JPH06235065A - Production of iridium oxide film - Google Patents
Production of iridium oxide filmInfo
- Publication number
- JPH06235065A JPH06235065A JP4440593A JP4440593A JPH06235065A JP H06235065 A JPH06235065 A JP H06235065A JP 4440593 A JP4440593 A JP 4440593A JP 4440593 A JP4440593 A JP 4440593A JP H06235065 A JPH06235065 A JP H06235065A
- Authority
- JP
- Japan
- Prior art keywords
- iridium oxide
- film
- ion
- torr
- ion beam
- 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.)
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- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、密着性の良い酸化イ
リジウム膜を形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an iridium oxide film having good adhesion.
【０００２】[0002]
【従来の技術】酸化イリジウム膜は、電気めっきにおけ
る不溶性陽極として電極表面を被覆して使用される。2. Description of the Related Art Iridium oxide film is used by coating the electrode surface as an insoluble anode in electroplating.
【０００３】従来の塗布焼き付け法による被覆方法で
は、皮膜中に空孔が多数あり、空孔に電解液が浸透して
基板を腐食するため、使用寿命が短くなってしまう等の
問題があった。In the conventional coating method by coating and baking, there are many pores in the film, and the electrolyte penetrates into the pores to corrode the substrate, resulting in a problem that the service life is shortened. .
【０００４】そこで、緻密な酸化イリジウム膜の作製方
法として、反応性スパッタあるいは反応性蒸着法で、イ
リジウム金属をスパッタリングするとともに基板近傍で
酸化させる方法が試みられている（日本写真学会誌（１
９８８）、Ｖｏｌ．５１，Ｎｏ．１，ｐ．３）。Therefore, as a method of forming a dense iridium oxide film, a method of sputtering iridium metal by a reactive sputtering method or a reactive vapor deposition method and oxidizing it near the substrate has been attempted (Journal of the Photographic Society of Japan (1
988), Vol. 51, No. 1, p. 3).
【０００５】しかし、この方法では、０．１μｍ以上の
実用的な密着性を有する厚膜は得られにくく、酸化イリ
ジウムの化学組成制御も困難であった。However, with this method, it was difficult to obtain a thick film having a practical adhesion of 0.1 μm or more, and it was difficult to control the chemical composition of iridium oxide.
【０００６】反応性スパッタあるいは反応性蒸着法で
は、イリジウムを反応ガスで酸化させるときに、反応速
度が遅いため化学組成の制御が難しく、化学量論組成の
化合物膜が得られにくい。また、０．１μｍ／時以下と
成膜速度も非常に遅い。In the reactive sputtering or reactive vapor deposition method, when oxidizing iridium with a reaction gas, the reaction rate is slow, so that it is difficult to control the chemical composition and it is difficult to obtain a compound film having a stoichiometric composition. In addition, the film forming rate is very slow, at 0.1 μm / hour or less.
【０００７】反応速度を増すために反応ガスを多く導入
すると、スパッタされた粒子が散乱されるために、高エ
ネルギー粒子の基板への入射は減り、皮膜密着性が得ら
れないという問題があった。When a large amount of reaction gas is introduced to increase the reaction rate, sputtered particles are scattered, so that the incidence of high-energy particles on the substrate is reduced and there is a problem that the film adhesion cannot be obtained. .
【０００８】例えば、反応性スパッタで作製した０．１
μｍ程度の酸化イリジウム膜の密着性は、スクラッチテ
スターによる測定で、臨界剥離荷重値５Ｎ以下であり、
実用レベル（１０Ｎ以上）には達していない。For example, 0.1 produced by reactive sputtering.
The adhesion of the iridium oxide film of about μm is a critical peeling load value of 5 N or less as measured by a scratch tester,
It has not reached the practical level (10N or higher).
【０００９】[0009]
【発明が解決しようとする課題】従来の方法では多孔質
になったり、密着性のある厚膜が得られにくい等、電極
材料として特性を満足する酸化イリジウム膜は得られて
いなかった。According to the conventional method, an iridium oxide film satisfying the characteristics as an electrode material has not been obtained, such as a porous film and a thick film having adhesiveness being difficult to obtain.
【００１０】そこで、本発明では、化学量論組成で皮膜
密着性があり、成膜速度が速い酸化イリジウム膜の形成
方法を提供しようとするものである。Therefore, the present invention is intended to provide a method for forming an iridium oxide film having a stoichiometric composition, film adhesion, and a high film formation rate.
【００１１】[0011]
【課題を解決するための手段】本発明は、イオンビーム
スパッタ法により皮膜を形成するにあたり、１×１０-4
〜１×１０-3Ｔｏｒｒの圧力下で、真空容器内に設けた
酸化イリジウムのターゲットをイオン銃から照射される
不活性ガスイオンでスパッタして皮膜を形成することを
特徴とする酸化イリジウム膜の製造方法である。According to the present invention, in forming a film by the ion beam sputtering method, 1 × 10 −4
A iridium oxide film characterized by forming a film by sputtering an iridium oxide target provided in a vacuum container with an inert gas ion irradiated from an ion gun under a pressure of ˜1 × 10 −3 Torr. It is a manufacturing method.
【００１２】イオンビームスパッタ法は、真空容器内に
おいてイオン銃から放出される不活性ガスイオンによっ
てターゲット原子を叩きだし、試料表面に、ターゲット
原子を付着させ薄膜を形成する方法である。The ion beam sputtering method is a method in which a target atom is tapped by an inert gas ion emitted from an ion gun in a vacuum container, and the target atom is attached to the sample surface to form a thin film.
【００１３】したがって、イオンプレーティング法など
の他のＰＶＤ法やＣＶＤ法に比べ、ターゲットの化学組
成に近い化合物皮膜の形成に有効である。Therefore, it is effective in forming a compound film having a chemical composition close to that of the target, as compared with other PVD methods such as the ion plating method and the CVD method.
【００１４】イオンビームスパッタ法は、コーティング
物質の運動エネルギーを利用して付着させるため、試料
を高温に加熱させずに低温で被覆が可能であり、真空蒸
着に比べても、付着の際のエネルギーが１００倍程度大
きいため密着性の良い膜が得られる利点があり、密着性
の得られにくい酸化イリジウムの成膜に適していること
がわかった。In the ion beam sputtering method, the kinetic energy of the coating substance is used for the deposition, so that the sample can be coated at a low temperature without being heated to a high temperature. It has been found that since it is about 100 times larger, there is an advantage that a film having good adhesion can be obtained, and it is suitable for film formation of iridium oxide which is difficult to obtain adhesion.
【００１５】図１は、本発明で用いたスパッタ装置の一
例を示すもので、真空チャンバー１内には、基板ホルダ
ー２が設置されており、この基板ホルダー２には基板３
が取付けられている。FIG. 1 shows an example of a sputtering apparatus used in the present invention. A substrate holder 2 is installed in a vacuum chamber 1, and a substrate 3 is placed in the substrate holder 2.
Is installed.
【００１６】また、基板３に対向する位置には酸化イリ
ジウムターゲット４が配置されている。一方、真空チャ
ンバー１の側壁には、加速電極５を備えたイオン源６が
設けられている。An iridium oxide target 4 is arranged at a position facing the substrate 3. On the other hand, on the side wall of the vacuum chamber 1, an ion source 6 having an acceleration electrode 5 is provided.
【００１７】イオン源６は、不活性ガスのボンベ７に接
続され、イオンを生成し、加速電極５でイオンビームと
して真空チャンバー１内に引き出して酸化イリジウムタ
ーゲット４に照射し、スパッタを行うものである。The ion source 6 is connected to a cylinder 7 of an inert gas to generate ions, which are extracted by an accelerating electrode 5 as an ion beam into the vacuum chamber 1 to irradiate the iridium oxide target 4 for sputtering. is there.
【００１８】本発明において、全圧を１×１０-4〜１×
１０-3Ｔｏｒｒとしたのは、１×１０-4Ｔｏｒｒより高
真空であると、イオン源の放電室内で放電が起きないた
めにイオンビームを引き出すことができなくなってしま
うからであり、一方、１×１０-3Ｔｏｒｒより高圧力で
あると、スパッタ粒子が散乱してしまうため、高エネル
ギーを保つことができないからである。In the present invention, the total pressure is 1 × 10 −4 to 1 ×.
The reason for setting 10 −3 Torr is that if the vacuum is higher than 1 × 10 −4 Torr, the ion beam cannot be extracted because the discharge does not occur in the discharge chamber of the ion source. This is because if the pressure is higher than 1 × 10 −3 Torr, sputtered particles will be scattered and high energy cannot be maintained.
【００１９】真空中のスパッタ粒子の平均自由行程は、
圧力が１×１０-3Ｔｏｒｒより高真空では約５ｃｍ以上
あり、通常、基板とターゲットとの距離はその程度ある
ので、スパッタ粒子はほとんど散乱されずに、高エネル
ギーで入射できる。The mean free path of sputtered particles in a vacuum is
The pressure is about 5 cm or more in a vacuum higher than 1 × 10 −3 Torr, and the distance between the substrate and the target is usually such that the sputtered particles are hardly scattered and can be incident with high energy.
【００２０】また、この際、酸素等の反応ガスが基板近
傍にあるとスパッタ粒子が散乱し、密着性が得られない
あるいは、成膜速度が遅くなる等の原因となるので、本
発明では反応ガスは使わず、ターゲットに酸化イリジウ
ムを使用し、これを不活性ガスイオンでスパッタし成膜
することとした。Further, at this time, if a reaction gas such as oxygen is present in the vicinity of the substrate, the sputtered particles will scatter, resulting in poor adhesion or a slow film formation rate. Instead of using gas, iridium oxide was used as the target, and this was sputtered with inert gas ions to form a film.
【００２１】化学量論組成の皮膜を得るには、ターゲッ
トの化学組成を化学量論組成の酸化イリジウムにしてお
くことが重要である。In order to obtain a film having a stoichiometric composition, it is important that the target has a stoichiometric composition of iridium oxide.
【００２２】上記の、イオン源から、不活性ガスのイオ
ンを生成し、加速電極でイオンビームとして真空チャン
バーに引き出して酸化イリジウムターゲットに照射し、
スパッタを行う方法は、皮膜の化学組成がターゲットの
組成からほとんどずれず、反応性スパッタのように、皮
膜中のイリジウムと酸素の比の制御が困難あるいは複雑
であることもない。From the above-mentioned ion source, ions of an inert gas are generated, and they are extracted as an ion beam by an accelerating electrode into a vacuum chamber to irradiate an iridium oxide target,
In the method of performing sputtering, the chemical composition of the film does not substantially deviate from the composition of the target, and unlike reactive sputtering, it is not difficult or complicated to control the ratio of iridium to oxygen in the film.
【００２３】また、成膜速度は、０．５μｍ／時程度可
能であり、０．１μｍ以上の密着性のある皮膜も短時間
に生成できる。The film forming rate can be about 0.5 μm / hour, and a film having an adhesiveness of 0.1 μm or more can be formed in a short time.
【００２４】上記の方法で得られた皮膜は、結晶化して
ない非晶質相を含むことがある。非晶質相を含むと皮膜
の硬度が落ち、耐摩耗性が著しく劣化する。The film obtained by the above method may contain an amorphous phase which is not crystallized. If the film contains an amorphous phase, the hardness of the film is reduced and the wear resistance is significantly deteriorated.
【００２５】使用中に他の部材に接触し、きずが入ると
そこから腐食が進行することがあるので、皮膜の硬度が
下がるのは好ましくない。It is not preferable that the hardness of the coating is lowered, because if a flaw comes into contact with another member during use, corrosion may proceed from there.
【００２６】そこで、非晶質相の結晶化を検討した結
果、５００℃以上での大気中焼成が効果的であることを
見いだした。Then, as a result of studying crystallization of the amorphous phase, it was found that firing in air at 500 ° C. or higher is effective.
【００２７】５００℃より低温では、結晶化が非常に起
こりにくいが、これは結晶化に要する反応エネルギーが
十分得られないためと思われる。At temperatures lower than 500 ° C., crystallization is very unlikely to occur, but this is probably because the reaction energy required for crystallization cannot be obtained sufficiently.
【００２８】この焼成は、皮膜と基板界面の元素の拡
散、皮膜内に形成された残留応力の開放等による密着性
向上効果もあり、イオンビームスパッタ法のみによる皮
膜の密着性をさらに向上させる場合にも適用するとよ
い。This firing also has the effect of improving the adhesiveness by diffusing the elements at the interface between the film and the substrate, releasing the residual stress formed in the film, etc., and further improving the adhesiveness of the film by only the ion beam sputtering method. It is good to apply to.
【００２９】なお、結晶化の程度は、例えばＸ線回折に
よるピーク強度や、ピーク強度の半分の強度を与える角
度巾であるピーク半値巾によって確認できる。結晶化し
ている酸化イリジウムでは通常ピーク半値巾が３度以下
である。The degree of crystallization can be confirmed by, for example, the peak intensity by X-ray diffraction or the peak half value width which is the angular width that gives half the peak intensity. Crystallized iridium oxide usually has a peak half-width of 3 degrees or less.
【００３０】[0030]
【００３１】[0031]
【実施例１】金属チタンを基板に、酸化イリジウムをタ
ーゲットとし、不活性ガスとしてアルゴンを用いた。Example 1 Metallic titanium was used as a substrate, iridium oxide was used as a target, and argon was used as an inert gas.
【００３２】イオン源にはアルゴンを８ｃｍ3／分導入
し、加速電圧７００Ｖでイオンビームを取り出した。真
空チャンバー内の全圧は５．０×１０-4Ｔｏｒｒとなる
ようにした。Argon was introduced into the ion source at 8 cm 3 / min, and an ion beam was taken out at an acceleration voltage of 700V. The total pressure in the vacuum chamber was set to 5.0 × 10 −4 Torr.
【００３３】イオンビームが酸化イリジウムターゲット
を照射し、スパッタされた粒子で基板上に皮膜を形成さ
せた。The iridium oxide target was irradiated by the ion beam to form a film on the substrate with the sputtered particles.
【００３４】８０分の成膜で、１μｍの膜厚が得られ
た。Ｘ線回折の結果、酸化イリジウムの回折ピークが確
認され、スクラッチテスターによる臨界剥離荷重値の測
定でも、１４Ｎという高い密着性を示した。A film thickness of 1 μm was obtained by film formation for 80 minutes. As a result of the X-ray diffraction, a diffraction peak of iridium oxide was confirmed, and the measurement of the critical peeling load value with a scratch tester showed high adhesion of 14N.
【００３５】[0035]
【実施例２】金属チタンを基板に、酸化イリジウムをタ
ーゲットとし、不活性ガスとしてアルゴンを用いた。Example 2 Titanium metal was used as a substrate, iridium oxide was used as a target, and argon was used as an inert gas.
【００３６】イオン源にはアルゴンを６ｃｍ3／分導入
し、加速電圧５００Ｖでイオンビームを取り出した。真
空チャンバー内の全圧は４．０ｘ１０-4Ｔｏｒｒとなる
ようにした。Argon was introduced into the ion source at 6 cm 3 / min, and an ion beam was taken out at an acceleration voltage of 500V. The total pressure in the vacuum chamber was set to 4.0 × 10 −4 Torr.
【００３７】イオンビームが酸化イリジウムターゲット
を照射し、スパッタされた粒子で基板上に皮膜を形成さ
せた。The iridium oxide target was irradiated by the ion beam to form a film on the substrate with the sputtered particles.
【００３８】５０分の成膜で、０．３μｍの膜厚が得ら
れた。その後、大気中７００℃で２時間焼成した。Ｘ線
回折の結果、酸化イリジウムの回折ピークが、成膜直後
の皮膜より高く鋭く確認され、結晶性が向上した。After film formation for 50 minutes, a film thickness of 0.3 μm was obtained. Then, it baked at 700 degreeC in the atmosphere for 2 hours. As a result of X-ray diffraction, the diffraction peak of iridium oxide was confirmed to be higher and sharper than that of the film immediately after film formation, and the crystallinity was improved.
【００３９】半値巾は１０度から２度に減少した。スク
ラッチテスターによる臨界剥離荷重値の測定でも、１７
Ｎという高い密着性を示し、焼成前の１２Ｎより向上し
た。The full width at half maximum was reduced from 10 degrees to 2 degrees. Even if the critical peel load value is measured with a scratch tester,
It showed a high adhesion of N and was improved from 12N before firing.
【００４０】[0040]
【発明の効果】イオンビームスパッタ装置によって、１
×１０-4〜１×１０-3Ｔｏｒｒの圧力下で、容器内に設
けた酸化イリジウムのターゲットをイオン銃から照射さ
れる不活性ガスイオンでスパッタすることによって、化
学量論組成で密着性の良い酸化イリジウム膜を、速い成
膜速度で形成することができる。According to the ion beam sputtering apparatus, 1
By sputtering an iridium oxide target provided in the container with an inert gas ion irradiated from an ion gun under a pressure of × 10 -4 to 1 × 10 -3 Torr, a stoichiometric composition and an adhesive property can be obtained. A good iridium oxide film can be formed at a high film formation rate.
【図１】本発明の各実施例で用いたスパッタ装置の概略
構成図である。FIG. 1 is a schematic configuration diagram of a sputtering apparatus used in each example of the present invention.
１ 真空チャンバー ２ 基板ホルダー ３ 基板 ４ 酸化イリジウムターゲット ５ 加速電極 ６ イオン源 ７ 不活性ガスのボンベ 1 Vacuum chamber 2 Substrate holder 3 Substrate 4 Iridium oxide target 5 Accelerating electrode 6 Ion source 7 Inert gas cylinder
Claims (2)
０-4〜１×１０-3Ｔｏｒｒの圧力下で、容器内に設けた
酸化イリジウムのターゲットをイオン銃から照射される
不活性ガスイオンでスパッタして皮膜を形成することを
特徴とする酸化イリジウム膜の製造方法。1. 1 × 1 by an ion beam sputtering method
An iridium oxide characterized by forming a film by sputtering an iridium oxide target provided in a container with an inert gas ion irradiated from an ion gun under a pressure of 0 −4 to 1 × 10 −3 Torr. Membrane manufacturing method.
下で、真空容器内に設けた酸化イリジウムのターゲット
をイオン銃から照射される不活性ガスイオンでスパッタ
するイオンビームスパッタ法で得られた皮膜を、大気中
５００℃以上で焼成して形成することを特徴とする結晶
化酸化イリジウム膜の製造方法。2. An ion beam sputtering method for sputtering an iridium oxide target provided in a vacuum container with an inert gas ion irradiated from an ion gun under a pressure of 1 × 10 −4 to 1 × 10 −3 Torr. A method for producing a crystallized iridium oxide film, which comprises forming the film obtained in 1 above by firing in air at 500 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4440593A JPH06235065A (en) | 1993-02-10 | 1993-02-10 | Production of iridium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4440593A JPH06235065A (en) | 1993-02-10 | 1993-02-10 | Production of iridium oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06235065A true JPH06235065A (en) | 1994-08-23 |
Family
ID=12690608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4440593A Withdrawn JPH06235065A (en) | 1993-02-10 | 1993-02-10 | Production of iridium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06235065A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6781179B2 (en) | 2001-05-30 | 2004-08-24 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device having a capacitor comprising an electrode with an iridium oxide film as an oxygen barrier film |
-
1993
- 1993-02-10 JP JP4440593A patent/JPH06235065A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6781179B2 (en) | 2001-05-30 | 2004-08-24 | Matsushita Electric Industrial Co., Ltd. | Semiconductor device having a capacitor comprising an electrode with an iridium oxide film as an oxygen barrier film |
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