JPH06163434A - Film forming method by pulse plasma cvd method - Google Patents
Film forming method by pulse plasma cvd methodInfo
- Publication number
- JPH06163434A JPH06163434A JP33510992A JP33510992A JPH06163434A JP H06163434 A JPH06163434 A JP H06163434A JP 33510992 A JP33510992 A JP 33510992A JP 33510992 A JP33510992 A JP 33510992A JP H06163434 A JPH06163434 A JP H06163434A
- Authority
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- Japan
- Prior art keywords
- gas
- film
- reaction chamber
- raw material
- film forming
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、被処理物表面にパル
スプラズマＣＶＤにて高品質の薄膜を形成する方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a high quality thin film on the surface of an object to be processed by pulse plasma CVD.
【０００２】[0002]
【従来の技術】プラズマＣＶＤ法は化学蒸着法の１方法
として被処理物表面への皮膜形成に広く採用されてい
る。このプラズマＣＶＤ法はガスの供給および電力供給
を連続的に行うものであり、面積当たりのプラズマエネ
ルギーの密度が重要である。しかし、供給されるガスの
分解はプラズマエネルギーのみでは不十分であり、加熱
される基板の熱にも頼っている。現在行われているプラ
ズマＣＶＤでは成膜温度は３００℃以上であるが、この
ような温度で皮膜を形成した合金工具鋼のような基板
は、それ自体が鈍って硬度が低下し、冷間処理用の金型
として用いることはできない。従って、そのような用途
には２００℃以下の皮膜温度が要求される。一方、成膜
組成としてＴｉＮの良質皮膜を得ようとすると、５００
℃以上の成膜温度を必要とすることから、使用する基板
材料が限定されるという問題がある。2. Description of the Related Art Plasma CVD is widely used as a method of chemical vapor deposition for forming a film on the surface of an object to be processed. The plasma CVD method continuously supplies gas and electric power, and the density of plasma energy per area is important. However, the plasma energy alone is not sufficient for the decomposition of the supplied gas, and it relies on the heat of the heated substrate. In plasma CVD currently performed, the film formation temperature is 300 ° C. or higher, but a substrate such as an alloy tool steel on which a film is formed at such a temperature becomes dull by itself and its hardness is lowered, so that the cold treatment is performed. It cannot be used as a mold. Therefore, coating temperatures below 200 ° C. are required for such applications. On the other hand, when trying to obtain a good quality TiN film as the film-forming composition,
Since a film forming temperature of ℃ or more is required, there is a problem that the substrate material used is limited.
【０００３】また、パルスプラズマＣＶＤ法も一部で発
表されているが、これは反応室内に被処理物と、高周波
電力が供給される電極とを間隔を隔てて配置し、反応室
内を排気し、複数の反応ガスを導入するとともに、上記
電極に間欠的に高周波電力を供給し、この高周波電力に
よって各反応ガスをそれぞれを構成する原子に解離させ
て、プラズマを発生させ、これら原子が被処理物上にお
いて化学反応して薄膜を形成させるものである。A part of the pulse plasma CVD method has also been announced, in which an object to be treated and an electrode to which high-frequency power is supplied are placed in a reaction chamber with a space therebetween, and the reaction chamber is evacuated. Introducing a plurality of reaction gases, intermittently supplying high frequency power to the electrode, and dissociating each reaction gas into atoms constituting each by this high frequency power to generate plasma, and these atoms are processed. It is a chemical reaction on an object to form a thin film.
【０００４】この方法では、低い電力でその供給時間と
休止時間の比率が１：１〜１：５程度でガス種も混合か
交互に供給されている。また、プラズマエネルギー密度
を高くするために、大電力を使用するパルスプラズマＣ
ＶＤ法ではパルス状にガスを供給し、ガスが反応室内に
充分拡散したころに高周波電力をパルス状に供給するも
のである。この方法は、１周期が原料ガスと放電用ガス
を同時に供給し、その後電力をパルス状に供給し、次に
反応ガスを供給し、さらに電力をパルス状に供給してい
る。In this method, the gas species are mixed or alternately supplied with a low electric power at a ratio of the supply time to the rest time of about 1: 1 to 1: 5. Also, in order to increase the plasma energy density, pulsed plasma C that uses a large amount of electric power
In the VD method, gas is supplied in pulses, and high-frequency power is supplied in pulses when the gas is sufficiently diffused in the reaction chamber. In this method, the source gas and the discharge gas are simultaneously supplied for one cycle, and then the power is supplied in a pulsed form, then the reaction gas is supplied, and then the power is supplied in a pulsed form.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
方法では反応室内が加熱されておらず、供給された原料
ガスが凝縮して反応室の壁面に付着したりするため、供
給された原料ガスを完全に分解することは難しく、従っ
て、未分解の元素が膜のなかに残ってしまい良質な膜が
得られないという問題があった。However, in the above method, the reaction chamber is not heated, and the supplied source gas is condensed and adheres to the wall surface of the reaction chamber. It is difficult to completely decompose it. Therefore, there is a problem that undecomposed elements remain in the film and a good quality film cannot be obtained.
【０００６】本発明者らは上記に鑑みて、成膜温度が低
くても未分解元素が残留することなく、良質な皮膜の得
られる成膜方法を提供することを目的とするものであ
る。In view of the above, it is an object of the present inventors to provide a film forming method capable of obtaining a high quality film without leaving undecomposed elements even when the film forming temperature is low.
【０００７】[0007]
【課題を解決するための手段】即ち、この発明の第１の
発明は排気され、加熱された反応室に成膜用原料ガス、
放電用ガスおよび原料分解用ガスを夫々別個にコントロ
ールしつつ間欠的に導入し、高周波電力をパルス状に供
給してパルスプラズマＣＶＤにて上記反応室内の被処理
物表面に皮膜を形成させるに当たり、その成膜工程にお
いて１回の成膜用原料ガスの供給に対して放電用ガス、
原料分解用ガスおよび高周波電力を複数回供給すること
を特徴とするパルスプラズマＣＶＤによる成膜方法であ
り、第２の発明は排気され、加熱された反応室に成膜用
原料ガス、放電用ガスおよび原料分解用ガスを夫々別個
にコントロールしつつ間欠的に導入し、高周波電力をパ
ルス状に供給してパルスプラズマＣＶＤにて上記反応室
内の被処理物表面に化合物皮膜を形成させるに当たり、
その成膜工程において化合物薄膜を構成する数種の成膜
用原料ガスを夫々別個に段階的に上記反応室に供給し、
これら成膜用原料ガスの供給の都度他の放電用ガス、原
料分解用ガスおよび高周波電力を供給することを特徴と
するパルスプラズマＣＶＤによる成膜方法を提供するも
のである。That is, the first aspect of the present invention is to provide an exhausted and heated reaction chamber with a raw material gas for film formation,
In order to form a film on the surface of the object to be processed in the reaction chamber by pulse plasma CVD by intermittently introducing the discharge gas and the raw material decomposing gas while controlling them separately, and supplying high-frequency power in a pulsed manner, In the film forming process, a discharge gas is supplied for each single supply of the film forming source gas,
A second aspect of the present invention is a film forming method by pulsed plasma CVD, characterized in that a gas for raw material decomposition and a high-frequency power are supplied multiple times. A second invention is a raw material gas for film formation and a gas for discharge in an exhausted and heated reaction chamber. And intermittently introducing the raw material decomposing gas while controlling them separately, and supplying a high frequency power in a pulsed manner to form a compound film on the surface of the object to be treated in the reaction chamber by pulse plasma CVD,
In the film forming step, several kinds of film forming raw materials forming the compound thin film are separately and stepwise supplied to the reaction chamber,
The present invention provides a film forming method by pulse plasma CVD characterized in that a discharge gas, a material decomposition gas, and a high-frequency power are supplied every time the film forming material gas is supplied.
【０００８】[0008]
【作用】プラズマＣＶＤによる成膜方法において成膜用
原料ガスとしては、化合物を用いる場合が多いが、この
化合物の分解を反応室内で完全に行うことは非常に難し
く、このため被処理物表面に成膜した薄膜中には未分解
の元素が残留していて良質な膜とは言いがたい。このよ
うな未分解の元素を除去するには、未分解の元素と反応
するガスを供給しながらタイミングよく電力を供給する
ことが必要である。In the film-forming method by plasma CVD, a compound is often used as a film-forming raw material gas, but it is very difficult to completely decompose this compound in the reaction chamber. Undecomposed elements remain in the formed thin film, so it is hard to say that it is a good film. In order to remove such undecomposed elements, it is necessary to supply electric power in good timing while supplying a gas that reacts with the undecomposed elements.
【０００９】この発明は成膜工程において、成膜用原料
ガスが１種の場合は、これをただ１回の供給に対して放
電用ガス、原料分解用ガス、高周波電力を複数回供給
し、また、数種の成膜用原料ガスを用いる場合は、これ
を夫々別個に段階的に供給し、その都度放電用ガス、原
料分解用ガス、高周波電力を複数回供給するようにした
ことによって、原料ガスの分解を完全に行い、未分解元
素を含まない良質な薄膜が得られるのである。According to the present invention, in the film forming process, when there is only one kind of film forming source gas, the discharge gas, the material decomposing gas, and the high-frequency power are supplied a plurality of times for only one supply. Further, when using several kinds of film-forming raw material gas, these are supplied separately in stages, and discharge gas, raw material decomposition gas, and high-frequency power are supplied multiple times each time, The raw material gas is completely decomposed, and a high-quality thin film containing no undecomposed element can be obtained.
【００１０】次に、図１に示すこの発明で使用するパル
スプラズマＣＶＤの成膜装置についてその概略を説明す
る。図において、１はその外周を加熱ヒータ２で覆った
反応室である。この反応室１の内部にはその下方寄りに
被処理物（基板）３を配置し、上方にはこの被処理物３
に対向するように高周波電極５を配置しており、この高
周波電極５はマッチングボックス（整合器）６を経てパ
ルス高周波電源７に接続している。被処理物３はその下
方に加熱ヒータ４を具えている。また、上記反応室１は
主弁８、ルーツポンプ９を介して油回転真空ポンプ１０
に接続されており、この油回転真空ポンプ１０の作動に
よって反応室１内が排気されるようになっている。な
お、油回転真空ポンプ１０には廃ガス処理装置（図示せ
ず）への導入管１２が接続されており、油回転真空ポン
プ１０とルーツポンプ９との間の分岐管には窒素ガスを
油回転真空ポンプ１０に供給する窒素ガス導入弁１１が
設けられている。Next, the outline of the pulse plasma CVD film forming apparatus used in the present invention shown in FIG. 1 will be described. In the figure, 1 is a reaction chamber whose outer periphery is covered with a heater 2. An object to be processed (substrate) 3 is arranged in the lower part of the reaction chamber 1, and the object to be processed 3 is arranged above the object.
A high-frequency electrode 5 is arranged so as to face with, and the high-frequency electrode 5 is connected to a pulse high-frequency power source 7 via a matching box (matching device) 6. The workpiece 3 has a heater 4 below it. Further, the reaction chamber 1 is provided with an oil rotary vacuum pump 10 via a main valve 8 and a roots pump 9.
The interior of the reaction chamber 1 is exhausted by the operation of the oil rotary vacuum pump 10. The oil rotary vacuum pump 10 is connected with an introduction pipe 12 to a waste gas treatment device (not shown), and a branch pipe between the oil rotary vacuum pump 10 and the roots pump 9 is filled with nitrogen gas. A nitrogen gas introduction valve 11 that supplies the rotary vacuum pump 10 is provided.
【００１１】１３は導入ガスストップバルブであり、該
バルブから成膜用原料ガス、放電用ガス、原料分解用ガ
スなどが反応室１に導入される。即ち、Ａｒガス、Ｈ2
ガスはマスフローコントロールバルブ１４、１７で流量
をコントロールしながらバッファタンク１５、１８に送
られ、そこからピエゾバルブ１６、１９を瞬間的に開閉
して導入ガスストップバルブ１３から反応室１へ送られ
る。また、原料ガスの１つとして用いるＮ2 ガスはマス
フローコントロールバルブ２０で流量をコントロールし
ながらバッファタンク２１に送られ、そこからピエゾバ
ルブ２２を瞬間的に開閉して導入ガスストップバルブ１
３から反応室１へ送られる。Reference numeral 13 denotes an introduction gas stop valve through which a film forming raw material gas, a discharge gas, a raw material decomposing gas and the like are introduced into the reaction chamber 1. That is, Ar gas, H 2
The gas is sent to the buffer tanks 15 and 18 while controlling the flow rates by the mass flow control valves 14 and 17, and from there, the piezo valves 16 and 19 are momentarily opened and closed to be sent from the introduction gas stop valve 13 to the reaction chamber 1. The N 2 gas used as one of the raw material gases is sent to the buffer tank 21 while controlling the flow rate by the mass flow control valve 20, and from there, the piezo valve 22 is opened and closed instantaneously to introduce the gas stop valve 1.
3 is sent to the reaction chamber 1.
【００１２】さらに、ＴｉＣｌ4 、ＡｌＣｌ3 のような
常温で液体の物質を原料として用いる時は恒温槽２７内
の原料２６をヒータ２８で加熱して気化させておき、こ
の気化させた反応ガスを、反応室へ供給する反応ガス導
入管３２にストップバルブ２９、３０を操作して導き、
この反応ガス導入管３２にキャリアガスとして用いるマ
スフローコントロールバルブ２３で流量をコントロール
されたＨ2 ガスをストップバルブ２９、３０を開閉して
供給し、このＨ2 ガスとともに反応ガスをバッファタン
ク２４、ピエゾバルブ２５を経て導入ガスストップバル
ブ１３から反応室１へ送るのである。この反応ガスを反
応室１へ供給するに当たっては、該ガスが供給途中の反
応ガス導入管３２内において凝縮するのを防ぐために、
反応ガス導入管３２の周囲には導入管加熱ヒータ３３を
取り付けておくことが好ましい。Further, when a material which is liquid at room temperature, such as TiCl 4 or AlCl 3 , is used as a raw material, the raw material 26 in the constant temperature bath 27 is heated by a heater 28 to be vaporized, and the vaporized reaction gas is By operating the stop valves 29, 30 to the reaction gas introduction pipe 32 to be supplied to the reaction chamber,
The H 2 gas whose flow rate is controlled by the mass flow control valve 23 used as a carrier gas is supplied to the reaction gas introduction pipe 32 by opening and closing the stop valves 29 and 30, and the reaction gas together with the H 2 gas is supplied to the buffer tank 24 and the piezo valve. It is sent from the introduced gas stop valve 13 to the reaction chamber 1 via 25. In supplying the reaction gas to the reaction chamber 1, in order to prevent the gas from condensing in the reaction gas introduction pipe 32 during the supply,
It is preferable to install an introduction pipe heater 33 around the reaction gas introduction pipe 32.
【００１３】なお、キャリアガスとしては、Ｈ2 のほか
にＡｒやＨｅ等を用いることができる。また、反応ガス
の１つであるＮ2 に代えてＮＨ3 ガスを用いてもよい。
さらに、酸化物を成膜する場合にはＮ2 に代えてＯ2 、
Ｎ2 Ｏ、ＣＯを用いることもできる。この発明において
被処理物としては、Ｓｉウエハー、高速度鋼、ダイス
鋼、ステンレス鋼などが用いられ、この発明の方法で表
面に導電性膜、絶縁性膜、バリヤ膜を形成したＳｉウエ
ハーは半導体デバイスや電子部品として使用され、超硬
質皮膜を形成した高速度鋼などは金型、切削工具や耐磨
耗性機械部品として用いられる。As the carrier gas, Ar, He or the like can be used in addition to H 2 . Further, NH 3 gas may be used instead of N 2 which is one of the reaction gases.
Furthermore, in case of forming an oxide in place of the N 2 O 2,
N 2 O and CO can also be used. In the present invention, an Si wafer, high speed steel, die steel, stainless steel or the like is used as the object to be treated, and a Si wafer having a conductive film, an insulating film or a barrier film formed on the surface by the method of the present invention is a semiconductor. Used as devices and electronic parts, high-speed steel with ultra-hard coating is used as molds, cutting tools and wear-resistant machine parts.
【００１４】[0014]
【実施例】以下、この発明を図１を参照し実施例により
詳細に説明する。 実施例１（ＴｉＮ膜の形成） まず、反応室１に接続している管の主弁８を開き、真空
ポンプ９、１０を作動して反応室１内を排気したのち、
加熱ヒータ２にて予め反応室１内を１００℃前後に加熱
する。一方、恒温槽２７に収容されている液化原料であ
る四塩化チタン（ＴｉＣｌ4 ）２６を加熱ヒータ２８で
加熱しておく。次に、被処理物３を加熱ヒータ４にて加
熱し、２００℃になったらＡｒガス、Ｈ2 ガスを夫々マ
スフローコントロールバルブ（以下、これをＭＦＣとい
う）１４および１７で流量を調節しながらバッファタン
ク１５、１８に溜め込んだのち、ピエゾバルブ１６、１
９を瞬間的に開閉し、導入ガスストップバルブ１３を開
いて反応室１にパルス状に導入する。これらの導入は、
２５ｍｓ周期で７ｍｓピエゾバルブを開くことを繰り返
すことで行われる。なお、導入ガスストップバルブ１３
は放電開始時点から放電終了まで開いたままにしてお
く。パルス状に導入したＡｒガス、Ｈ2 ガスが反応室１
に充分拡散したら、パルス高周波電源７から高周波電極
５にパルス状に４０ＫＷ，１３．５６ＭＨｚの高周波電
力を印加してプラズマを発生させて、反応室１の内壁面
および被処理物３に付着している水分を除去する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to an embodiment with reference to FIG. Example 1 (Formation of TiN film) First, after opening the main valve 8 of the pipe connected to the reaction chamber 1 and operating the vacuum pumps 9 and 10 to exhaust the inside of the reaction chamber 1,
The inside of the reaction chamber 1 is preheated to about 100 ° C. by the heater 2. On the other hand, titanium tetrachloride (TiCl 4 ) 26, which is a liquefied raw material, contained in a constant temperature bath 27 is heated by a heater 28. Next, the object to be treated 3 is heated by the heater 4, and when the temperature reaches 200 ° C., the Ar gas and the H 2 gas are buffered while adjusting the flow rates by the mass flow control valves (hereinafter referred to as MFC) 14 and 17, respectively. After storing in tanks 15 and 18, piezo valves 16 and 1
9 is opened and closed instantaneously, the introduction gas stop valve 13 is opened, and the gas is introduced into the reaction chamber 1 in a pulsed manner. These introductions
It is performed by repeating opening of the 7 ms piezo valve at a cycle of 25 ms. The introduced gas stop valve 13
Remains open from the beginning of discharge to the end of discharge. Ar gas and H 2 gas introduced in pulse form are used in the reaction chamber 1.
Once sufficiently diffused, pulsed high-frequency power source 7 applies high-frequency power of 40 KW, 13.56 MHz to high-frequency electrode 5 in a pulsed manner to generate plasma, which adheres to the inner wall surface of reaction chamber 1 and object 3 to be treated. Remove any water that is present.
【００１５】次に、成膜工程の第１段階としてまず最初
に、恒温槽２７で加熱して気化せしめたＴｉＣｌ4 ガス
を成膜用原料ガスとしてストップバルブ２９、３０から
反応ガス導入管３２に導入し、同時にＭＦＣ２３で流量
を調節したＨ2 ガスをキャリアガスとしてストップバル
ブ２９、３０を開閉して上記反応ガス導入管３２に導入
して、このキャリアガスとともにＴｉＣｌ4 ガスと、Ｍ
ＦＣ１４、１７で流量を調節したＡｒガス、Ｈ2 ガスと
を同期して２５ｍｓ周期で７ｍｓピエゾバルブ２５、１
６、１９を開き、これを繰り返して間欠的に反応室１内
に導入する。これらのガスが反応室１内に充分拡散した
とき、パルス高周波電源７から１５０μｓの間上記と同
じ高周波電力を印加してＴｉＣｌ4 ガスを分解し、Ｔｉ
元素を被処理物上に膜として堆積させる。Next, as the first step of the film forming process, first, TiCl 4 gas heated and vaporized in a constant temperature bath 27 is used as a film forming source gas from the stop valves 29 and 30 to the reaction gas introducing pipe 32. At the same time, the H 2 gas whose flow rate was adjusted by the MFC 23 was used as a carrier gas to open and close the stop valves 29 and 30 to introduce it into the reaction gas introducing pipe 32, and together with this carrier gas, TiCl 4 gas and M
7ms piezo valve 25, 1 with a 25ms cycle in synchronization with Ar gas and H 2 gas whose flow rates are adjusted by FC14, 17
6 and 19 are opened, and this is repeated to intermittently introduce into the reaction chamber 1. When these gases are sufficiently diffused in the reaction chamber 1, the same high frequency power as described above is applied between the pulse high frequency power source 7 and 150 μs to decompose the TiCl 4 gas,
The element is deposited as a film on the object to be processed.
【００１６】さらに、ＭＦＣ１４、１７で流量を調節し
たＡｒガス、Ｈ2 ガスを２５ｍｓ周期で７ｍｓピエゾバ
ルブを開くことを６〜７回繰り返して間欠的に供給し、
同時に高周波電力をもその都度間欠的に供給することに
より、膜中に残存しているＣｌやＯ元素を除去する。Further, the Ar gas and the H 2 gas whose flow rates have been adjusted by the MFCs 14 and 17 are intermittently supplied by repeating the 7 ms piezo valve opening every 25 ms for 6 to 7 times,
At the same time, high-frequency power is also intermittently supplied each time to remove the Cl and O elements remaining in the film.
【００１７】次に、成膜工程の第２段階として成膜用原
料ガスとしてのＮ2 ガスをＭＦＣ２０で流量を調節し
て、ＭＦＣ１４、１７からのＡｒガス、Ｈ2 ガスととも
に上記と同じ条件で２〜３回繰り返し間欠的に供給する
とともに、高周波電力をも複数回間欠的に供給すること
により、被処理物上のＴｉ元素にＮ2 ガスを反応させ
る。さらに、Ａｒガス、Ｈ2 ガスを５〜６回とこれとほ
ぼ同期して高周波電力を間欠的に供給してＴｉＮ膜の形
成時に膜中に残存しがちなＣｌやＯ元素を除去する。か
くして、被処理物上にＴｉＮ膜を形成した。Next, as the second stage of the film forming process, the flow rate of N 2 gas as a film forming source gas is adjusted by the MFC 20, and the Ar gas and H 2 gas from the MFCs 14 and 17 are used under the same conditions as above. N 2 gas is made to react with the Ti element on the object to be processed by intermittently supplying the high-frequency power a plurality of times as well as intermittently supplying it a few times repeatedly. Further, Ar gas and H 2 gas are supplied 5 to 6 times, in synchronism with this, to intermittently supply high-frequency power to remove Cl and O elements that tend to remain in the TiN film during formation. Thus, a TiN film was formed on the object to be processed.
【００１８】上記における成膜工程の所要時間は３００
〜５００ｍｓ、反応室内圧力は０．０８〜０．１５Ｔｏ
ｒｒで、成膜速度は０．５〜１．５μｍ／ｈであった。
また、得られた膜の硬さはヌープ硬さ（Ｈｋ）１８００
〜２５００であり、オージェ電子分光法（ＡＥＳ）によ
る分析の結果、Ｃｌ，Ｏ元素は夫々１％、５％以下しか
認められなかった。The time required for the above film forming process is 300.
~ 500ms, pressure in the reaction chamber is 0.08 ~ 0.15To
In rr, the film forming rate was 0.5 to 1.5 μm / h.
The hardness of the obtained film is Knoop hardness (Hk) 1800.
˜2500, and as a result of analysis by Auger electron spectroscopy (AES), only 1% and 5% or less of Cl and O elements were recognized.
【００１９】実施例２（Ａｌ膜の形成） 実施例１のＴｉＣｌ4 に代えて塩化アルミニウム（Ａｌ
Ｃｌ3 ）を液化原料として用いた。また、反応室１の内
壁面および被処理物３に付着している水分を除去するま
での工程を実施例１と同様に行ったのち、成膜工程とし
てまず最初に、恒温槽２７で加熱して気化せしめたＡｌ
Ｃｌ3 ガスを成膜用原料ガスとしてストップバルブ２
９、３０から反応ガス導入管３２に導入し、同時にＭＦ
Ｃ２３で流量を調節したＨ2 ガスをキャリアガスとして
ストップバルブ２９、３０を開閉して上記反応ガス導入
管３２に導入して、このキャリアガスとともにＡｌＣｌ
3 ガスと、ＭＦＣ１４、１７で流量を調節したＡｒガ
ス、Ｈ2 ガスとを同期して２５ｍｓ周期で７ｍｓピエゾ
バルブを開き、これを数回繰り返して間欠的に反応室１
内に導入する。これらのガスが反応室１内に充分拡散し
たとき、パルス高周波電源７から約１５０μｓの間４０
ＫＷ，１３．５６ＭＨｚの高周波電力を数回印加してＡ
ｌＣｌ3 ガスを分解し、Ａｌ元素を被処理物上に膜とし
て堆積させる。Example 2 (Formation of Al film) Instead of TiCl 4 of Example 1, aluminum chloride (Al film) was formed.
Cl 3 ) was used as a liquefaction raw material. Moreover, after performing the steps up to removing the water adhering to the inner wall surface of the reaction chamber 1 and the object 3 to be processed in the same manner as in Example 1, first, as a film forming step, first, heating in the constant temperature bath 27 is performed. Vaporized Al
Stop valve 2 using Cl 3 gas as a raw material gas for film formation
It is introduced into the reaction gas introduction pipe 32 from 9 and 30, and at the same time MF
The stop valves 29 and 30 are opened / closed by using H 2 gas whose flow rate is adjusted by C23 as a carrier gas and introduced into the reaction gas introducing pipe 32, and AlCl together with the carrier gas.
The 3 gas and the Ar gas and the H 2 gas whose flow rates were adjusted by the MFCs 14 and 17 were synchronized and the 7 ms piezo valve was opened in a cycle of 25 ms, and this was repeated several times to intermittently react with the reaction chamber 1.
Introduce inside. When these gases are sufficiently diffused in the reaction chamber 1, the pulse high frequency power source 7 keeps the temperature for about 150 μs.
Applying high frequency power of kW, 13.56MHz several times A
lCl 3 gas is decomposed and Al element is deposited as a film on the object to be processed.
【００２０】さらに、ＭＦＣ１４、１７で流量を調節し
たＡｒガス、Ｈ2 ガスを２５ｍｓ周期で７ｍｓピエゾバ
ルブを開き、これを１２〜１３回繰り返して間欠的に供
給し、同時に高周波電力をも間欠的に供給することによ
り、膜中に残存しているＣｌやＯ元素を除去して純粋な
Ａｌ膜を形成した。上記における成膜工程の所要時間は
１５０〜３００ｍｓ、反応室内圧力は０．０８〜０．１
５Ｔｏｒｒで、成膜速度は１．０〜２．０μｍ／ｈであ
った。Further, the Ar gas and the H 2 gas whose flow rates are adjusted by the MFCs 14 and 17 are opened at a 7 ms piezo valve in a cycle of 25 ms, and this is repeated 12 to 13 times to intermittently supply high frequency power at the same time. By supplying, the Cl and O elements remaining in the film were removed to form a pure Al film. The time required for the above film forming step is 150 to 300 ms, and the pressure in the reaction chamber is 0.08 to 0.1.
At 5 Torr, the film formation rate was 1.0 to 2.0 μm / h.
【００２１】この他、実施例１のＴｉＮ膜の形成と同じ
ような成膜工程を用い、ＳｉＮ膜、ＳｉＯ2 膜の形成を
行ったところ、ＳｉＮ膜では原料ガスとしてＳｉＨ4 と
Ｎ2ガスを使用して成膜速度は１．５〜２．５μｍ／ｈ
であった。また、ＳｉＯ2 膜では原料ガスとしてＳｉＨ
4 、Ｏ2 、Ａｒガスを使用して成膜速度は２．０〜３．
０μｍ／ｈであった。In addition, when a SiN film and a SiO 2 film were formed using the same film forming process as the TiN film of Example 1, SiH 4 and N 2 gas were used as the source gas in the SiN film. The film formation rate used is 1.5 to 2.5 μm / h
Met. Further, in the SiO 2 film, SiH is used as a source gas.
The film forming rate is 2.0 to 3 using O 4 , O 2 and Ar gas.
It was 0 μm / h.
【００２２】[0022]
【発明の効果】以上説明したように、この発明によれ
ば、排気した反応室内に成膜用原料ガス、放電用ガス、
原料分解用ガスを導入し、高周波電力を印加して反応室
内の被処理物表面に薄膜を形成するに際して、成膜用原
料ガスの１回の供給に対して他の放電用ガス、原料分解
用ガスを複数回供給し、その都度高周波電力を印加する
こと、あるいは数種の成膜用原料ガスを用いる場合にそ
れらの原料ガスを夫々別個に段階的に供給し、その都度
他の放電用ガス、原料分解用ガスの供給と、高周波電力
の印加を行うこと、さらに反応室内を加温状態に保持す
ることによって、反応室内に導入された原料ガスの凝縮
を防止し、且つ原料ガスをほぼ完全に分解することがで
きるので、パルスプラズマＣＶＤ法で２００℃あるいは
それ以下の温度で被処理物表面に未分解元素を含まない
高品質の薄膜を得ることができる。As described above, according to the present invention, the film forming raw material gas, the discharge gas,
When a raw material decomposition gas is introduced and a high-frequency power is applied to form a thin film on the surface of the object to be processed in the reaction chamber, a single supply of the film forming raw material gas to another discharge gas or the raw material decomposition gas Gas is supplied multiple times and high frequency power is applied each time, or when several kinds of film forming source gases are used, these source gases are separately supplied in stages, and another discharge gas each time. By supplying the gas for decomposing the raw material, applying high-frequency power, and keeping the reaction chamber warm, the condensation of the raw material gas introduced into the reaction chamber is prevented and the raw material gas is almost completely removed. Therefore, a high-quality thin film containing no undecomposed element on the surface of the object to be treated can be obtained at a temperature of 200 ° C. or lower by the pulse plasma CVD method.
【図１】この発明で用いるパルスプラズマＣＶＤ成膜装
置の１例を示す概略図である。FIG. 1 is a schematic view showing an example of a pulse plasma CVD film forming apparatus used in the present invention.
１ 反応室 ３ 被処理物 ５ 高周波電極 ７ 高周波電源 １３ 導入ガスストップバルブ ２５ ピエゾバルブ ２６ 液化原料 ２７ 恒温槽 ３２ 反応ガス導入管 DESCRIPTION OF SYMBOLS 1 Reaction chamber 3 Processing object 5 High frequency electrode 7 High frequency power supply 13 Introduction gas stop valve 25 Piezo valve 26 Liquefaction raw material 27 Constant temperature bath 32 Reaction gas introduction pipe
Claims (2)
料ガス、放電用ガスおよび原料分解用ガスを夫々別個に
コントロールしつつ間欠的に導入し、高周波電力をパル
ス状に供給してパルスプラズマＣＶＤにて上記反応室内
の被処理物表面に皮膜を形成させるに当たり、その成膜
工程において１回の成膜用原料ガスの供給に対して放電
用ガス、原料分解用ガスおよび高周波電力を複数回供給
することを特徴とするパルスプラズマＣＶＤによる成膜
方法。1. A raw material gas for film formation, a gas for discharge, and a gas for raw material decomposition are separately controlled and intermittently introduced into an evacuated and heated reaction chamber, and high-frequency power is supplied in a pulsed manner. When forming a film on the surface of the object to be processed in the reaction chamber by pulse plasma CVD, the discharge gas, the raw material decomposition gas and the high frequency power are supplied to the film forming raw material gas once in the film forming step. A film forming method by pulsed plasma CVD, which is supplied a plurality of times.
料ガス、放電用ガスおよび原料分解用ガスを夫々別個に
コントロールしつつ間欠的に導入し、高周波電力をパル
ス状に供給してパルスプラズマＣＶＤにて上記反応室内
の被処理物表面に化合物薄膜を形成させるに当たり、そ
の成膜工程において化合物薄膜を構成する数種の成膜用
原料ガスを夫々別個に段階的に上記反応室に供給し、こ
れら成膜用原料ガスの供給の都度他の放電用ガス、原料
分解用ガスおよび高周波電力を供給することを特徴とす
るパルスプラズマＣＶＤによる成膜方法。2. A raw material gas for film formation, a gas for discharge and a gas for raw material decomposition are separately controlled and intermittently introduced into the evacuated and heated reaction chamber, and high-frequency power is supplied in a pulsed manner. When a compound thin film is formed on the surface of an object to be processed in the reaction chamber by pulse plasma CVD, several kinds of film-forming raw material gases that form the compound thin film in the film forming process are separately and stepwise introduced into the reaction chamber. A method for forming a film by pulse plasma CVD, which comprises supplying a discharge gas, a material decomposition gas, and a high-frequency power each time the film forming material gas is supplied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33510992A JP3186872B2 (en) | 1992-11-19 | 1992-11-19 | Film forming method by pulse plasma CVD |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33510992A JP3186872B2 (en) | 1992-11-19 | 1992-11-19 | Film forming method by pulse plasma CVD |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06163434A true JPH06163434A (en) | 1994-06-10 |
| JP3186872B2 JP3186872B2 (en) | 2001-07-11 |
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ID=18284876
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33510992A Expired - Fee Related JP3186872B2 (en) | 1992-11-19 | 1992-11-19 | Film forming method by pulse plasma CVD |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004050948A1 (en) * | 2002-12-05 | 2004-06-17 | Tokyo Electron Limited | Film-forming method and apparatus using plasma cvd |
| US6905549B2 (en) | 2002-04-11 | 2005-06-14 | Hitachi Kokusai Electric Inc. | Vertical type semiconductor device producing apparatus |
| JP2006222265A (en) * | 2005-02-10 | 2006-08-24 | Hitachi Kokusai Electric Inc | Substrate processing apparatus |
| JP2007016277A (en) * | 2005-07-07 | 2007-01-25 | Shinko Seiki Co Ltd | Method for forming silicon oxide film |
| JP2007526399A (en) * | 2004-03-05 | 2007-09-13 | レール・リキード−ソシエテ・アノニム・ア・ディレクトワール・エ・コンセイユ・ドゥ・スールベイランス・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method for forming insulating film or metal film |
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|---|---|---|---|---|
| DE102004056170A1 (en) * | 2004-08-06 | 2006-03-16 | Aixtron Ag | Apparatus and method for high throughput chemical vapor deposition |
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1992
- 1992-11-19 JP JP33510992A patent/JP3186872B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6905549B2 (en) | 2002-04-11 | 2005-06-14 | Hitachi Kokusai Electric Inc. | Vertical type semiconductor device producing apparatus |
| US7622396B2 (en) | 2002-04-11 | 2009-11-24 | Hitachi Kokusai Electric Inc. | Method of producing a semiconductor device |
| WO2004050948A1 (en) * | 2002-12-05 | 2004-06-17 | Tokyo Electron Limited | Film-forming method and apparatus using plasma cvd |
| KR100788061B1 (en) * | 2002-12-05 | 2007-12-21 | 동경 엘렉트론 주식회사 | Film-forming method and apparatus using plasma cvd |
| KR100788060B1 (en) * | 2002-12-05 | 2007-12-21 | 동경 엘렉트론 주식회사 | Film-forming method and apparatus using plasma cvd |
| JP2007526399A (en) * | 2004-03-05 | 2007-09-13 | レール・リキード−ソシエテ・アノニム・ア・ディレクトワール・エ・コンセイユ・ドゥ・スールベイランス・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method for forming insulating film or metal film |
| JP2006222265A (en) * | 2005-02-10 | 2006-08-24 | Hitachi Kokusai Electric Inc | Substrate processing apparatus |
| JP2007016277A (en) * | 2005-07-07 | 2007-01-25 | Shinko Seiki Co Ltd | Method for forming silicon oxide film |
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|---|---|
| JP3186872B2 (en) | 2001-07-11 |
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