JPH02113201A - Article coated with optical multilayered film - Google Patents
Article coated with optical multilayered filmInfo
- Publication number
- JPH02113201A JPH02113201A JP63267611A JP26761188A JPH02113201A JP H02113201 A JPH02113201 A JP H02113201A JP 63267611 A JP63267611 A JP 63267611A JP 26761188 A JP26761188 A JP 26761188A JP H02113201 A JPH02113201 A JP H02113201A
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- layers
- film
- aluminum
- sputtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract 4
- 239000000758 substrate Substances 0.000 claims description 23
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 19
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract description 2
- 229910021332 silicide Inorganic materials 0.000 abstract 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 67
- 239000011521 glass Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 9
- 239000012788 optical film Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、透明基体上に薄膜を形成した物品に関し、特
に直流スパッタリング法によって、大きな透明基体上に
膜厚を均一に、被覆することが可能なアルミニウム珪酸
化物膜を用いた光学膜を被覆した物品に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an article in which a thin film is formed on a transparent substrate, and in particular, it is possible to coat a large transparent substrate with a uniform film thickness by using a direct current sputtering method. The present invention relates to an article coated with an optical film using a possible aluminum silicate film.
（従来の技術〕
光学膜を被覆した物品は、その機能により非常に多くの
種類があり、その膜構成は様々であるが、高屈折率膜と
低屈折率膜を交互に積層したものを用いることが多い。(Prior art) There are many types of articles coated with optical films depending on their functions, and their film configurations vary; There are many things.
例えば、透明基体表面の反射を低減する反射防止膜は、
第５図に示す高屈折率膜Ｉ ＣＺｒ０ｔなど）と低屈
折率膜４ （ＭｇＦｚなど）を透明基体３の上に積層し
た４層構成のものがデイスプレィ用を始めとして広く用
いられている。また、可視光を透過し、近赤外波長域の
熱線を反射するコールドフィルターも、第６図に示すよ
うに高屈折率膜１ （Ｔｉ（ｈなど）と低屈折率膜４
（Ｓｉｎｇなど）を透明基体３の上に繰り返し積層し
た膜構成になっている。For example, an antireflection film that reduces reflection on the surface of a transparent substrate is
A four-layer structure in which a high refractive index film (I CZr0t, etc.) and a low refractive index film 4 (MgFz, etc.) shown in FIG. In addition, a cold filter that transmits visible light and reflects heat rays in the near-infrared wavelength range is also made of a high refractive index film 1 (such as Ti (h)) and a low refractive index film 4, as shown in Figure 6.
It has a film structure in which a film (such as Sing) is repeatedly laminated on a transparent substrate 3.
従来、これらの光学膜を被膜した物品は比較的膜の被覆
面積が小さかったので、真空蒸着法によって作成するこ
とができた。例えばデイスプレィ用反射防止膜の寸法は
、最も良く用いられる１４インチおよび２０インチデイ
スプレィで、それぞれ約２４０ｘ３１０鶴、３５０Ｘ４
６０龍である。Conventionally, articles coated with these optical films had a relatively small area covered by the film, so they could be produced by vacuum evaporation. For example, the dimensions of anti-reflective coating for displays are approximately 240x310 and 350x4 for the most commonly used 14-inch and 20-inch displays, respectively.
It is 60 dragons.
また、複写機用コールドフィルターで、約３００Ｘ３Ｑ
ｍである。しかし真空蒸着法においては、より面積の大
きい基板、例えば今後普及すると予想される５０インチ
（約８００Ｘ１２００．ｗ）以上のデイスプレィや、１
５００Ｘ１０００ｕもある乗用車の窓ガラスに対して、
膜厚の均一性を確保することが難しいという問題があっ
た。In addition, with a cold filter for copying machines, approximately 300 x 3Q
It is m. However, in the vacuum evaporation method, substrates with larger areas, such as displays of 50 inches (approximately 800 x 1200.
For passenger car window glass, which is 500x1000u,
There was a problem in that it was difficult to ensure uniformity of film thickness.
一方、建築物の窓ガラスのように寸法がたとえば２４０
０Ｘ３６００ｍｍにもなる大面積の透明基体への光学膜
の被膜方法として、直流スパッタリング法が用いられて
いる。この方法は、大面積の基体上での膜厚均一性が真
空蒸着法に比べて本質的に良いという利点を持っている
が、次の理由で実現されていない。すなわち低屈折率膜
であるＭｇＦｔ膜を直流スパッタリング法で被覆するに
は、Ｍｇターゲットをフッ素を含むガス中で直流スパッ
タする方法が考えられるが、フッ素を含むガス中で被覆
したＭｇＦ、膜は耐磨耗性が極めて悪い事が報告されて
いる（Ｗｉｌｌｉａｍ Ｊ、 Ｃｏｌｅｍａｎ、八ＰＰ
ＬＩＥＤＯＰＴＩＣＳ、 Ｖｏｌ、 １３． Ｎｏ、４
Ａｐｒｉｌ １９７４ ｐｐ ９４６−９５１）。On the other hand, the dimensions of building window glass, for example, are 240 mm.
A direct current sputtering method is used as a method for coating an optical film on a transparent substrate with a large area of 0x3600 mm. Although this method has the advantage that film thickness uniformity on a large-area substrate is essentially better than that of the vacuum evaporation method, it has not been realized for the following reasons. In other words, in order to coat a MgFt film, which is a low refractive index film, by direct current sputtering, a method of direct current sputtering of an Mg target in a fluorine-containing gas can be considered, but the MgF film coated in a fluorine-containing gas has poor resistance. It has been reported that the abrasion resistance is extremely poor (William J, Coleman, 8PP
LIEDOPTICS, Vol. 13. No, 4
April 1974 pp 946-951).
ＭｇＦ、ターゲットを用いる方法は、Ｍｇｐｚターゲッ
トの導電性がなく直流スパッタリングができないため、
高周波スパッタリング法を用いなければならない。しか
し、高周波スパッタリング法は１辺が１０００１ｍ以上
の大きい基体に安定して行うのは困難であるため、真空
蒸着法と同様に大面積の基体への被覆は適さない。また
、５ｉｆｔ （屈折率１．４６）、＾ＪｚＯｓ（屈折率
１．６３） 、ＭｇＯ（屈折率１．７０）などの低屈折
率膜として機能する物質をスパッタリング法で基体に被
覆することは、Ｓｔ、 Ａｌ、 Ｍｇをそれぞれター
ゲットとする減圧された酸素ガスを含む反応性スパッタ
リングにおいては、ターゲット表面の酸化により長時間
安定して被覆を実施することが困難であり、ＳｉＯ□、
Ａｌｔｏｓ 、 ＭｇＯ材料をターゲットとする高
周波スパッタリング法では、とくに被覆すべき基体の面
積が大きい場合には、ＭｇＦ ｔの場合と同様安定して
被覆することが困難である。そのため、大面積の透明基
体上に第５図や第６図で示される光学膜を被覆した物品
を製造することは極めて困難である。The method using MgF target is because the Mgpz target has no conductivity and cannot perform DC sputtering.
High frequency sputtering methods must be used. However, since it is difficult to stably apply the high frequency sputtering method to a large substrate with a side of 10001 m or more, it is not suitable for coating a large area substrate like the vacuum evaporation method. In addition, coating the substrate with a substance that functions as a low refractive index film such as 5ift (refractive index 1.46), ^JzOs (refractive index 1.63), and MgO (refractive index 1.70) by sputtering In reactive sputtering using reduced pressure oxygen gas targeting St, Al, and Mg, it is difficult to perform stable coating over a long period of time due to oxidation of the target surface.
In the high-frequency sputtering method that targets Altos and MgO materials, it is difficult to coat the substrate stably, as in the case of MgFt, especially when the area of the substrate to be coated is large. Therefore, it is extremely difficult to manufacture an article in which a large-area transparent substrate is coated with the optical film shown in FIGS. 5 and 6.
本発明の目的は、上記従来の問題点を解決するために、
直流スパッタリングにより大面積の基体に、膜厚を均一
に被覆可能な低屈折率材料を用いた、光学膜を被覆した
物品を提供することにある。The purpose of the present invention is to solve the above-mentioned conventional problems.
An object of the present invention is to provide an article coated with an optical film using a low refractive index material that can uniformly coat a large area substrate with a film thickness by direct current sputtering.
本発明は第１図に示すような、透明基体３の上に高屈折
率材料Ｉと低屈折率材料２とを交互に積層した光干渉作
用を利用した多層膜を被覆した物品において、低屈折率
材料２としてアルミニウムの珪酸化物を用いる。The present invention provides an article with a low refractive index coated with a multilayer film utilizing optical interference, in which a high refractive index material I and a low refractive index material 2 are alternately laminated on a transparent substrate 3, as shown in FIG. As the material 2, aluminum silicate is used.
本発明に用いられるアルミニウムの珪酸化物の膜組成は
、ＡＩ５１ｘ０２ｘ＊１．Ｓで表わされる化学式でＸが
０．０５以上で、１．０を越えない範囲、すなわちＳｉ
／Ａｌの原子比で０．０５〜１．０の範囲内にあること
が好ましく、膜中の酸素はＡＩとＳｉに対して、ほぼ化
学量論組成であることが好ましい。Ｘの値が０．０５よ
り小さくなると、アルミニウムの珪酸化物の膜の屈折率
が１．６２を越え、低屈折率材料としての価値が低下し
てしまう。Ｘが１．０より大きくなると、用いるアルミ
ニウム珪化ｔｌターゲットの表面の導電性が悪くなり安
定して直流スパッタリングによる被覆をすることができ
なくなる。Ｘが１．０のときのアルミニウムの珪酸化物
の膜の屈折率は１．５４になり、したがって本発明にか
かる低屈折率材料の膜として用いることができるアルミ
ニウムの珪酸化物の屈折率の値は１．５４〜１．６２の
範囲は１．５４になり、したがって本発明にかかる低屈
折率材料の膜として用いることができるアルミニウムの
珪酸化物の屈折率の値は１．５４〜１．６２の範囲とな
る。また、アルミニウムの珪酸化物の膜を安定して直流
スパッタリングで行うという観点からは、Ｓｉ／Ａｌの
原子比すなわちＸの値は０．０５〜０．２５の範囲であ
ることが最も好ましい。The film composition of aluminum silicate used in the present invention is AI51x02x*1. In the chemical formula represented by S, X is 0.05 or more and does not exceed 1.0, that is, Si
The atomic ratio of /Al is preferably in the range of 0.05 to 1.0, and the oxygen in the film is preferably approximately stoichiometric with respect to AI and Si. When the value of X is smaller than 0.05, the refractive index of the aluminum silicate film exceeds 1.62, and its value as a low refractive index material decreases. When X is larger than 1.0, the surface conductivity of the aluminum silicide tl target used becomes poor and stable coating by DC sputtering becomes impossible. When X is 1.0, the refractive index of the aluminum silicate film is 1.54. Therefore, the refractive index value of the aluminum silicate film that can be used as the film of the low refractive index material according to the present invention is The range of 1.54 to 1.62 is 1.54. Therefore, the refractive index value of aluminum silicate that can be used as the film of the low refractive index material according to the present invention is 1.54 to 1.62. range. Further, from the viewpoint of stably forming a film of aluminum silicate by direct current sputtering, it is most preferable that the Si/Al atomic ratio, that is, the value of X, is in the range of 0.05 to 0.25.
また高屈折率物質としては、ＴｔＯ□（屈折率２．４）
、ＴａｚＯｓ （屈折率２．１） 、ＺｒＯ！（屈折
率２．１）、ＺｎＯ（屈折率２．０） 、Ｓｎｏｗ （
屈折率２．０）、■Ｔ。In addition, as a high refractive index material, TtO□ (refractive index 2.4)
, TazOs (refractive index 2.1), ZrO! (refractive index 2.1), ZnO (refractive index 2.0), Snow (
refractive index 2.0), ■T.
（屈折率２．０）などが使用可能である。もちろんこれ
らの高屈折率材料の膜は、従来から行われているように
、それぞれＴｉ、 Ｔａ５Ｚｒｓ Ｚｎ、、Ｓｎｓ
（Ｉｎ＋Ｓｎ）などの金属ターゲットを用い、酸素ガス
または酸素ガスとアルゴンガスなどの不活性ガスの混合
ガス雰囲気中で直流スパッタリングをおこなうことによ
り被覆することができる。ただしＩＴＯの場合は金属タ
ーゲットの代わりに焼結された酸化物ターゲットでも、
導電性が充分あるので直流スパッタリングのターゲット
として用いることができる。(refractive index 2.0), etc. can be used. Of course, the films of these high refractive index materials are Ti, Ta5Zrs, Zn, Sns, respectively, as has been conventionally done.
The coating can be performed by direct current sputtering using a metal target such as (In+Sn) in an atmosphere of oxygen gas or a mixed gas of oxygen gas and an inert gas such as argon gas. However, in the case of ITO, even if a sintered oxide target is used instead of a metal target,
Since it has sufficient conductivity, it can be used as a target for DC sputtering.
アルミニウムの珪酸化物は、アルミニウムの珪化物ター
ゲットを用い、酸素ガスまたは、酸素ガスとアルゴンガ
スなどの不活性ガスの混合ガス雰囲気中で、直流スパッ
タリングをおこなうことにより成膜される。基体をアル
ミニウム珪化物ターゲットの表面に対向する位置を通過
させる、マグネトロンスパッタリング法で実施すること
が、大きな面積の基体に膜厚を均一に被覆する上で最も
好ましい。アルミニウム珪酸化物膜の化学組成は、被覆
時の膜の堆積スピードと雰囲気ガスの条件たとえば、ガ
ス組成、ガス圧力などにより、被覆される膜が実質的に
透明になるように設定される。Aluminum silicide is formed by direct current sputtering using an aluminum silicide target in an atmosphere of oxygen gas or a mixed gas of oxygen gas and an inert gas such as argon gas. A magnetron sputtering method in which the substrate is passed through a position opposite to the surface of an aluminum silicide target is most preferable in order to coat a large area of the substrate with a uniform film thickness. The chemical composition of the aluminum silicate film is determined by the deposition speed of the film during coating and atmospheric gas conditions, such as gas composition and gas pressure, so that the coated film becomes substantially transparent.
本発明にかかる低屈折率膜として用いるアルミニウムの
珪酸化物の被膜を、アルミニウムの珪化物から酸素を含
む減圧された雰囲気ガスにおいて直流の反応性スパッタ
リングで実施することは、アルミニウム珪化物のターゲ
ットの表面の酸化による電気絶縁層が形成されにり＜、
導電性が長時間に渡って確保されるので、従来のＡＩや
Ｍｇなとの金属をターゲットとする酸素ガスを含む減圧
された雰囲気下で直流スパッタリング法が存している欠
点、すなわちターゲットの表面が急速に酸化され、被膜
堆積速度が経時的に変化するのと同時に、グロー放電プ
ラズマが不安定になってしまう欠点が克服される。さら
にターゲット表面の導電性が確保されることは、大きな
面積の基体に、膜厚を均一に被覆するうえで好ましい。The aluminum silicide film used as the low refractive index film according to the present invention is formed by direct current reactive sputtering in a reduced pressure atmosphere gas containing oxygen from the aluminum silicide on the surface of the aluminum silicide target. An electrical insulating layer is formed by the oxidation of
Since conductivity is ensured for a long time, it eliminates the drawbacks of conventional DC sputtering methods that target metals such as AI and Mg in a reduced pressure atmosphere containing oxygen gas, i.e., the surface of the target. This overcomes the drawbacks of rapid oxidation of the film, changes in film deposition rate over time, and instability of the glow discharge plasma. Furthermore, it is preferable that the conductivity of the target surface is ensured in order to coat a large area of the substrate with a uniform film thickness.
本発明にかかる各層の膜厚および層数は、目標とする波
長および帯域に於ける光の干渉効果を利用して決められ
る。また透明基体としてはガラス、プラスチックスのい
ずれでも適用できる。The film thickness and number of layers according to the present invention are determined using the interference effect of light in a target wavelength and band. Further, as the transparent substrate, either glass or plastic can be used.
本発明にかかる光学多層膜を形成するアルミニウムの珪
酸化物からなる層は、１．５４〜１．６２の低い屈折率
を有しているので、屈折率が２．０以上の高屈折率材料
からなる層と積層されることにより、低屈折率の層とし
て光干渉作用を呈し、光学機能を透明基体に付与せしめ
る。またアルミニウムの珪酸化物膜を酸素を含む減圧さ
れた雰囲気下で直流スパッタリングで被覆するに際して
、アルミニウムの珪化物ターゲットは、表面の酸化によ
る電気絶縁層の形成を少なくし、ターゲット表面を導電
性に維持させるので、長時間安定してアルミニウムの珪
酸化物の膜の被覆をおこなうことができる。The layer made of aluminum silicate that forms the optical multilayer film according to the present invention has a low refractive index of 1.54 to 1.62, so it is made of a high refractive index material with a refractive index of 2.0 or more. When laminated with other layers, it exhibits an optical interference effect as a layer with a low refractive index, thereby imparting an optical function to the transparent substrate. In addition, when coating an aluminum silicate film by DC sputtering in a reduced pressure atmosphere containing oxygen, the aluminum silicide target reduces the formation of an electrically insulating layer due to surface oxidation and maintains the target surface conductivity. As a result, aluminum can be coated with a silicate film stably for a long period of time.
以下、実施例により、さらに詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
使用したスパッタリング装置は、真空槽内に２つのプレ
ーナー型マグネトロンカソードが並設された装置で、真
空槽内の一方の端にあるガラスホルダーにセットされた
ガラス板を、２つのターゲツト面に対向する位置を通過
させながら、ターゲット材料をスパッタリングさせて膜
を被覆し、真空槽内の他方の端にガラス板を移動させる
方法を用いた。Example 1 The sputtering device used was a device in which two planar magnetron cathodes were arranged side by side in a vacuum chamber, and a glass plate set in a glass holder at one end of the vacuum chamber was placed between two target surfaces. A method was used in which the target material was sputtered to coat the film while the glass plate was passing through a position opposite to the glass plate, and the glass plate was then moved to the other end of the vacuum chamber.
このスパッタリング装置の２つのカソードのうち一方の
端に近いカソードにＳｎターゲットを他方の端に近いカ
ソードに７１１ Ｓｒｏ、 ｒ組成のアルミニウムの珪
化物ターゲットをセットした。真空槽内の一方の端にあ
るガラスホルダーに１．１鶴の厚みの洗浄したガラス板
をセットし、クライオポンプにより真空槽の圧力を１．
３ Ｘ １０−”Ｐａ以下まで排気した０次に酸素ガス
５０体積％アルゴンガス５０体積％の割合の混合ガス１
００ｃｃをガスパイプから導入し、真空槽内の圧力を０
．６７Ｐａになるようにクライオポンプのオリフィスバ
ルブで調節した。Of the two cathodes of this sputtering apparatus, an Sn target was set at the cathode near one end, and an aluminum silicide target having a composition of 711 Sro, r was set at the cathode near the other end. A cleaned glass plate with a thickness of 1.1 mm was set in the glass holder at one end of the vacuum chamber, and the pressure of the vacuum chamber was increased to 1.1 mm using a cryopump.
Mixed gas 1 with a ratio of 0-order oxygen gas 50% by volume and argon gas 50% by volume exhausted to 3 X 10-”Pa or less
00cc is introduced from the gas pipe, and the pressure inside the vacuum chamber is reduced to 0.
．． The pressure was adjusted to 67 Pa using the orifice valve of the cryopump.
Ｓｎターゲットｈよびアルミニウムの珪化物ターゲ７）
に、それぞれ４ｋＷ／ａｍ”の電力を直流電源から印加
し、スパッタリングを開始した。その後ガラス板の移動
速度をＳｎターゲツト面に対向する位置を通過するとき
は、３８０ ｗ／ｗｉｎで、アルミニウムの珪化物ター
ゲツト面に対向する位置を通過するときは？（１１１１
／ｌｌ１ｎにして２層の膜を被覆し、ガラスを他方の端
に移した。放電を停止し、ガス導入を停止し、真空槽を
大気圧にしてガラス板を取出した。得られた２層の膜を
被覆したガラス板の第１層のアルミニウムの珪酸化物か
らなる膜および第２層の酸化錫膜の屈折率をエリプソメ
ーターにより、光学膜厚をタリステップの測定値から計
算して求め、第１表を得た。また分光反射スペクトルを
測定して第２図を得た。Sn target h and aluminum silicide target 7)
Sputtering was started by applying a power of 4 kW/am" from a DC power supply to each of the glass plates. After that, the moving speed of the glass plate was changed to 380 w/win when passing the position facing the Sn target surface, and the aluminum was silicified. What happens when the object passes through a position opposite to the target surface? (1111
/ll1n and two layers of membrane were applied and the glass was transferred to the other end. The discharge was stopped, the gas introduction was stopped, the vacuum chamber was brought to atmospheric pressure, and the glass plate was taken out. The refractive index of the first layer of the aluminum silicate film and the second layer of the tin oxide film of the glass plate coated with the obtained two-layer film was measured using an ellipsometer, and the optical film thickness was determined from the measured value of Talystep. This was calculated and Table 1 was obtained. Further, the spectral reflection spectrum was measured and FIG. 2 was obtained.
また得られたアルミニウムの珪酸化物膜の化学組成をＸ
ｉマイクロアナライザーで調べたところ、Ａ Ｉ Ｓｉ
ｎ、 ｔＯ＋、 ｑの組成を得た。また膜の被覆にあた
っては、グロー放電プラズマは安定していた。In addition, the chemical composition of the obtained aluminum silicate film is
When I checked it with i Micro Analyzer, A I Si
The compositions of n, tO+, and q were obtained. Furthermore, the glow discharge plasma was stable in coating the film.
第 １ 表
実施例２
実施例１と同じスパッタリング装置で、Ｓｎターゲット
の代りにＴｉターゲットをカソードにセットした。洗浄
したガラス板を真空槽内の一方の端にあるガラスホルダ
ーにセントし、真空槽内をクライオポンプにより１．３
Ｘ １０−’Ｐａ以下に排気し、その後ガスパイプか
ら酸素ガス５０体積％、アルゴンガス５０体積％の割合
の混合ガス１００ｃｃを導入し、同様に０．６７Ｐａの
圧力に調節した。Ｔｉターゲットに５Ｗ／Ｃ１ｌ”、ア
ルミニウムの珪化物ターゲットに４ Ｗ ／ ｃｍ ”
の電力を直流電源から印加し、ガラス板の移動速度をＴ
ｉターゲット表面に対向する位置を通過するときは２０
ｍｍ／ｍｆｎに、アルミニウムの珪化物ターゲット表面
に対向する位置を通過するときは５５１ｍ／ｍｔｎにし
、一方の端から他方の端に移動させ２層の膜を被覆した
。その後両ターゲットの電力の印加を停止し、ガラス板
を一方の端に移動させた。同様の操作をさらに３回繰返
し、合計８層の膜を被覆した。その後ガラスを一方の端
から他方の端に４Ｗ／ｃ＋ａ”の電力を印加したＴｉタ
ーゲットの前面を通過させるときは２０ｍ／ｗｉｎで、
５ Ｗ ／ ａｍ ”の電力を印加したアルミニウム珪
化物のターゲツト面を通過させるときは１１０ ｍｍ／
ｗｉｎにして移動させ、合計１０層の膜の被覆を完了し
た。放電を停止し、ガス導入を停止し真空槽内を大気圧
に戻して、ガラスを取出した。Table 1 Example 2 Using the same sputtering apparatus as in Example 1, a Ti target was set at the cathode instead of the Sn target. Place the cleaned glass plate in a glass holder at one end of the vacuum chamber, and pump the inside of the vacuum chamber for 1.3 minutes using a cryopump.
The pressure was evacuated to below X 10-'Pa, and then 100 cc of a mixed gas containing 50% by volume of oxygen gas and 50% by volume of argon gas was introduced from the gas pipe, and the pressure was similarly adjusted to 0.67Pa. 5W/C1l” for Ti target, 4W/cm” for aluminum silicide target
power is applied from a DC power source, and the moving speed of the glass plate is T
i 20 when passing through a position facing the target surface
mm/mfn, and 551 m/mtn when passing a position facing the aluminum silicide target surface, and was moved from one end to the other to coat two layers of film. Thereafter, the application of power to both targets was stopped and the glass plate was moved to one end. The same operation was repeated three more times to coat a total of 8 layers of film. After that, when passing the glass in front of a Ti target to which a power of 4W/c+a" was applied from one end to the other, the speed was 20m/win.
When passing through an aluminum silicide target surface to which a power of 5 W/am” was applied, the distance was 110 mm/
The film was moved in the win mode, and a total of 10 layers of film were coated. The discharge was stopped, the gas introduction was stopped, the inside of the vacuum chamber was returned to atmospheric pressure, and the glass was taken out.
Ｔｉｅ、膜の屈折率はエリプソメーターで測定して２．
４０を得た。得られたｌ０ＪＷからなる多層膜の構成を
第２表に示す。また分光透過率曲線を測定し第３図の特
性を得た。またいずれの膜の被覆に際してもグロー放電
プラズマは安定していた。Tie, the refractive index of the film was measured with an ellipsometer and was 2.
I got 40. Table 2 shows the structure of the obtained multilayer film made of l0JW. Further, the spectral transmittance curve was measured and the characteristics shown in FIG. 3 were obtained. Furthermore, the glow discharge plasma was stable when coating with any film.
第
表
実施例３
実施例２と同じスパッタ装置においてＴｉターゲットの
代りにＴａターゲットをカソードにセットした。洗浄さ
れた１、１鰭の厚みのガラス板を一方の端にあるガラス
ホルダーにセットした。クライオポンプにより真空槽内
の圧力を１．３ Ｘ １０−３Ｐａ以下まで排気した。Table 1 Example 3 In the same sputtering apparatus as in Example 2, a Ta target was set at the cathode instead of the Ti target. A cleaned glass plate 1.1 fin thick was placed in a glass holder at one end. The pressure inside the vacuum chamber was evacuated to 1.3×10 −3 Pa or less using a cryopump.
次に酸素ガス５０体積％、アルゴンガス５０体積％の割
合でガスパイプより混合ガス１００ｃｃを導入し、真空
槽内の圧力が０．６７Ｐａになるようにクライオポンプ
のオリフィスバルブで調節した。Ｔａターゲットに５Ｗ
／ａｍ”、アルミニウムの珪化物ターゲットに４ Ｗ
／ ａｍ ”の電力を直流電源から印加し、Ｔａターゲ
ツト面に対向する位置およびアルミニウムの珪化物ター
ゲツト面に対向する位置を通過させるときのガラス板の
移動速度をそれぞれ７０ ｍｍ／ｌｌｌ１ｎ 、 ５
５ ｆｌ／ｍｉｎにしてガラス板を移動させ、他方の端
にガラス板を移した。両ターゲットへの電力の印加を停
止し、ガラス板を一方の端に戻して２層からなる膜の被
覆を完了した。同じ操作を繰返し、さらに２層の膜を被
覆し合計４層とした。その後さらに５Ｗ／ｃＩｌ”の電
力が印加されたＴａターゲツト面に対向する位置および
アルミニウム珪化物ターゲツト面に対向する位置をそれ
ぞれ７０關／ｍｉｎ、 １１０ ｍｍ／ｍｉｎの速度
で通過させ合計６層からなる膜の被覆を完了した。放電
を停止し、ガスの導入を停止して、真空槽内を大気圧に
戻してガラス板を取出した。得られた熱線反射膜付ガラ
スのＴａ、０．の屈折率は２．１５であった。Next, 100 cc of a mixed gas of 50% by volume of oxygen gas and 50% by volume of argon gas was introduced from the gas pipe, and the pressure in the vacuum chamber was adjusted to 0.67 Pa using the orifice valve of the cryopump. 5W to Ta target
/am”, 4 W on aluminum silicide target
/ am'' was applied from a DC power source, and the moving speed of the glass plate was set to 70 mm/ll1n and 5 when passing the glass plate through a position facing the Ta target surface and a position facing the aluminum silicide target surface, respectively.
The glass plate was moved at 5 fl/min and transferred to the other end. Application of power to both targets was stopped, and the glass plate was returned to one end to complete coating of the two-layer film. The same operation was repeated to coat two more layers for a total of four layers. Thereafter, a power of 5 W/cIl'' was applied to a position facing the Ta target surface and a position facing the aluminum silicide target surface at a speed of 70 mm/min and 110 mm/min, respectively, to form a total of 6 layers. The coating of the film was completed.The discharge was stopped, the introduction of gas was stopped, the inside of the vacuum chamber was returned to atmospheric pressure, and the glass plate was taken out.The refraction of Ta, 0. The ratio was 2.15.
膜の構成と分光透過率曲線を第３表および第４図に示す
。また可視光線透過率（標準Ａ光源）および日射エネル
ギー透過率はそれぞれ９１．３％。The structure of the film and the spectral transmittance curve are shown in Table 3 and FIG. In addition, visible light transmittance (standard A light source) and solar energy transmittance are each 91.3%.
７２．９％であった。It was 72.9%.
第 ３ 表
〔発明の効果〕
本発明のアルミニウムの珪酸化物膜を低屈折率材料とし
て用いた、低屈折率からなる膜と光屈折率からなる膜の
交互積層膜は、大面積の基体上に安定して被覆できる直
流スパッタリング法で作成することができるので、大型
デイスプレィ用の反射防止膜や、建築物や自動車の窓材
への熱線反射膜として用いることができる。Table 3 [Effects of the Invention] An alternately laminated film of a film having a low refractive index and a film having a light refractive index, which uses the aluminum silicate film of the present invention as a low refractive index material, can be applied on a large-area substrate. Since it can be produced using a direct current sputtering method that provides stable coating, it can be used as an antireflection film for large displays and a heat ray reflective film for window materials of buildings and automobiles.
第１図は本発明の、アルミニウムの珪酸化物を低屈折率
の膜とし、高屈折率材料からなる膜と交互に積層した多
層膜の構造を示す断面図、第２図から第４図は、本発明
の実施例の分光スペクトル特性を示す図、第５図、第６
図は従来の真空蒸着法で作成されたそれぞれ反射防止膜
、コールドフィルタの一例の構造を示す断面図である。
１・・・高屈折率材料からなる層、２・・・本発明のア
ルミニウムの珪酸化物を用いた低屈折率材料からなる層
、３・・・透明基体、４・・・従来の低屈折率材料から
なる層。
第
図
第
図
第
閃FIG. 1 is a cross-sectional view showing the structure of a multilayer film according to the present invention, in which aluminum silicate is used as a film with a low refractive index, and films made of a high refractive index material are alternately laminated, and FIGS. 2 to 4 are Figures 5 and 6 showing the spectral characteristics of the embodiments of the present invention.
The figure is a cross-sectional view showing the structure of an example of an antireflection film and a cold filter, respectively, produced by a conventional vacuum evaporation method. DESCRIPTION OF SYMBOLS 1... Layer made of a high refractive index material, 2... Layer made of a low refractive index material using aluminum silicate of the present invention, 3... Transparent substrate, 4... Conventional low refractive index material A layer of material. Figure Figure Figure Flash
Claims (4)
率材料からなる層とを交互に積層した、２層以上からな
る光学干渉型多層膜が被覆された物品において、前記低
屈折率材料からなる層がアルミニウムの珪酸化物からな
り、前記高屈折率材料からなる層が可視域での屈折率が
２．０以上である金属酸化物からなる光学多層膜を被覆
した物品(1) In an article coated with an optical interference multilayer film consisting of two or more layers in which layers made of a low refractive index material and layers made of a high refractive index material are alternately laminated on a transparent substrate, the low refractive index An article coated with an optical multilayer film in which the layer made of a high refractive index material is made of aluminum silicate, and the layer made of the high refractive index material is made of a metal oxide with a refractive index of 2.0 or more in the visible region.
成がＳｉ／Ａｌの原子比で０．０５〜１．０であって、
ほぼ化学量論組成の酸素を含む特許請求範囲第１項記載
の物品(2) The chemical composition of the layer made of aluminum silicate has an atomic ratio of Si/Al of 0.05 to 1.0,
Article according to claim 1, comprising a substantially stoichiometric composition of oxygen.
２Ｏ＿５、ＺｒＯ＿２、ＺｎＯ、ＳｎＯ＿２、Ｉｎ＿２
Ｏ＿３からなる群からいずれか１つ、または少なくとも
２つ以上が選ばれた混合物からなる特許請求範囲第１項
記載の物品(3) The layer made of the metal oxide is TiO_2, Ta_
2O_5, ZrO_2, ZnO, SnO_2, In_2
The article according to claim 1, comprising a mixture of one or at least two selected from the group consisting of O_3.
ムの珪酸化物からなる層が、それぞれ前記金属のターゲ
ットおよび、アルミニウムの珪化物をターゲットとして
、減圧された酸素を含む雰囲気中での直流スパッタリン
グにより被覆された、特許請求範囲第１項乃至第３項の
いずれかの項記載の物品(4) The layer made of the metal oxide and the layer made of the aluminum silicate are coated by DC sputtering in a reduced pressure atmosphere containing oxygen, using the metal target and the aluminum silicide as targets, respectively. The article according to any one of claims 1 to 3,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63267611A JPH02113201A (en) | 1988-10-24 | 1988-10-24 | Article coated with optical multilayered film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63267611A JPH02113201A (en) | 1988-10-24 | 1988-10-24 | Article coated with optical multilayered film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02113201A true JPH02113201A (en) | 1990-04-25 |
Family
ID=17447121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63267611A Pending JPH02113201A (en) | 1988-10-24 | 1988-10-24 | Article coated with optical multilayered film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02113201A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007127725A (en) * | 2005-11-01 | 2007-05-24 | Canon Inc | Antireflection film |
| JP2007270279A (en) * | 2006-03-31 | 2007-10-18 | Sony Corp | Sputtering film deposition method and antireflection film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63131101A (en) * | 1986-11-21 | 1988-06-03 | Nippon Sheet Glass Co Ltd | Multi-layered antireflection film |
-
1988
- 1988-10-24 JP JP63267611A patent/JPH02113201A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63131101A (en) * | 1986-11-21 | 1988-06-03 | Nippon Sheet Glass Co Ltd | Multi-layered antireflection film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007127725A (en) * | 2005-11-01 | 2007-05-24 | Canon Inc | Antireflection film |
| JP2007270279A (en) * | 2006-03-31 | 2007-10-18 | Sony Corp | Sputtering film deposition method and antireflection film |
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