JP2699695B2 - 化学気相成長法 - Google Patents

化学気相成長法

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Publication number
JP2699695B2
JP2699695B2 JP3136426A JP13642691A JP2699695B2 JP 2699695 B2 JP2699695 B2 JP 2699695B2 JP 3136426 A JP3136426 A JP 3136426A JP 13642691 A JP13642691 A JP 13642691A JP 2699695 B2 JP2699695 B2 JP 2699695B2
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Japan
Prior art keywords
silicon oxide
oxide film
fluorine
vapor deposition
chemical vapor
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JPH04360533A (ja
Inventor
哲哉 本間
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NEC Corp
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NEC Corp
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Priority to JP3136426A priority Critical patent/JP2699695B2/ja
Priority to US07/894,584 priority patent/US5288518A/en
Priority to KR1019920009794A priority patent/KR960013151B1/ko
Priority to DE69226814T priority patent/DE69226814T2/de
Priority to EP92305192A priority patent/EP0517548B1/en
Publication of JPH04360533A publication Critical patent/JPH04360533A/ja
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Publication of JP2699695B2 publication Critical patent/JP2699695B2/ja
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45514Mixing in close vicinity to the substrate
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45561Gas plumbing upstream of the reaction chamber
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45595Atmospheric CVD gas inlets with no enclosed reaction chamber

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)

Description

【発明の詳細な説明】
【0001】
【産業上の利用分野】本発明は化学気相成長法に関し、
特にシリコン酸化膜の形成方法に関する。
【0002】
【従来の技術】従来、この種の化学気相成長法は、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S
i(OC2 5 4 )を用い、常圧でシリコン酸化膜を
形成する方法がある。すなわち、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 5
4 )、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、チャンバー内でオ
ゾン発生器で発生させたオゾンを混合し、リン、ホウ素
含有シリコン酸化膜を形成していた。また、ドーピング
ガスを用いずにシリコン酸化膜の形成も行っていた(電
気化学および工業物理化学、vol56、No7(19
88)、P527)。
【0003】
【発明が解決しようとする課題】上述した従来のオゾン
存在下でシリコン酸化膜を形成する方法は、以下の問題
点があった。すなわち、成膜温度が350〜400℃と
高いにもかかわらず、形成された膜は良質なものとはい
えない。これは、ソースガスの分解温度が高いために加
熱による縮重合が不充分であることから、この程度の温
度では良質なシリコン酸化膜を得ることはできない。ま
た、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1×109 dyn/cm2 の強い引張応力であ
り、成膜温度が350〜400℃と高いことから、厚膜
を形成したり多層化したりすると熱応力に起因する亀裂
が生じ、実用化は難しいものである。さらに、成膜温度
が高いことから、例えばアルミニウム配線上に形成した
時には、配線表面にヒロックと呼ばれる突起物が生成し
て上層配線と短縮してしまい、著しく製造歩留りを低下
させてしまうという問題も有している。
【0004】
【課題を解決するための手段】本発明の化学気相成長法
は、アルコキシシラン(化学式Si(OR)4 、R:ア
ルキル基)又はその重合体をソースガスとして用い、フ
ルオロアルコキシシラン(化学式Si(OR’)n
4-n 、R’:アルキル基、n:1〜3の整数)を添加せ
しめることによって、フッ素を含有するシリコン酸化膜
を低温で形成することを特徴とする。
【0005】さらに、上記フッ素を含有するシリコン酸
化膜を形成する際に、有機リン、有機ホウ素等のリン原
子、ホウ素原子を含有する化合物のうちの少くとも1つ
を気化させてドーピングガスとして用い、上記フッ素を
含有するシリコン酸化膜中にリン又はホウ素を添加せし
めることを特徴とする。
【0006】さらに、上記のフッ素含有シリコン酸化膜
は、オゾンガスの存在下、又は紫外光照射下、又はガス
プラズマの存在下で形成せしめることを特徴とする。
【0007】
【実施例】次に本発明について図面を参照して説明す
る。図1は本発明の第1の実施例に基づくフッ素含有シ
リコン酸化膜形成のための装置の概略図である。同図に
おいて、O2 ガスを流量コントローラー106で流量を
10SLMにコントロールし、オゾン発生器105に導
入し、約20000ppmの濃度のオゾンを発生させ、
ディスパージョンヘッド104から反応室に導入する。
同時にN2 ガスを流量コントローラー107に導入し、
流量コントローラー108、109でそれぞれ流量2S
LMにコントロールし、バブラー110、111に導入
し、それぞれ60℃の温度に保たれたテトラエチルオル
ソシリケート(Si(OC2 5 4 )、フルオロトリ
エトキシシラン(FSi(OC2 5 3 )を気化させ
た後、ディスパージョンヘッド104から反応室に導入
する。これらのガスは反応室内で混合され、加熱用ヒー
タ102で200℃の温度に保たれたサセプター103
上の半導体基板101上で成膜される。
【0008】本装置によってシリコン基板上に厚さ約1
μmのフッ素含有シリコン酸化膜を形成し、その膜特性
を調べた。まず、形成した膜をX線光電子分光分析によ
って膜の組成を調べた結果、その組成はSiO1.85
0.15であり、フッ素原子は厚さ方向にほぼ均一に分布し
ていることがわかった。次に、膜の物理・化学特性、電
気特性について調べた。形成した膜の屈折率は約1.4
25であり、従来法で形成した膜の屈折率1.45に比
べて小さい値であった。
【0009】図2は本実施例と従来法とを比較した図
で、本実施例によりシリコン基板上に基板温度200℃
で形成したフッ素含有シリコン酸化膜の赤外吸収スペク
トル(a)と、従来法により基板温度400℃で形成し
たフッ素を含有しないシリコン酸化膜の赤外吸収スペク
トル(b)を示している。同図において、本実施例に基
づくフッ素含有シリコン酸化膜のSi−O結合による吸
収ピーク位置は、波数約1080cm-1にあり、これは
従来法によって形成したシリコン酸化膜のSi−O結合
による吸収ピーク位置(波数約1067cm-1)に比べ
て大きい値である。これは、本実施例に基づくフッ素含
有シリコン酸化膜のSi−O結合が、従来法によって形
成したシリコン酸化膜のそれよりも、そのSi−O結合
が強い結合であることを示している。
【0010】また、同図において、波数3400cm-1
付近に見られるOH基による吸収ピークの大きさは、従
来法で形成したシリコン酸化膜に比べて本実施例に基づ
くフッ素含有シリコン酸化膜よりも大きいことがわか
る。これは、本実施例に基づくフッ素含有シリコン酸化
膜の含有水分量が小さいことを示している。これらの赤
外吸収スペクトルから得られた結果から、本実施例に基
ずくフッ素含有シリコン酸化膜は200℃の低温で形成
しているにもかかわらず、400℃で形成した従来のシ
リコン酸化膜に比べて良質な膜であることを示してい
る。
【0011】また、1:30のバッファード弗酸による
エッチングレートを調べた結果、従来法で形成したシリ
コン酸化膜では約1000オングストローム/分あった
が、本実施例に基ずくフッ素含有シリコン酸化膜では、
約800オングストローム/分であった。このことは、
本実施例に基づくフッ素含有シリコン酸化膜が、従来法
で形成したシリコン酸化膜に比べて緻密であることを示
している。膜中応力は、本実施例に基づくフッ素含有シ
リコン酸化膜では2×108dyn/cm2 であり、従
来法で形成したシリコン酸化膜の膜中応力(1×109
dyn/cm2 )に比べて約1桁小さい値であった。
【0012】電気的特性については、膜上に約4mm2
の面積のアルミニウム電極を形成し測定を行った。この
試料に5Vの電圧を印加した時のリーク電流密度は、本
実施例に基づくフッ素含有シリコン酸化膜では、約5×
10-11 A/cm2 であり、これは、従来法で形成した
シリコン酸化膜のリーク電流密度(約2×10-10 A/
cm2 )に比べて小さい値であった。さらに、周波数1
MHzにおける容量−電圧特性から求めた比誘電率は、
本実施例に基づくフッ素含有シリコン酸化膜では約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
4.1に比べて小さい値であった。
【0013】次に本発明の第2の実施例について図面を
用いて説明する。図3は第2の実施例であるフッ素含有
シリコン酸化膜形成のためのプラズマ化学気相成長装置
の概略図である。同図において、反応室301は一定圧
力になるように排気されており、流量コントローラー3
06を介してO2 ガスが反応室301に導入されてい
る。カソード電極303には周波数13.56MHzの
高周波電力が供給される。アノード電極302は接地さ
れており、加熱用ヒータ304によって半導体基板30
5は一定温度に保たれている。反応ガスとしては、テト
ラエチルオルソシリケート(Si(OC2 5 4
と、フルオロトリエトキシシラン(FSi(OC
2 5 3 )とが、それぞれバブラー309、310に
よって気化され、反応室に導入される。バブラー30
9、310には、それぞれ流量コントローラ307、3
08を通してN2 ガスが導入されている。
【0014】本実施例では、成膜条件として、基板温度
200℃、反応室内圧力0.3torr、高周波電力密
度0.5W/cm2 なる条件で、厚さ約1μmのフッ素
含有シリコン酸化膜を形成した。形成したフッ素含有シ
リコン酸化膜の膜質を調べた結果、第1の実施例で述べ
た結果と同等の結果が得られた。
【0015】なお、第1及び第2の実施例においては、
フッ素含有シリコン酸化膜への不純物添加は行っていな
いが、必要に応じてリン又はホウ素のうちの少なくとも
1つを有する有機ソース、例えば、トリメトキシリン酸
(PO(OCH3 3 )、又はトリメトキシボロン(B
(OCH3 3 )等を同様にバブリングによって気化せ
しめてドーピングガスとして用い、リン又はホウ素のう
ちの少なくとも1つをフッ素含有シリコン酸化膜に添加
することができる。さらに、成膜温度は200℃以上で
良く、また、その他の成膜条件は必要に応じて変化させ
ることができる。また、本発明は本実施例で述べた以
外、例えばガスプラズマ等の熱化学気相成長法、紫外光
を用いる光化学気相成長法などにも適用できるものであ
る。
【0016】
【発明の効果】以上説明したように本発明は、有機ソー
スを用いる化学気相成長法において、フルオロアルコキ
シシランを添加することによって、低温で膜特性の優れ
たシリコン酸化膜を形成することが可能となる。さら
に、低温形成にもかかわらず含有水分を減少させること
が可能となる。従って半導体装置に用いた場合には、そ
の信頼性を著しく向上せしめることが可能となる。
【0017】また、アルミニウム配線等の多層配線層間
絶縁膜として用いる場合には、成膜温度が低いこと、緻
密な膜であること膜応力が小さいことなどから、厚膜を
形成しても亀裂の発生がなく、さらに、アルミニウムの
ヒロックの発生も全くない。従って、多層配線を有する
半導体装置の製造歩留り及び信頼性を著しく向上せしめ
ることができるという利点も有している。
【図面の簡単な説明】
【図1】本発明の第1の実施例であるフッ素含有シリコ
ン酸化膜形成のための装置の概略図である。
【図2】第1の実施例と従来法とを比較するための赤外
吸収スペクトル図である。
【図3】本発明の第2の実施例であるフッ素含有シリコ
ン酸化膜形成のためのプラズマ化学気相成長装置の概略
図である。
【符号の説明】
101 半導体基板 102 加熱用ヒータ 103 サセプター 104 ディスパージョンヘッド 105 オゾン発生器 106 流量コントローラー(O2 ガス) 107 流量コントローラー(N2 ガス) 108 流量コントローラー(テトラエチルオルソシ
リケート) 109 流量コントローラー(フルオロトリエトキシ
シラン) 110 バブラー(テトラエチルオルソシリケート) 111 バブラー(フルオロトリエトキシシラン) 301 反応室 302 アノード電極 303 カソード電極 304 加熱用ヒータ 305 半導体基板 306 流量コントローラー 307 流量コントローラー 308 流量コントローラー 309 バブラー(テトラエチルオルソシリケート) 310 バブラー(フルオロトリエトキシシラン)

Claims (3)

    (57)【特許請求の範囲】
  1. 【請求項1】 アルコキシシラン又はその重合体をソー
    スガスとして用い、フルオロアルコキシシランを添加せ
    しめることによってフッ素を含有するシリコン酸化膜を
    形成することを特徴とする化学気相成長法。
  2. 【請求項2】 前記フッ素を含有するシリコン酸化膜を
    形成する際に、有機リン、有機ホウ素等のリン原子、ホ
    ウ素原子を含有する化合物のうちの少くとも1つを気化
    させ、前記フッ素を含有するシリコン酸化膜中にリン又
    はホウ素を添加せしめる請求項1記載の化学気相成長
    法。
  3. 【請求項3】 前記フッ素含有シリコン酸化膜は、オゾ
    ンガスの存在下、又は紫外光照射下、又はガスプラズマ
    の存在下で形成せしめる請求項1記載の化学気相成長
    法。
JP3136426A 1991-06-07 1991-06-07 化学気相成長法 Expired - Fee Related JP2699695B2 (ja)

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US07/894,584 US5288518A (en) 1991-06-07 1992-06-05 Chemical vapor deposition method for forming fluorine containing silicon oxide film
KR1019920009794A KR960013151B1 (ko) 1991-06-07 1992-06-05 산화규소 막을 형성시키기 위한 화학 증착법
DE69226814T DE69226814T2 (de) 1991-06-07 1992-06-05 CVD-Methode zur Bildung eines Siliziumoxydfilms
EP92305192A EP0517548B1 (en) 1991-06-07 1992-06-05 Chemical vapor deposition method for forming silicon oxide film

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US5288518A (en) 1994-02-22
JPH04360533A (ja) 1992-12-14
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KR930001347A (ko) 1993-01-16

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