JPH073461A - Chemical vapor deposition method - Google Patents
Chemical vapor deposition methodInfo
- Publication number
- JPH073461A JPH073461A JP14740693A JP14740693A JPH073461A JP H073461 A JPH073461 A JP H073461A JP 14740693 A JP14740693 A JP 14740693A JP 14740693 A JP14740693 A JP 14740693A JP H073461 A JPH073461 A JP H073461A
- Authority
- JP
- Japan
- Prior art keywords
- vapor deposition
- reaction
- raw material
- temp
- chemical vapor
- 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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- Chemical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐摩耗性材料や半導体
材料などの各種薄膜を均一に成長する化学気相蒸着方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical vapor deposition method for uniformly growing various thin films such as wear resistant materials and semiconductor materials.
【０００２】[0002]
【従来の技術】基材に均一に薄膜を形成することは、薄
膜の機能を十分に発揮させる上で極めて重要な意味を持
つ。従来、薄膜を均一に形成するために、原料ガスの
導入を均一にしたり、基材を回転して原料ガスとの接
触を均一にする方法が提案され、一定の効果を上げてい
る。化学気相蒸着方法では、特に原料ガスの均一な導入
が極めて重要であり、ガス導入部分をシャワー状にした
り、ガス導入と排気の位置関係を工夫することが提案さ
れている。2. Description of the Related Art The uniform formation of a thin film on a substrate has a very important meaning in order to fully exhibit the function of the thin film. Conventionally, in order to uniformly form a thin film, a method has been proposed in which the introduction of the raw material gas is made uniform or the base material is rotated to make the contact with the raw material gas uniform, and a certain effect has been achieved. In the chemical vapor deposition method, in particular, it is extremely important to uniformly introduce the raw material gas, and it has been proposed to make the gas introduction portion into a shower shape or devise the positional relationship between the gas introduction and the exhaust.
【０００３】しかし、導入する原料ガス若しくは原料ガ
スから分解生成する低次化合物の生成若しくは分解の性
質に着目して、目的の蒸着物質からなる均一な薄膜を形
成しようとした例はほとんどない。わずかに、導入する
原料ガス自体の昇華圧を考慮して、原料ガスがガス導入
経路や反応室内壁に析出しないように、加熱することが
行われていたにすぎない。However, there are few examples in which a uniform thin film made of a target vapor deposition substance is formed by paying attention to the property of the raw material gas to be introduced or the lower-order compound which is decomposed and produced from the raw material gas, or the decomposition property. In consideration of the sublimation pressure of the raw material gas itself to be introduced, the heating is merely performed so that the raw material gas is not deposited on the gas introduction path or the inner wall of the reaction chamber.
【０００４】[0004]
【発明が解決しようとする課題】しかし、壁面を原料ガ
スの昇華温度以上に加熱して原料ガスの析出を防止する
方法は、原料ガスそのものの析出による消耗を防ぐ点で
効果があるが、反応室内で原料ガスが分解、反応して生
成する新たな化合物については全く考慮されていない。
しかし、原料ガスとその反応系の種類によっては、蒸着
物質よりさらに高い昇華温度を示す物質が反応室内で生
成される場合があり、そのような物質が壁面に析出する
と、反応室内の原料ガス分布が変化して基板上に均一な
薄膜の形成を妨げられる場合がある。However, the method of preventing the deposition of the raw material gas by heating the wall surface to a temperature not lower than the sublimation temperature of the raw material gas is effective in preventing the consumption of the raw material gas itself due to the deposition. No consideration is given to new compounds generated by decomposition and reaction of the raw material gas in the room.
However, depending on the type of source gas and its reaction system, a substance that has a higher sublimation temperature than the vapor deposition substance may be generated in the reaction chamber.If such a substance deposits on the wall surface, the source gas distribution in the reaction chamber May change to prevent formation of a uniform thin film on the substrate.
【０００５】そこで、本発明は、蒸着物質よりさらに高
い昇華温度を示す物質が反応室内で生成される化学気相
反応系においても均一な薄膜を形成することのできる化
学気相蒸着方法を提供しようとするものである。Therefore, the present invention provides a chemical vapor deposition method capable of forming a uniform thin film even in a chemical vapor phase reaction system in which a substance having a sublimation temperature higher than that of a vapor deposition substance is generated in a reaction chamber. It is what
【０００６】[0006]
【課題を解決するための手段】本発明は、化学気相反応
により基板上に蒸着物質を蒸着する方法において、原料
ガスから分解した低次化合物の昇華温度若しくは分解温
度以上に反応室の内壁を加熱して気相蒸着することを特
徴とする化学気相蒸着方法である。The present invention relates to a method for depositing a vapor deposition material on a substrate by a chemical vapor reaction, in which the inner wall of the reaction chamber is heated to a temperature higher than the sublimation temperature or the decomposition temperature of the lower-order compound decomposed from the source gas. It is a chemical vapor deposition method characterized by heating and vapor deposition.
【０００７】[0007]
【作用】化学気相蒸着方法は、一般に数種類の原料ガス
の化学気相反応により、基材表面に目的とする固体薄膜
を形成する方法で、ガス状の反応生成物は系外に排気さ
れる。それ故、原料系の出発ガスと反応生成系の最終生
成ガスに着目して、反応可能性を判断するための熱力学
的計算と、ガスの取扱い性を考慮して使用原料ガスを決
定していたが、原料ガスの実際の反応過程についてはあ
まり検討されておらず、特に、プラズマやレーザによる
熱的非平衡な反応を利用する化学気相蒸着方法では、現
象が非常に複雑なため、ほとんど解明されていない。The chemical vapor deposition method is a method of forming a desired solid thin film on the surface of a substrate by the chemical vapor reaction of several kinds of raw material gases, and the gaseous reaction product is exhausted out of the system. . Therefore, paying attention to the starting gas of the raw material system and the final product gas of the reaction producing system, the thermodynamic calculation for judging the reaction possibility and the raw material gas to be used are determined in consideration of the handling property of the gas. However, the actual reaction process of the raw material gas has not been studied so much, and especially in the chemical vapor deposition method utilizing a thermal non-equilibrium reaction by plasma or laser, since the phenomenon is very complicated, Not understood.
【０００８】本発明者は、上記の化学気相蒸着の反応過
程に着目し、原料ガスの反応過程と形成される薄膜の均
一性との関係について鋭意検討を重ねた結果、原料ガス
の分解過程で生成する低次化合物に、昇華温度の高い固
相化合物が存在する場合には、形成される薄膜の均一性
が悪くなり、その際、壁面に上記の低次化合物が析出し
ていることを見出した。The present inventor has paid attention to the reaction process of the chemical vapor deposition, and as a result of repeated studies on the relationship between the reaction process of the raw material gas and the uniformity of the thin film to be formed, as a result, the decomposition process of the raw material gas. When the solid phase compound having a high sublimation temperature is present in the low-order compound generated in step 1, the uniformity of the formed thin film is deteriorated, and at that time, the low-order compound is precipitated on the wall surface. I found it.
【０００９】そこで、本発明では、原料ガスの分解過程
で生成する低次化合物などの固相化合物の昇華温度ある
いは分解温度以上に反応室などの内壁を加熱し、固相化
合物の析出を防止して原料ガスの消耗を回避し、反応空
間のガス濃度分布を均一にすることにより、基材の位置
によらず、均一な薄膜の形成が可能になった。なお、反
応室等のガスが接する部分の加熱温度は、上記固相化合
物の昇華温度又は分解温度を若干越える程度が好まし
い。必要以上に加熱すると、壁面などで基材表面と同様
の成膜反応が起きて原料ガスを消耗するので、薄膜を不
均一にする原因となるので、成膜反応温度より低く保持
する必要がある。Therefore, in the present invention, the inner wall of the reaction chamber or the like is heated to a temperature higher than the sublimation temperature or the decomposition temperature of the solid phase compound such as a low order compound produced in the decomposition process of the raw material gas to prevent the precipitation of the solid phase compound. By avoiding the consumption of the raw material gas and making the gas concentration distribution in the reaction space uniform, it is possible to form a uniform thin film regardless of the position of the substrate. The heating temperature of the portion in contact with the gas, such as the reaction chamber, is preferably slightly above the sublimation temperature or decomposition temperature of the solid phase compound. If heating is performed more than necessary, the same film formation reaction as the surface of the base material will occur on the wall surface and the raw material gas will be consumed, which will cause non-uniformity of the thin film, so it is necessary to keep it below the film formation reaction temperature. .
【００１０】図１は、本発明を実施するためのプラズマ
化学気相蒸着装置の概念図である。プラズマ発生装置を
備えた反応室１内に基材２を配置し、基材２の前後にガ
ス回り込み防止板４を配置し、反応室１の周囲には低次
化合物を昇華若しくは分解するための加熱ヒータ３を設
けた。原料ガスは矢印の方向に流して基材上に薄膜を蒸
着し、残余のガスを矢印のように排気する。FIG. 1 is a conceptual diagram of a plasma enhanced chemical vapor deposition apparatus for carrying out the present invention. A base material 2 is arranged in a reaction chamber 1 equipped with a plasma generator, a gas sneak prevention plate 4 is arranged in front of and behind the base material 2, and for sublimating or decomposing lower-order compounds around the reaction chamber 1. The heater 3 was provided. The source gas is flowed in the direction of the arrow to deposit a thin film on the substrate, and the remaining gas is exhausted as shown by the arrow.
【００１１】[0011]
（実施例１，比較例１）図１のプラズマ化学気相蒸着装
置を用いて、四塩化チタン（ＴｉＣｌ4 ）、メタン（Ｃ
Ｈ4 ）、水素（Ｈ2 ）及びアルゴン（Ａｒ）を原料ガス
として、基材上に窒化チタン（ＴｉＮ）薄膜を形成し
た。四塩化チタンは常温で液体状であるため、四塩化チ
タンのポットを４０℃に加熱し、水素ガスでバブリング
して飽和蒸気圧分だけ反応室に供給した。上記ポットと
反応室を接続する配管をリボンヒータで５０℃に加熱し
たが、反応室の周囲は加熱せず、基材をプラズマで加熱
して薄膜を蒸着した。(Example 1 and Comparative Example 1) Titanium tetrachloride (TiCl 4 ) and methane (C
A titanium nitride (TiN) thin film was formed on the base material using H 4 ), hydrogen (H 2 ) and argon (Ar) as source gases. Since titanium tetrachloride is liquid at room temperature, the titanium tetrachloride pot was heated to 40 ° C., bubbled with hydrogen gas, and the saturated vapor pressure was supplied to the reaction chamber. The pipe connecting the pot to the reaction chamber was heated to 50 ° C. with a ribbon heater, but the periphery of the reaction chamber was not heated and the substrate was heated with plasma to deposit a thin film.
【００１２】基材上に形成された窒化チタン薄膜は、反
応ガスの流れ方向に図２のＣ１のように膜厚が変化し
た。ガス配管には、四塩化チタンなどの付着は認められ
なかったが、反応室の内壁には紫色の粉末が多量に付着
していた。上記の蒸着において、反応室の内壁は基材の
プラズマ加熱により１００℃程度まで温度上昇し、四塩
化チタンの蒸発温度より高いにもかかわらず、多量の付
着物が発生していたので、原料ガスの四塩化チタンの分
解過程を調べたところ、固体状、紫色の三塩化チタン
（ＴｉＣｌ3 ：分解温度４４０℃）が付着していたこと
が確認された。The thickness of the titanium nitride thin film formed on the substrate changed in the direction of the reaction gas flow, as shown by C1 in FIG. No adhesion of titanium tetrachloride or the like was found in the gas pipe, but a large amount of purple powder adhered to the inner wall of the reaction chamber. In the above vapor deposition, the inner wall of the reaction chamber was heated to about 100 ° C. by the plasma heating of the base material, and a large amount of deposit was generated even though it was higher than the evaporation temperature of titanium tetrachloride. When the decomposition process of titanium tetrachloride was examined, it was confirmed that solid, purple titanium trichloride (TiCl 3 : decomposition temperature 440 ° C.) was attached.
【００１３】そこで、図１の反応室周囲のヒータで反応
室内壁を４５０℃に加熱しながら四塩化チタン薄膜を蒸
着したところ、薄膜の膜厚の変化は図２の１に示したよ
うに、反応ガスの流れ方向で極めて均一な薄膜が得られ
たことが分かる。Then, when a titanium tetrachloride thin film was vapor-deposited while the inner wall of the reaction chamber was heated to 450 ° C. by the heater around the reaction chamber of FIG. 1, the change in the thickness of the thin film was as shown in 1 of FIG. It can be seen that an extremely uniform thin film was obtained in the flow direction of the reaction gas.
【００１４】（実施例２）図１のプラズマ化学気相蒸着
装置を用いて、四塩化チタン（ＴｉＣｌ4 ）の代わり
に、五塩化タンタル（ＴａＣｌ5 ）を用い、反応室の内
壁を四塩化タンタル（ＴａＣｌ4 ）の昇華温度４７５℃
以上に加熱し、また、五塩化タングステン（ＷＣｌ5 ）
を用い、反応室の内壁を四塩化タングステン（ＷＣ
ｌ4 ）の昇華温度３２０℃以上に加熱し、四塩化ゲルマ
ニウム（ＧｅＣｌ4 ）を用い、反応室の内壁を二塩化ゲ
ルマニウム（ＧｅＣｌ2 ）の分解温度４５０℃以上に加
熱して、基材上にそれぞれ薄膜を蒸着したところ、反応
室内壁などに付着物が発生せず、実施例１と同様にいず
れも均一な薄膜を形成することができた。Example 2 Using the plasma chemical vapor deposition apparatus of FIG. 1, tantalum pentachloride (TaCl 5 ) was used in place of titanium tetrachloride (TiCl 4 ) and the inner wall of the reaction chamber was tantalum tetrachloride. Sublimation temperature of (TaCl 4 ) 475 ° C
Heat to above and also tungsten pentachloride (WCl 5 )
The inner wall of the reaction chamber with tungsten tetrachloride (WC
l 4 ) is heated to a sublimation temperature of 320 ° C. or higher, germanium tetrachloride (GeCl 4 ) is used, and the inner wall of the reaction chamber is heated to a decomposition temperature of germanium dichloride (GeCl 2 ) of 450 ° C. or higher to form a substrate. When thin films were vapor-deposited, deposits did not occur on the inner wall of the reaction chamber, etc., and as in Example 1, it was possible to form uniform thin films.
【００１５】なお、上記の蒸着は、ガスの流れが横方向
のプラズマ化学気相蒸着装置を用いて、原料ガスとして
金属の塩化物を用いる場合について説明したが、本発明
はこれらに限定されることなく、反応系に各種の固相化
合物を生成する場合に、ガスの流れ方向や反応活性化方
法によらず、上記の効果を発揮させることができる。In the above vapor deposition, the case where the metal chloride is used as the raw material gas by using the plasma chemical vapor deposition apparatus in which the gas flow is in the lateral direction has been described, but the present invention is not limited thereto. In the case where various solid phase compounds are produced in the reaction system, the above effect can be exhibited regardless of the gas flow direction and the reaction activation method.
【００１６】[0016]
【発明の効果】本発明は、上記の構成を採用することに
より、反応ガスの流れ方向に均一な膜厚の薄膜を容易に
蒸着することができるようになった。特に、プラズマや
レーザを用いた熱的非平衡な状態における反応を利用す
る方法は、基材の他を加熱しない、いわゆるコールドウ
ォール方式を用いることが多いため、本発明の方法が顕
著な効果を発揮する。According to the present invention, by adopting the above structure, it becomes possible to easily deposit a thin film having a uniform film thickness in the flow direction of the reaction gas. In particular, the method of utilizing the reaction in a thermally non-equilibrium state using plasma or laser often uses a so-called cold wall method in which the other parts of the substrate are not heated, and therefore the method of the present invention has a remarkable effect. Demonstrate.
【図１】本発明の化学気相蒸着方法を実施するための装
置の概念図である。FIG. 1 is a conceptual diagram of an apparatus for carrying out a chemical vapor deposition method of the present invention.
【図２】実施例１及び比較例１で得た薄膜の、ガスの流
れ方向での変化を示したグラフである。2 is a graph showing changes in the gas flow direction of the thin films obtained in Example 1 and Comparative Example 1. FIG.
Claims (2)
蒸着する方法において、原料ガスから分解した低次化合
物の昇華温度若しくは分解温度以上に反応室の内壁を加
熱して気相蒸着することを特徴とする化学気相蒸着方
法。1. A method for depositing a deposition material on a substrate by a chemical vapor reaction, in which vapor deposition is carried out by heating the inner wall of a reaction chamber to a sublimation temperature or a decomposition temperature of a lower-order compound decomposed from a source gas. A chemical vapor deposition method characterized by the above.
とする請求項１記載の化学蒸着成長方法。2. The chemical vapor deposition growth method according to claim 1, wherein plasma or laser is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14740693A JPH073461A (en) | 1993-06-18 | 1993-06-18 | Chemical vapor deposition method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14740693A JPH073461A (en) | 1993-06-18 | 1993-06-18 | Chemical vapor deposition method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH073461A true JPH073461A (en) | 1995-01-06 |
Family
ID=15429581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14740693A Withdrawn JPH073461A (en) | 1993-06-18 | 1993-06-18 | Chemical vapor deposition method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH073461A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6072579A (en) * | 1998-08-27 | 2000-06-06 | Ricoh Company, Ltd. | Optical pickup apparatus having improved holographic optical element and photodetector |
-
1993
- 1993-06-18 JP JP14740693A patent/JPH073461A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6072579A (en) * | 1998-08-27 | 2000-06-06 | Ricoh Company, Ltd. | Optical pickup apparatus having improved holographic optical element and photodetector |
| US6618344B1 (en) | 1998-08-27 | 2003-09-09 | Ricoh Company, Ltd. | Optical pickup apparatus having improved holographic optical element and photodetector |
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