JP2910005B2 - Ruthenium dioxide thin film forming method - Google Patents
Ruthenium dioxide thin film forming methodInfo
- Publication number
- JP2910005B2 JP2910005B2 JP22573192A JP22573192A JP2910005B2 JP 2910005 B2 JP2910005 B2 JP 2910005B2 JP 22573192 A JP22573192 A JP 22573192A JP 22573192 A JP22573192 A JP 22573192A JP 2910005 B2 JP2910005 B2 JP 2910005B2
- Authority
- JP
- Japan
- Prior art keywords
- ruo
- ruthenium
- film
- heat treatment
- ruthenium 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.)
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Links
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- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Vapour Deposition (AREA)
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。The present invention relates to a (hereinafter abbreviated as RuO 2) ruthenium dioxide relates to a method of forming a thin film, particularly ruthenium oxide containing higher oxides such as ruthenium tetroxide (RuO 4) (hereinafter RuO X ) Stable 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 sputtering.
In the case of forming an X film, a RuO X film is formed by sputtering in a mixed gas of argon (Ar) and oxygen (O 2 ) using metal ruthenium (Ru) as a target. However, Ru immediately after formation by sputtering is used.
O X film is not promoted too much crystallization, RuO 4 in the film
And higher oxides. This RuO 4 has a high vapor pressure at room temperature and is soluble in water and organic solvents. Therefore, if this RuO X film is left at room temperature for a long time, RuO X
RuO 4 in the film absorbs moisture or sublimes. Consequently cracks occurred in 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。SUMMARY OF THE INVENTION The present invention relates to the above conventional R
An object of the present invention is to form a stable RuO 2 film at room temperature, which prevents cracks, which is a drawback of the uO X film, from occurring.
【０００４】[0004]
【課題を解決するための手段】第１の発明である二酸化
ルテニウム薄膜形成方法は、二酸化ルテニウム（ＲｕＯ
2 ）と四酸化ルテニウム（ＲｕＯ 4 ）を含むルテニウム酸
化物（ＲｕＯ X ）膜をスパッタリング法により形成する
工程と、前記ルテニウム酸化物膜を不活性ガス中で４０
０乃至９００℃の熱処理をすることにより前記四酸化ル
テニウムを昇華させながら前記二酸化ルテニウムの結晶
粒を成長させる工程とを含むことを特徴とする。第２の
発明である二酸化ルテニウム薄膜形成方法は、前記ルテ
ニウム酸化物膜を酸素中で４００乃至９００℃の熱処理
をする工程を含むことを特徴とする。 第３の発明である
二酸化ルテニウム薄膜形成方法は、前記ルテニウム酸化
物膜を不活性ガスと酸素との混合気中で４００乃至９０
０℃の熱処理をする工程を含むことを特徴とする。 Means for Solving the Problems] ruthenium dioxide thin film forming method which is the first invention, ruthenium dioxide (RuO
2 ) and ruthenic acid containing ruthenium tetroxide (RuO 4 )
Product of (RuO X) film formed by sputtering
And a step of subjecting the ruthenium oxide film to an inert gas for 40 minutes.
0 to the tetroxide le by a heat treatment at 900 ° C.
Ruthenium dioxide crystals while sublimating ruthenium
Characterized in that it comprises a step of growing grains. Second
Ruthenium dioxide thin film forming method is invention, heat treatment at 400 to 900 ° C. in oxygen the lutein <br/> onium oxide film
And a step of performing The third invention is a <br/> ruthenium dioxide thin film forming method, the ruthenium oxide film in a gas mixture of inert gas and oxygen 400 to 90
The method includes a step of performing a heat treatment at 0 ° C.
【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。According to the present invention, by performing the heat treatment of RuO X film 400 to 900 ° C. formed by a sputtering method, RuO 2 crystal grains in the film grows, RuO 4 sublimates from the membrane. FIG. 1 is a cross-sectional view of the RuO X film before heat treatment.
FIG. 1A is a cross-sectional view of the RuO 2 film after the heat treatment, and FIG.
Are shown below. In this manner, RuO 4 having a high vapor pressure is sublimated from the unstable RuO X film, and 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, conditions for forming a RuO x film by a sputtering method will be described. Figure 2 shows an example of a DC magnetron sputtering apparatus used in the RuO X film formed in this embodiment. For the target 1, metal ruthenium (Ru) is used. 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. When the temperature of the substrate 2 is heated to about 300 ° C. during the sputtering, cracks after the film formation can be suppressed. This is because R
This is because uO 4 sublimates during sputtering, and only a stable RuO 2 film is deposited. However, in order to obtain a low-resistance RuO 2 film, a higher temperature heat treatment is required.
【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。[0007] The above conditions after deposition of the RuO X film, When you put the RuO X film into the atmosphere it is necessary to heat treatment within 12 hours. Even if the film is left for about several days in an inert gas atmosphere, cracks and the like do not occur in the film, but RuO 4 in the film sublimates and the film quality deteriorates. For this reason, in order to obtain a high quality RuO 2 film, it is desirable to perform the heat treatment as soon as possible after the deposition or to continue the heat treatment 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４００〜９００℃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 the heat treatment will be described. The heat treatment is performed at a temperature of 400 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. If the heat treatment temperature is further increased to 900 ° C. or higher, RuO 2 is decomposed and the film quality is deteriorated.
【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 a change in the X-ray diffraction spectrum of the RuO 2 film deposited on the silicon (Si) substrate due to the heat treatment. RuO 2 (101) at a heat treatment temperature of 400 ° C.
It can also be seen from the diffraction spectrum intensity that the crystallization progresses with an increase in the heat treatment temperature.
【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 sharply decreases as the crystal grains grow. This crystallization allows RuO
(2) The resistivity of the film decreases and is about 60 μΩ for a 200 nm thick thin 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。While the preferred embodiment has been described, it is not intended to limit the scope of the invention. The scope of the present invention should be limited only by the appended claims. From the above description, as the conditions for the heat treatment, any conditions can be set in an atmosphere of any inert gas, oxygen or a mixture of inert gas and oxygen, and a temperature range from 400 ° C. to 900 ° C.
【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,
The effect of growing the RuO 2 crystal grains in the RuO X film and improving the film quality by sublimating the RuO 4 in the film to obtain a low-resistivity RuO 2 film that does not cause cracks or the like in the film can be obtained. 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 a 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 DESCRIPTION OF SYMBOLS 1 Target (Ru) 2 Substrate (Si) 3 Sputter chamber
フロントページの続き (56)参考文献 特開 昭61−96704（ＪＰ，Ａ) Ａ．Ｊ．ＭｃＥｖｏｙ ａｎｄ Ｗ. Ｇｉｓｓｉｅｒ，”Ａ ｒｕｔｈｅｎｉ ｕｍ ｄｉｏｘｉｄｅ−ｓｅｍｉｃｏｎ ｄｕｃｔｏｒ Ｓｃｈｏｔｔｋｙ ｂａ ｒｒｉｅｒ ｐｈｏｔｏｖｏｌｔａｉｃ ｄｅｖｉｃｅ”，Ｊ．Ａｐｐｌ．Ｐｈ ｙｓ．，Ｆｅｂｒｕａｒｙ 1982，53 （２），ｐ．1251−1252 (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 14/00 - 14/58 C30B 33/02 Continuation of front page (56) References JP-A-61-96704 (JP, A) J. McEvoy and W. Gissier, "Aruthenium dioxide-semiconductor Schottky barrier photovoltaic device", J. Amer. Appl. Phys. , February 1982, 53 (2), p. 1251-1252 (58) Field surveyed (Int.Cl. 6 , DB name) C23C 14/00-14/58 C30B 33/02
Claims (3)
ルテニウム（ＲｕＯ 4 ）を含むルテニウム酸化物（Ｒｕ
Ｏ X ）膜をスパッタリング法により形成する工程と、 前記 ルテニウム酸化物膜を不活性ガス中で４００乃至９
００℃の熱処理をすることにより前記四酸化ルテニウム
を昇華させながら前記二酸化ルテニウムの結晶粒を成長
させる工程と、 を含むことを特徴とする二酸化ルテニウム薄膜形成方
法。1. Ruthenium dioxide (RuO 2 ) and tetroxide
Ruthenium oxide (RuO ) containing ruthenium (RuO 4 )
O X) and forming a film by sputtering, the ruthenium oxide film to 400 in an inert gas 9
The ruthenium tetroxide is subjected to a heat treatment at 00 ° C.
Grow the ruthenium dioxide crystal grains while sublimating
Ruthenium dioxide thin film forming method which comprises the step of causing, the.
ルテニウム（ＲｕＯ 4 ）を含むルテニウム酸化物（Ｒｕ
Ｏ X ）膜をスパッタリング法により形成する工程と、 前記ルテニウム酸化物膜を酸素中で４００乃至９００℃
の熱処理をすることにより前記四酸化ルテニウムを昇華
させながら前記二酸化ルテニウムの結晶粒を成長させる
工程と、 を含むことを特徴とする二酸化ルテニウム薄膜形成方
法。2. Ruthenium dioxide (RuO 2 ) and tetroxide
Ruthenium oxide (RuO ) containing ruthenium (RuO 4 )
O x ) forming a film by sputtering, and forming the ruthenium oxide film in oxygen at 400 to 900 ° C.
Sublimating the ruthenium tetroxide by the heat treatment
Ruthenium dioxide film forming method characterized by comprising, a <br/> step of growing a crystal grain of the ruthenium dioxide while.
ルテニウム（ＲｕＯ 4 ）を含むルテニウム酸化物（Ｒｕ
Ｏ X ）膜をスパッタリング法により形成する工程と、 前記ルテニウム酸化物膜を不活性ガスと酸素との混合気
中で４００乃至９００℃の熱処理をすることにより前記
四酸化ルテニウムを昇華させながら前記二酸化ルテニウ
ムの結晶粒を成長させる工程と、 を含むことを特徴とする二酸化ルテニウム薄膜形成方
法。3. Ruthenium dioxide (RuO 2 ) and tetroxide
Ruthenium oxide (RuO ) containing ruthenium (RuO 4 )
O X) forming a film by sputtering, said by the heat treatment at 400 to 900 ° C. in air fuel mixture of the ruthenium oxide film an inert gas and oxygen
Ruthenium dioxide while sublimating ruthenium tetroxide
Ruthenium dioxide thin film forming method which comprises the step of growing the crystal grains of the arm, the.
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 JPH0665716A (en) | 1994-03-08 |
| JP2910005B2 true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100333667B1 (en) * | 1999-06-28 | 2002-04-24 | 박종섭 | Method for fabricating capacitor of ferroelectric random access memory device |
| 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
Non-Patent Citations (1)
| Title |
|---|
| Ａ．Ｊ．ＭｃＥｖｏｙ ａｎｄ Ｗ．Ｇｉｓｓｉｅｒ，"Ａ ｒｕｔｈｅｎｉｕｍ ｄｉｏｘｉｄｅ−ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｓｃｈｏｔｔｋｙ ｂａｒｒｉｅｒ ｐｈｏｔｏｖｏｌｔａｉｃ ｄｅｖｉｃｅ"，Ｊ．Ａｐｐｌ．Ｐｈｙｓ．，Ｆｅｂｒｕａｒｙ １９８２，５３（２），ｐ．１２５１−１２５２ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665716A (en) | 1994-03-08 |
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