JPH06338497A - Chemical vapor growth method - Google Patents

Chemical vapor growth method

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Publication number
JPH06338497A
JPH06338497A JP12694393A JP12694393A JPH06338497A JP H06338497 A JPH06338497 A JP H06338497A JP 12694393 A JP12694393 A JP 12694393A JP 12694393 A JP12694393 A JP 12694393A JP H06338497 A JPH06338497 A JP H06338497A
Authority
JP
Japan
Prior art keywords
film
gas
chemical vapor
shower head
vapor deposition
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.)
Granted
Application number
JP12694393A
Other languages
Japanese (ja)
Other versions
JP2508581B2 (en
Inventor
Hiroshi Ishikawa
拓 石川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEC Corp
Original Assignee
NEC Corp
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Filing date
Publication date
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Priority to JP5126943A priority Critical patent/JP2508581B2/en
Publication of JPH06338497A publication Critical patent/JPH06338497A/en
Application granted granted Critical
Publication of JP2508581B2 publication Critical patent/JP2508581B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Formation Of Insulating Films (AREA)

Abstract

PURPOSE:To provide a silicon nitride and silicon oxynitride film of high quality and excellent coating property having no moisture and carbon component in the film. CONSTITUTION:The inside of a chamber 3 is made into a reduced pressure state about several torr, individual gases to be used for film formation are mixed inside a shower head electrode 4 for being introduced from the shower head electrode 4 into the chamber 3. High frequency voltage is impressed between the shower head electrode 4 and a lower part electrode 1 from high frequency power supply 12 so as to make gas mixed by the shower head electrode 4 inside the chamber 3 and to cause chemical reaction for forming a reactive intermediate. A film having an excellent coating property on a substrate 2 by this reactive intermediates. As reactant gas, trisilylamine 6 and ammonium gas are used when a nitride film is formed and when an oxynitride film is formed, nitrogen suboxide (N2O) gas is used in addition to trisilylamine 6 and ammonium gas.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、半導体装置の製造法、
特に配線層のパッシベーション膜（保護膜）を形成させ
る化学気相成長法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device manufacturing method,
In particular, it relates to a chemical vapor deposition method for forming a passivation film (protective film) of a wiring layer.

【０００２】[0002]

【従来の技術】半導体装置の微細化に伴い、半導体装置
が構成する配線の間隔が１μｍ以下の非常に狭い設計ル
ールにより開発されている。このように非常に微細な配
線を保護するため、従来シリコンナイトライド及びシリ
コンオキシナイトライド膜が保護膜として配線を覆うよ
うに形成されてきた。しかし、このような微細配線で
は、配線間の隙間に保護するに充分な膜厚を持つシリコ
ンナイトライド及びシリコンオキシナイトライド膜を形
成することができず、また、配線間に大きな隙間（ボイ
ド）を残したまま保護膜が形成され、ホトリソグラフィ
ーの際、ボイド内に残留していたガスが加熱を受けて爆
発し、保護膜上に形成されたレジスト膜を吹き飛ばして
しまうという欠点がある。2. Description of the Related Art With the miniaturization of semiconductor devices, it has been developed according to a very narrow design rule in which the distance between wirings of the semiconductor device is 1 μm or less. In order to protect such extremely fine wiring, silicon nitride and silicon oxynitride films have conventionally been formed as protective films so as to cover the wiring. However, with such fine wiring, it is not possible to form a silicon nitride film and a silicon oxynitride film having a film thickness sufficient to protect the gap between the wirings, and a large gap (void) is formed between the wirings. The protective film is formed with the above remaining, and during photolithography, the gas remaining in the void is heated and explodes, which blows off the resist film formed on the protective film.

【０００３】このような現象は、保護膜の被膜性が良く
ないために発生する。そこで被膜性を改善するために、
有機シラン，オゾンに過酸化水素，水を添加した反応ガ
スを用いたパルスプラズマ法による化学気相成長法によ
り、酸化膜の被膜性を向上させる方法が提案された（特
願平４−３２０９７３号）。また、ビスジターシャリブ
トキシアミノシランイミド〔（ｔ−Ｃ4Ｈ9Ｏ）ＳｉＮＨ
2〕2ＮＨを用いたプラズマ気相化学成長法で、被膜性の
良いシリコンオキシナイトライドを形成する方法も提案
されている（特願平２−２６５２４２号）。Such a phenomenon occurs because the coating property of the protective film is not good. Therefore, in order to improve the coating properties,
A method of improving the film forming property of an oxide film by a chemical vapor deposition method by a pulse plasma method using a reaction gas obtained by adding hydrogen peroxide and water to organic silane and ozone has been proposed (Japanese Patent Application No. 4-320973). ). Moreover, bis-di-tertiary butoxy aminosilane imide [(t-C 4 H 9 O ) SiNH
2 ] A method of forming silicon oxynitride having good film-forming property by a plasma chemical vapor deposition method using 2 NH has also been proposed (Japanese Patent Application No. 2-265242).

【０００４】[0004]

【発明が解決しようとする課題】しかし、有機シラン，
オゾンに過酸化水素，水を添加した反応ガスを用いたパ
ルスプラズマ法による化学気相成長法では、反応ガス内
に水分があるため、どのようなプラズマによる改質効果
を行ったとしても、形成された膜の中に水分がかなりの
量で含まれてしまう。膜中に水分が多いと、配線金属が
腐食されたり、外部からの水分が半導体装置内に入りや
すくなり、保護膜としての性能が著しく低下してしま
う。However, the organic silane,
In the chemical vapor deposition method based on the pulse plasma method using a reaction gas in which hydrogen peroxide and water are added to ozone, there is water in the reaction gas. Moisture is contained in a considerable amount in the formed film. If the film contains a large amount of water, the wiring metal will be corroded, or water from the outside will easily enter the semiconductor device, and the performance as a protective film will be significantly reduced.

【０００５】また、ビスジターシャリブトキシアミノシ
ランイミド〔（ｔ−Ｃ4Ｈ9Ｏ）ＳｉＮＨ2〕2ＮＨを用い
たプラズマ気相化学成長法では、形成されたシリコンオ
キシナイトライド膜中にかなりの量で炭素が混入する。
膜中に炭素成分があると、耐湿性が低下するほかに、下
地の配線金属や絶縁膜との接着力が低下し、膜の剥がれ
が発生する。Further, in the plasma chemical vapor deposition method using bisditertiarybutoxyaminosilane imide [(t-C 4 H 9 O) SiNH 2 ] 2 NH, a considerable amount is contained in the formed silicon oxynitride film. Carbon is mixed in.
If a carbon component is contained in the film, the moisture resistance is reduced, and the adhesion to the underlying wiring metal or the insulating film is reduced, so that the film is peeled off.

【０００６】本発明の目的は、膜中に水分や炭素のよう
な成分のない高品位で、しかも被膜性の良い膜を形成さ
せる化学気相成長法を提供することにある。An object of the present invention is to provide a chemical vapor deposition method for forming a high-quality film having high quality and free of components such as water and carbon in the film and having good film-forming property.

【０００７】[0007]

【課題を解決するための手段】前記目的を達成するた
め、本発明に係る化学気相成長法は、反応ガスをプラズ
マ化し、化学反応を生じさせて基板上に気相成長膜を成
長させる化学気相成長法であって、反応ガスは、少なく
ともシリコンソースガスとしてシリルアミン化合物を含
むものであり、気相成長膜は、シリコンナイトライド膜
又はシリコンオキシナイトライド膜である。In order to achieve the above object, the chemical vapor deposition method according to the present invention is a chemical method for converting a reaction gas into plasma and causing a chemical reaction to grow a vapor growth film on a substrate. In the vapor phase growth method, the reaction gas contains at least a silylamine compound as a silicon source gas, and the vapor phase growth film is a silicon nitride film or a silicon oxynitride film.

【０００８】また、反応ガスは、前記シリルアミン化合
物のほかにアンモニアガスを含むものであり、気相成長
膜は、シリコンナイトライド膜である。The reaction gas contains ammonia gas in addition to the silylamine compound, and the vapor phase growth film is a silicon nitride film.

【０００９】また、反応ガスは、前記シリルアミン化合
物のほかにアンモニアガスと、亜酸化窒素ガスを含むも
のであり、気相成長膜は、シリコンオキシナイトライド
膜である。The reaction gas contains ammonia gas and nitrous oxide gas in addition to the silylamine compound, and the vapor phase growth film is a silicon oxynitride film.

【００１０】[0010]

【作用】シリコンソースガスとしてのシリルアミン化合
物を主成分とする反応ガスをプラズマ化して反応中間体
を形成し、この反応中間体により、基板上にシリコンナ
イトライド膜，シリコンオキシナイトライド膜を形成す
る。[Function] A reaction gas containing a silylamine compound as a main component as a silicon source gas is converted into plasma to form a reaction intermediate, and the reaction intermediate forms a silicon nitride film or a silicon oxynitride film on a substrate. .

【００１１】[0011]

【実施例】以下に、本発明による化学気相成長法の一実
施例を図１に基づき詳細に説明する。図１は、本発明に
よる化学気相成長法を実施するための化学気相成長装置
を示す概略図である。EXAMPLE An example of the chemical vapor deposition method according to the present invention will be described in detail below with reference to FIG. FIG. 1 is a schematic diagram showing a chemical vapor deposition apparatus for carrying out the chemical vapor deposition method according to the present invention.

【００１２】図１において、チャンバー３内を数ｔｏｒ
ｒ前後の減圧状態にする。成膜に用いる個々のガスは、
シャワーヘッド電極４内で混合し、シャワーヘッド電極
４からチャンバー３内に導入する。ここで、チャンバー
３内に上下に対向して設置されたシャワーヘッド電極４
及び下部電極１間に、高周波電源１２より、高周波電圧
を加える。これにより、シャワーヘッド電極４内で混合
されたガスは、プラズマ化され、化学反応が起こり、下
部電極１の基板２上に反応ガスによる膜が形成される。In FIG. 1, the inside of the chamber 3 is several torr.
Reduce the pressure to around r. The individual gas used for film formation is
They are mixed in the showerhead electrode 4 and introduced into the chamber 3 from the showerhead electrode 4. Here, the shower head electrodes 4 installed in the chamber 3 so as to face each other vertically.
A high frequency voltage is applied from a high frequency power source 12 between the lower electrode 1 and the lower electrode 1. As a result, the gas mixed in the shower head electrode 4 is turned into plasma and a chemical reaction occurs, and a film of the reaction gas is formed on the substrate 2 of the lower electrode 1.

【００１３】反応ガスは、ナイトライド膜を形成する際
は、トリシリルアミン６とアンモニアガスを用い、オキ
シナイトライド膜を形成する際は、トリシリルアミン６
とアンモニアガスの他に亜酸化窒素（Ｎ2Ｏ）ガスを用
いる。これらのガス中で、アンモニアガスと亜酸化窒素
（Ｎ2Ｏ）ガスは、常温で気体のため、それぞれのガス
ボンベ１０から流量調整器１１を通してガス配管７，８
からシャワーヘッド電極４へ個別に導入される。トリシ
リルアミン６については、常温で液体のため、キャリア
ーガスとしてヘリウムを用い、ガスボンベ１０からヘリ
ウムを液体材料気化器５内のトリシリルアミン６中に吹
き込み、トリシリルアミン６をヘリウムでバブリング
し、気化されたトリシリルアミン６をガス配管９からシ
ャワーヘッド電極４へ導入する。また、液体材料気化器
５に供給されるヘリウムの流量を流量調整器１１で調整
することにより、ガス配管９を通してシャワーヘッド電
極４に導入されるトリシリルアミン６の流量を決定す
る。As the reaction gas, trisilylamine 6 and ammonia gas are used when forming a nitride film, and trisilylamine 6 is used when forming an oxynitride film.
In addition to ammonia gas, nitrous oxide (N 2 O) gas is used. Among these gases, the ammonia gas and the nitrous oxide (N 2 O) gas are gases at room temperature, so that the gas pipes 7 and 8 are passed from the respective gas cylinders 10 through the flow rate adjusters 11.
Are individually introduced into the showerhead electrode 4. Since the trisilylamine 6 is liquid at room temperature, helium is used as a carrier gas, helium is blown from the gas cylinder 10 into the trisilylamine 6 in the liquid material vaporizer 5, and the trisilylamine 6 is bubbled with helium. The vaporized trisilylamine 6 is introduced into the showerhead electrode 4 from the gas pipe 9. Further, the flow rate of the helium supplied to the liquid material vaporizer 5 is adjusted by the flow rate adjuster 11 to determine the flow rate of the trisilylamine 6 introduced into the showerhead electrode 4 through the gas pipe 9.

【００１４】シャワーヘッド電極４から導入されるトリ
シリルアミン６は、チャンバー３内でプラズマ化された
際、化学反応を起こす。その際、トリシリルアミン６
は、反応中間体〔−Ｈ2Ｓｉ（ＮＨ）−〕ｎを形成す
る。この反応中間体〔−Ｈ2Ｓｉ（ＮＨ）−〕ｎ中のｎ
は重合度を示し、成膜を行っている圧力（数ｔｏｒｒ）
では、反応中間体同士の重合が進まず、ｎの値は、ほぼ
１と見られる。The trisilylamine 6 introduced from the showerhead electrode 4 causes a chemical reaction when it is turned into plasma in the chamber 3. At that time, trisilylamine 6
The reaction intermediate [-H 2 Si (NH) -] to form an n. The reaction intermediate [-H 2 Si (NH) -] n in n
Indicates the degree of polymerization, and the pressure at which the film is formed (several torr)
Then, the polymerization of the reaction intermediates does not proceed, and the value of n seems to be about 1.

【００１５】この中間体の化学式を見ると、中間体を構
成する元素は、水素，窒素，シリコンの３種類のみであ
る。これは、信頼性の高いシランを原料とするシリコン
ナイトライド及びシリコンオキシナイトライド膜に含ま
れているもののみであり、不純物の少ない高品位な膜質
を提供することができる。Looking at the chemical formula of this intermediate, the elements constituting the intermediate are only three kinds: hydrogen, nitrogen and silicon. This is only contained in the silicon nitride and silicon oxynitride films made of highly reliable silane as a raw material, and it is possible to provide high-quality film quality with few impurities.

【００１６】成膜反応時、この反応中間体は基板上に堆
積し、基板表面を流動することにより、被膜性の良い膜
を形成する。さらに基板表面を流動する反応中間体は、
プラズマから基板へ入射する活性な粒子によって、重合
が進む。この際、基板に入射する活性な粒子の入射エネ
ルギーを調整すること、すなわち、シャワーヘッド電極
４と下部電極１との間に加わる高周波電圧を変えること
により、反応中間体の重合する速度を変えることができ
る。これにより、図２のように、隣接する配線１４，１
４間の微細なスペースを隙間なく被膜するような優れた
被膜性をもつシリコンナイトライド及びシリコンオキシ
ナイトライド膜１３を形成することができる。図２中、
１６は基板，１５は絶縁膜である。During the film formation reaction, this reaction intermediate is deposited on the substrate and flows on the surface of the substrate to form a film having a good coating property. Furthermore, the reaction intermediate that flows on the substrate surface is
Polymerization is driven by the active particles entering the substrate from the plasma. At this time, the incident energy of the active particles incident on the substrate is adjusted, that is, the high frequency voltage applied between the showerhead electrode 4 and the lower electrode 1 is changed to change the polymerization rate of the reaction intermediate. You can As a result, as shown in FIG.
It is possible to form the silicon nitride and silicon oxynitride film 13 having an excellent film-forming property so as to form a fine space between the four without gaps. In FIG.
Reference numeral 16 is a substrate, and 15 is an insulating film.

【００１７】ここで、図３に、種々の方法によるシリコ
ンナイトライド及びシリコンオキシナイトライド膜の耐
湿試験の結果を示す。試験の条件は、湿度１００％，温
度１２５℃，２気圧の加圧状態に膜を放置して、膜中に
侵入する水分を調べたものである。水や炭素を成膜材料
として成膜されたシリコン膜中には、水分又は炭素が膜
中に始めから含まれるため、それぞれ試験開始直後から
膜中への水分の侵入が見られる。これに対し、シリルア
ミン化合物によるシリコンナイトライド及びシリコンオ
キシナイトライド膜では、試験２００時間後でも膜への
水分の侵入は、見られない。Here, FIG. 3 shows the results of humidity resistance tests of silicon nitride and silicon oxynitride films by various methods. The conditions of the test are that the film is left in a pressurized state of humidity 100%, temperature 125 ° C., and 2 atm, and water entering the film is examined. In a silicon film formed by using water or carbon as a film-forming material, water or carbon is contained in the film from the beginning, so that the infiltration of water into the film is observed immediately after the start of the test. On the other hand, in the silicon nitride and silicon oxynitride films formed by the silylamine compound, no infiltration of water into the film is observed even after 200 hours of the test.

【００１８】なお本実施例において、シリルアミン化合
物としてシリルアミンを用いて説明しているが、シリル
アミン化合物としては、シリルアミン以外に、（Ｓｉ2
Ｈ5）3Ｎ，（ＳｉＨ3ＮＳｉＨ2）3，（ＳｉＨ3）4Ｎ2な
どを用いても同様な効果が得られる。In the present embodiment, silylamine is used as the silylamine compound, but silylamine compounds other than silylamine (Si 2
Similar effects can be obtained by using H 5 ) 3 N, (SiH 3 NSiH 2 ) 3 , or (SiH 3 ) 4 N 2 .

【００１９】[0019]

【発明の効果】以上説明したように本発明のプラズマに
よる化学気相成長法によれば、シリコンソースガスとし
てシリルアミン化合物を用いることにより、膜中に水分
や炭素のような成分のない高品位、かつ被膜性の良いシ
リコンナイトライド及びシリコンオキシナイトライド膜
を提供することができる。この高品位、かつ被膜性の良
いシリコンナイトライド及びシリコンオキシナイトライ
ド膜を半導体装置、例えばトランジスタに用いることに
より、トランジスタへの水分の侵入を抑え、トランジス
タのホットキャリアー耐性を伸ばし、トランジスタの寿
命を従来のものに比べ１０％伸ばすことができる。As described above, according to the chemical vapor deposition method using plasma of the present invention, by using a silylamine compound as a silicon source gas, it is possible to obtain a high quality product having no components such as water and carbon in the film. Further, it is possible to provide a silicon nitride film and a silicon oxynitride film having good film-forming properties. By using the silicon nitride and silicon oxynitride films with high quality and good film-forming property in semiconductor devices, such as transistors, the intrusion of water into the transistors is suppressed, the hot carrier resistance of the transistors is extended, and the life of the transistors is extended. It can be extended by 10% compared to the conventional one.

【００２０】以上のように高品位、かつ被膜性の良いシ
リコンナイトライド及びシリコンオキシナイトライド膜
を用いることにより、信頼性の高い半導体装置を供給す
ることができる。As described above, a highly reliable semiconductor device can be supplied by using the silicon nitride and silicon oxynitride films having high quality and good coating properties.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明に係るプラズマによる化学気相成長法を
実施するための化学気相成長装置を示す概略図である。FIG. 1 is a schematic view showing a chemical vapor deposition apparatus for carrying out a chemical vapor deposition method using plasma according to the present invention.

【図２】本発明による化学気相成長膜を用いて製造した
半導体装置を示す断面図である。FIG. 2 is a cross-sectional view showing a semiconductor device manufactured using the chemical vapor deposition film according to the present invention.

【図３】本発明によるシリコンナイトライド及びシリコ
ンオキシナイトライド膜の耐湿試験の結果を示した図で
ある。FIG. 3 is a diagram showing a result of a moisture resistance test of a silicon nitride film and a silicon oxynitride film according to the present invention.

【符号の説明】[Explanation of symbols]

１ 下部電極 ２ 基板 ３ チャンバー ４ シャワーヘッド電極 ５ 液体材料気化器 ６ トリシリルアミン ７ ガス配管（アンモニア） ８ ガス配管（亜酸化窒素） ９ ガス配管（トリシリルアミン） １０ ガスボンベ １１ 流量調整器 １２ 高周波電源 １３ 本発明によるシリコンナイトライド又はシリコン
オキシナイトライド膜 １４ 配線 １５ 絶縁膜 １６ 基板1 Lower Electrode 2 Substrate 3 Chamber 4 Showerhead Electrode 5 Liquid Material Vaporizer 6 Trisilylamine 7 Gas Pipe (Ammonia) 8 Gas Pipe (Nitrous Oxide) 9 Gas Pipe (Trisilylamine) 10 Gas Cylinder 11 Flow Regulator 12 High Frequency Power supply 13 Silicon nitride or silicon oxynitride film according to the present invention 14 Wiring 15 Insulating film 16 Substrate

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 反応ガスをプラズマ化し、化学反応を生
じさせて基板上に気相成長膜を成長させる化学気相成長
法であって、 反応ガスは、少なくともシリコンソースガスとしてシリ
ルアミン化合物を含むものであり、 気相成長膜は、シリコンナイトライド膜又はシリコンオ
キシナイトライド膜であることを特徴とする化学気相成
長法。1. A chemical vapor deposition method in which a reaction gas is made into plasma to cause a chemical reaction to grow a vapor growth film on a substrate, the reaction gas containing at least a silylamine compound as a silicon source gas. The chemical vapor deposition method is characterized in that the vapor phase growth film is a silicon nitride film or a silicon oxynitride film. 【請求項２】 反応ガスは、前記シリルアミン化合物の
ほかにアンモニアガスを含むものであり、 気相成長膜は、シリコンナイトライド膜であることを特
徴とする請求項１に記載の化学気相成長法。2. The chemical vapor deposition according to claim 1, wherein the reaction gas contains ammonia gas in addition to the silylamine compound, and the vapor growth film is a silicon nitride film. Law. 【請求項３】 反応ガスは、前記シリルアミン化合物の
ほかにアンモニアガスと、亜酸化窒素ガスを含むもので
あり、 気相成長膜は、シリコンオキシナイトライド膜であるこ
とを特徴とする請求項１に記載の化学気相成長法。3. The reaction gas contains ammonia gas and nitrous oxide gas in addition to the silylamine compound, and the vapor-phase growth film is a silicon oxynitride film. The chemical vapor deposition method described in.
JP5126943A 1993-05-28 1993-05-28 Chemical vapor deposition Expired - Lifetime JP2508581B2 (en)

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