JPH0665716A - Forming of ruthenium dioxide thin film - Google Patents
Forming of ruthenium dioxide thin filmInfo
- Publication number
- JPH0665716A JPH0665716A JP22573192A JP22573192A JPH0665716A JP H0665716 A JPH0665716 A JP H0665716A JP 22573192 A JP22573192 A JP 22573192A JP 22573192 A JP22573192 A JP 22573192A JP H0665716 A JPH0665716 A JP H0665716A
- Authority
- JP
- Japan
- Prior art keywords
- film
- ruo
- heat treatment
- sputtering
- forming
- 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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Links
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- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は二酸化ルテニウム（以下
ＲｕＯ2と略す）薄膜を形成する方法に係り、特に四酸
化ルテニウム（ＲｕＯ4）等の高次の酸化物を含むルテ
ニウム酸化物（以下ＲｕＯXと略す）薄膜から安定なＲ
ｕＯ2薄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 a ruthenium dioxide (hereinafter referred to as RuO 2 ) thin film, and more particularly to a ruthenium oxide (hereinafter referred to as RuO 4 ) containing a higher-order oxide such as ruthenium tetraoxide (RuO 4 ). Abbreviated as X ) Stable R from thin film
The present invention relates to a method for forming a uO 2 thin film.
【０００２】[0002]
【従来の技術】従来、スパッタリング法を用いてＲｕＯ
X膜を形成する場合、金属ルテニウム（Ｒｕ）をターゲ
ットとし、アルゴン（Ａｒ）と酸素（Ｏ2）の混合ガス
中でスパッタすることによりＲｕＯX膜を形成してい
た。しかしながら、スパッタリング法で形成直後のＲｕ
ＯX膜は、あまり結晶化が進んでおらず、膜中にＲｕＯ4
等の高次の酸化物が存在する。このＲｕＯ4は常温で蒸
気圧が高く、しかも水や有機溶媒に可溶である。このた
め、このＲｕＯX膜を常温で長時間放置すると、ＲｕＯX
膜中のＲｕＯ4が吸湿したり、昇華したりする。この結
果ＲｕＯX膜にクラックが発生していた。2. Description of the Related Art Conventionally, RuO has been used by a sputtering method.
When forming the X film, RuO x film was formed by sputtering metal ruthenium (Ru) in a mixed gas of argon (Ar) and oxygen (O 2 ). However, Ru immediately after formation by the sputtering method
O X film is not promoted too much crystallization, RuO 4 in the film
There are higher order oxides such as. This RuO 4 has a high vapor pressure at room temperature and is soluble in water and organic solvents. Therefore, when left for a long time the RuO X film at room temperature, RuO X
RuO 4 in the film absorbs moisture or sublimes. As a result, cracks were generated in the RuO x film.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記従来のＲ
ｕＯX膜の欠点であるクラックの発生を防止した常温で
安定なＲｕＯ2膜を形成することを課題とする。The present invention is based on the above-mentioned conventional R
It is an object to form a RuO 2 film which is stable at room temperature and which prevents the generation of cracks, which is a drawback of the uO x film.
【０００４】[0004]
【課題を解決するための手段】本発明の二酸化ルテニウ
ム薄膜形成方法は、スパッタリング法により形成したル
テニウム酸化物（ＲｕＯX）膜をヘリウム、アルゴン、
窒素等の不活性ガス中で４００乃至９００℃の熱処理す
る工程を包含することにより、前記課題を解決するもの
である。また、本発明の二酸化ルテニウム薄膜形成方法
は、スパッタリング法により形成したルテニウム酸化物
（ＲｕＯX）膜を酸素中で４００乃至９００℃の熱処理
する工程を包含することにより、前記課題を解決するも
のである。また、本発明の二酸化ルテニウム薄膜形成方
法は、スパッタリング法により形成したルテニウム酸化
物（ＲｕＯX）膜をヘリウム、アルゴン、窒素等の不活
性ガスと酸素との混合気中で４００乃至９００℃の熱処
理する工程を包含することにより、前記課題を解決する
ものである。A method for forming a ruthenium dioxide thin film according to the present invention is a method for forming a ruthenium oxide (RuO x ) film formed by a sputtering method with helium, argon,
The above problem is solved by including a step of heat treatment at 400 to 900 ° C. in an inert gas such as nitrogen. The method for forming a ruthenium dioxide thin film of the present invention solves the above problems by including a step of heat-treating a ruthenium oxide (RuO X ) film formed by a sputtering method in oxygen at 400 to 900 ° C. is there. The ruthenium dioxide thin film forming method of the present invention is a ruthenium oxide (RuO x ) film formed by a sputtering method, which is heat-treated at 400 to 900 ° C. in a mixture of oxygen and an inert gas such as helium, argon, or nitrogen. The above problem is solved by including the step of
【０００５】[0005]
【作用】本発明においては、スパッタリング法により形
成したＲｕＯX膜を４００〜９００℃の熱処理を行うこ
とにより、膜中のＲｕＯ2の結晶粒は成長し、ＲｕＯ4は
膜から昇華する。熱処理前のＲｕＯX膜の断面図を図１
（ａ）に、熱処理後のＲｕＯ2膜の断面図を図１（ｂ）
にそれぞれ示す。このようにして、不安定なＲｕＯX膜
から蒸気圧の高いＲｕＯ4を昇華させ、ＲｕＯ2の結晶粒
を成長させて安定なＲｕＯ2膜を形成することができ
る。In the present invention, the RuO x film formed by the sputtering method is heat-treated at 400 to 900 ° C., whereby the RuO 2 crystal grains in the film grow and RuO 4 sublimes from the film. Figure 1 is a sectional view of the RuO X film before heat treatment
FIG. 1B shows a cross-sectional view of the RuO 2 film after heat treatment in FIG.
Are shown respectively. In this way, RuO 4 having a high vapor pressure is sublimated from the unstable RuO x film, and the crystal grains of RuO 2 are grown to form a stable RuO 2 film.
【０００６】[0006]
【実施例】以下、図面を参照して本発明の実施例を説明
する。まず最初にＲｕＯx膜をスパッタリング法で形成
する条件を示す。図２は本実施例のＲｕＯX膜形成に使
用するＤＣマグネトロンスパッタリング装置の例を示
す。ターゲット１には金属ルテニウム（Ｒｕ）を用い
る。スパッタガスはアルゴン（Ａｒ）と酸素（Ｏ2）の
混合ガスで、Ａｒ：Ｏ2＝８：２〜６：４の混合比でス
パッタチャンバー３内に導入する。スパッタリング装置
のＤＣパワー密度は１〜３Ｗ／ｃｍ2、スパッタチャン
バー３内の圧力は１０〜２０ｍＴｏｒｒを用いる。また
スパッタ時に基板２の温度を３００℃程度まで加熱する
と膜形成後のクラックは抑制できる。これは、膜中のＲ
ｕＯ4がスパッタ中に昇華し、安定なＲｕＯ2膜のみ堆積
されるためである。しかしながら、低抵抗なＲｕＯ2膜
を得るためにはさらに高温度の熱処理を必要とする。Embodiments of the present invention will be described below with reference to the drawings. First, the conditions for forming the RuO x film by the sputtering method are shown. FIG. 2 shows an example of a DC magnetron sputtering apparatus used for forming the RuO x film of this embodiment. Metal ruthenium (Ru) is used for the target 1. The sputtering gas is a mixed gas of argon (Ar) and oxygen (O 2 ), and is introduced into the sputtering chamber 3 at a mixing ratio of Ar: O 2 = 8: 2 to 6: 4. The DC power density of the sputtering apparatus is 1 to 3 W / cm 2 , and the pressure in the sputtering chamber 3 is 10 to 20 mTorr. Further, when the temperature of the substrate 2 is heated to about 300 ° C. during sputtering, cracks after the film formation can be suppressed. This is the R in the film
This is because uO 4 sublimes during sputtering and only a stable RuO 2 film is deposited. However, heat treatment at a higher temperature is required to obtain a RuO 2 film having a low resistance.
【０００７】以上の条件でＲｕＯX膜を堆積後、大気中
にＲｕＯX膜を置くときは１２時間以内に熱処理が必要
である。不活性ガス雰囲気中では数日間程度放置しても
膜にクラック等は発生しないが、膜中のＲｕＯ4が昇華
し膜質は劣化する。このため、良質なＲｕＯ2膜を得る
には堆積後できるだけ早く熱処理を行うか、真空を破ら
ずに膜堆積後続けて熱処理を行うことが望ましい。After depositing the RuO X film under the above conditions, heat treatment is required within 12 hours when the RuO X film is placed in the atmosphere. Even if the film is left to stand in an inert gas atmosphere for several days, cracks and the like do not occur in the film, but RuO 4 in the film sublimes and the film quality deteriorates. Therefore, in order to obtain a good quality RuO 2 film, it is desirable to perform the heat treatment as soon as possible after the deposition, or to perform the heat treatment continuously after the film deposition without breaking the vacuum.
【０００８】次に熱処理の条件を示す。熱処理は、温度
が５００〜９００℃で、ヘリウム、アルゴン、または窒
素等の不活性ガス雰囲気中で行う。又、熱処理の時間は
通常３０分〜１２０分程度とする。熱処理温度をさらに
９００℃以上に上げるとＲｕＯ2が分解し膜質が劣化す
る。Next, the conditions of heat treatment will be shown. The heat treatment is performed at a temperature of 500 to 900 ° C. in an atmosphere of an inert gas such as helium, argon, or nitrogen. The heat treatment time is usually about 30 minutes to 120 minutes. When the heat treatment temperature is further raised to 900 ° C. or higher, RuO 2 decomposes and the film quality deteriorates.
【０００９】次に、図３にシリコン（Ｓｉ）基板上に堆
積したＲｕＯ2膜のＸ線回折スペクトルの熱処理による
変化を示す。熱処理温度４００℃でＲｕＯ2（１０１）
に配向しており、熱処理温度の上昇と共に結晶化が進ん
でいるのが回折スペクトル強度からもわかる。Next, FIG. 3 shows changes in the X-ray diffraction spectrum of the RuO 2 film deposited on the silicon (Si) substrate due to heat treatment. RuO 2 (101) at heat treatment temperature of 400 ° C
It can be seen from the diffraction spectrum intensity that the crystallization is promoted and the crystallization progresses as the heat treatment temperature rises.
【００１０】また図４にＲｕＯ2膜の抵抗率の熱処理温
度依存性を示す。ＲｕＯ2膜の抵抗率も結晶粒の成長に
従って急激な低下が見られる。この結晶化によりＲｕＯ
2膜の抵抗率は減少し２００ｎｍ厚の薄膜で約６０μΩ
ｃｍとなる。FIG. 4 shows the heat treatment temperature dependence of the resistivity of the RuO 2 film. The resistivity of the RuO 2 film also decreases sharply as the crystal grains grow. Due to this crystallization, RuO
The resistivity of the two films is reduced to about 60 μΩ for a 200 nm thick film.
cm.
【００１１】以上、好ましい実施例を説明したが、これ
は本発明の範囲を限定するものではない。本発明の範囲
は前記特許請求の範囲によってのみ限定されるべきであ
る。以上の説明から熱処理の条件として、任意の不活性
ガス、酸素または不活性ガスと酸素の混合気のいずれか
の雰囲気と、４００℃から９００℃までの温度範囲で自
由な条件を取り得る。Although a preferred embodiment has been described above, this does not limit the scope of the invention. The scope of the invention should be limited only by the appended claims. From the above description, as the heat treatment condition, any inert gas, oxygen or a mixture of an inert gas and oxygen, and a temperature range of 400 ° C. to 900 ° C. can be freely set.
【００１２】[0012]
【発明の効果】以上説明したとおり、本発明によれば、
ＲｕＯX膜中のＲｕＯ2結晶粒を成長させるとともに、膜
中のＲｕＯ4を昇華させて膜質を改善し、膜にクラック
などが生じない低抵抗率のＲｕＯ2膜を得ることができ
るという効果がある。As described above, according to the present invention,
It is possible to grow the RuO 2 crystal grains in the RuO x film and to sublimate RuO 4 in the film to improve the film quality and to obtain a low-resistivity RuO 2 film that does not cause cracks in the film. is there.
【図１】図１（ａ）は、熱処理前のＲｕＯX膜の断面
図、図１（ｂ）は、熱処理後のＲｕＯ2膜の断面図であ
る。FIG. 1A is a cross-sectional view of a RuO X film before heat treatment, and FIG. 1B is a cross-sectional view of a RuO 2 film after heat treatment.
【図２】図２は、ＤＣマグネトロンスパッタリング装置
の概念図である。FIG. 2 is a conceptual diagram of a DC magnetron sputtering apparatus.
【図３】図３は、ＲｕＯ2膜のＸ線回折スペクトルの熱
処理温度依存性を示すグラフである。FIG. 3 is a graph showing the heat treatment temperature dependence of the X-ray diffraction spectrum of the RuO 2 film.
【図４】図４は、ＲｕＯ2膜の抵抗率の熱処理温度依存
性を示すグラフである。FIG. 4 is a graph showing the heat treatment temperature dependence of the resistivity of the RuO 2 film.
１ ターゲット（Ｒｕ） ２ 基板（Ｓｉ） ３ スパッタチャンバー 1 Target (Ru) 2 Substrate (Si) 3 Sputter chamber
Claims (3)
ウム酸化物（ＲｕＯX）膜をヘリウム、アルゴン、窒素
等の不活性ガス中で４００乃至９００℃の熱処理する工
程を含むことを特徴とする二酸化ルテニウム（Ｒｕ
Ｏ2）薄膜形成方法。1. A ruthenium oxide formed by sputtering (RuO X) film of helium, argon, ruthenium dioxide, characterized in that it comprises a step of heat treatment at 400 to 900 ° C. in an inert gas such as nitrogen (Ru
O 2 ) Thin film forming method.
ウム酸化物（ＲｕＯX）膜を酸素中で４００乃至９００
℃の熱処理する工程を含むことを特徴とする二酸化ルテ
ニウム（ＲｕＯ2）薄膜形成方法。2. A ruthenium oxide (RuO x ) film formed by a sputtering method in oxygen at 400 to 900.
A method for forming a ruthenium dioxide (RuO 2 ) thin film, characterized by including a step of heat treatment at ℃.
ウム酸化物（ＲｕＯX）膜をヘリウム、アルゴン、窒素
等の不活性ガスと酸素との混合気中で４００乃至９００
℃の熱処理する工程を含むことを特徴とする二酸化ルテ
ニウム（ＲｕＯ2）薄膜形成方法。3. A ruthenium oxide (RuO x ) film formed by a sputtering method in a mixed gas of oxygen and an inert gas such as helium, argon or nitrogen at 400 to 900.
A method for forming a ruthenium dioxide (RuO 2 ) thin film, characterized by including a step of heat treatment at ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22573192A JP2910005B2 (en) | 1992-08-25 | 1992-08-25 | Ruthenium dioxide thin film forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22573192A JP2910005B2 (en) | 1992-08-25 | 1992-08-25 | Ruthenium dioxide thin film forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0665716A true JPH0665716A (en) | 1994-03-08 |
| JP2910005B2 JP2910005B2 (en) | 1999-06-23 |
Family
ID=16833946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22573192A Expired - Fee Related JP2910005B2 (en) | 1992-08-25 | 1992-08-25 | Ruthenium dioxide thin film forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2910005B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001036029A (en) * | 1999-06-28 | 2001-02-09 | Hyundai Electronics Ind Co Ltd | Semiconductor device used for memory cell and method of manufacturing the same. |
| KR100434489B1 (en) * | 2001-03-22 | 2004-06-05 | 삼성전자주식회사 | Method for depositing ruthenium layer having Ru02 seeding layer |
-
1992
- 1992-08-25 JP JP22573192A patent/JP2910005B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001036029A (en) * | 1999-06-28 | 2001-02-09 | Hyundai Electronics Ind Co Ltd | Semiconductor device used for memory cell and method of manufacturing the same. |
| KR100434489B1 (en) * | 2001-03-22 | 2004-06-05 | 삼성전자주식회사 | Method for depositing ruthenium layer having Ru02 seeding layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2910005B2 (en) | 1999-06-23 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |