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JPH0684888A - 絶縁膜の形成方法 - Google Patents

絶縁膜の形成方法

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Publication number
JPH0684888A
JPH0684888A JP33472392A JP33472392A JPH0684888A JP H0684888 A JPH0684888 A JP H0684888A JP 33472392 A JP33472392 A JP 33472392A JP 33472392 A JP33472392 A JP 33472392A JP H0684888 A JPH0684888 A JP H0684888A
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JP
Japan
Prior art keywords
film
insulating film
material gas
oxidizing gas
organic silane
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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Application number
JP33472392A
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English (en)
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JP2506539B2 (ja
Inventor
Hideo Izawa
秀雄 井澤
Yutaka Nishi
豊 西
Hiroshi Morimoto
弘 森本
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.)
G T C KK
GTC Corp
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G T C KK
GTC Corp
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  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)
  • Thin Film Transistor (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

(57)【要約】 【目的】 有機シラン材料ガスと酸化性ガスを用い、プ
ラズマCVD法により良好な膜質、特に優れた電気特性
を有する絶縁膜の形成方法を提供すること。 【構成】 有機シラン材料ガスと酸化性ガスを成膜チャ
ンバーに供給し、プラズマCVD法によって絶縁膜を形
成する方法において、成膜チャンバー内に酸化性ガスを
先に導入し、プラズマ放電を起こし、所定の時間t1
過後、放電を中断させることなく、有機シラン材料ガス
を導入して、絶縁膜を形成後、放電を中断することなく
有機シラン材料ガスの供給を止め、この後、酸化性ガス
のプラズマ放電を所定の時間t2 続ける。

Description

【発明の詳細な説明】
【0001】
【産業上の利用分野】本発明は絶縁膜の形成方法に関
し、ことに薄膜トランジスタ等のゲート絶縁膜の形成に
きわめて有用な方法に関するものである。
【0002】
【従来の技術】一般に、有機シラン材料と酸化性ガスを
用いたプラズマCVD法による絶縁膜の形成は図3に示
すようなプラズマCVD装置を用いる。酸化性ガスは酸
化性ガス導入口10より開閉バルブ20、マスフローコ
ントローラー12を通されて成膜チャンバー14内に導
入される。一方、有機シラン材料ガスは気化器11より
開閉バルブ21、マスフローコントローラー13を通さ
れて、上記酸化性ガスと同時に成膜チャンバー14内に
導入される。圧力安定後、高周波プラズマ放電により有
機シラン材料ガスを分解、酸化させて基板17上にSi
酸化膜を形成させる。所定の膜厚が形成された後、放電
を止め、両方のガスの供給を止めるという手順でSi酸
化膜の形成が行われる。図4は、従来の絶縁膜の形成方
法を説明するための主要な操作のタイムチャートを示す
ものである。まず、時刻6において有機シラン材料ガス
の開閉バルブ21と酸化性ガスの開閉バルブ20とが同
時に閉から開にされ、成膜チャンバー14内に両方のガ
スが導入され、圧力安定化の為に、時間t0 経過後、時
刻7において高周波電源19より高周波電力が印加さ
れ、プラズマ放電が開始され、基板17上に成膜が開始
される。所定の膜厚成膜後、時刻8において高周波電力
が切られ、同時に有機シラン材料ガスの開閉バルブ21
と、酸化性ガスの開閉バルブ20とが閉じられる。
【0003】
【発明が解決しようとする課題】しかしながら、従来の
絶縁膜の形成方法ではプラズマ放電の初期においては、
酸素ラジカル、酸素イオンの発生量が少なく、酸化が十
分に進まず有機シラン材料ガスの中間反応生成物がSi
酸化膜になりきらずに堆積するため、Si酸化膜中にO
H基、C等の不純物が多量に含まれてしまう。また、成
膜終了時にも、プラズマ放電を停止すると、成膜チャン
バー14内に存在する未反応の有機シラン材料ガスやそ
の中間反応生成物がSi酸化膜表面に堆積してしまう。
このように、従来の絶縁膜の形成方法では成膜したSi
酸化膜の基板17との界面および表面にOH基、C等の
不純物が多量に含まれ、膜質、特に電気特性が悪化して
いた。特にTFT等のゲート絶縁膜に用いる場合には大
きな問題となっていた。そこで、本発明の目的は有機シ
ラン材料ガスと酸化性ガスを用い、プラズマCVD法に
より良好な膜質、特に優れた電気特性を有する絶縁膜の
形成方法を提供することにある。
【0004】
【課題を解決するための手段】かかる課題は、有機シラ
ン材料ガスと酸化性ガスを成膜チャンバーに供給し、プ
ラズマCVD法によって絶縁膜を形成する方法におい
て、成膜チャンバー内に酸化性ガスを先に導入し、プラ
ズマ放電を起こし、所定の時間t1 経過後、放電を中断
させることなく、有機シラン材料ガスを導入して、絶縁
膜を形成後、放電を中断することなく有機シラン材料ガ
スの供給を止め、この後、酸化性ガスのプラズマ放電を
所定の時間t2 続ける方法で解決される。
【0005】また、有機シラン材料ガスと酸化性ガスを
成膜チャンバーに供給し、プラズマCVD法によって絶
縁膜を形成する方法において、成膜チャンバー内に酸化
性ガスを先に導入し、プラズマ放電を起こし、成膜中は
プラズマ放電、酸化性ガスの供給は中断することなく、
有機シラン材料ガスの供給を間欠的に行う方法で解決さ
れる。
【0006】以下、本発明を詳しく説明する。図1に本
発明の絶縁膜の形成方法の第一の例を説明するための主
要な操作のタイムチャートを示す。時刻1において図3
に示したプラズマCVD装置の酸化性ガスの開閉バルブ
20を閉から開にし、成膜チャンバー14内に酸化性ガ
スを導入する。ついで、圧力安定化の為時間t0 後、時
刻2において高周波電源19より高周波電力を印加し
て、プラズマ放電を開始する。時刻3において有機シラ
ン材料ガスの開閉バルブ21を開にし、成膜チャンバー
14内に有機シラン材料ガスを導入すると、絶縁膜の形
成が開始される。所定の膜厚成膜後、時刻4において有
機シラン材料ガスの開閉バルブ21を閉じ、成膜チャン
バー14内に酸化性ガスのみを供給し、プラズマ放電を
継続する。時間t2 経過後、時刻5において高周波電力
を切り、同時に酸化性ガスの開閉バルブ20を閉じる。
【0007】圧力安定化時間t0 は通常0.5〜2分程
度とされる。酸化性ガスのみを成膜チャンバー14内に
供給しているプラズマ放電時間t1およびt2はそれぞれ
10秒以上であれば安定するが、0.5〜20分の範囲
が好ましい。
【0008】有機シラン材料としては、テトラエチルオ
ルソシリケイト(以下、TEOSと略記する。)、ジエ
チルシラン、トリエトキシシラン、テトラメチルシクロ
テトラシロキサンなどの各種有機シラン材料が用いられ
る。酸化性ガスとしては、酸素、亜酸化窒素、オゾン含
有酸素等が用いられる。
【0009】つぎに、本発明の絶縁膜の形成方法の第二
の例を説明する。図2に、この第二の例の絶縁膜の形成
方法を説明するための主要な操作のタイムチャートを示
す。この絶縁膜の形成方法が上述の第一の例と異なると
ころは、時刻3から時刻4の間において、プラズマ放
電、酸化性ガスの供給は中断することなく、有機シラン
材料ガスの供給を行い続ける代わりに、有機シラン材料
ガスの供給を間欠的に行う。
【0010】その方法の一例としては、時刻3におい
て、プラズマ放電、酸化性ガスの供給は中断することな
く、有機シラン材料ガスの開閉バルブ21を開にし、成
膜チャンバー14内に有機シラン材料ガスを導入して、
絶縁膜の形成を開始させる。そして、時間tA経過後、
有機シラン材料ガスの開閉バルブ21を閉じ、成膜チャ
ンバー14内に酸化性ガスのみを供給し、プラズマ放電
を継続する。時間tB経過後、再び有機シラン材料ガス
の開閉バルブ21を開にし、成膜チャンバー14内に有
機シラン材料ガスを導入する。このように有機シラン材
料ガスの供給は開閉バルブ21の開閉動作を複数回繰り
返すことにより間欠的に行われる。そして、所定の膜厚
成膜後、時刻4において有機シラン材料ガスの開閉バル
ブ21を閉じ、成膜チャンバー14内に酸化性ガスのみ
を供給し、プラズマ放電を継続する。
【0011】有機シラン材料ガスの供給時間tAおよび
供給停止時間tBはそれぞれ10秒以上あれば放電は安
定するが、0.5〜10分の範囲が好ましい。開閉動作
の繰り返しの回数は多い方が特性は良くなるが、処理時
間との兼ね合いから実際の成膜においては2〜10回で
行うことが好ましい。
【0012】この発明の絶縁膜の形成方法においては、
プラズマ放電直後の不安定時には有機シラン材料ガスを
供給せず十分に酸素ラジカル、酸素イオンを発生させ、
成膜チャンバー内及び絶縁膜が形成される基板上の吸着
分子を減少させ、酸素ラジカルおよび酸素イオンが十分
に発生した状態で有機シラン材料ガスを導入し成膜する
ため、成膜初期に形成される絶縁膜中のOH基、C等の
不純物が減少する。
【0013】また、有機シラン材料ガスを間欠的に供給
することにより、まず最初に有機シラン材料ガスが成膜
チャンバー内に供給されると、この有機シラン材料ガス
がプラズマ放電により分解され、絶縁膜が成膜される。
その後、有機シラン材料ガスの供給が停止されると、酸
化性ガスのみのプラズマ放電により発生した酸素ラジカ
ル、酸素イオン等によって、先に成膜された絶縁膜中の
OH基、C等の不純物の除去が効率良く行われる。
【0014】また、プラズマ放電終了時には有機シラン
材料ガスは先に供給が止められているため、酸化性ガス
のプラズマにより残留した有機シラン材料ガス等は十分
に分解、酸化され、H2 O,CO,CO2 等の気体分子
として排気することができるため、プラズマ放電を終了
しても、形成した絶縁膜上に酸化不十分な中間反応生成
物が堆積することはなくなり、絶縁膜表面の不純物が減
少する。従って、この発明の絶縁膜の形成方法によって
絶縁膜を形成すると、絶縁膜における、半導体との界面
部分および表面部分の不純物のみならず、内部の不純物
も効率良く除去でき、このために絶縁膜の膜質、特に電
気特性が向上する。
【0015】
【実施例】以下この発明を実施例を用いて説明するが、
この発明を限定するものではない。 (実施例1)まず、図3に示したものと同様のプラズマ
CVD装置を用意した。そして、成膜チャンバー14内
のカソード電極15の下方にあり、平行平板電極のアノ
ードを構成する試料台16上に基板17をセットし、成
膜チャンバー14内部の空気を真空排気口18から排気
し高真空とした。試料台16内部にはヒーターが内蔵さ
れており、基板17がプロセス中315℃に保たれるよ
うに制御した。
【0016】そして、図1に示す本発明による絶縁膜の
形成方法の第一の例を説明するためのタイムチャートに
従ってガス導入、高周波電力の印加を制御した。まず、
時刻1において酸化性ガスの開閉バルブ20を開にし
て、酸化性ガス導入口10からマスフローコントローラ
ー12を通して、成膜チャンバー14内に酸化性ガスと
して酸素を導入した。酸素の流量はマスフローコントロ
ーラー12により100sccm(スタンダードcc/
min)に制御した。成膜チャンバー14内の圧力は真
空排気口18に接続されたコンダクタンスバルブ22を
可変することにより1.0Torrに制御した。
【0017】ついで、圧力安定化のために時間t0 とし
て1分経過後、時刻2において高周波電源19より1
3.56MHzの高周波電力250Wを印加した。酸化
性ガスのみ供給によりプラズマ放電を続け、時間t1
して10分経過後、時刻3において有機シラン材料ガス
の開閉バルブ21を開にし、マスフローコントローラー
13を通して、成膜チャンバー14内にTEOSを導入
した。TEOSの流量はマスフローコントローラー13
により8sccmに制御した。このとき気化器11内の
TEOSを70℃、気化器11から成膜チャンバー14
までの配管を95℃に加熱した。
【0018】ついで、SiO2 の成膜が開始され、所定
の膜厚1000Å成膜後、時刻4において開閉バルブ2
1を閉じ、TEOSの供給を止めた。この後、時間t2
として10分間、酸化性ガスのみを成膜チャンバー14
内に供給し、プラズマ放電を継続した。時刻5において
高周波電力を止め、開閉バルブ20を閉じた。そして、
成膜チャンバー14内を高真空に排気し、その後大気圧
にし成膜チャンバー14を開けて絶縁膜が形成された基
板17を取り出した。
【0019】(実施例2)図3に示したものと同様のプ
ラズマCVD装置を用意し、時刻3から時刻4間につい
ては図2に示す本発明による絶縁膜の形成方法の第二の
例を説明するためのタイムチャートに従って以下に述べ
るようにしてガス導入、高周波電力の印加を制御した以
外は実施例1と同様にして基板17に絶縁膜を形成し
た。時刻3において、プラズマ放電、酸化性ガスの供給
を中断することなく、有機シラン材料ガスの開閉バルブ
21を開にし、マスフローコントローラー13を通し
て、成膜チャンバー14内にTEOSを導入した。TE
OSの流量はマスフローコントローラー13により8s
ccmに制御した。このとき気化器11内のTEOSを
70℃、気化器11から成膜チャンバー14までの配管
を95℃に加熱した。ついで、SiO2 の成膜が開始さ
れ、時間tAとして2分経過後、有機シラン材料ガスの
開閉バルブ21を閉にし、酸化性ガスのみを成膜チャン
バー14内に供給し、プラズマ放電を継続した。酸化性
ガスのみによるプラズマ放電を時間tBとして2分経過
後、有機シラン材料ガスの開閉バルブ21を開にし、成
膜チャンバー14内に有機シラン材料ガスを供給し、絶
縁膜の成膜を行った。このような有機シラン材料ガスの
開閉バルブ21の開閉動作をそれぞれ時間tA、tBによ
り4回繰り返した。所定の膜厚1000Å成膜後、時刻
4において開閉バルブ21を閉じ、TEOSの供給を止
めた。
【0020】(試験例)本発明の絶縁膜の形成方法の第
一および第二の例と従来の絶縁膜の形成方法により成膜
パラメータ(ガス流量,圧力,高周波電力,基板温度
等)は同一にしてそれぞれ図1、図2および図4のタイ
ムチャートに基づいて、Siウェハー上に1000Åの
SiO2 膜を成膜しその上に面積0.05cm2のAl
電極をもつMOSキャパシタを作成して特性の比較を行
った。その結果を表1に示す。
【0021】
【表1】
【0022】表1中、リーク電流は2MVcm-1の電界
を加えて測定されたものである。上記表1に示した結果
から明らかなように、本発明の絶縁膜の形成方法の第一
の例および第二の例によって形成した絶縁膜は従来の形
成方法によるものより絶縁耐圧が高く、界面準位密度、
リーク電流が小さく、非常に良好な電気特性を有してい
ることが確認された。これは薄膜トランジスタ、MIS
トランジスタなどのゲート絶縁膜として十分な特性をも
つものである。
【0023】
【発明の効果】以上詳細に説明したように、この発明の
絶縁膜の形成方法は、有機シラン材料ガスと酸化性ガス
を成膜チャンバーに供給し、プラズマCVD法によって
絶縁膜を形成する場合に、絶縁膜の膜質、特に電気特性
を大幅に向上させることができる。従って、低温で良質
のゲート絶縁膜が形成でき、とりわけ低融点の基板を用
いた薄膜トランジスタのゲート絶縁膜の形成には特に有
効である。
【図面の簡単な説明】
【図1】本発明の絶縁膜の形成方法の第一の例を説明す
るためのタイムチャートである。
【図2】本発明の絶縁膜の形成方法の第二の例を説明す
るためのタイムチャートである。
【図3】絶縁膜の形成方法に用いられるプラズマCVD
装置の模式図である。
【図4】従来の絶縁膜の形成方法を説明するためのタイ
ムチャートである。
【符号の説明】
10 ガス導入口 11 気化器 12 マスフローコントローラー 13 マスフローコントローラー 14 成膜チャンバー 15 カソード電極 16 試料台 17 基板 18 真空排気口 19 高周波電源 20 開閉バルブ 21 開閉バルブ 22 コンダクタンスバルブ
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 H01L 29/784

Claims (7)

    【特許請求の範囲】
  1. 【請求項1】 有機シラン材料ガスと酸化性ガスを成膜
    チャンバーに供給し、プラズマCVD法によって絶縁膜
    を形成する方法において、成膜チャンバー内に酸化性ガ
    スを先に導入し、プラズマ放電を起こし、所定の時間t
    1 経過後、放電を中断させることなく、有機シラン材料
    ガスを導入して、絶縁膜を形成後、放電を中断すること
    なく有機シラン材料ガスの供給を止め、この後、酸化性
    ガスのプラズマ放電を所定の時間t2 続けることを特徴
    とする絶縁膜の形成方法。
  2. 【請求項2】 有機シラン材料ガスと酸化性ガスを成膜
    チャンバーに供給し、プラズマCVD法によって絶縁膜
    を形成する方法において、成膜チャンバー内に酸化性ガ
    スを先に導入し、プラズマ放電を起こし、成膜中はプラ
    ズマ放電、酸化性ガスの供給は中断することなく、有機
    シラン材料ガスの供給を間欠的に行うことを特徴とする
    絶縁膜の形成方法。
  3. 【請求項3】 酸化性ガスの放電時間t1 およびt2
    それぞれ0.5〜20分とすることを特徴とする請求項
    1記載の絶縁膜の形成方法。
  4. 【請求項4】 有機シラン材料ガスの供給の断続を成膜
    中に2回以上行うことを特徴とする請求項2記載の絶縁
    膜の形成方法。
  5. 【請求項5】 有機シラン材料ガスがテトラエチルオル
    ソシリケイトであることを特徴とする請求項1〜4のい
    ずれか一つに記載の絶縁膜の形成方法。
  6. 【請求項6】 有機シラン材料ガスが、トリエトキシシ
    ラン、ジエチルシラン、テトラメチルシクロテトラシロ
    キサンのうちから選択される一種であることを特徴とす
    る請求項1〜4のいずれか一つに記載の絶縁膜の形成方
    法。
  7. 【請求項7】 酸化性ガスが、酸素であることを特徴と
    する請求項1〜6のいずれか一つに記載の絶縁膜の形成
    方法。
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