JPH0649596B2 - Silicon dioxide thin film - Google Patents
Silicon dioxide thin filmInfo
- Publication number
- JPH0649596B2 JPH0649596B2 JP62017232A JP1723287A JPH0649596B2 JP H0649596 B2 JPH0649596 B2 JP H0649596B2 JP 62017232 A JP62017232 A JP 62017232A JP 1723287 A JP1723287 A JP 1723287A JP H0649596 B2 JPH0649596 B2 JP H0649596B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- sio
- film
- tio
- silicon dioxide
- 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.)
- Expired - Lifetime
Links
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- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は反射鏡等の基板面を被覆する二酸化珪素薄膜の
改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to an improvement of a silicon dioxide thin film for coating the surface of a substrate such as a reflecting mirror.
（従来の技術） 一般に二酸化珪素(SiO2)薄膜はアルミニウムを反射面と
した基板の保護膜や光学的多層膜における低屈折率物質
として幅広く使用されている。そして、このSiO2薄膜を
たとえばアルミ鏡の保護膜として被着させる場合、主と
して真空蒸着法が採用され、その蒸着手段として電子ビ
ーム加熱による直接蒸着、または酸素雰囲気中における
抵抗加熱による反応蒸着等がある。(Prior Art) Generally, a silicon dioxide (SiO 2 ) thin film is widely used as a low-refractive index material in a protective film of a substrate having aluminum as a reflection surface and an optical multilayer film. When depositing this SiO 2 thin film as a protective film of, for example, an aluminum mirror, a vacuum vapor deposition method is mainly adopted, and direct vapor deposition by electron beam heating or reactive vapor deposition by resistance heating in an oxygen atmosphere is employed as the vapor deposition means. is there.
ところが、上記手段によって成膜されるSiO2薄膜はいず
れも下記に示す欠点を有している。However, each of the SiO 2 thin films formed by the above means has the following drawbacks.
すなわち、第７図示のようにアルミ鏡面上に0.2μｍのS
iO2の保護膜を被着させたものと、同じく0.2μｍの酸化
アルミニウム(Al2O3)薄膜の保護膜を被着させたものと
を高温、高湿(温度50℃、湿度90％)の雰囲気中に放置し
た場合、両薄膜の最高反射率の変化から明らかなように
SiO2薄膜はAl2O3 薄膜に比較して耐湿性に極めて劣るこ
とが判る。したがって、単なる保護膜としてはSiO2薄膜
の代りにAl2O3 薄膜を使用することが一応の改善策とし
て考えられる。That is, as shown in Fig. 7, 0.2 μm S on the aluminum mirror surface.
High-temperature, high-humidity (temperature 50 ° C, humidity 90%) with a protective film of iO 2 and a protective film of 0.2 μm aluminum oxide (Al 2 O 3 ) thin film As can be seen from the change in the maximum reflectance of both thin films when left in the atmosphere of
It can be seen that the SiO 2 thin film is extremely inferior in moisture resistance as compared with the Al 2 O 3 thin film. Therefore, the use of an Al 2 O 3 thin film instead of the SiO 2 thin film as a simple protective film can be considered as a temporary improvement measure.
しかしながら、Al2O3 薄膜を低屈折率物質として光学的
薄膜に使用する場合、(特にコールドミラーやバンドパ
スフィルタ等)Al2O3 の屈折率が1.63とSiO2の1.46に比
べてかなり高いため、同じ層数の多層膜であってもSiO2
を含む多層膜と比較して反射域の幅、反射率の低下を招
く欠点を有している。However, when an Al 2 O 3 thin film is used as an optical thin film as a low refractive index material (especially a cold mirror or a bandpass filter), the refractive index of Al 2 O 3 is significantly higher than 1.63 and 1.46 of SiO 2. Therefore, even if it is a multilayer film with the same number of layers, SiO 2
It has a defect that the width of the reflection region and the reflectance are lowered as compared with the multilayer film containing
（発明が解決しようとする問題点） 上述したように従来のSiO2薄膜は屈折率が低い反面、耐
湿性に劣る欠点を有しているため、屈折率に変化を与え
ることなく、しかもAl2O3 薄膜と同程度以上の高温、高
湿に対する耐久性を備えてなる二酸化珪素薄膜を提供す
ることを目的とする。(Problems to be Solved by the Invention) As described above, the conventional SiO 2 thin film has a low refractive index, but has a defect of poor moisture resistance. Therefore, it does not change the refractive index, and Al 2 It is an object of the present invention to provide a silicon dioxide thin film having durability against high temperature and high humidity which is equal to or higher than that of an O 3 thin film.
（問題点を解決するための手段） 光学薄膜またはその保護膜用の低屈折率物質として二酸
化チタン０．５〜１０重量％含有の二酸化珪素を使用し
たことを特徴とする。(Means for Solving the Problems) Silicon dioxide containing 0.5 to 10% by weight of titanium dioxide is used as a low refractive index substance for an optical thin film or a protective film thereof.
（作 用） SiO2の融点は1,700℃，TiO2の融点は1,640℃と近いため
これらの混合物の蒸発が容易であり、また、第６図示の
ようにTiO2の添加量が10重量％以下ではこれを含有させ
たSiO2の屈折率に変化を与えることがない。さらにTiO2
添加よる耐湿性の向上については、第１図示のように最
高反射率が85％に低下するまでの時間が従来は約120 時
間であったものが250 時間以上となりAl2O3 薄膜以上の
高耐湿性を得ることができた。(Operation) Since the melting point of SiO 2 is close to 1700 ° C and the melting point of TiO 2 is close to 1640 ° C, it is easy to evaporate these mixtures, and as shown in Fig. 6, the addition amount of TiO 2 is 10% by weight or less. Does not change the refractive index of SiO 2 containing this. Furthermore, TiO 2
Regarding the improvement of moisture resistance by addition, as shown in the first diagram, the time until the maximum reflectance dropped to 85% was about 120 hours in the past, but it became 250 hours or more, which is higher than that of Al 2 O 3 thin film. Moisture resistance could be obtained.
（実施例） 以下、本発明を実施例について図面を参照して説明す
る。(Example) Hereinafter, an example of the present invention will be described with reference to the drawings.
まず、本発明者はSiO2とTiO2との混合重量比と、これに
対応する薄膜の屈折率との関係について実験し、第６図
に示す結果を得た。蒸着条件としては下記のとおりであ
る。First, the present inventor conducted an experiment on the relationship between the mixing weight ratio of SiO 2 and TiO 2 and the refractive index of the corresponding thin film, and obtained the results shown in FIG. The vapor deposition conditions are as follows.
１ 真空度 １×10-4〜５×10-4トール ２ 基板温度 250゜〜300℃ ３ 蒸発源 電子ビーム ４ 蒸発剤 両者の混合物 これにより、TiO2の添加量がSiO2に対して10重量％以下
ではSiO2の屈折率1.46にほぼ等しい値を示し変化を与え
ないことが判明した。1 degree of vacuum 1 × 10 −4 to 5 × 10 −4 torr 2 substrate temperature 250 ° to 300 ° C. 3 evaporation source electron beam 4 evaporating agent a mixture of both, whereby the addition amount of TiO 2 is 10 wt% with respect to SiO 2 . It was found that when the ratio is less than%, the refractive index of SiO 2 is almost equal to 1.46 and does not change.
次にTiO2の添加量が10重量％以下におけるSiO2薄膜の高
温、高湿に対する耐久性について実験し第１図に示す結
果を得た。すなわち、第１図はアルミ鏡面からなる基板
に0.2μｍのSiO2薄膜、(TiO2の添加量が0.1・0.3・0.5
・１・３・５・７・10各重量％)の各保護膜を成膜した
アルミ鏡を高温高湿(温度50℃、湿度90％)の雰囲気中に
放置した場合の膜の最高反射率の変化を示すものであ
る。したがって、Al2O3 保護膜と比較してTiO2添加量0.
1・0.3重量％のものはAl2O3 保護膜の250 時間に対し13
0〜190時間で反射率が85％に低下して不可となる。ま
た、TiO2添加量0.5〜10重量％のSiO2保護膜は0.5 重量
％でAl2O3 保護膜とほぼ同程度の耐久性が得られ、かつ
添加量の増量とともに耐久性が増大することが判明し
た。さらにSiO2中のTiO2含有量を0.5 ないし10重量％と
限定した理由については、添加量が0.5 重量％を下回る
場合は上記のようにAl2O3 膜と対比して反射率の低下が
著しくなり、また10重量％を上回る場合は屈折率が高く
なり同じく反射率の低下を招くこととなる。Next, the durability of the SiO 2 thin film against high temperature and high humidity when the amount of TiO 2 added was 10 wt% or less was tested, and the results shown in FIG. 1 were obtained. That is, Fig. 1 shows a 0.2 μm SiO 2 thin film on a substrate made of an aluminum mirror surface (the addition amount of TiO 2 is 0.1 ・ 0.3 ・ 0.5
・ Maximum reflectance of the film when an aluminum mirror with each protective film (1, 3, 5, 7, 10% by weight) is left in an atmosphere of high temperature and high humidity (temperature 50 ° C, humidity 90%). It shows the change of. Therefore, the amount of TiO 2 added is less than that of the Al 2 O 3 protective film.
1 0.3% by weight is 13 for 250 hours of the Al 2 O 3 protective film.
In 0 to 190 hours, the reflectivity drops to 85% and becomes impossible. Further, the SiO 2 protective film with 0.5 to 10% by weight of TiO 2 is 0.5% by weight, and the durability is almost the same as that of the Al 2 O 3 protective film, and the durability is increased as the amount of TiO 2 is increased. There was found. The reason for limiting the TiO 2 content in SiO 2 to 0.5 to 10% by weight is that when the addition amount is less than 0.5% by weight, the reflectance decreases as compared with the Al 2 O 3 film as described above. When it exceeds 10% by weight, the refractive index becomes high and the reflectance also decreases.
次にTiO2含有のSiO2薄膜を低屈折率物質として多層膜に
応用した実施例について述べる。表(Ａ)はTiO2７重量％
を含有させたSiO2膜を低屈折率物質とし、高屈折率物質
としてはTiO2(屈折率2.31)を使用しこれらを交互に積層
して成膜した。表(Ｂ)は比較例として成膜したSiO2，Ti
O2膜の交互層、表(Ｃ)は同じく比較例として成膜したAl
2O3,TiO2膜の交互層で、 いずれもその蒸着条件は下記のとおりである。Next, an example in which a SiO 2 thin film containing TiO 2 is applied as a low refractive index material to a multilayer film will be described. Table (A) shows TiO 2 7% by weight
The SiO 2 film containing TiO 2 was used as a low-refractive index material, and TiO 2 (refractive index 2.31) was used as a high-refractive index material. Table (B) shows SiO 2 and Ti deposited as comparative examples.
Alternating layers of O 2 film, Table (C) is also the Al film formed as a comparative example.
Alternating layers of 2 O 3 and TiO 2 films, The vapor deposition conditions for both are as follows.
１．真空度 １×10-4〜５×10-4トール ２．基板温度 250〜300℃ ３．蒸発源 電子ビーム なお、各膜構成による分光透過率は第２図ないし第４図
によって示す。また上記膜構成によって得られた試料を
用いて耐久性の評価を実施した。サンシャインウエザー
メーターテストの条件は下記のとおりである。1. Vacuum degree 1 × 10 -4 to 5 × 10 -4 Torr 2. Substrate temperature 250-300 ℃ 3. Evaporation source electron beam The spectral transmittance of each film structure is shown in FIGS. 2 to 4. In addition, durability evaluation was performed using the sample obtained by the above-mentioned film configuration. The conditions of the sunshine weather meter test are as follows.
１ 温 度 63±３℃ ２ 水噴射条件 120 分照射中に18分間 上記テストの結果からTiO2を適当量含有させたSiO2薄膜
はSiO2単体の薄膜はもち論、Al2O3 薄膜よりも高温、高
湿に対する耐久性が格段に向上することが認められた。1 Temperature 63 ± 3 ° C. 2 water injection condition 120 min SiO 2 thin film which contains an appropriate amount of TiO 2 from 18 minutes results of the tests during irradiation SiO 2 single thin film course, from Al 2 O 3 thin film It was also confirmed that the durability against high temperature and high humidity was remarkably improved.
本発明は上述したように光学薄膜またはその保護膜用の
低屈折率物質として二酸化チタン0.5 ないし10重量％含
有の二酸化珪素を使用した二酸化珪素薄膜であるから、
二酸化珪素自体の屈折率に変化を与えることなく、しか
も耐久性の格段な向上を可能とする利点を有する。ま
た、反射防止膜と保護膜とを兼用することも可能となっ
た。As described above, the present invention is a silicon dioxide thin film using silicon dioxide containing 0.5 to 10% by weight of titanium dioxide as a low refractive index substance for an optical thin film or a protective film thereof,
It has an advantage that the durability can be remarkably improved without changing the refractive index of silicon dioxide itself. Further, it has become possible to use both the antireflection film and the protective film.
第１図は本発明の実施例を示すTiO2添加をしたSiO2薄膜
の高温高湿放置による最高反射率の変化を示すグラフ。
第２図、第３図および第４図は表(Ａ)(Ｂ)(Ｃ)にそれぞ
れ対応する分光透過率の変化を示すグラフ。第５図は表
(Ａ)(Ｂ)(Ｃ)の各膜構成に対するサンシャインウエザー
テストによる最高反射率の変化を示すグラフ、第６図は
SiO2に対するTiO2混合比に対する屈折率の変化を示すグ
ラフであり、第７図は従来例を示すSiO2保護膜とAl2O3
保護膜との高温高湿時における最高反射率の変化を示す
グラフである。FIG. 1 is a graph showing a change in maximum reflectance of a SiO 2 thin film added with TiO 2 according to an embodiment of the present invention when left at high temperature and high humidity.
FIGS. 2, 3, and 4 are graphs showing changes in spectral transmittance corresponding to Tables (A), (B), and (C), respectively. Figure 5 is a table
Fig. 6 is a graph showing the change in maximum reflectance by the sunshine weather test for each film constitution of (A) (B) (C).
Is a graph showing the change in refractive index with respect to TiO 2 mixture ratio SiO 2, FIG. 7 is SiO 2 protective film and the Al 2 O 3 showing a conventional example
It is a graph which shows the change of the maximum reflectance with a protective film at the time of high temperature and high humidity.
Claims (1)
質として二酸化チタン０．５〜１０重量％含有の二酸化
珪素を使用したことを特徴とする二酸化珪素薄膜。1. A silicon dioxide thin film characterized by using silicon dioxide containing 0.5 to 10% by weight of titanium dioxide as a low refractive index substance for an optical thin film or a protective film thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62017232A JPH0649596B2 (en) | 1987-01-29 | 1987-01-29 | Silicon dioxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62017232A JPH0649596B2 (en) | 1987-01-29 | 1987-01-29 | Silicon dioxide thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63185842A JPS63185842A (en) | 1988-08-01 |
| JPH0649596B2 true JPH0649596B2 (en) | 1994-06-29 |
Family
ID=11938200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62017232A Expired - Lifetime JPH0649596B2 (en) | 1987-01-29 | 1987-01-29 | Silicon dioxide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0649596B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119126284B (en) * | 2024-04-08 | 2025-05-30 | 上海泊睿科学仪器有限公司 | Optical filter for material photo-aging test and plating method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5334727B2 (en) * | 1972-07-13 | 1978-09-22 |
-
1987
- 1987-01-29 JP JP62017232A patent/JPH0649596B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63185842A (en) | 1988-08-01 |
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