JPH04239750A - フッ素含有シリコン酸化膜の形成方法 - Google Patents

フッ素含有シリコン酸化膜の形成方法

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Publication number
JPH04239750A
JPH04239750A JP3006312A JP631291A JPH04239750A JP H04239750 A JPH04239750 A JP H04239750A JP 3006312 A JP3006312 A JP 3006312A JP 631291 A JP631291 A JP 631291A JP H04239750 A JPH04239750 A JP H04239750A
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JP
Japan
Prior art keywords
film
silicon oxide
oxide film
fluorine
temperature
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Granted
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JP3006312A
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English (en)
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JP2697315B2 (ja
Inventor
Tetsuya Honma
哲哉 本間
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NEC Corp
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NEC Corp
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Priority to JP3006312A priority Critical patent/JP2697315B2/ja
Priority to US07/820,254 priority patent/US5215787A/en
Priority to EP92300422A priority patent/EP0496543B1/en
Priority to DE69224924T priority patent/DE69224924T2/de
Priority to KR1019920000782A priority patent/KR960000376B1/ko
Publication of JPH04239750A publication Critical patent/JPH04239750A/ja
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Publication of JP2697315B2 publication Critical patent/JP2697315B2/ja
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
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    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

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、特に、フッ素含有シリコン酸化膜の形成方法に関す
る。
【０００２】
【従来の技術】従来、この種のシリコン酸化膜の形成に
は化学気相成長法が多用されている。例えば、ソースガ
スとして、テトラエチルオルソシリケート（化学式Ｓｉ
（ＯＣ２　Ｈ５　）４　），をバブリングによって気化
した後、反応室内でオゾンと混合し、基板温度３００〜
４００℃で常圧下で、シリコン酸化膜を形成する方法が
ある。また、ドーピングガスとして、トリメトキシリン
酸（化学式ＰＯ（ＯＣＨ３　）３　）トリメトキシボロ
ン（化学式Ｂ（ＯＣＨ３　）３　）を用い、リン，ホウ
素をドーピングする方法も用いられいてる（電気化学お
よび工業物理化学，Ｖｏｌ．５６，Ｎｏ．７（１９８８
），Ｐ５２７）。
【０００３】
【発明が解決しようとする課題】この従来のシリコン酸
化膜の形成方法は、以下のような問題点があった。すな
わち、成膜温度が３００〜４００℃と高いことからフォ
トレジスト膜等の有機膜をマスクとして用いて、選択的
にシリコン酸化膜を形成することが不可能であった。ま
た、成膜温度を下げると膜特性が著しく劣化し、実用に
供することができないという欠点も有している。さらに
、従来の方法で形成したシリコン酸化膜は、その内部応
力が、約１×１０の９乗ｄｙｎ／平方ｃｍの強い引張応
力であり、２μｍ以上の厚膜を形成すると、亀裂が発生
しやすいという大きな問題が有り、アルミニウム配線等
の凹凸を有する基板上には形成することが難しいという
欠点を有している。
【０００４】
【課題を解決するための手段】本発明のフッ素含有シリ
コン酸化膜の形成方法は、アルコキシフルオロシラン（
化学式Ｆｎ−Ｓｉ（ＯＲ）４−ｎ　，Ｒ：アルキル基，
ｎ：１〜３の整数）を主成分とする蒸気を用いて一定の
温度を有する反応室内で、かつ２００℃以下の温度で形
成せしめたことを特徴とする。さらに本発明は、フォト
レジスト膜，テフロン膜あるいはポリイミド膜等の有機
膜パターンを有する基板表面に、上記のアルコキシフル
オロシランを主成分とする蒸気を用いて、一定の温度を
有する反応室内で、かつ１５０℃以下の温度で、該有機
膜パターンのない部分に選択的に形成せしめることを特
徴とする。
【０００５】
【実施例】次に本発明を図面を参照して説明する。本実
施例では、アルコキシフルオロシランとしてトリエトキ
シフルオロシラン（化学式Ｆ−Ｓｉ（ＯＣ２Ｈ５　）３
　）を用いた。
【０００６】成膜装置の概略を図１に示す。同図におい
て反応室１０１内にサセプター１０２を有し、サセプタ
ーは、加熱用ヒーター１０３を有しており、半導体基板
１０４は、サセプター上に固定される。なお、サセプタ
ーは、装置の上下のどちらにも設置でき、半導体基板表
面は、上下どちらを向いても良い。トリエトキシフルオ
ロシランは一定温度に保たれたバブラー１０７内に有り
、流量コントローラー１０５で一定流量にコントロール
された窒素ガスによって、バブリングされ、反応室内に
導入される。また、トリエトキシフルオロシランを縮合
せしめるための水蒸気は、純水を有し、かつ一定温度に
保たれたバブラー１０８から、流量コントローラー１０
６で一定流量にコントロールされた窒素ガスによって、
バブリングされ、反応室内に導入される。反応室は、常
に排気され、一定の圧力に保たれている。また、各バブ
ラーから、反応室までのガスの輸送管は、加熱用ヒータ
ー１０９，１１０によって一定の温度に保たれている。
【０００７】上記の装置を用いて、直径６インチのシリ
コン基板上にシリコン酸化膜を形成した。トリエトキシ
フルオロシランのバブラーは４０℃にまた、純水のバブ
ラーは、６０℃にそれぞれ保ち、バブリングに用いる窒
素ガスの流量は、１ＳＬＭとし、基板温度は３０℃に固
定し、反応室内の圧力は約７００Ｔｏｒｒとした。
【０００８】図２は、本実施例と従来方法の比較を示す
もので、本実施例により、６０分間、膜堆積を行い、厚
さ約０．５μｍのフッ素含有シリコン酸化膜を形成した
とき、１００で示すような赤外吸収スペクトル（ＦＴ−
ＩＲ）を得た。一方、従来の方法で、２５０℃と３５０
℃の温度で、厚さ約０．５μｍのシリコン酸化膜を形成
したときはそれぞれ１１０，１２０で示す赤外吸収スペ
クトル（ＦＴ−ＩＲ）を得た。本実施例（１００）では
、波数，約３３００ｃｍ−１，約１０７０ｃｍ−１，約
９３０ｃｍ−１付近に、それぞれ、ＯＨ基，Ｓｉ−Ｏ結
合，Ｓｉ−ＯＨ結合に相当する吸収ピークが見られ、Ｓ
ｉ−Ｏを主成分とする膜が形成されていることがわかる
。ＯＨ基に相当する吸収ピークは３０℃の極低温で形成
したにもかかわらず、従来法で２５０℃の温度で形成し
たシリコン酸化膜のＯＨ基の吸収ピークよりも小さいこ
とがわかる。このことは、本発明に基づくシリコン酸化
膜は従来法で、２５０℃という比較的低温で形成したシ
リコン酸化膜よりも含有水分量が少ないことを示してい
る。 さらに、従来法で、３５０℃で形成したシリコン酸化膜
と比べると、ＯＨ基の吸収ピークの大きさは、同等であ
る。すなわち、本発明に基づいて３０℃の極低温で形成
したシリコン酸化膜の含有水分量は、３５０℃で形成し
た従来のシリコン酸化膜と同等である。
【０００９】さらに、本実施例で形成したシリコン酸化
膜の屈折率は、１．４２と、従来のシリコン酸化膜の屈
折率（１．４５）よりも小さい値であった。また、Ｘ線
光電子分光分析によって膜中のフッ素含有量を調べたと
ころ、フッ素原子の濃度は、約７原子％であった。また
、膜応力は、２×１０８　ｄｙｎ／ｃｍ２　であり、従
来法で形成したシリコン酸化膜の膜応力（１×１０９　
ｄｙｎ／ｃｍ２　）に比べて小さい値であった。
【００１０】本実施例で形成したシリコン酸化膜上に面
積約４平方ｍｍのアルミニウム電極を形成し、電気特性
を調べた。５Ｖ印加時のリーク電流密度は、約５×１０
−１１　Ａ／平方ｃｍであり、これは、従来法で３５０
℃で形成した同じ厚さのシリコン酸化膜のリーク電流（
約２×１０−１０　Ａ／平方ｃｍ）に比べて小さいもの
であった。また、絶縁耐圧は、５ＭＶ／ｃｍであり、従
来法で形成したシリコン酸化膜の絶縁耐圧（４ＭＶ／ｃ
ｍ）と比べて大きなものであった。さらに１ＭＨｚの容
量・電圧特性から求めた比誘電率は３．７であり、従来
法で形成したシリコン酸化膜の比誘電率（４．０）と比
べて小さい値であった。
【００１１】本実施例で用いた成膜条件は一例であって
基板温度，反応室内圧力，ガス流量等は変化させること
ができるものである。
【００１２】次に、本発明の第２の実施例を図面を参照
して説明する。本実施例においても、前実施例で用いた
成膜条件を用いた。
【００１３】図３は、本発明の第２の実施例であるシリ
コン酸化膜の選択成長法を用い２層アルミニウム配線構
造体の層間絶縁膜に適用したときの工程断面図を示す。 同図（ａ）において、半導体基板３０１上、に厚さ約０
．５μｍのＰＳＧ膜、厚さ約１μｍの第１のアルミニウ
ム配線３０３，３０３′が順次形成されている。ここで
、アルミニウム配線をパターニングした時のフォトレジ
スト膜３０４，３０４′は残したままである。次に、同
図（ｂ）に示すように、本発明に基づき厚さ約１μｍの
フッ素含有シリコン酸化膜３０５をＰＳＧ膜上のみに、
選択的に形成する。続いて、フォトレジスト膜を酸素プ
ラズマ中で灰化した後、同図（ｃ）に示すように再度、
本発明に基づく、厚さ約０．７μｍのフッ素含有シリコ
ン酸化膜３０６を形成する。次に同図（ｄ）に示すよう
に開孔３０７，３０７′を公知のフォトエッチング法に
より形成する。最後に、同図（ｅ）に示すように第２の
アルミニウム配線３０８，３０８′を形成し完全に平坦
な２層アルミニウム配線が形成される。
【００１４】上記の工程により形成した２層アルミニウ
ム配線構造体は、上層アルミニウム配線の断線，短絡は
全くなく良好な歩留りが得られた。また、亀裂の発生も
全く認められなかった。
【００１５】本実施例では、配線材料として、アルミニ
ウムを用いているが、これは、ポリシリコン，アルミニ
ウム合金，金，タングステン，モリブデン，チタン合金
のうちの少なくとも１つから成る配線であっても良い。
【００１６】また、フォトレジスト膜を灰化した後に形
成するフッ素含有シリコン酸化膜の替りに、他の方法で
形成した絶縁膜を用いることもできる。さらに、フォト
レジスト膜を残さずに、全面に、フッ素含有シリコン酸
化膜を形成し、層間絶縁膜に用いることも可能である。
【００１７】本実施例では、多層配線層間膜への適用に
ついて述べているが、選択的にシリコン酸化膜を形成す
る方法として、他の用途への適用も可能である。
【００１８】
【発明の効果】以上説明したように本発明はアルコキシ
フルオロシランを主成分とする蒸気を用いることによっ
て、２００℃以下の低温、特に、室温でもシリコン酸化
膜が形成できるという大きな利点を有している。本発明
に基づいて形成したシリコン酸化膜の膜特性は、従来の
方法で形成したものに比べて良好であり、半導体装置に
用いる絶縁膜として実用が可能であるという利点を有し
ている。
【００１９】さらに本発明は、１５０℃以下の温度でシ
リコン酸化膜を形成できることから、フォトレジスト膜
等の有機膜をマスクとして用いて、選択的にシリコン酸
化膜が形成できるという大きな利点を有しており、半導
体装置の製造過程で発生する表面の凹凸を容易に平坦化
できるという利点も併せ持つようになる。
【００２０】したがって本発明は、半導体装置の製造に
多大な効果をもたらす。さらに、他の電子デバイスへの
適用も充分可能である。
【図面の簡単な説明】
【図１】本発明で用いたシリコン酸化膜の形成装置の概
略図である。
【図２】本発明の効果を示すための図であり、赤外吸収
スペクトルを示すものである。
【図３】本発明の第２の実施例の製造方法を示す工程断
面図である。

Claims (2)

    【特許請求の範囲】
  1. 【請求項１】　　アルコキシフルオロシラン（化学式Ｆ
    ｎ−Ｓｉ（ＯＲ）４−ｎ　，Ｒ：アルキル基，ｎ：１〜
    ３の整数）を主成分とする蒸気を用いて一定の温度を有
    する反応室内で、かつ２００℃以下の温度で形成せしめ
    たことを特徴とするフッ素含有シリコン酸化膜の形成方
    法。
  2. 【請求項２】　　フォトレジスト膜，テフロン膜あるい
    はポリイミド膜等の有機膜パターンを有する基板表面に
    、アルコキシフルオロシランを主成分とする蒸気を用い
    て、一定の温度を有する反応室内で、かつ１５０℃以下
    の温度で、該有機膜パターンのない部分に選択的に形成
    せしめることを特徴とするフッ素含有シリコン酸化膜の
    形成方法。
JP3006312A 1991-01-23 1991-01-23 フッ素含有シリコン酸化膜の形成方法 Expired - Fee Related JP2697315B2 (ja)

Priority Applications (5)

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JP3006312A JP2697315B2 (ja) 1991-01-23 1991-01-23 フッ素含有シリコン酸化膜の形成方法
US07/820,254 US5215787A (en) 1991-01-23 1992-01-14 Method of forming silicon oxide film containing fluorine
EP92300422A EP0496543B1 (en) 1991-01-23 1992-01-17 Method of forming silicon oxide film containing fluorine
DE69224924T DE69224924T2 (de) 1991-01-23 1992-01-17 Verfahren zur Ablagerung von Fluor-enthaltenden Silizium-Dioxid-Schichten
KR1019920000782A KR960000376B1 (ko) 1991-01-23 1992-01-21 플루오르를 함유한 실리콘 산화막 형성 방법

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JP3006312A JP2697315B2 (ja) 1991-01-23 1991-01-23 フッ素含有シリコン酸化膜の形成方法

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JPH04239750A true JPH04239750A (ja) 1992-08-27
JP2697315B2 JP2697315B2 (ja) 1998-01-14

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DE69224924T2 (de) 1998-09-24
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EP0496543A3 (en) 1993-10-27
KR960000376B1 (ko) 1996-01-05
US5215787A (en) 1993-06-01
KR920015484A (ko) 1992-08-27
EP0496543A2 (en) 1992-07-29
DE69224924D1 (de) 1998-05-07

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