JP6302688B2 - High reflection film, substrate with high reflection film, and method of manufacturing high reflection film - Google Patents
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Description
本発明は、銀膜を使用した高反射膜、高反射膜付き基板及び高反射膜の製造方法に関する。 The present invention relates to a highly reflective film using a silver film, a substrate with a highly reflective film, and a method for producing the highly reflective film.
カメラ、望遠鏡、顕微鏡、複写機、投影機、プロジェクター、携帯端末、レーザー機器をはじめ、軍事用、医療用、民生用、産業用等の多方面で光学機器は使用されている。
これらの光学機器の中で反射鏡は、その数も多く種類や形状も多種多様であり、用途が広範囲であるため反射率は勿論のこと、あらゆる環境下での耐久性も合わせて要求される。
Optical devices are used in various fields such as cameras, telescopes, microscopes, copiers, projectors, projectors, portable terminals, and laser devices, as well as military, medical, consumer, and industrial devices.
Among these optical devices, the number of reflectors is many, and there are many types and shapes. Because of the wide range of applications, not only the reflectance but also the durability in all environments is required. .
反射鏡の中でも、特定波長に対する反射率が重要となるレーザーミラーや、特定波長帯のみを選択反射させる光学フィルターには、低屈折率と高屈折率の誘電体膜を交互に積層する方法によるものや、さらには中間屈折率を持つ誘電体膜を適宜選定して組み合わせて積層する誘電体多層膜がある。これらの反射鏡は、積層膜が十数層から数十層、場合によっては百層にも及ぶ。
また、反射鏡のその他のタイプとして、アルミニウム（Ａｌ）や銀（Ａｇ）等の金属膜を形成した後、その上に金属膜の特性を大きく損なわないように保護膜を形成する方法もある。また、金属膜の上に、数層の屈折率の異なる誘電体膜を積層することにより増反射効果を促して、より反射率を高めることができる金属高反射膜がある。これらの反射鏡は、層数が少なくて済むうえに安価に作製することができる。このため、赤外域や紫外域等の特殊用途を除いては、ＡｌやＡｇ及びこれらの合金の膜を用いた高反射膜が、反射鏡の多数を占めている。
Among reflective mirrors, laser mirrors where reflectivity for a specific wavelength is important, and optical filters that selectively reflect only a specific wavelength band are based on a method of alternately laminating low-refractive index and high-refractive index dielectric films. In addition, there is a dielectric multilayer film in which dielectric films having an intermediate refractive index are appropriately selected and combined and laminated. These reflecting mirrors have ten to several tens of laminated films, and in some cases, hundreds of layers.
As another type of reflecting mirror, there is a method in which after forming a metal film such as aluminum (Al) or silver (Ag), a protective film is formed on the metal film so as not to greatly impair the characteristics of the metal film. In addition, there is a metal highly reflective film that can increase the reflectivity by laminating several dielectric films having different refractive indexes on the metal film to promote the effect of increasing reflection. These reflecting mirrors require a small number of layers and can be manufactured at low cost. For this reason, except for special uses such as the infrared region and the ultraviolet region, a highly reflective film using a film of Al, Ag, or an alloy thereof occupies many of the reflecting mirrors.
薄膜化したアルミニウム膜の反射率は可視域で略９０％であり、同様に薄膜化した銀膜は、可視域での平均反射率が略９５〜９６％である。何れの薄膜を使用した反射鏡においても、より反射率の向上を図る目的で、薄膜化した金属膜上に低屈折率と高屈折率の薄膜を交互に複数積層して、使用する波長の反射帯を中心にした光学設計により増反射処理を施して高反射率を確保している。 The reflectance of the thinned aluminum film is approximately 90% in the visible region, and the silver film similarly thinned has an average reflectance in the visible region of approximately 95 to 96%. In any reflector using any thin film, for the purpose of further improving the reflectance, a plurality of thin films having a low refractive index and a high refractive index are alternately laminated on the thinned metal film to reflect the wavelength used. An optical design centered on the belt is applied to increase reflection to ensure high reflectivity.
Ａｌ又はＡｌ合金からなるアルミニウム膜は、安価でその取り扱いも比較的容易であることから、広範囲で使用されている。それに対し、Ａｇ又はＡｇ合金からなる銀膜は、反射材料として使用した場合に、アルミニウム膜と比較して高反射率を確保できるというメリットがある。 Aluminum films made of Al or Al alloys are widely used because they are inexpensive and relatively easy to handle. On the other hand, a silver film made of Ag or an Ag alloy has an advantage that a high reflectance can be ensured as compared with an aluminum film when used as a reflective material.
しかし、銀膜は硫化し易く、硫化の程度によっては銀膜表面が黄化してさらには黒化に至る。また、マイグレーションも起こり易いため、銀膜の基板側又は基板逆側に隣接して設けられた薄膜中に、Ａｇイオンが拡散したり、離脱する電子の影響等により独特な粒成長や突起物を形成したり、化合物を生成させたりする。このため、銀膜特有の高い反射率は低下し易い。 However, the silver film is easily sulfided, and depending on the degree of sulfuration, the surface of the silver film is yellowed and further blackened. In addition, since migration is likely to occur, unique grain growth and protrusions are caused by the influence of electrons that diffuse or detach from Ag ions in the thin film provided adjacent to the substrate side of the silver film or the opposite side of the substrate. Form or form a compound. For this reason, the high reflectance peculiar to a silver film tends to fall.
また、多くの金属では、薄膜形成過程における成膜初期段階で、多数の核形成から次第に薄膜が成長して、金属の薄膜が形成されるが、Ａｇは、このような多くの金属とは異なる薄膜成長過程を辿る。つまり、銀膜は、成膜初期段階の少ない核形成から、瞬時に二次元的に薄膜が成長して形成されるため、いろいろな基板との密着力が特に弱い。 In many metals, the thin film grows gradually from the formation of a large number of nuclei and forms a thin metal film at the initial stage of film formation in the thin film formation process, but Ag is different from such many metals. Follow the thin film growth process. That is, since the silver film is formed by instantly growing a thin film two-dimensionally from nucleation with few initial stages of film formation, the adhesion with various substrates is particularly weak.
銀膜を使用した反射鏡におけるこれらの課題解決を目的として、基板と銀膜との間、或いは、銀膜とその上に成膜された低屈折率膜と高屈折率膜の多層膜との間に、密着性を高める等の目的で、下地層や中間層を形成する技術が提案されている（例えば、特許文献１〜６）。
特許文献１には、特定の添加材料を含む銀合金膜と低屈折率膜であるＳｉＯ２膜との間に中間層を形成して密着力を確保する方法が記載されている（特許文献１の段落００２８等）。
また、特許文献２には、金を含む銀合金膜の基板逆側に成膜される低屈折率膜を窒化珪素膜とし、さらに基板と銀合金膜との間に密着改善層としてＺｎＯ、ＳｎＯ、Ｉｎ２Ｏ３、Ａｌ２Ｏ３、及びＴｉＯ２、ＺｎＯにＧａ、Ｓｎ、Ｓｉ、Ｔｉの１種類以上を含む膜を形成する技術が開示されている（特許文献２の段落００３５、００５０〜００５２）。
For the purpose of solving these problems in a reflector using a silver film, or between a substrate and a silver film, or between a silver film and a multilayer film of a low refractive index film and a high refractive index film formed thereon. In the meantime, a technique for forming an underlayer or an intermediate layer has been proposed for the purpose of improving adhesion (for example, Patent Documents 1 to 6).
Patent Document 1 describes a method of securing an adhesive force by forming an intermediate layer between a silver alloy film containing a specific additive material and a SiO 2 film that is a low refractive index film (Patent Document 1). Paragraph 0028 etc.).
In Patent Document 2, a low refractive index film formed on the opposite side of a silver alloy film containing gold is a silicon nitride film, and ZnO, SnO is used as an adhesion improving layer between the substrate and the silver alloy film. , In 2 O 3 , Al 2 O 3 , TiO 2 , and ZnO have been disclosed a technique for forming a film containing one or more of Ga, Sn, Si, and Ti (paragraphs 0035 and 0050 of Patent Document 2). 0052).
特許文献３には、銀膜表面に、耐湿性、耐硫黄性向上を目的として窒化珪素膜を形成し、さらにその上に硬質炭素膜を積層する方法（特許文献３の段落００１９）が、また、基板と銀膜との密着性向上を目的として、基板と銀膜との間にＴｉＯｘ膜を形成する方法（特許文献３の段落００１４）が開示されている。
特許文献４には、銀又はＡＰＣ合金の上に酸化防止層としてＩＴＯあるいはＺｎＯｘ膜を形成し、その上に高屈折率膜と低屈折率膜を形成する方法が開示されている（特許文献４の請求項１〜４、図２）。
Patent Document 3 discloses a method of forming a silicon nitride film on a silver film surface for the purpose of improving moisture resistance and sulfur resistance, and further laminating a hard carbon film thereon (paragraph 0019 of Patent Document 3). For the purpose of improving the adhesion between the substrate and the silver film, a method of forming a TiO x film between the substrate and the silver film (paragraph 0014 of Patent Document 3) is disclosed.
Patent Document 4 discloses a method of forming an ITO or ZnO x film as an antioxidant layer on silver or an APC alloy and forming a high refractive index film and a low refractive index film thereon (Patent Document). 4 claims 1-4, FIG. 2).
特許文献５には、耐湿性、耐硫化性を目的として最表層にカーボン膜を、基板と銀膜との間に密着層として、酸素欠損の酸化チタンターゲットによる酸化チタン膜を形成する構成が開示されている（特許文献５の段落００１９、００２１、００２４、００２５）。
特許文献６には、金属又は金属酸化物からなる密着層を、基板と銀合金膜との間に形成し、さらに銀合金層の上にＩＴＯ、Ａｌ、Ｇａのいずれかを添加したＺｎＯ膜を密着層として形成する方法が開示されている（特許文献６の段落００３６、００５５、００５６）。
Patent Document 5 discloses a structure in which a carbon film is formed as an outermost layer for the purpose of moisture resistance and sulfidation resistance, and a titanium oxide film by an oxygen-deficient titanium oxide target is formed as an adhesion layer between a substrate and a silver film. (Patent Document 5, paragraphs 0019, 0021, 0024, and 0025).
Patent Document 6 discloses a ZnO film in which an adhesion layer made of a metal or a metal oxide is formed between a substrate and a silver alloy film, and ITO, Al, or Ga is added on the silver alloy layer. A method of forming an adhesive layer is disclosed (paragraphs 0036, 0055, and 0056 of Patent Document 6).
しかしながら、上記特許文献のように密着層を設けるには、密着層を形成するための蒸発源やこれに伴った電源を、別途新たに附加する必要がある。また、密着層を形成するため、その分、成膜時間が長くなり、工程全体としての管理負荷が増大するとともに生産性が低下する。 However, in order to provide an adhesion layer as in the above-mentioned patent document, it is necessary to newly add an evaporation source for forming the adhesion layer and a power supply associated therewith. In addition, since the adhesion layer is formed, the film formation time is increased correspondingly, the management load of the entire process is increased, and productivity is lowered.
基板と銀膜との間や、銀膜と誘電体多層膜との間に、バリア膜や密着力を向上させる膜など、何らかの機能を有する薄膜を成膜する必要があるが、銀膜は、酸素プラズマによって酸化が促進されたり、化合物を形成したりするなど、酸素プラズマの影響を受け易い性質を持っているため、バリア膜や密着力を向上させる膜などを成膜する際には、できるだけ酸素プラズマの影響が少ない製造方法が必要となる。 It is necessary to form a thin film having some function, such as a barrier film or a film that improves adhesion, between the substrate and the silver film, or between the silver film and the dielectric multilayer film. Oxidation is promoted by oxygen plasma, or it is easily affected by oxygen plasma, such as forming a compound. Therefore, when forming a barrier film or a film that improves adhesion, etc. A manufacturing method with less influence of oxygen plasma is required.
本発明は、上記の課題に鑑みてなされたものであり、本発明の目的は、銀膜とその基板側又は基板逆側に成膜された膜との間の密着力を向上させると同時に、銀膜における硫化及びマイグレーションを防ぐことが可能な高反射膜、高反射膜付き基板及び高反射膜の製造方法を提供することにある。
本発明の他の目的は、増反射設計を可能にする低屈折率の誘電体薄膜を見出して、耐硫化、耐マイグレーション、密着力、反射率の全てにおいて実用上十分な高反射膜を得ることが可能な高反射膜、高反射膜付き基板及び高反射膜の製造方法を提供することにある。
The present invention has been made in view of the above problems, and an object of the present invention is to improve the adhesion between a silver film and a film formed on the substrate side or the substrate opposite side, An object of the present invention is to provide a highly reflective film, a substrate with a highly reflective film, and a method for producing a highly reflective film capable of preventing sulfuration and migration in a silver film.
Another object of the present invention is to find a low-refractive-index dielectric thin film that enables an increased reflection design, and to obtain a highly reflective film that is practically sufficient in all of anti-sulfurization, anti-migration, adhesion, and reflectivity. It is an object to provide a highly reflective film, a substrate with a highly reflective film, and a method for producing the highly reflective film.
前記課題は、請求項１の高反射膜によれば、基板上に設けられ、銀膜と、該銀膜上に前記銀膜に接して設けられた誘電体多層膜と、を備えた高反射膜であって、前記誘電体多層膜は、低屈折率の無機誘電体膜と高屈折率の無機誘電体膜が、少なくとも２層以上交互に積層されることにより形成され、前記誘電体多層膜のうち、前記銀膜に隣接する層は、前記低屈折率の前記無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有し、前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であること、により解決される。 According to the highly reflective film of claim 1, the object is a highly reflective film provided on a substrate, and comprising a silver film and a dielectric multilayer film provided on the silver film in contact with the silver film. The dielectric multilayer film is formed by alternately laminating at least two layers of an inorganic dielectric film having a low refractive index and an inorganic dielectric film having a high refractive index, and the dielectric multilayer film. among the layer adjacent to the silver layer, the a said inorganic dielectric film having a low refractive index, in the inorganic dielectric film containing ZnO and SiO 2 as a main component, adjacent to the silver layer, This is solved by the fact that the ratio Zn / (Zn + Si) of the Zn content to the sum of Zn and Si is 0.53 at% to 18.52 at% .
このように、誘電体多層膜のうち、銀膜に隣接する層が、ＳｉＯ２を主成分としてＺｎＯを含有する膜からなるため、銀膜と誘電体多層膜との密着性を向上させることができる。
ＳｉＯ２を主成分としてＺｎＯを含有する膜は、ＳｉＯ２膜よりも屈折率が若干高くなるが、誘電体多層膜全体の構成としては、反射率を著しく低下させることなく、実用上十分な高い反射率を維持できる。従って、実用上十分な反射率を保ちつつ、誘電体多層膜と銀膜との密着性を向上させることができる。
Thus, since the layer adjacent to the silver film in the dielectric multilayer film is made of a film containing ZnO containing SiO 2 as a main component, the adhesion between the silver film and the dielectric multilayer film can be improved. it can.
A film containing SiO 2 as a main component and containing ZnO has a slightly higher refractive index than that of the SiO 2 film, but the overall structure of the dielectric multilayer film is sufficiently high in practical use without significantly reducing the reflectance. The reflectance can be maintained. Therefore, the adhesion between the dielectric multilayer film and the silver film can be improved while maintaining a practically sufficient reflectance.
また、誘電体多層膜のうち、銀膜に隣接する層は、低屈折率の無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有しているため、高反射膜の構成(設計)において、低屈折率層と密着層の二つの機能を兼ね備える膜となる。従って、新たな密着層を設けてソースの増強を行う必要が無く、装置負荷を増大させずに成膜工程の短縮ができる。
誘電体多層膜の銀膜に隣接する低屈折率の無機誘電体膜として、ＳｉＯ２を主成分とする層を、密着層として利用するため、ＳｉＯ２膜が従来から持ち備えるＡｇの耐硫化性、耐マイグレーション性はそのまま維持した状態で密着性を確保できる。
Also, among the dielectric multilayer films, the layer adjacent to the silver film is an inorganic dielectric film having a low refractive index and contains ZnO containing SiO 2 as a main component. ), A film having both functions of a low refractive index layer and an adhesion layer. Therefore, it is not necessary to provide a new adhesion layer to enhance the source, and the film forming process can be shortened without increasing the apparatus load.
As a low refractive index of the inorganic dielectric film adjacent to the silver film of the dielectric multilayer film, a layer mainly composed of SiO 2, for use as an adhesion layer, sulfidation resistance Ag, SiO 2 film is provided has conventionally Adhesion can be ensured while maintaining the migration resistance.
このように、ＳｉＯ２膜に一定量以上のＺｎＯを添加した無機誘電体膜にすることにより、ＳｉＯ２のみからなる膜を用いた場合と比較して、銀膜と無機誘電体膜との間の密着性を大きく向上させることができる。 As this, by the inorganic dielectric film added with a certain amount or more of ZnO in the SiO 2 film, as compared with the case of using a film made of only SiO 2, of silver film and the inorganic dielectric film The adhesion between them can be greatly improved.
このとき、前記銀膜に隣接する前記無機誘電体膜は、屈折率が、１．４８０〜１．６９４であり、消衰係数が、０．０８６以下であるとよい。
ＳｉＯ２にＺｎＯを添加した膜は、屈折率が、ＳｉＯ２膜の屈折率（１．４６）よりは若干高くなるが、屈折率を、１．４８０〜１．６９４とし、消衰係数を、０．０８６以下としているので、反射率特性を著しく低下させることなく実用上十分な増反射特性を維持できる。
At this time, the inorganic dielectric film adjacent to the silver film may have a refractive index of 1.480 to 1.694 and an extinction coefficient of 0.086 or less.
The film obtained by adding ZnO to SiO 2 has a refractive index slightly higher than the refractive index (1.46) of the SiO 2 film, but the refractive index is 1.480 to 1.694, and the extinction coefficient is Since it is 0.086 or less, practically sufficient increased reflection characteristics can be maintained without significantly reducing the reflectance characteristics.
このとき、前記銀膜は、前記基板との間に、チタン（Ｔｉ）、クロム（Ｃｒ）、ニッケル（Ｎｉ）又はこれらの金属が任意の組み合わせで混合された合金からなる密着性向上膜を、一層以上備えているとよい。
このように構成しているため、基板上に銀膜を直接成膜した場合よりも、基板と銀膜との間の密着性を向上させることができる。
At this time, the silver film is an adhesion improving film made of titanium (Ti), chromium (Cr), nickel (Ni) or an alloy in which these metals are mixed in an arbitrary combination with the substrate. It is good to have one or more layers.
Since it comprises in this way, the adhesiveness between a board | substrate and a silver film can be improved rather than the case where a silver film is directly formed on a board | substrate.
このとき、前記銀膜は、Ａｇを主成分とする膜又はＡｇとその他の金属との合金膜であるとよい。
このように構成しているため、銀膜を必ずしもＡｇ単体から形成する必要がなく、合金として形成することもできるため、銀膜の構成の自由度が高まる。
At this time, the silver film may be a film containing Ag as a main component or an alloy film of Ag and another metal.
Since it comprises in this way, since a silver film does not necessarily need to be formed from Ag single-piece | unit and can also form as an alloy, the freedom degree of a structure of a silver film increases.
前記課題は、請求項５の高反射膜付き基板によれば、基板と、該基板上に設けられた、銀膜と、該銀膜上に前記銀膜に接して設けられた誘電体多層膜と、を備えた高反射膜付き基板であって、前記誘電体多層膜は、低屈折率の無機誘電体膜と高屈折率の無機誘電体膜が、少なくとも２層以上交互に積層されることにより形成され、前記誘電体多層膜のうち、前記銀膜に隣接する層は、前記低屈折率の前記無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有し、前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であること、により解決される。 According to the substrate with a highly reflective film according to claim 5 , the subject is a substrate, a silver film provided on the substrate, and a dielectric multilayer film provided on the silver film in contact with the silver film. The dielectric multilayer film includes a low-refractive index inorganic dielectric film and a high-refractive index inorganic dielectric film alternately laminated in at least two layers. is formed by, out of the dielectric multilayer film, the layer adjacent to the silver layer, the a said inorganic dielectric film having a low refractive index, containing ZnO and SiO 2 as the main component, the silver layer In the adjacent inorganic dielectric film, the ratio Zn / (Zn + Si) of Zn content to the sum of Zn and Si is 0.53 at% to 18.52 at% .
このように、誘電体多層膜のうち、銀膜に隣接する層が、ＳｉＯ２を主成分としてＺｎＯを含有する膜からなるため、銀膜と誘電体多層膜との密着性を向上させることができる。
ＳｉＯ２を主成分としてＺｎＯを含有する膜は、ＳｉＯ２膜よりも屈折率が若干高くなるが、誘電体多層膜全体の構成としては、反射率を著しく低下させることなく、実用上十分な高い反射率を維持できる。従って、実用上十分な反射率を保ちつつ、誘電体多層膜と銀膜との密着性を向上させることができる。
Thus, since the layer adjacent to the silver film in the dielectric multilayer film is made of a film containing ZnO containing SiO 2 as a main component, the adhesion between the silver film and the dielectric multilayer film can be improved. it can.
A film containing SiO 2 as a main component and containing ZnO has a slightly higher refractive index than that of the SiO 2 film, but the overall structure of the dielectric multilayer film is sufficiently high in practical use without significantly reducing the reflectance. The reflectance can be maintained. Therefore, the adhesion between the dielectric multilayer film and the silver film can be improved while maintaining a practically sufficient reflectance.
また、誘電体多層膜のうち、銀膜に隣接する層は、低屈折率の無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有しているため、高反射膜の構成(設計)において、低屈折率層と密着層の二つの機能を兼ね備える膜となる。従って、新たな密着層を設けてソースの増強を行う必要が無く、装置負荷を増大させずに成膜工程の短縮ができる。
誘電体多層膜の銀膜に隣接する低屈折率の無機誘電体膜として、ＳｉＯ２を主成分とする層を、密着層として利用するため、ＳｉＯ２膜が従来から持ち備えるＡｇの耐硫化性、耐マイグレーション性はそのまま維持した状態で密着性を確保できる。
Also, among the dielectric multilayer films, the layer adjacent to the silver film is an inorganic dielectric film having a low refractive index and contains ZnO containing SiO 2 as a main component. ), A film having both functions of a low refractive index layer and an adhesion layer. Therefore, it is not necessary to provide a new adhesion layer to enhance the source, and the film forming process can be shortened without increasing the apparatus load.
As a low refractive index of the inorganic dielectric film adjacent to the silver film of the dielectric multilayer film, a layer mainly composed of SiO 2, for use as an adhesion layer, sulfidation resistance Ag, SiO 2 film is provided has conventionally Adhesion can be ensured while maintaining the migration resistance.
前記課題は、請求項６の高反射膜の製造方法によれば、基板上に、Ａｇを主成分とする膜又はＡｇとその他の金属との合金膜からなる銀膜を成膜する銀膜成膜工程と、前記銀膜の上に、ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜を酸素プラズマにさらすことなく成膜する工程であって、前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であり、前記ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜の表面上に、高屈折率の無機誘電体膜と、低屈折率の無機誘電体膜とを、少なくとも１層以上交互に積層する工程と、を備えること、により解決される。 According to the method for producing a highly reflective film of claim 6 , the object is to form a silver film formed on a substrate by forming a film containing Ag as a main component or a silver film made of an alloy film of Ag and another metal. a membrane process, on the silver film, a step of depositing without exposing the inorganic dielectric film having a low refractive index containing ZnO and SiO 2 as a main component in an oxygen plasma, adjacent to the silver layer A ratio Zn / (Zn + Si) of Zn content to the sum of Zn and Si in the inorganic dielectric film is 0.53 at% to 18.52 at%, and the low content containing ZnO containing SiO 2 as a main component. Solving the problem by providing a step of alternately laminating at least one or more layers of an inorganic dielectric film having a high refractive index and an inorganic dielectric film having a low refractive index on the surface of the inorganic dielectric film having a refractive index. Is done.
このように、銀膜の上に、ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜を、酸素プラズマにさらすことなく成膜する工程と、前記ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜の表面上に、高屈折率の無機誘電体膜と、低屈折率の無機誘電体膜とを、少なくとも１層以上交互に積層する工程と、を備えているため、銀膜と誘電体多層膜との密着性を向上させることができる。
ＳｉＯ２を主成分としてＺｎＯを含有する膜は、ＳｉＯ２膜よりも屈折率が若干高くなるが、誘電体多層膜全体の構成としては、反射率を著しく低下させることなく、実用上十分な高い反射率を維持できる。従って、実用上十分な反射率を保ちつつ、誘電体多層膜と銀膜との密着性を向上させることができる。
また、ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜を、酸素プラズマにさらすことなく成膜するため、酸素プラズマに弱い銀膜をプラズマにさらすことを抑制でき、銀膜のマイグレーションや酸化が抑制され、反射率の高い高反射膜が達成される。
Thus, over the silver film, ZnO a low refractive index of the inorganic dielectric film containing ZnO and SiO 2 as a main component, a step of forming without exposure to oxygen plasma, the SiO 2 as a main component A step of alternately laminating at least one layer of a high refractive index inorganic dielectric film and a low refractive index inorganic dielectric film on the surface of the low refractive index inorganic dielectric film containing Therefore, the adhesion between the silver film and the dielectric multilayer film can be improved.
A film containing SiO 2 as a main component and containing ZnO has a slightly higher refractive index than that of the SiO 2 film, but the overall structure of the dielectric multilayer film is sufficiently high in practical use without significantly reducing the reflectance. The reflectance can be maintained. Therefore, the adhesion between the dielectric multilayer film and the silver film can be improved while maintaining a practically sufficient reflectance.
In addition, since a low refractive index inorganic dielectric film containing SiO 2 as a main component and containing ZnO is formed without being exposed to oxygen plasma, it is possible to suppress exposure of a silver film that is weak to oxygen plasma to plasma. Migration and oxidation are suppressed, and a highly reflective film with high reflectivity is achieved.
このとき、前記銀膜成膜工程の前に、前記基板上に、チタン（Ｔｉ）、クロム（Ｃｒ）、ニッケル（Ｎｉ）又はこれらの金属が任意の組み合わせで混合された合金からなる密着性向上膜を、一層以上成膜してもよい。
このように構成しているため、基板上に銀膜を直接成膜した場合よりも、基板と銀膜との間の密着性を向上させることができる。
At this time, before the silver film forming step, the adhesion improvement is made of titanium (Ti), chromium (Cr), nickel (Ni) or an alloy in which these metals are mixed in any combination on the substrate. One or more films may be formed.
Since it comprises in this way, the adhesiveness between a board | substrate and a silver film can be improved rather than the case where a silver film is directly formed on a board | substrate.
本発明によれば、誘電体多層膜のうち、銀膜に隣接する層が、ＳｉＯ２を主成分としてＺｎＯを含有する膜からなるため、銀膜と誘電体多層膜との密着性を向上させることができる。
ＳｉＯ２を主成分としてＺｎＯを含有する膜は、ＳｉＯ２膜よりも屈折率が若干高くなるが、誘電体多層膜全体の構成としては、反射率を著しく低下させることなく、実用上十分な高い反射率を維持できる。従って、実用上十分な反射率を保ちつつ、誘電体多層膜と銀膜との密着性を向上させることができる。
According to the present invention, among the dielectric multilayer film, the layer adjacent to the silver film, to become a film containing ZnO and SiO 2 as a main component, to improve the adhesion between the silver film and the dielectric multilayer film be able to.
A film containing SiO 2 as a main component and containing ZnO has a slightly higher refractive index than that of the SiO 2 film, but the overall structure of the dielectric multilayer film is sufficiently high in practical use without significantly reducing the reflectance. The reflectance can be maintained. Therefore, the adhesion between the dielectric multilayer film and the silver film can be improved while maintaining a practically sufficient reflectance.
また、誘電体多層膜のうち、銀膜に隣接する層は、低屈折率の無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有しているため、高反射膜の構成(設計)において、低屈折率層と密着層の二つの機能を兼ね備える膜となる。従って、新たな密着層を設けてソースの増強を行う必要が無く、装置負荷を増大させずに成膜工程の短縮ができる。
誘電体多層膜の銀膜に隣接するＳｉＯ２層を、密着層として利用するため、ＳｉＯ２膜が従来から持ち備えるＡｇの耐硫化性、耐マイグレーション性はそのまま維持した状態で密着性を確保できる。
Also, among the dielectric multilayer films, the layer adjacent to the silver film is an inorganic dielectric film having a low refractive index and contains ZnO containing SiO 2 as a main component. ), A film having both functions of a low refractive index layer and an adhesion layer. Therefore, it is not necessary to provide a new adhesion layer to enhance the source, and the film forming process can be shortened without increasing the apparatus load.
Since the SiO 2 layer adjacent to the silver film of the dielectric multilayer film is used as an adhesion layer, the adhesion can be secured while maintaining the sulfidation resistance and migration resistance of Ag conventionally possessed by the SiO 2 film. .
＜＜高反射膜付き基板１＞＞
以下、本発明の一実施形態に係る高反射膜付き基板１について、図１〜図９を参照しながら説明する。なお、以下に説明する材料、配置、構成等は、本発明を限定するものではなく、本発明の趣旨の範囲内で種々改変できるものである。
本明細書における高反射膜とは、増反射膜と同義である。
本実施形態の高反射膜付き基板１は、図１に示すように、基板１０上に、密着性向上膜２０、銀膜３０、誘電体多層膜４０が形成されたものである。銀膜３０、誘電体多層膜４０の積層体、又は、密着性向上膜２０、誘電体多層膜４０の積層体が、特許請求の範囲の高反射膜に該当する。
<< Substrate with High Reflective Film 1 >>
Hereinafter, the board | substrate 1 with a highly reflective film which concerns on one Embodiment of this invention is demonstrated, referring FIGS. The materials, arrangements, configurations, and the like described below do not limit the present invention and can be variously modified within the scope of the gist of the present invention.
In the present specification, the highly reflective film is synonymous with the enhanced reflective film.
As shown in FIG. 1, the substrate 1 with a highly reflective film according to the present embodiment has an adhesion improving film 20, a silver film 30, and a dielectric multilayer film 40 formed on a substrate 10. The laminated body of the silver film 30 and the dielectric multilayer film 40 or the laminated body of the adhesion improving film 20 and the dielectric multilayer film 40 corresponds to the highly reflective film in the claims.
基板１０は、硝子、金属、セラミックス、フィルム状、板状の樹脂成形体など、表面に高反射膜を成膜可能なものであればよく、基板１０の材質は問わない。また、基板１０は、表面が平面、凹凸面のいずれであってもよく、また、フレキシブル基板であってもよい。 The substrate 10 may be any material as long as it can form a highly reflective film on the surface, such as glass, metal, ceramics, film-like, or plate-like resin moldings. Further, the surface of the substrate 10 may be either a flat surface or an uneven surface, or may be a flexible substrate.
基板１０は、表面を、できるだけ鏡面に近い状態に仕上げた面とすると好適である。本実施形態では、金属膜を反射膜材料として用いているため、このように構成することにより、より良い反射膜を得ることが可能となる。なお、フロントライト方式の電子ペーパーのように、高い拡散光（散乱光）を必要とする特殊用途では、必要とする反射率を得るために、表面に任意の凹凸を形成するか、梨地処理をして粗に加工してもよい。
基板１０は、成膜前に清浄に処理されて使用される。
The substrate 10 is preferably a surface whose surface is finished as close to a mirror surface as possible. In this embodiment, since the metal film is used as the reflective film material, it is possible to obtain a better reflective film by configuring in this way. In addition, in special applications that require high diffused light (scattered light), such as front-lighted electronic paper, in order to obtain the required reflectivity, an arbitrary unevenness is formed on the surface, or a satin treatment is performed. And may be processed roughly.
The substrate 10 is used after being cleanly processed before film formation.
基板１０上には、図１に示すように、基板１０と銀膜３０との密着性を向上させる目的で、チタン（Ｔｉ）、クロム（Ｃｒ）、ニッケル（Ｎｉ）又はこれらの金属が任意の組み合わせで混合された合金からなる密着性向上膜２０が成膜されている。密着性向上膜２０は、図１に示すように、１層のみでもよいし、２層以上の膜を備えていてもよい。また、密着性向上膜２０を備えず、基板１０上に直接銀膜３０が形成されていてもよい。
密着性向上膜２０を備えていることにより、より安定した反射膜とすることができる。
Ｔｉ、Ｃｒ及びＮｉは、基板１０との密着力及び銀膜３０との密着力が高く、銀膜３０へのマイグレーションが少ないため、銀膜３０内における異常粒子の成長や欠陥を少なくすることができ、その結果、銀膜３０の反射率の低下を抑止可能となる。
On the substrate 10, as shown in FIG. 1, for the purpose of improving the adhesion between the substrate 10 and the silver film 30, titanium (Ti), chromium (Cr), nickel (Ni) or any of these metals may be used. An adhesion improving film 20 made of an alloy mixed in combination is formed. As shown in FIG. 1, the adhesion improving film 20 may include only one layer or may include two or more layers. Further, the silver film 30 may be formed directly on the substrate 10 without providing the adhesion improving film 20.
By providing the adhesion improving film 20, a more stable reflective film can be obtained.
Since Ti, Cr, and Ni have high adhesion to the substrate 10 and adhesion to the silver film 30 and less migration to the silver film 30, the growth of abnormal particles and defects in the silver film 30 may be reduced. As a result, a decrease in the reflectance of the silver film 30 can be suppressed.
銀膜３０は、Ａｇを主成分とする膜又はＡｇとその他の金属との合金膜からなる。
Ａｇを主成分とする膜は、Ａｇ単体からなる膜、又は、Ａｇと、Ａｇ以外の微量成分を含む膜である。
また、Ａｇとその他の金属との合金膜は、Ａｇと、金（Ａｕ）、パラジウム（Ｐｄ）、錫（Ｓｎ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）、銅（Ｃｕ）、チタン（Ｔｉ）、セリウム（Ｃｅ）、ネオジム（Ｎｅ）、ビスマス（Ｂｉ）、バナジウム（Ｖ）、ゲルマニウム（Ｇｅ）、亜鉛（Ｚｅ）を含む群から選択された一以上の金属との合金からなる膜である。
銀膜３０は、膜厚が、一般的に入射光が全反射する１００ｎｍ以上であると好適であるが、必要以上に厚くする必要はない。但し、入射光が全反射するよう、膜厚１００ｎｍ以上としても、可視域での平均反射率は、Ａｌで略９０％、Ａｇで略９６％であり、これ以上の反射率は望めない。
また、銀膜３０を半透過膜として使用する場合は、所望の反射率に合わせて膜厚を数十ｎｍとするとよい。
The silver film 30 is made of a film containing Ag as a main component or an alloy film of Ag and other metals.
The film containing Ag as a main component is a film made of Ag alone, or a film containing Ag and a trace component other than Ag.
In addition, an alloy film of Ag and other metals includes Ag, gold (Au), palladium (Pd), tin (Sn), gallium (Ga), indium (In), copper (Cu), and titanium (Ti). , Cerium (Ce), neodymium (Ne), bismuth (Bi), vanadium (V), germanium (Ge), and a film made of an alloy with one or more metals selected from the group including zinc (Ze).
The silver film 30 preferably has a film thickness of 100 nm or more where incident light is totally reflected, but it need not be thicker than necessary. However, even if the film thickness is 100 nm or more so that incident light is totally reflected, the average reflectance in the visible region is approximately 90% for Al and approximately 96% for Ag, and a reflectance higher than this cannot be expected.
Further, when the silver film 30 is used as a semi-transmissive film, the film thickness is preferably set to several tens of nm in accordance with a desired reflectance.
誘電体多層膜４０は、図１に示すように、低屈折率膜４０ｂと高屈折率膜４０ａとが交互に、少なくとも１層ずつ、合計２層以上積層されて構成されている。本実施形態では、低屈折率膜４０ｂと高屈折率膜４０ａを１層ずつ備えた最もシンプルな構成となっている。 As shown in FIG. 1, the dielectric multilayer film 40 is configured by laminating at least one low refractive index film 40b and high refractive index film 40a in total, ie, two or more layers. In the present embodiment, the simplest configuration includes one low refractive index film 40b and one high refractive index film 40a.
Ａｇよりも高い反射率を持ち備える金属は存在しないため、反射膜に、金属膜又は合金膜単体を用いた場合は、達成可能な反射率は、Ａｇ又はＡｇ合金が固有に備える反射率に依存してしまう。
しかし、反射膜に、より高い反射率を必要とする場合には、屈折率の異なる誘電体等の薄膜を、屈折率の異なるそれぞれの光学膜厚ｎｄが、所望する波長λの１／４に相当するようにして、交互に複数回積層することにより、より高い反射率が達成可能である。但し、λは、所望する波長の中心波長、ｎは屈折率、ｄは実際の膜厚である。
銀膜３０と誘電体多層膜４０の積層体における反射は、積層体に光が入射したときに、誘電体多層膜４０の最表面で反射される光と、複数層からなる誘電体多層膜４０を通った光が各膜の界面で反射して戻る光と、銀膜３０で反射して戻る光とが合成されることにより全体として反射する光の量が増大することによるものである。すなわち、界面での光は、低屈折率から高屈折率の媒体に入射した後に反射してくる場合は位相が反転して戻ってくる。また、高屈折率から低屈折率の媒体に入射した後に反射してくる場合は、位相が反転せずにそのまま戻ってくるので、それぞれの反射光の位相が同一方向に重なることにより振幅が増強されるためである。
Since there is no metal having a reflectivity higher than Ag, when a metal film or an alloy film alone is used for the reflective film, the achievable reflectivity depends on the reflectivity inherent in Ag or the Ag alloy Resulting in.
However, when a higher reflectance is required for the reflective film, a thin film such as a dielectric having a different refractive index is used so that each optical film thickness nd having a different refractive index is ¼ of the desired wavelength λ. In a corresponding manner, higher reflectivity can be achieved by alternately laminating several times. Where λ is the center wavelength of the desired wavelength, n is the refractive index, and d is the actual film thickness.
The reflection in the laminated body of the silver film 30 and the dielectric multilayer film 40 includes the light reflected from the outermost surface of the dielectric multilayer film 40 and the dielectric multilayer film 40 composed of a plurality of layers when light enters the laminated body. This is because the amount of light reflected as a whole is increased by combining the light that passes through and returns from the interface of each film and the light that reflects back from the silver film 30. In other words, when the light at the interface is reflected after entering a medium having a low refractive index to a high refractive index, the phase is reversed and returned. In addition, when the light is reflected after being incident on a medium having a low refractive index from a high refractive index, the phase returns without changing the phase. Therefore, the amplitude of each reflected light is increased by overlapping in the same direction. It is to be done.
従って、高反射率を得るには、最表面層が高屈折率膜４０ａでなければならない。
また、低屈折率膜４０ｂと高屈折率膜４０ａとを複数組繰り返して２回以上積層する場合、中心波長での反射率は高くなるものの、両端の波長では、低屈折率膜４０ｂと高屈折率膜４０ａとをそれぞれ１層ずつのみ備えた２層のみの場合よりも、反射率が低くなるので、積層回数は、用途により選定する必要がある。
Therefore, in order to obtain a high reflectance, the outermost surface layer must be the high refractive index film 40a.
Further, when a plurality of low refractive index films 40b and high refractive index films 40a are repeatedly laminated two or more times, the reflectance at the center wavelength is high, but the low refractive index film 40b and the high refractive index are obtained at both wavelengths. Since the reflectance is lower than in the case of only two layers each including only one layer of the rate film 40a, the number of laminations needs to be selected depending on the application.
高屈折率膜４０ａは、相対的に高屈折率の材料から成膜された膜であり、ＴｉＯ２、Ｎｂ２Ｏ５、Ｃｅ２Ｏ３、ＴａＮ、ＺｒＯ２等の材料からなる膜、又は、これらの材料とこれらの材料以外の微量成分を含む膜からなる。
低屈折率膜４０ｂは、相対的に低屈折率の材料から成膜された膜であり、ＭｇＦ２、ＳｉＯ２、Ａｌ２Ｏ３等の材料からなる膜、又は、これらの材料とこれらの材料以外の微量成分を含む膜からなる。低屈折率膜４０ｂは、耐硫化性が高く、マイグレーションの抑制効果の高いＳｉＯ２からなると好適である。
低屈折率膜４０ｂ及び高屈折率膜４０ａを、これらの材料から構成すると、低屈折率膜と高屈折率膜率との屈折率の差を大きくすることができ、より効果的な増反射効果を得ることができる。
The high refractive index film 40a is a film formed from a material having a relatively high refractive index, and is a film made of a material such as TiO 2 , Nb 2 O 5 , Ce 2 O 3 , TaN, ZrO 2 , or It consists of a film containing these materials and trace components other than these materials.
The low refractive index film 40b is a film formed from a material having a relatively low refractive index, and is a film made of a material such as MgF 2 , SiO 2 , Al 2 O 3 , or these materials and these materials. It consists of a film containing trace components other than The low refractive index film 40b is preferably made of SiO 2 having a high resistance to sulfidation and a high effect of suppressing migration.
When the low-refractive index film 40b and the high-refractive index film 40a are made of these materials, the difference in refractive index between the low-refractive index film and the high-refractive index film ratio can be increased, and a more effective enhanced reflection effect. Can be obtained.
一以上の低屈折率膜４０ｂのうち、銀膜３０の直上の低屈折率膜４０ｂは、ＳｉＯ２に一定量のＺｎＯを添加した膜からなる。
更に具体的には、銀膜３０の直上の低屈折率膜４０ｂには、膜中におけるＺｎとＳｉの合計に対するＺｎの含有量の割合、つまり、Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％、より好ましくは０．５３ａｔ％〜１６．０８ａｔ％の範囲となるように、ＳｉＯ２にＺｎＯが添加されている。
銀膜３０の直上の低屈折率膜４０ｂをこのように構成することにより、密着力が高く、銀膜３０に対する耐硫化性が高く、マイグレーション抑制効果があり、且つ、高反射膜としての要求を満足できる程度の低屈折率を備えた膜を達成することができる。その結果、反射率を低下させることなく、銀膜３０と誘電体多層膜４０との間の密着性を向上できる。
また、銀膜３０の直上の低屈折率膜４０ｂを、このように構成していることにより、誘電体多層膜４０とは別個に新たな密着層を設ける必要がなくなるため、最低限の装置構成と最低限の膜構成で、高反射膜を製作可能となり、生産性の面及び価格面において優位な膜構成を達成できる。
Of one or more low-refractive-index film 40b, the low refractive index film 40b directly above the silver film 30 is formed of a film obtained by adding a certain amount of ZnO to SiO 2.
More specifically, in the low refractive index film 40b immediately above the silver film 30, the ratio of the Zn content to the total of Zn and Si in the film, that is, Zn / (Zn + Si) is 0.53 at% to ZnO is added to SiO 2 so that it is in the range of 18.52 at%, more preferably 0.53 at% to 16.08 at%.
By constructing the low refractive index film 40b immediately above the silver film 30 in this way, the adhesive strength is high, the sulfide resistance to the silver film 30 is high, the migration is effective, and the demand as a highly reflective film is met. A film with a satisfactory low refractive index can be achieved. As a result, the adhesion between the silver film 30 and the dielectric multilayer film 40 can be improved without reducing the reflectance.
Further, since the low refractive index film 40b immediately above the silver film 30 is configured in this way, it is not necessary to provide a new adhesion layer separately from the dielectric multilayer film 40. With a minimum film configuration, a highly reflective film can be manufactured, and a film configuration superior in productivity and price can be achieved.
ＳｉＯ２に一定量のＺｎＯを添加した膜は、屈折率が、１．４８０〜１．６９４の範囲で、消衰係数が０．００８６以下、より好ましくは、屈折率が１．４８０〜１．６５７の範囲で、消衰係数が０．００４９８以下である。 A film in which a certain amount of ZnO is added to SiO 2 has a refractive index in the range of 1.480 to 1.694 and an extinction coefficient of 0.0086 or less, more preferably a refractive index of 1.480 to 1 .. In the range of 657, the extinction coefficient is 0.00498 or less.
＜＜高反射多層膜の製造方法＞＞
以上の高反射多層膜及び高反射多層膜付き基板１は、以下の方法により製造される。
まず、基板１０を、湿式、乾式、プラズマ、ＵＶ、その他の方法、好適には、湿式の超音波洗浄により、清浄化する。
次いで、不図示のスパッタリング装置に、ＺｎＯターゲットを備えたＺｎＯ用のカソード、ＳｉＯ２のターゲットを備えたＳｉＯ2用のカソード、Ａｇターゲットを備えたＡｇ用のカソード、Ｔｉ等の密着性向上膜２０成膜用材料のターゲットを備えた密着性向上膜用カソードを、セットする。
次いで、基板１０を、装置内の基板ホルダーに設置し、装置内を５．０×Ｅ−４Ｐａまで排気する。
装置内にアルゴンガスを２．０×Ｅ−１Ｐａになるまで導入し、その状態を保ちながら、Ｔｉ等の密着性向上膜２０の成膜用材料のターゲットを用い、磁場４００ＧにてＤＣスパッタリング法により、膜厚５０ｎｍのＴｉからなる密着性向上膜２０を成膜する。
<< Manufacturing Method of High Reflective Multilayer Film >>
The above highly reflective multilayer film and the substrate 1 with a highly reflective multilayer film are manufactured by the following method.
First, the substrate 10 is cleaned by wet, dry, plasma, UV, other methods, preferably wet ultrasonic cleaning.
Then, the sputtering device not shown, cathode for a ZnO having a ZnO target, a cathode for SiO 2 having a SiO 2 target, a cathode for Ag having a Ag target, adhesion enhancing film, such as Ti 20 An adhesion improving film cathode provided with a film forming material target is set.
Subsequently, the board | substrate 10 is installed in the board | substrate holder in an apparatus, and the inside of an apparatus is exhausted to 5.0xE-4Pa.
Argon gas was introduced into the apparatus until 2.0 × E-1 Pa, and while maintaining this state, a target of a material for forming the adhesion improving film 20 such as Ti was used, and a DC sputtering method with a magnetic field of 400 G Thus, an adhesion improving film 20 made of Ti having a thickness of 50 nm is formed.
次に、同じ真空雰囲気中において、Ａｇターゲットを用いたＤＣスパッタリング法により、膜厚１２０ｎｍのＡｇからなる銀膜３０を成膜する。
その後、装置内の圧力が２．２×Ｅ−１Ｐａになるまで、アルゴンガスのみを導入し、磁場６００Ｇにて、ＺｎＯカソードに０．１ｋｗの電力と、ＳｉＯ２カソードに１．２ｋｗの電力をそれぞれ投入した２元ＲＦスパッタリング法により、膜厚６０．３ｎｍの低屈折率膜４０ｂを成膜する。
Next, in the same vacuum atmosphere, a silver film 30 made of Ag with a film thickness of 120 nm is formed by DC sputtering using an Ag target.
Thereafter, only argon gas is introduced until the pressure in the apparatus becomes 2.2 × E-1 Pa, and at a magnetic field of 600 G, a power of 0.1 kW is applied to the ZnO cathode and a power of 1.2 kW is applied to the SiO 2 cathode. A low-refractive-index film 40b having a film thickness of 60.3 nm is formed by a binary RF sputtering method that has been introduced.
装置内のカソード数の制限があるため、低屈折率膜４０ｂまで成膜した基板１０を取り出して別のスパッタリング装置に移し、酸化チタン（ＴｉＯｘ）等の高屈折率材料のターゲットを用いて、アルゴンガス中に酸素ガスを含む雰囲気で、２．２×Ｅ−１Ｐａで、ＤＣスパッタリング法により、膜厚３９ｎｍのＴｉＯ２等の高屈折率材料からなる高屈折率膜４０ａを成膜する。
以上の方法により、図１に示すように、基板１０上に、密着性向上膜２０、銀膜３０、誘電体多層膜４０が積層された４層構成の高反射膜を成膜し、本実施形態の高反射膜付き基板を作製する。
なお、高屈折率膜４０ａの成膜を、他の膜の成膜と同じスパッタリング装置内で行ってもよい。
また、Ａｇ用のカソードと共に、Ｔｉ、Ｃｒ及び／又はＮｉのターゲットを備えたカソードをスパッタリング装置内に設置し、Ａｇターゲット及びＴｉ、Ｃｒ及び／又はＮｉのターゲットを用いたスパッタリングとを同時に行って、銀膜３０を、ＡｇとＴｉ、Ｃｒ及び／又はＮｉとの合金としてもよい。
Since the number of cathodes in the apparatus is limited, the substrate 10 formed up to the low refractive index film 40b is taken out and transferred to another sputtering apparatus, and using a target of a high refractive index material such as titanium oxide (TiO x ), A high refractive index film 40a made of a high refractive index material such as TiO 2 having a thickness of 39 nm is formed by DC sputtering at 2.2 × E-1 Pa in an atmosphere containing oxygen gas in argon gas.
By the above method, as shown in FIG. 1, a high-reflection film having a four-layer structure in which the adhesion improving film 20, the silver film 30, and the dielectric multilayer film 40 are laminated is formed on the substrate 10, and this embodiment is performed. A substrate with a highly reflective film in the form is manufactured.
Note that the high refractive index film 40a may be formed in the same sputtering apparatus as other films.
In addition, a cathode provided with a target of Ti, Cr and / or Ni together with a cathode for Ag is installed in a sputtering apparatus, and sputtering using an Ag target and a target of Ti, Cr and / or Ni is simultaneously performed. The silver film 30 may be an alloy of Ag and Ti, Cr and / or Ni.
以下、本発明を、実施例に基づき、更に詳細に説明するが、本発明は、以下の実施例の範囲に限定されるものではない。
（実験１）
低屈折率膜４０ｂにおけるＳｉＯ2に対するＺｎＯの添加量について調査するために、実験１を行った。
実験１では、自社製のスパッタリング装置ＧＲＤＳ８００で、到達圧力５．０Ｅ−４Ｐａ以下、室温下で、ターゲットサイズ１５０φの酸化亜鉛（ＺｎＯ）、酸化シリコン（ＳｉＯ２）のターゲットを備えたＺｎＯのカソードとＳｉＯ2のカソードを用い、磁場６００Ｇにて、２元ＲＦスパッタリング法により、実験例１〜６の膜厚１００ｎｍのＳｉＯ2−ＺｎＯの単層膜を成膜した。
このときのＺｎＯのカソードとＳｉＯ2のカソードの投入電力は、表１の通りであった。
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to the range of a following example.
(Experiment 1)
Experiment 1 was conducted to investigate the amount of ZnO added to SiO 2 in the low refractive index film 40b.
In Experiment 1, a ZnO cathode provided with a zinc oxide (ZnO) target having a target size of 150φ and a silicon oxide (SiO 2 ) target at room temperature under an ultimate pressure of 5.0E-4 Pa with an in-house sputtering apparatus GRDS800; A single layer film of SiO 2 —ZnO having a thickness of 100 nm of Experimental Examples 1 to 6 was formed by a binary RF sputtering method using a SiO 2 cathode at a magnetic field of 600 G.
The input power of the ZnO cathode and the SiO 2 cathode was as shown in Table 1.
また、ＺｎＯのカソードには電力を投入せず、ＳｉＯ2のカソードにのみ、１．３０ｋＷの電力を投入して、対比例１の膜厚１００ｎｍのＳｉＯ2単層膜を成膜した。
実験例１〜６の単層膜について、ＸＰＳ（X-ray Photoelectron Spectroscopy、Ｘ線光電子分光法）装置（日本電子株式会社製、ＪＰＳ-９０００ＭＣ）を用いて、Ｚｎ、Ｏ、Ｓｉの成分分析を行い、エッチング時間２秒、１５秒、３０秒、５０秒、７０秒における各成分の含有量（ａｔ％）を測定した。
エッチング時間とは、ＸＰＳ装置を用いた成分分析操作中に、ＸＰＳ装置に付属のイオン源により、単層膜に対してアルゴンエッチングを行った時間を示す。エッチング時間は、分析目的のために薄膜表面からエッチングした時間であるが、単層膜の深さ方向における分析値を読み取ることができる。
成分分析の測定結果を、表２に示す。
In addition, power was not applied to the ZnO cathode, but power of 1.30 kW was applied only to the SiO 2 cathode to form a SiO 2 single layer film having a relative thickness of 100 nm.
Using the XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy) apparatus (JPS-9000MC, manufactured by JEOL Ltd.), the component analysis of Zn, O, and Si was performed on the monolayer films of Experimental Examples 1-6. Then, the content (at%) of each component at the etching time of 2 seconds, 15 seconds, 30 seconds, 50 seconds, and 70 seconds was measured.
The etching time indicates the time during which argon etching was performed on the single layer film by the ion source attached to the XPS apparatus during the component analysis operation using the XPS apparatus. The etching time is the time of etching from the surface of the thin film for the purpose of analysis, but the analysis value in the depth direction of the single layer film can be read.
Table 2 shows the measurement results of the component analysis.
表２の結果より、実験例１から実験例６にかけて、ＺｎＯのカソードに印加するＲＦ電力が増加するに従って、単層膜中のＺｎの含有量が高くなることが分かった。
次いで、表２の実験例１〜６の単層膜のＸＰＳのエッチング時間におけるＺｎ、Ｓｉの成分量測定値から、単層膜中のＺｎ／（Ｚｎ＋Ｓｉ）の比率を算出した。算出したＺｎ／（Ｚｎ＋Ｓｉ）の計算値を表３に、計算値をプロットしたグラフを図２に示す。
From the results of Table 2, it was found that the Zn content in the single layer film increased as the RF power applied to the ZnO cathode increased from Experimental Example 1 to Experimental Example 6.
Next, the ratio of Zn / (Zn + Si) in the single layer film was calculated from the measured amounts of Zn and Si components in the XPS etching time of the single layer films in Experimental Examples 1 to 6 in Table 2. The calculated values of Zn / (Zn + Si) calculated are shown in Table 3, and a graph plotting the calculated values is shown in FIG.
表３、図２の結果より、実験例２〜６では、エッチング時間が長いほど、つまり、単層膜の表面からの深さが深い位置ほど、Ｚｎの比率が高くなっていた。
また、分光エリプソメータ（株式会社堀場製作所製、UVISEL/DH10+460-VIS-AGMS-G）を用いて、実験例１〜６及び対比例１の単層膜の屈折率及び消衰係数を測定した。
波長５５０ｎｍにおける屈折率ｎ、消衰係数ｋの測定値を表４及び図３、４に、波長３５０〜７５０ｎｍにおける屈折率ｎ、消衰係数ｋの測定値を表５及び図５、６に示す。
From the results of Table 3 and FIG. 2, in Experimental Examples 2 to 6, the longer the etching time, that is, the deeper the position from the surface of the single layer film, the higher the Zn ratio.
In addition, using a spectroscopic ellipsometer (Horiba, Ltd., UVISEL / DH10 + 460-VIS-AGMS-G), the refractive index and extinction coefficient of single-layer films of Experimental Examples 1 to 6 and Comparative Example 1 were measured. .
The measured values of the refractive index n and the extinction coefficient k at a wavelength of 550 nm are shown in Table 4 and FIGS. 3 and 4, and the measured values of the refractive index n and the extinction coefficient k at a wavelength of 350 to 750 nm are shown in Table 5 and FIGS. .
表４、５、図３、５の結果より、実験例１〜６の単層膜の屈折率は、実験例１、２では、対比例１と略同程度であったのに対し、実験例３〜６では、対比例１よりも０．１〜０．２５程度高くなっていた。 From the results shown in Tables 4 and 5 and FIGS. In 3-6, it was about 0.1-0.25 higher than the comparative 1.
（実施例１）
本実施例では、以下の手順により、本発明の一実施例に係る高反射膜を成膜した。
板厚１．１ｍｍ、基板サイズ１００ｍｍ×１００ｍｍの硝子製の基板１０を湿式の超音波洗浄により清浄化した。
一方、スパッタリング装置（自社製、ＧＲＤＳ８００）内に、複数のカソードを設置し、それぞれのカソードに、Ａｇ、Ｔｉ、ＺｎＯ、ＳｉＯ２のターゲットをセットした。
基板１０を、装置内の基板ホルダーに設置した後、装置内を５．０×Ｅ−４Ｐａまで排気した。
装置内にアルゴンガスを２．０×Ｅ−１Ｐａになるまで導入し、その状態を保ちながら、Ｔｉターゲットを用い、磁場４００ＧにてＤＣスパッタリング法により、膜厚５０ｎｍのＴｉからなる密着性向上膜２０を成膜した。
Example 1
In this example, a highly reflective film according to an example of the present invention was formed by the following procedure.
A glass substrate 10 having a plate thickness of 1.1 mm and a substrate size of 100 mm × 100 mm was cleaned by wet ultrasonic cleaning.
On the other hand, a plurality of cathodes were installed in a sputtering apparatus (manufactured by GRDS800), and targets of Ag, Ti, ZnO, and SiO 2 were set on each cathode.
After the substrate 10 was placed on the substrate holder in the apparatus, the inside of the apparatus was evacuated to 5.0 × E-4 Pa.
Argon gas is introduced into the apparatus until it reaches 2.0 × E-1 Pa, and while maintaining this state, an adhesion improving film made of Ti having a thickness of 50 nm is formed by DC sputtering using a Ti target and a magnetic field of 400 G. 20 was deposited.
次に、同じ真空雰囲気中において、Ａｇターゲットを用いたＤＣスパッタリング法により、膜厚１２０ｎｍのＡｇからなる銀膜３０を成膜した。
その後、装置内の圧力が２．２×Ｅ−１Ｐａになるまで、アルゴンガスのみを導入し、磁場６００Ｇにて、ＺｎＯカソードに０．１ｋｗの電力と、ＳｉＯ２カソードに１．２ｋｗの電力をそれぞれ投入した２元ＲＦスパッタリング法により、膜厚６０．３ｎｍの低屈折率膜４０ｂを成膜した。
Next, a silver film 30 made of Ag having a thickness of 120 nm was formed by DC sputtering using an Ag target in the same vacuum atmosphere.
Thereafter, only argon gas is introduced until the pressure in the apparatus becomes 2.2 × E-1 Pa, and at a magnetic field of 600 G, a power of 0.1 kW is applied to the ZnO cathode and a power of 1.2 kW is applied to the SiO 2 cathode. A low-refractive-index film 40b having a film thickness of 60.3 nm was formed by the binary RF sputtering method that was put in each case.
装置内のカソード数の制限があるため、低屈折率膜４０ｂまで成膜した基板１０を取り出して別装置（シンクロン製 ＨＳＣ−１０００）に移し、続いて酸化チタン（ＴｉＯｘ）のターゲットを用いて、アルゴンガス中に酸素ガスを含む雰囲気で、２．２×Ｅ−１Ｐａで、ＤＣスパッタリング法により、膜厚３９ｎｍのＴｉＯ２からなる高屈折率膜４０ａを成膜した。
以上の方法により、図１に示す、基板１０上に、密着性向上膜２０、銀膜３０、誘電体多層膜４０が積層された４層構成の実施例１の高反射膜を作製した。
なお、本実施例では、使用した装置の能力に制限があったため、高屈折率膜４０ａの成膜を、他の膜の成膜とは異なる装置を用いて行ったが、同じ装置内で連続して行ってもよいことは当然である。
Since there is a limit on the number of cathodes in the apparatus, the substrate 10 formed up to the low refractive index film 40b is taken out and transferred to another apparatus (HSC-1000 manufactured by SYNCHRON), and subsequently using a target of titanium oxide (TiOx), A high refractive index film 40a made of TiO 2 having a film thickness of 39 nm was formed by DC sputtering at 2.2 × E-1 Pa in an atmosphere containing oxygen gas in argon gas.
By the above method, the highly reflective film of Example 1 having a four-layer structure in which the adhesion improving film 20, the silver film 30, and the dielectric multilayer film 40 are laminated on the substrate 10 shown in FIG.
In this example, since the capability of the apparatus used was limited, the film formation of the high refractive index film 40a was performed using an apparatus different from the film formation of other films, but it was continuously performed in the same apparatus. Of course, it may be done.
（実施例２）
低屈折率膜４０ｂ成膜時のＺｎＯカソードの投入電力を０．２ｋｗとし、ＳｉＯ２カソードの投入電力を１．１ｋｗとし、低屈折率膜４０ｂの膜厚を５９．８ｎｍとしたことを除いては、実施例１と同様の方法により、実施例１と同様の基板１０上に、図１に示す、密着性向上膜２０、銀膜３０、誘電体多層膜４０が積層された４層構成の実施例２の高反射膜を作製した。
(Example 2)
Except that the input power of the ZnO cathode during the formation of the low refractive index film 40b is 0.2 kW, the input power of the SiO 2 cathode is 1.1 kW, and the film thickness of the low refractive index film 40b is 59.8 nm. Is a four-layer structure in which the adhesion improving film 20, the silver film 30, and the dielectric multilayer film 40 shown in FIG. 1 are laminated on the same substrate 10 as in the first embodiment by the same method as in the first embodiment. A highly reflective film of Example 2 was produced.
（実施例３〜６）
低屈折率膜４０ｂ成膜時のＺｎＯカソード及びＳｉＯ２カソードの投入電力と、低屈折率膜４０ｂの膜厚を表１の通りとしたことを除いては、実施例１と同様の方法により、実施例１と同様の基板１０上に、図１に示す、密着性向上膜２０、銀膜３０、誘電体多層膜４０が積層された４層構成の実施例３〜６の高反射膜を作製した。
つまり、実施例３〜６において、低屈折率膜４０ｂ成膜時のＺｎＯカソード及びＳｉＯ２カソードの投入電力と、低屈折率膜４０ｂの膜厚は、次の表６の通りとした。
(Examples 3 to 6)
Except that the input power of the ZnO cathode and the SiO 2 cathode at the time of forming the low refractive index film 40b and the film thickness of the low refractive index film 40b are as shown in Table 1, the same method as in Example 1 is used. A highly reflective film of Examples 3 to 6 having a four-layer structure in which an adhesion improving film 20, a silver film 30, and a dielectric multilayer film 40 are laminated on the substrate 10 similar to that of Example 1 is manufactured. did.
That is, in Examples 3 to 6, the input power of the ZnO cathode and the SiO 2 cathode at the time of forming the low refractive index film 40b and the film thickness of the low refractive index film 40b were as shown in Table 6 below.
（対比例２）
本対比例では、実施例１〜６の高反射膜との対比のため、低屈折率膜４０ｂを、ＺｎＯを含まないＳｉＯ２単体の膜とした従来の高反射膜を成膜した。
本対比例では、低屈折率膜４０ｂ成膜時に、ＳｉＯ２カソードを稼働せず、ＺｎＯカソードの投入電力を１．３ｋＷとし、ＺｎＯを含まない低屈折率膜４０ｂの膜厚を６１ｎｍとしたことを除いては、実施例１と同様の方法により、実施例１と同様の基板１０上に、図１に示す、密着性向上膜２０、銀膜３０、誘電体多層膜４０が積層された４層構成の対比例２の反射膜を作製した。
(Comparison 2)
In this comparison, for comparison with the high reflection films of Examples 1 to 6, a conventional high reflection film in which the low refractive index film 40b is a single SiO 2 film containing no ZnO is formed.
In this comparison, when the low refractive index film 40b was formed, the SiO 2 cathode was not operated, the input power of the ZnO cathode was 1.3 kW, and the film thickness of the low refractive index film 40b not containing ZnO was 61 nm. 4 except that the adhesion improving film 20, the silver film 30, and the dielectric multilayer film 40 shown in FIG. 1 are laminated on the same substrate 10 as in Example 1 by the same method as in Example 1. A reflective film having a two-layer structure was produced.
（対比例３）
本対比例では、実施例３で成膜したＴｉからなる密着性向上膜２０の代わりに、基板１０と銀膜３０との間に、ＳｉＯ２−ＺｎＯ薄膜を成膜した。
清浄化した基板１０を不図示のスパッタリング装置内の基板ホルダーに設置した後、装置内を５．０×Ｅ−４Ｐａまで排気した。
その後、装置内の圧力が２．２×Ｅ−１Ｐａになるまで、アルゴンガスのみを導入し、磁場６００Ｇにて、ＺｎＯカソードに０．３ｋｗの電力と、ＳｉＯ２カソードに１．０ｋｗの電力をそれぞれ投入した２元ＲＦスパッタリング法により、膜厚５０ｎｍのＳｉＯ２−ＺｎＯ薄膜を成膜した。
その他は実施例３と同様の方法を実施し、実施例３と同様の基板１０上に、ＳｉＯ２−ＺｎＯ薄膜、銀膜３０、誘電体多層膜４０が積層された４層構成の対比例３の反射膜を作製した。
(Comparison 3)
In this comparative example, a SiO 2 —ZnO thin film was formed between the substrate 10 and the silver film 30 instead of the adhesion improving film 20 made of Ti formed in Example 3.
After the cleaned substrate 10 was placed on a substrate holder in a sputtering apparatus (not shown), the inside of the apparatus was evacuated to 5.0 × E-4 Pa.
Thereafter, only argon gas is introduced until the pressure in the apparatus becomes 2.2 × E-1 Pa, and at a magnetic field of 600 G, power of 0.3 kW is applied to the ZnO cathode and power of 1.0 kW is applied to the SiO 2 cathode. A SiO 2 —ZnO thin film having a thickness of 50 nm was formed by a binary RF sputtering method, which was respectively charged.
Otherwise, the same method as in Example 3 was carried out, and a three-layer structure in which a SiO 2 —ZnO thin film, a silver film 30 and a dielectric multilayer film 40 were laminated on the same substrate 10 as in Example 3 A reflective film was prepared.
（実施例１〜６及び対比例２、３の成膜後の反射率及び密着性評価）
実施例１〜６及び対比例２、３の膜付き基板について、成膜後速やかに、日立ハイテクノロジーズ製の自記分光光度計Ｕ−４１００を用いて、反射率を測定した。
成膜後の反射率の測定結果を、図７に示す。
成膜後の反射率の測定結果では、図７に示すように、対比例３のほか、実施例６、実施例５に、反射率の低下がみられた。実施例１と対比して、実施例３、４の反射率が若干低く、実施例５、６でさらに低くなっていた。このように、Ｚｎの添加量が増加するに従って、分光反射率が低下しており、実施例６のＺｎの含有量が最も多いＳｉＯ２−ＺｎＯ薄膜で大きな低下がみられた。
実施例６以上のＺｎＯの添加は、さらに反射率の低下を促すことが予想されるため、反射率を維持するためには、実施例６が、ＳｉＯ２に対するＺｎＯの添加量限界と思われる。
(Evaluation of reflectance and adhesion after film formation in Examples 1 to 6 and Comparative Examples 2 and 3)
About Examples 1-6 and the board | substrate with a film of contrast 2 and 3, the reflectance was measured using Hitachi High-Technologies self-recording spectrophotometer U-4100 immediately after film-forming.
The measurement results of the reflectance after film formation are shown in FIG.
In the measurement results of the reflectance after film formation, as shown in FIG. 7, the reflectance was decreased in Example 6 and Example 5 in addition to Comparative Example 3. Compared with Example 1, the reflectances of Examples 3 and 4 were slightly lower, and were even lower in Examples 5 and 6. Thus, the spectral reflectance decreased as the amount of Zn added increased, and a large decrease was observed in the SiO 2 —ZnO thin film having the highest Zn content in Example 6.
Since addition of ZnO in Example 6 or more is expected to further promote a decrease in reflectance, Example 6 seems to be the limit of the amount of ZnO added to SiO 2 in order to maintain the reflectance.
また、成膜後の実施例１〜６及び対比例２、３の膜付き基板について、ニットーセロハンテープ−Ｎｏ２９を基板表面にしっかりと張り付けた後、スナップをきかせてテープを引き剥がすことにより、密着性評価をおこなった。
密着性評価の結果を、表７の左列（成膜後）に示す。
In addition, for Examples 1 to 6 after film formation and the substrates with films 2 and 3, the Nitto cellophane tape No. 29 was firmly attached to the substrate surface, and then the snap was applied to peel off the tape. Sex evaluation was performed.
The results of adhesion evaluation are shown in the left column of Table 7 (after film formation).
表７に示すように、対比例２、３では、剥離があり、実施例１では、僅かに剥離があったのに対し、実施例２〜６では、剥離がみられなかった。
なお、ここでの「成膜後の」とは、成膜後、速やかに、反射率の測定及び密着性評価を行ったことを意味している。
As shown in Table 7, there was peeling in the comparative examples 2 and 3, and in Example 1, there was slight peeling, while in Examples 2-6, no peeling was observed.
Note that “after film formation” in this case means that measurement of reflectance and adhesion evaluation were performed immediately after film formation.
（実施例１〜６及び対比例２、３の耐湿試験後の反射率及び密着性評価）
実施例１〜６及び対比例２、３の膜付き基板を、６０−９５％の湿度雰囲気中に２０時間、２００時間放置する耐湿試験を行い、その後に、成膜後の反射率及び密着性評価と同様の手順により、反射率と密着性評価を実施した。
耐湿試験後の反射率の測定結果を、図８に示す。
耐湿試験後の反射率の測定結果では、図８に示すように、対比例３のほか、Ｚｎの添加量が多い実施例５、６に、短波長域を主とする反射率の低下がみられた。Ｚｎの添加量が多い実施例での反射率の低下は、ＳｉＯ２−ＺｎＯ薄膜からなる低屈折率膜４０ｂ中のＺｎＯに起因しているものと考えられる。
(Reflectance and adhesion evaluation after moisture resistance tests of Examples 1 to 6 and comparative 2, 3)
A moisture resistance test was performed in which the substrates with films of Examples 1 to 6 and comparative examples 2 and 3 were left in a 60-95% humidity atmosphere for 20 hours and 200 hours, and then the reflectance and adhesion after film formation. The reflectance and adhesion were evaluated by the same procedure as the evaluation.
The reflectance measurement results after the moisture resistance test are shown in FIG.
In the measurement results of the reflectance after the moisture resistance test, as shown in FIG. 8, in addition to the comparative 3, in Examples 5 and 6 where the amount of Zn added is large, a decrease in reflectance mainly in the short wavelength region is observed. It was. It is considered that the decrease in the reflectance in the example with a large amount of Zn added is caused by ZnO in the low refractive index film 40b made of the SiO 2 —ZnO thin film.
実施例１〜６では、ＳｉＯ２−ＺｎＯ薄膜を成膜する際、酸素及びプラズマの影響を少なくするため、不活性ガスであるアルゴンガスのみで成膜を行った。従って、低屈折率膜４０ｂ中のＺｎＯは、酸素ガスを用いずに、やや酸素不足の状態で成膜されたため、不安定な状態にある。
この不安定な状態のＺｎＯを多く含有する実施例５、６では、耐湿試験中に、湿度雰囲気中に曝されたことで、ＳｉＯ２−ＺｎＯ薄膜が水分吸着により体積が膨張し、また、充填率が増加するなどにより、屈折率が高めにシフトして光学膜厚が増加したと考えられる。
In Examples 1 to 6, when the SiO 2 —ZnO thin film was formed, the film was formed using only an inert gas, argon gas, in order to reduce the influence of oxygen and plasma. Accordingly, the ZnO in the low refractive index film 40b is in an unstable state because it is formed in a slightly oxygen-deficient state without using oxygen gas.
In Examples 5 and 6 containing a large amount of ZnO in an unstable state, the volume of the SiO 2 -ZnO thin film expanded due to moisture adsorption due to exposure to a humidity atmosphere during the moisture resistance test. It is considered that the optical film thickness is increased by shifting the refractive index higher due to the increase in the refractive index.
また、耐湿試験後の実施例１〜６及び対比例２、３の膜付き基板について、密着性評価をおこなった結果を、表７の中央及び右列（２０ｈ、２００ｈ）に示す。
実施例１と対比例３を除いて、実施例２〜６は、成膜後、湿度試験後において、密着性について良好な結果が得られていた。
Moreover, the result of having performed adhesiveness evaluation about the Examples 1-6 after a moisture-proof test and the board | substrate with a film of contrast 2 and 3 was shown in the center of Table 7, and the right column (20h, 200h).
Except for Comparative Example 3 and Example 3, Examples 2 to 6 had good results on adhesion after film formation and after a humidity test.
（実施例１〜６及び対比例２、３の加熱恒温試験後の反射率及び密着性評価）
実施例１〜６及び対比例２、３の膜付き基板を、１２０℃の恒温雰囲気中に２０時間、２００時間放置する加熱恒温試験を行い、その後に、成膜後の反射率及び密着性評価と同様の手順により、反射率と密着性評価を実施した。
加熱恒温試験後の反射率の測定結果を、図９に示す。
(Reflectance and adhesion evaluation after heating constant temperature test of Examples 1 to 6 and comparative 2, 3)
A heating and isothermal test was performed in which Examples 1 to 6 and the substrates with a film of Comparative Examples 2 and 3 were left in a constant temperature atmosphere at 120 ° C. for 20 hours and 200 hours, and then the reflectivity and adhesion evaluation after film formation were performed. According to the same procedure as described above, the reflectance and adhesion were evaluated.
The measurement results of the reflectance after the heating and isothermal test are shown in FIG.
図９に示した加熱恒温試験後の分光反射率では、湿度試験後に見られた短波長域での反射率の低下がみられなかった。反射率は、ＳｉＯ２−ＺｎＯ薄膜のＺｎの添加量に依存する傾向がみられ、特に、ＳｉＯ２−ＺｎＯ薄膜からなる低屈折率膜４０ｂ中のＺｎの含有量の多い実施例５、６に、顕著な反射率の向上がみられた。
この現象は、ＳｉＯ２−ＺｎＯ薄膜の成膜が、銀膜３０への酸素の影響を避ける目的でアルゴンガスのみのスパッタにより行われた結果、成膜直後には、ＺｎＯが若干吸収を帯びた薄膜となっているところ、加熱雰囲気中で酸素と結合することにより、膜中の吸収が低下したことによって、反射率が向上したために起こったと考えられる。
また、加熱恒温試験後の実施例１〜６及び対比例２、３の膜付き基板について、密着性評価をおこなった結果を、表８の中央及び右列（２０ｈ、２００ｈ）に示す。なお、表８の左列には、成膜後の密着性評価の結果を示している。
In the spectral reflectance after the heating and isothermal test shown in FIG. 9, no decrease in reflectance in the short wavelength region observed after the humidity test was observed. Reflectivity tends to depend on the amount of SiO 2 -ZnO thin Zn is observed, in particular, to many examples 5 and 6 of the content of Zn in the low refractive index film 40b made of SiO 2 -ZnO film A remarkable improvement in reflectance was observed.
This phenomenon is caused by the fact that the SiO 2 —ZnO thin film was formed by sputtering with only argon gas for the purpose of avoiding the influence of oxygen on the silver film 30. As a result, ZnO slightly absorbed immediately after the film formation. When the film is thin, it is thought that this occurred because the reflectivity was improved due to a decrease in absorption in the film due to bonding with oxygen in a heated atmosphere.
Moreover, the result of having performed adhesiveness evaluation about Examples 1-6 after a heating constant temperature test and the board | substrate with a film of contrast 2 and 3 is shown to the center of Table 8, and the right column (20h, 200h). The left column of Table 8 shows the results of the adhesion evaluation after film formation.
表７、表８の結果を総合すると、実施例１と比較例２を除いて、実施例２から実施例６までは、成膜後、湿度試験後、加熱恒温試験後のいずれも、密着性について良好な結果が得られた。
この結果より、ＳｉＯ２−ＺｎＯ薄膜からなる低屈折率膜４０ｂのＺｎ＋Ｓｉに対するＺｎの添加量の割合が、実施例２と同程度以上であれば、密着性が改善されることが分かった。
実施例２のＳｉＯ２カソードとＺｎＯカソードの投入電力は、表１に示すように、実験例２と同様であるため、実施例２の低屈折率膜４０ｂにおけるＺｎ＋Ｓｉに対するＺｎの添加量の割合が、表３に示す実験例２と同じ０．５３ａｔ％以上であれば、密着性が良いことがわかった。
Summarizing the results in Tables 7 and 8, except for Example 1 and Comparative Example 2, from Example 2 to Example 6, the adhesion was observed after film formation, after the humidity test, and after the heating and isothermal test. Good results were obtained for.
From this result, it was found that if the ratio of the amount of Zn added to Zn + Si in the low refractive index film 40b made of the SiO 2 —ZnO thin film is equal to or higher than that in Example 2, the adhesion is improved.
As shown in Table 1, the input power of the SiO 2 cathode and the ZnO cathode of Example 2 is the same as that of Experimental Example 2. Therefore, the ratio of the amount of Zn added to Zn + Si in the low refractive index film 40b of Example 2 is It was found that the adhesiveness was good when it was 0.53 at% or more, which was the same as Experimental Example 2 shown in Table 3.
また、表７、８に示すように、対比例３では、成膜後、耐湿試験後、加熱恒温試験後のいずれにおいても、基板１０と銀膜３０との間に形成されたＳｉＯ２−ＺｎＯ薄膜と、基板１０との界面から剥離が発生していた。従って、基板１０と銀膜３０との間の密着性向上膜としては、ＳｉＯ２−ＺｎＯ薄膜よりも、Ｔｉ膜が高い密着効果を奏することが分かった。 Further, as shown in Tables 7 and 8, in Comparative Example 3, the SiO 2 —ZnO formed between the substrate 10 and the silver film 30 after film formation, after the moisture resistance test, and after the heating and isothermal test. Peeling occurred from the interface between the thin film and the substrate 10. Therefore, it was found that the Ti film has a higher adhesion effect than the SiO 2 —ZnO thin film as the adhesion improving film between the substrate 10 and the silver film 30.
（耐硫化性評価として、生ゴムを投入した高温雰囲気中における変色の確認）
生ゴムを投入した高温雰囲気中（大気中８０℃）に、実施例１〜６及び対比例２、３の膜付き基板を、２０〜２００時間放置して、変色が起こるかどうかを確認した。
その結果、対比例２では、表面が茶色から黒く変色することを確認したが、実施例２から実施例６及び対比例３では、変色していないことを確認できた。
(As a sulfidation resistance evaluation, confirmation of discoloration in a high temperature atmosphere with raw rubber added)
In the high temperature atmosphere (80 degreeC in air | atmosphere) which supplied raw rubber, Example 1-6 and the board | substrate with a film of contrast 2 and 3 were left to stand for 20 to 200 hours, and it was confirmed whether discoloration occurred.
As a result, in Comparative Example 2, it was confirmed that the surface was changed from brown to black, but in Examples 2 to 6 and Comparative Example 3, it was confirmed that there was no color change.
１ 高反射膜付き基板
１０ 基板
２０ 密着性向上膜
３０ 銀膜
４０ 誘電体多層膜
４０ａ 高屈折率膜
４０ｂ 低屈折率膜
DESCRIPTION OF SYMBOLS 1 Substrate with high reflection film 10 Substrate 20 Adhesion improving film 30 Silver film 40 Dielectric multilayer film 40a High refractive index film 40b Low refractive index film
Claims (7)
前記誘電体多層膜は、低屈折率の無機誘電体膜と高屈折率の無機誘電体膜が、少なくとも２層以上交互に積層されることにより形成され、
前記誘電体多層膜のうち、前記銀膜に隣接する層は、前記低屈折率の前記無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有し、
前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であることを特徴とする高反射膜。 A highly reflective film provided on a substrate, comprising: a silver film; and a dielectric multilayer film provided on the silver film in contact with the silver film,
The dielectric multilayer film is formed by alternately laminating at least two layers of a low refractive index inorganic dielectric film and a high refractive index inorganic dielectric film,
Of the dielectric multilayer film, a layer adjacent to the silver film is the inorganic dielectric film having the low refractive index, and contains ZnO containing SiO 2 as a main component ,
The high reflectivity characterized in that the ratio Zn / (Zn + Si) of Zn to the sum of Zn and Si in the inorganic dielectric film adjacent to the silver film is 0.53 at% to 18.52 at%. film.
前記誘電体多層膜は、低屈折率の無機誘電体膜と高屈折率の無機誘電体膜が、少なくとも２層以上交互に積層されることにより形成され、
前記誘電体多層膜のうち、前記銀膜に隣接する層は、前記低屈折率の前記無機誘電体膜であって、ＳｉＯ２を主成分としてＺｎＯを含有し、
前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であることを特徴とする高反射膜付き基板。 A substrate with a highly reflective film comprising a substrate, a silver film provided on the substrate, and a dielectric multilayer film provided on the silver film in contact with the silver film,
The dielectric multilayer film is formed by alternately laminating at least two layers of a low refractive index inorganic dielectric film and a high refractive index inorganic dielectric film,
Of the dielectric multilayer film, a layer adjacent to the silver film is the inorganic dielectric film having the low refractive index, and contains ZnO containing SiO 2 as a main component ,
The high reflectivity characterized in that the ratio Zn / (Zn + Si) of Zn to the sum of Zn and Si in the inorganic dielectric film adjacent to the silver film is 0.53 at% to 18.52 at%. Substrate with film.
前記銀膜の上に、ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜を酸素プラズマにさらすことなく成膜する工程であって、前記銀膜に隣接する前記無機誘電体膜における、ＺｎとＳｉの和に対するＺｎの含有量の割合Ｚｎ／（Ｚｎ＋Ｓｉ）が、０．５３ａｔ％〜１８．５２ａｔ％であり、
前記ＳｉＯ２を主成分としてＺｎＯを含有する低屈折率の無機誘電体膜の表面上に、高屈折率の無機誘電体膜と、低屈折率の無機誘電体膜とを、少なくとも１層以上交互に積層する工程と、を備えることを特徴とする高反射膜の製造方法。 A silver film forming step of forming a silver film composed of a film containing Ag as a main component or an alloy film of Ag and another metal on a substrate;
On the silver film, a step of depositing without exposing the inorganic dielectric film having a low refractive index containing ZnO and SiO 2 as a main component in an oxygen plasma, the inorganic dielectric adjacent to the silver layer The ratio Zn / (Zn + Si) of Zn content to the sum of Zn and Si in the film is 0.53 at% to 18.52 at%,
On the surface of the low refractive index of the inorganic dielectric film containing ZnO said SiO 2 as a main component, and an inorganic dielectric film having a high refractive index and an inorganic dielectric film having a low refractive index, at least one layer alternately And a step of laminating to the substrate.
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