JPH06338497A - 化学気相成長法 - Google Patents

化学気相成長法

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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
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Prior art keywords
film
gas
chemical vapor
shower head
vapor deposition
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JP12694393A
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JP2508581B2 (ja
Inventor
Hiroshi Ishikawa
拓 石川
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NEC Corp
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NEC Corp
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Abstract

(57)【要約】 【目的】 膜中に水分や炭素成分のない高品位、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。 【構成】 チャンバー3内を数torr前後の減圧状態
にし、成膜に用いる個々のガスは、シャワーヘッド電極
4内で混合され、シャワーヘッド電極4からチャンバー
3内に導入する。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により、高周波電圧を加え、シャワ
ーヘッド電極4で混合されたガスを、チャンバー3内で
プラズマ化し、化学反応を起して反応中間体を形成す
る。この反応中間体により、基板2上に被膜性の良い膜
を形成する。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。

Description

【発明の詳細な説明】
【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。
【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。
【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−C49O)SiNH
22NH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)。
【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。
【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−C49O)SiNH22NH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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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。
【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
53N,(SiH3NSiH23,(SiH342
どを用いても同様な効果が得られる。
【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。
【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。
【図面の簡単な説明】
【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。
【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。
【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。
【符号の説明】
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

Claims (3)

    【特許請求の範囲】
  1. 【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。
  2. 【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。
  3. 【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。
JP5126943A 1993-05-28 1993-05-28 化学気相成長法 Expired - Lifetime JP2508581B2 (ja)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
JP5126943A JP2508581B2 (ja) 1993-05-28 1993-05-28 化学気相成長法

Publications (2)

Publication Number Publication Date
JPH06338497A true JPH06338497A (ja) 1994-12-06
JP2508581B2 JP2508581B2 (ja) 1996-06-19

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