JPH049369B2 - - Google Patents

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Publication number
JPH049369B2
JPH049369B2 JP57168463A JP16846382A JPH049369B2 JP H049369 B2 JPH049369 B2 JP H049369B2 JP 57168463 A JP57168463 A JP 57168463A JP 16846382 A JP16846382 A JP 16846382A JP H049369 B2 JPH049369 B2 JP H049369B2
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Prior art keywords
thin film
gas
sih
film
reaction
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JP57168463A
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JPS5958819A (ja
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Priority to JP57168463A priority Critical patent/JPS5958819A/ja
Priority to US06/534,686 priority patent/US4495218A/en
Priority to EP83109690A priority patent/EP0104658B1/en
Priority to DE8383109690T priority patent/DE3364979D1/de
Publication of JPS5958819A publication Critical patent/JPS5958819A/ja
Publication of JPH049369B2 publication Critical patent/JPH049369B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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    • 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
    • H01L21/02112—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 characterised by the material of the layer
    • H01L21/02123—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 characterised by the material of the layer the material containing silicon
    • H01L21/02164—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 characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical 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
    • C23C16/24—Deposition of silicon only
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide
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    • H01L21/02123—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 characterised by the material of the layer the material containing silicon
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    • H01L21/02211—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 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/02425—Conductive materials, e.g. metallic silicides
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment 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
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604—Deposition from a gas or vapour
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
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    • H01L21/31—Treatment 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
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Description

【発明の詳細な説明】 本発明は薄膜形成方法に関するものにして、特
にケイ素を含む薄膜形成に好適な方法に関するも
のである。 従来、SiO2、Si3N4、あるいはａ−Si膜を形成
する場合、高温下でSiH4を含むガスを熱分解さ
せることにより形成していたが、半導体プロセス
では、プロセスの低温化が強く望まれており、そ
れに対応して放電プラズマを利用したプラズマ
CVDが低温成膜可能な方法として研究が進めら
れてきた。例えば：R.C.G.Swann et al.；J.
Electro−chem.Soc.，114，713（1967），R.J.
Joyce et al.；Thin Solid Films，１，481
（1967），Y.Kuwano；Japan J.Appl.Phys.，７，
88（1968），R.Greht et al.；J.Electrochem.Soc.，
119No.９，1249（1972），A.K.Sirha et al.；ibid.，
125，No.４，601（1978），M.J.Helix et al.；Thin
Solid Films，55，143（1978），W.Kern et al.；
J.Vac.Sci.Tech.，14，No.５，1082（1777），など
が挙げられる。しかしながら、プラズマを用いた
CVDでは、低温膜形成は可能であるが、エネル
ギーが高く、化学量論的に反応を制御することが
難しく、副生成物をなくすことが難しい。 最近、エネルギー源として、紫外線やレーザー
を用いた光CVDの研究が急速に進んできた。こ
の方法では原料ガスの光励起や光分解を利用し
て、低温で薄膜形成を行うことが可能であり、し
かも化学量論的な反応制御がしやすいという利点
がある。たとえば、Hughes社のSarkozyは、
SiH4とO2を原料ガスにし、Hg蒸気を増感剤とし
て紫外線照射によりSiO2膜を形成し（Technical
Digest of 1981 Symposium on VLSI
Technology pp.68Sept.1981）、同社のPetersら
はSiH4とN2O、あるいはSiH4とNH3を各々原料
ガスとし、Hg蒸気を光増感剤として紫外線照射
し、SiO2やSi3N4膜を100℃以下の低温で形成し
ている。これらの方法は、大面積のデポジシヨン
を目的としているが、デポジシヨンの速度が非常
に遅く実用に供し得ない。 CO2レーザーを用いてSi−Ｈ結合を励起し、
SiH4からａ−Si膜を低温形成した例（英、応用
物理学会結晶工学分科会第８回講習会予稿、
1981、10）もあるが、この場合、SiH4濃度が高
いと光が吸収されてしまい、また、反応室内の空
間でも反応が起こり、濃度が低いとデポジシヨン
速度が遅くなるという欠点がある。 本発明の目的は、上記に述べたような従来技術
の欠点をなくし、低温で、高速にａ−Si、SiO2、
Si3N4膜を形成するとのできる薄膜形成方法を提
供することにある。 本発明者等は、最大振幅の波長が200nm〜
260nmである紫外光をエネルギー源としたCVD
装置による薄膜形成において、ａ−Si、SiO2、
Si3N4膜等を形成する際のシラン原料として、
Si2H6、Si3H8、Si4H10を用いることにより、光
反応の効率が向上し、デポジシヨン速度が大きく
なることを見出した。これは、従来用いられてい
るSiH4は真空紫外域にしか吸収がないが、ポリ
シランSioH2o+2では、Si−Si結合が増加するにつ
れて吸収が長波長側に移り、紫外光を効率よく吸
収すること、さらに、Si−Si結合が切れやすいこ
とから、結果的にデポジシヨン速度が、SiH4を
用いた場合に比べて速くなるものと考えられる。
（SiH4の紫外線吸収は180nm以下であるが、
Si2H6では約200nm、Si3H8では約215nm、Si4H10
では約240nmと増加する。） 上記の本発明者等の知見に基づく、本発明の薄
膜形成方法の特徴とするところは、最大振幅の波
長が200nm〜260nmである紫外光をエネルギー源
としたCVD装置による薄膜形成において、原料
の反応性化合物として、下記の分子式(1)、 SioH2o+2 …(1) （ここに、ｎは、２、３、または４である） で示される物質を用いてなることにある。このよ
うな物質を用いることにより、上記に述べたよう
に、ａ−Si、SiO2、Si3N4等の薄膜が、CVD装置
により、効率よく、高速度にデポジシヨンできる
ものである。 次に、本発明の薄膜形成方法に用いることので
きるCVD装置について、一具体例につき、第１
図を参照して説明する。 第１図は、一具体例のCVD装置の概略説明図
である。第１図において、符号１は反応容器、２
は石英窓、３はガス導入口、４は排気口、５は可
変バルブ、６は基板、７はシースヒーター、８は
試料台、９は光取出窓、１０は原料ガスである。 反応容器１はステンレス製、内径167mmのもの
である。光源としては、低圧水銀灯（2537Å、10
ｍＷ／cm2）あるいはエキシマレーザー（ラムダフ
イジツク社製EMG101、KrF249nm）等を用いこ
の光が石英窓２を通つて反応容器内の基板６に照
射される。反応容器内の圧力は目的に応じて異な
るが、0.1〜1Torrが好ましい。圧力が小さすぎ
ると成膜速度がおそく、圧力が高すぎると成膜性
が悪くなる。基板は常温〜300℃の温度範囲で加
熱することが好ましい。また、反応を効率よく行
うため、光増感剤としてHg蒸気を混合すること
が可能であり、この場合、反応容器内に水銀溜を
置き、その蒸気圧を利用する。反応させるシラン
ガス等は、ガス導入口３から反応容器内に入つて
くる。 以下に、本発明を実施例につき、さらに詳細に
説明する。 実施例 １ 第１図に示した反応容器１内に基板６として、
３インチシリコンウエハを固定した。この反応容
器内を、まず10-5Torrの真空状態に排気した後、
Si2H6ガス（b.p.−15℃、合成はG.W.Bethke，
M.K.Wilson.J.Chem.Phys.26，1107（1957），H.
Kriegsmann，Z.anorg.u.allgem.Chem.，300，
210（1959）を参照した。）を10％含有するヘリウ
ムガスを10ml／min、N2Oガスを10ml／min、を
ガス導入口３から流しながら、石英窓２を通し
て、低圧水銀灯（10ｍＷ／cm2、254nm）から紫外
光を照射した。このときのガス圧は約1Torrであ
る。反応容器内には、水銀溜を置き、約30℃〜40
℃に加熱した。また、基板加熱温度は約50℃であ
る。その結果、約700Å／minの成膜速度で酸化
ケイ素（SiO2）膜が形成された。（原料にSiH4ガ
スを用いた場合は約400Å／minである。）膜厚の
ばらつきは、±５％以内であつた。生成したSiO2
膜をフツ酸系エツチング液でエツチングした所、
通常の光CVD法でSiH4ガスを用いた場合と同程
度であつた。 実施例 ２ 実施例１と同様な方法で、原料ガスとして、
NH3／Si2H6）流速比）を約10〜20で流した。基
板は250℃程度まで加熱した。得られたSi3N4膜
は、赤外スペクトルにより確認したが、プラズマ
CVDによるものとほぼ同じであつた。 実施例 ３ 実施例１と同様の方法で、原料ガスとして、
Si2H6を10％含むHeガスを10ml／minで流し、エ
キシマレーザー（KrF249nm）を光源として紫外
線を照射した。このときのガス圧は約0.5Torrで
あつた。デポジシヨン速度は、1000Å／minであ
り、SiH4を同じ条件で用いた場合の700Å／min
よりも高速であつた。生成した膜はアモルフアス
状態のシリコンであり、水銀の混入はSIMSでは
検出できなかつた。 実施例 ４〜６ 第１表に示した条件で反応ガスを流し、紫外線
を照射した。その結果、第１表に示される結果が
得られた。 【表】 以上に述べたように、本発明によれば、低温
で、効率よく、ａ−Si、SiO2、Si3N4膜を形成で
きるものであり、従つて本発明の薄膜形成方法
は、半導体等の薄膜製品、とくに多層構造を有す
る薄膜製品の製造において、その生産性を著しく
向上させる効果を有するものであることは明らか
である。
【図面の簡単な説明】
第１図は本発明方法の実施に用いることのでき
る光CVD装置の一具体例の概略説明図である。 １……反応容器；２……石英窓；３……ガス導
入口；４……排気口；５……可変バルブ；６……
基板；７……シースヒーター；８……試料台；９
……光取出窓；１０……原料ガス。

Claims (1)

  1. 【特許請求の範囲】 １ 最大振幅の波長が200nm〜260nmである紫外
    光をエネルギー源としたCVD装置による薄膜形
    成において、原料の反応性化合物として、下記の
    分子式(1)、 SioH2o+2 …(1) （ここに、ｎ＝２，３、または４） で示される物質を用いてなることを特徴とする薄
    膜形成方法。
JP57168463A 1982-09-29 1982-09-29 薄膜形成方法 Granted JPS5958819A (ja)

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JP57168463A JPS5958819A (ja) 1982-09-29 1982-09-29 薄膜形成方法
US06/534,686 US4495218A (en) 1982-09-29 1983-09-22 Process for forming thin film
EP83109690A EP0104658B1 (en) 1982-09-29 1983-09-28 Process for forming thin film
DE8383109690T DE3364979D1 (en) 1982-09-29 1983-09-28 Process for forming thin film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57168463A JPS5958819A (ja) 1982-09-29 1982-09-29 薄膜形成方法

Publications (2)

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JPS5958819A JPS5958819A (ja) 1984-04-04
JPH049369B2 true JPH049369B2 (ja) 1992-02-20

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ID=15868574

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Country Status (4)

Country Link
US (1) US4495218A (ja)
EP (1) EP0104658B1 (ja)
JP (1) JPS5958819A (ja)
DE (1) DE3364979D1 (ja)

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JPS5958819A (ja) 1984-04-04
EP0104658A1 (en) 1984-04-04
DE3364979D1 (en) 1986-09-04
US4495218A (en) 1985-01-22
EP0104658B1 (en) 1986-07-30

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