0025]
【発明の効果】以上のように、本発明によるときは、多
層薄膜の反射防止膜を構成する多層薄膜のうちの少なく
とも１層の薄膜をＴｉ、Ｓｉ、Ａｌ、Ｔａ、Ｍｇ、Ｚｒ
のいずれかの元素の酸化物が２種以上混入している薄膜
としたので、緻密で擦傷硬度が高く透過率の良い射防止
多層薄膜が得られ、その混入比を変更することで膜の発
色性も自在に変更でき、不慮の引っ掻き傷が付きにくい
反射防止多層膜が得られる効果があり、また本発明の方
法と装置によれば、導電性のある合金ターゲットを用い
るため、反応性ＤＣスパッタリングが採用でき、高速で
低温成膜が可能となり、反射防止多層薄膜の生産性が向
上する等の効果がある。As described above, according to the present invention, at least one thin film of the multilayer thin films constituting the antireflection film of the multilayer thin film is made of Ti, Si, Al, Ta, Mg, Zr.
Since it is a thin film in which two or more kinds of oxides of any of the above elements are mixed, a multi-layered anti-reflection thin film that is dense and has high scratch hardness and good transmittance can be obtained, and the coloring ratio of the film can be changed by changing the mixing ratio. The property is that the antireflection multilayer film that can be freely changed and that is unlikely to be scratched accidentally is obtained. Further, according to the method and apparatus of the present invention, since a conductive alloy target is used, reactive DC sputtering is performed. Can be adopted, high-speed low-temperature film formation is possible, and the productivity of the antireflection multilayer thin film is improved.
【図１】従来の反射防止多層薄膜の構成の模式図FIG. 1 is a schematic diagram of the configuration of a conventional antireflection multilayer thin film.
【図２】従来の反射防止多層薄膜の成膜装置の概略的側
面図FIG. 2 is a schematic side view of a conventional anti-reflection multilayer thin film forming apparatus.
【図３】従来の反射防止多層薄膜の単層膜の擦傷硬度図FIG. 3 is a scratch hardness diagram of a conventional single layer film of an antireflection multilayer thin film.
【図４】本発明の反射防止多層薄膜の成膜装置の実施例
の概略的側面図FIG. 4 is a schematic side view of an embodiment of an antireflection multilayer thin film forming apparatus of the present invention.
【図５】本発明の反射防止多層薄膜の構成の模式図FIG. 5 is a schematic diagram of the constitution of the antireflection multilayer thin film of the present invention.
【図６】図５に示した反射防止多層薄膜の反射率特性曲
線図6 is a reflectance characteristic curve diagram of the antireflection multilayer thin film shown in FIG.
【図７】図５に示した反射防止多層薄膜の透過率特性曲
線図7 is a transmittance characteristic curve diagram of the antireflection multilayer thin film shown in FIG.
【図８】本発明の反射防止多層薄膜の擦傷硬度図FIG. 8 is a scratch hardness diagram of the antireflection multilayer thin film of the present invention.
【図９】混入比を変化させた本発明の反射防止多層薄膜
の擦傷硬度図FIG. 9 is a scratch hardness diagram of the antireflection multilayer thin film of the present invention in which the mixing ratio is changed.
【図１０】混入比を変化させた本発明の反射防止多層薄
膜の屈折率の線図FIG. 10 is a diagram of the refractive index of the antireflection multilayer thin film of the present invention in which the mixing ratio is changed.
【符号の説明】 ３ 基板 ５ 成膜チャンバ
ー ６ 基板搬送手段 ７ 直流電源 ９ マグネトロンカソード １０、１０ａ、１０ｂ、１０ｃ、１０ｄ 合金ターゲッ
ト １１、１２ ガス導入系[Explanation of reference numerals] 3 substrate 5 film forming chamber 6 substrate transfer means 7 direct current power supply 9 magnetron cathode 10, 10a, 10b, 10c, 10d alloy target 11, 12 gas introduction system
───────────────────────────────────────────────────── フロントページの続き (72)発明者 太田 賀文 千葉県山武郡山武町横田523 日本真空技 術株式会社千葉超材料研究所内 (72)発明者 松本 昌弘 千葉県山武郡山武町横田523 日本真空技 術株式会社千葉超材料研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kafumi Ota 523 Yokota, Yamatake-cho, Sanmu-gun, Chiba Japan Vacuum Technology Co., Ltd. Chiba Institute for Super Materials (72) Inventor Masahiro Matsumoto 523 Yokota, Yamatake-cho, Yamatake-gun, Chiba Japan Vacuum Technology Co., Ltd. Chiba Institute for Materials Research
Claims (5)
数層に積層した多層薄膜の反射防止膜に於いて、該多層
薄膜のうちの少なくとも１層の薄膜をＴｉ、Ｓｉ、Ａ
ｌ、Ｔａ、Ｍｇ、Ｚｒのいずれかの元素の酸化物が２種
以上混入している薄膜としたことを特徴とする反射防止
多層薄膜。1. An antireflection film of a multi-layered thin film in which a plurality of thin films of materials having different refractive indexes are laminated on a substrate, and at least one of the multi-layered thin films is made of Ti, Si, A.
An antireflection multilayer thin film, which is a thin film in which two or more kinds of oxides of any one of 1, 1, Ta, Mg, and Zr are mixed.
記基板はガラス等のセラミックス基板、ポリエチレンテ
レフタレート、ポリメチルメタアクリレート等の高分子
フィルム基板のいずれかであることを特徴とする請求項
１に記載の反射防止多層薄膜。2. The substrate and the multilayer thin film are transparent, and the substrate is any one of a ceramic substrate such as glass and a polymer film substrate such as polyethylene terephthalate and polymethylmethacrylate. The antireflection multilayer thin film as described in.
リングガスを同時に導入しながら、Ｔｉ、Ｓｉ、Ａｌ、
Ｔａ、Ｍｇ、Ｚｒのいずれかの元素から成るターゲット
をＤＣマグネトロンスパッタ法によりスパッタして、該
ターゲットの前方を移動する基板上に屈折率の異なった
材料の薄膜を順次に積層することにより多層薄膜の反射
防止膜を成膜する方法に於いて、該多層薄膜の少なくと
も１層の薄膜を、該ターゲットとしてＴｉ、Ｓｉ、Ａ
ｌ、Ｔａ、Ｍｇ、Ｚｒのいずれかの元素を２種以上混入
させた合金ターゲットを使用すると共に反応性ガスとし
て酸素を含むガスを使用してＴｉ、Ｓｉ、Ａｌ、Ｔａ、
Ｍｇ、Ｚｒのいずれかの元素の酸化物が２種以上混入し
た薄膜に成膜することを特徴とする反射防止多層膜の成
膜方法。3. Ti, Si, Al, while simultaneously introducing a reactive gas and a sputtering gas into the film forming chamber,
A multi-layer thin film is formed by sputtering a target made of any one of Ta, Mg, and Zr by DC magnetron sputtering, and sequentially laminating thin films of materials having different refractive indexes on a substrate moving in front of the target. In the method for forming an antireflection film, the thin film of at least one of the multilayer thin films is used as the target of Ti, Si, A
Ti, Si, Al, Ta, using an alloy target in which two or more of any one of Ta, Mg, Zr are mixed and using a gas containing oxygen as a reactive gas.
A method for forming an antireflection multilayer film, which comprises forming a thin film in which two or more kinds of oxides of any one of Mg and Zr are mixed.
記基板はガラス等のセラミックス基板、ポリエチレンテ
レフタレート、ポリメチルメタアクリレート等の高分子
フィルム基板のいずれかであることを特徴とする請求項
３に記載の反射防止多層薄膜の成膜方法。4. The substrate and the multilayer thin film are transparent, and the substrate is any one of a ceramic substrate such as glass and a polymer film substrate such as polyethylene terephthalate and polymethylmethacrylate. The method for forming an antireflection multilayer thin film according to [4].
チャンバー内に配設された複数個のＤＣマグネトロンカ
ソードと、各カソードに設けられるターゲットと、基板
を各ターゲットの前方を通過させる基板搬送手段と、該
成膜チャンバー内へ反応性ガスとスパッタリングガスと
を導入するガス導入系とから成る成膜装置であって、該
ガス導入系から反応性ガスとスパッタリングガスを成膜
チャンバー内へ導入すると共に該基板上に各ターゲット
の材料の薄膜を多層に形成する装置に於いて、該ターゲ
ットのうちの少なくとも１つをＴｉ、Ｓｉ、Ａｌ、Ｔ
ａ、Ｍｇ、Ｚｒのいずれかの元素を２種以上混合した合
金ターゲットとしたことを特徴とする反射防止多層膜の
成膜装置。5. A film forming chamber having an exhaust system, a plurality of DC magnetron cathodes arranged in the film forming chamber, a target provided on each cathode, and a substrate passing in front of each target. A film forming apparatus comprising a substrate transfer means and a gas introducing system for introducing a reactive gas and a sputtering gas into the film forming chamber, wherein the reactive gas and the sputtering gas are supplied from the gas introducing system into the film forming chamber. A thin film of the material of each target in multiple layers on the substrate and at least one of the targets is Ti, Si, Al, T
A film forming apparatus for an antireflection multilayer film, which is an alloy target in which two or more elements of a, Mg and Zr are mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17359995A JPH0925562A (en) | 1995-07-10 | 1995-07-10 | Thin anitireflection multilater coating film, formation of the same coating film and film forming device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17359995A JPH0925562A (en) | 1995-07-10 | 1995-07-10 | Thin anitireflection multilater coating film, formation of the same coating film and film forming device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0925562A true JPH0925562A (en) | 1997-01-28 |
Family
ID=15963596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17359995A Pending JPH0925562A (en) | 1995-07-10 | 1995-07-10 | Thin anitireflection multilater coating film, formation of the same coating film and film forming device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0925562A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237630A (en) * | 1996-04-12 | 1998-09-08 | Asahi Glass Co Ltd | Oxide coating, laminated body and heir production |
| US6833058B1 (en) | 2000-10-24 | 2004-12-21 | Honeywell International Inc. | Titanium-based and zirconium-based mixed materials and sputtering targets |
| JP2006337672A (en) * | 2005-06-01 | 2006-12-14 | Bridgestone Corp | Antireflection film |
| GB2431931A (en) * | 2005-11-04 | 2007-05-09 | Fu Ching Technologies Co Ltd | Anti-reflection layer and manufacturing method and apparatus |
| CN104616726A (en) * | 2014-12-17 | 2015-05-13 | 青岛墨烯产业科技有限公司 | Indium-free transparent electrode and preparation method thereof |
| US20160369386A1 (en) * | 2013-06-26 | 2016-12-22 | Oerlikon Surface Solutions Ag, Trubbach | Decorative hipims hard material layers |
| CN116559984A (en) * | 2023-05-06 | 2023-08-08 | 佛山纳诺特科技有限公司 | Inorganic wear-resistant homogeneous refractive index change antireflection film and preparation method and application thereof |
-
1995
- 1995-07-10 JP JP17359995A patent/JPH0925562A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237630A (en) * | 1996-04-12 | 1998-09-08 | Asahi Glass Co Ltd | Oxide coating, laminated body and heir production |
| US6833058B1 (en) | 2000-10-24 | 2004-12-21 | Honeywell International Inc. | Titanium-based and zirconium-based mixed materials and sputtering targets |
| JP2006337672A (en) * | 2005-06-01 | 2006-12-14 | Bridgestone Corp | Antireflection film |
| GB2431931A (en) * | 2005-11-04 | 2007-05-09 | Fu Ching Technologies Co Ltd | Anti-reflection layer and manufacturing method and apparatus |
| US20160369386A1 (en) * | 2013-06-26 | 2016-12-22 | Oerlikon Surface Solutions Ag, Trubbach | Decorative hipims hard material layers |
| US11060181B2 (en) * | 2013-06-26 | 2021-07-13 | Oerlikon Surface Solutions Ag, Pfaffikon | Decorative HIPIMS hard material layers |
| CN104616726A (en) * | 2014-12-17 | 2015-05-13 | 青岛墨烯产业科技有限公司 | Indium-free transparent electrode and preparation method thereof |
| CN116559984A (en) * | 2023-05-06 | 2023-08-08 | 佛山纳诺特科技有限公司 | Inorganic wear-resistant homogeneous refractive index change antireflection film and preparation method and application thereof |
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