JPS5958819A - 薄膜形成方法 - Google Patents

薄膜形成方法

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Publication number
JPS5958819A
JPS5958819A JP57168463A JP16846382A JPS5958819A JP S5958819 A JPS5958819 A JP S5958819A JP 57168463 A JP57168463 A JP 57168463A JP 16846382 A JP16846382 A JP 16846382A JP S5958819 A JPS5958819 A JP S5958819A
Authority
JP
Japan
Prior art keywords
film
thin film
sih4
light
cvd equipment
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.)
Granted
Application number
JP57168463A
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English (en)
Other versions
JPH049369B2 (ja
Inventor
Kazufumi Azuma
和文 東
Mitsuo Nakatani
中谷　光雄
Kazuo Nate
和男 名手
Masaaki Okunaka
正昭 奥中
Ataru Yokono
中 横野
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.)
Hitachi Ltd
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Hitachi Ltd
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Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
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
Granted legal-status Critical Current

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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】 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、５１０２．５１３Ｎ４、あるいはａ−８ｉ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が低混成膜可能な
方法として研究が進められてきた。例えば：　Ｒ，Ｃ，
Ｇ、　Ｓｗａｎｎ　ｅｔ　ａｔ、　；　Ｊ、　Ｅ＆ｃｔ
ｒｏ−ｃｈｅｍ、　Ｓｏｃ、、　１１４　、７１３　（
１９６７）、　Ｒ，Ｊ−Ｊｏｙｃｅｅｔ　ａｔ、　；　
Ｔｈ１ｎ　５ｏｔｉｄ　Ｆｉｔｍｓ、　１＋　４８１　
（１９６７）＋Ｙ、　Ｋｕｗａｎｏ　；　Ｊａｐａｎ　
Ｊ、　Ａｐｐ７．　Ｐｈｙｓ、、　ｌ　、　８８（１９
６８）、　　Ｒ，Ｑｒｅｈｔ　ｅｔ　ａｔ、；　Ｊ、　
　Ｅｔｅｃｔｒｏｃｈｅｍ。
Ｓｏｃ、、　１１９　Ａ　９．１２４９　（１９７２）
、　Ａ、　Ｋ、　５ｉｒｈａｅｔａｔ、　；　１ｂｉｄ
、、　１２５　、　Ａ４　、６０１　（１９７８）、　
Ｍ、　Ｊ。
Ｈｅｔｉｘ　ｅｔ　ａｔ、　；　Ｔｈ１ｎ　５ｏｔｉｄ
　Ｆｉｔｍｓ、　　５５　、１４３（１９７８）、　　
　　ｗ、　　　Ｋｅｒｎ　　ｅｔ　　ａｔ、　　　；　
　　　Ｊ、　　　Ｖａｃ、　　Ｓｃｉ、　　Ｔｅｃｈ。
１４　、　Ａ　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
５ａｒｋｏｚｙは、５ＩＨ４と０２を原料ガスにし、Ｈ
ｇ蒸気を増感剤として紫外線照射により５１０２膜を形
成しく　Ｔｅｃｂｎｊ、ｃａ７　Ｄｉｇｅｓｔｏｆ　１
９８１　Ｓｙｍｐｏｓｊｕｍ　ｏｎ　ＶＬＳＩ　Ｔｅｃ
ｈｎｏｔｅｇｙ　ｐｐ、６８Ｓｅｐｔ、　１９８１　）
、同社のＰｅｔｅｒｓらはＳｉＨ４とＮ、、Ｑ。
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、５１０２や５１３Ｎ
４膜を１００℃以下の低温で形成している。これらの方
法は、大面積のデポジションを目的としているが、デポ
ジショ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５ｉ−１−１結合を励起し、Ｓ
ｉＨからａ−８ｉ膜を低湿形成した例（英、応用物理学
会結晶工学分科会筒８回講習会予稿、１９８１．１０）
もあるが、この場合、５ＩＨ４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ョ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、Ｓｉｎ、、、８１
３Ｎ４膜を形成するこ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、光をエネルギー源としたＣＶＤ装置によ
る薄膜形成におイテ、ａ−８ｉ、ＳｉＯ２、Ｓｉ３Ｎ４
膜等を形成する際のシラン原料として、５１２Ｉ４６．
５ｉ３Ｈ６ｓ　Ｓｉ、Ｈ，（、を用いることにより、光
反応の効率が向上し、デポジショ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５１ｎ１−
１　　　では、Ｓｉ　−Ｓｉ結合が増加するにつれて吸
２ｎ＋２ 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、５ｉ−８ｉ結合が切れやすいことから、結果的
にデポジション速度が、５ｉｌ−１４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１８０ｎ、ｍ以下であるが、Ｓ１□１１６では約２
００ｎ　ｍ　％　Ｓ　ｉ　３１（ｇでは約２１５　ｎｍ
　Ｘ５ｉ４Ｈ，ｏては約２４０　ｎｍ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、光をエネルギー源としたＣＶ
Ｄ装置による簿膜形成において、原料の反応性化合物と
して、下記の分子式（１）１％式％（１） ） 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　−Ｓ
ｉ、Ｓ　１０２．５１３Ｎ４等の薄膜が、ＣＶＤ装置に
より、効率よく、高速度にデポジションできるものであ
る。
次に、本発明の薄膜形成方法に用いることのできるＣＶ
Ｄ装置について、−具体例につき１第１図を参照して説
明する。
第１図は、−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１６７ｍのものである
。光源としては、低圧水銀灯（２５３７Ａ、１０　ｍＷ
／ｃｍ２）　するいはエキシマレーザ−（ラムダフィシ
ツク社製ＥＭＧＩＯＩ　、ＫｒＦ　２４９　ｎｍ　）等
を用い】の光が石英窓２を通っ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〜ｌ　Ｔｏｒｒ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
に入ってく　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
シリコンウェハを固定した。この反応容器内を、まず１
Ｏ−５Ｔｏｒｒの真空状態に排気した後、Ｓ　１２　Ｈ
６ガス（ｂ、　ｐ、−１５℃、合成はＧ、　Ｗ、　Ｂｅ
ｔｈｋｅ　。
Ｍ、　Ｋ、　　Ｗｉｔｓｏｎ、　　　Ｊ、　　　Ｃｈｅ
ｍ、　　Ｐｈｙｓ、　　２６　　、　　１１０７　　（
１９５７）。
Ｈ，Ｋｒｉｅｇｓｍａｎｎ、　　　Ｚ、　　　ａｎｏｒ
ｇ、　　　ｕ、　　　ａｔｔｇｅｍ、　　　Ｃｈｅｍ、
。
−現用、　２１０　（１９５９）を参照した。）を１０
％含有するヘリウムガスを１０ｍ１／ｍｉｎ　ｚ　Ｎ２
０ガスを１０　ｍ４／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／
ｃｒｎ２．２５４　ｎｍ　）から紫外光を照射した。こ
のときのガス圧は約Ｉ　Ｔｏｒｒである。
反応容器内には、水銀溜を置き、約３０°Ｃ〜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７００　Ａ／ｍｉｎの成膜速度で酸化ケイ
素（Ｓ１０２）膜が形成された。（原料にＳｉＨ４ガス
を用いた場合は約４ｏｏ　Ａ／ｍｉｎである。）膜厚の
ばらつきは、±５％以内であった。生成した５１０２膜
をフッ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った
０ 実施例　２ 実施例１と同様な方法で、原料ガスとして、Ｎ１−１゜
／Ｓｉ、、ｌ−１６（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Ｓｉ３Ｎ
、膜は、赤外スペクトルにより確認したが、プラズマＣ
ＶＤによるものとほぼ同じであった。
実施例 実施例１と同様の方法で、原料ガスとして１Ｓｉ２Ｈ６
を１０％含むＨｅガスを１０　ｍｌ／ｍｉｎで流し、エ
キシマレーザ−（ＫｒＰ　２４９　ｎｍ　）を光源とし
て紫外線を照射した。このときのガス圧は約０．５　Ｔ
ｏｒｒであった。デポジション速度は、１ｏｏｏ＾／ｍ
　１ｎ　であり・５ｉＪ（４を同じ条件で用いた場合の
７００λ／ｍｉｎよりも高速であった。生成した膜はア
モルファス状態のンリコンであり、水銀の混入はＳＩＭ
Ｓでは検出できなかった。
実施例　４〜９ 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。
以下余白 第　　１　　表 以上に述べたように、本発明によれば、低温で、効率よ
＜　、ａ−８ｉ、　Ｓｉｆ□、５１３Ｎ４膜を形成でき
るものであり、従っ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０
【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ＣＶ
Ｄ装置の一興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Ａ　；９・・・光取出窓；１０・・・原料ガス。 代理人弁理士　中　村　純之助 式会社日立製作所生産技術研究 所内

Claims (1)

  1. 【特許請求の範囲】 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）
    、 ５１ｎＨ２ｎ＋、・・・（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１・１膜形成方法。
JP57168463A 1982-09-29 1982-09-29 薄膜形成方法 Granted JPS5958819A (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
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)

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

Family

ID=15868574

Family Applications (1)

Application Number Title Priority Date Filing Date
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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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JPS59147437A (ja) * 1983-02-10 1984-08-23 Mitsui Toatsu Chem Inc 窒化シリコン膜の形成法
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JPS61234534A (ja) * 1985-04-11 1986-10-18 Semiconductor Energy Lab Co Ltd 窒化珪素被膜作成方法
JPS61234533A (ja) * 1985-04-11 1986-10-18 Semiconductor Energy Lab Co Ltd 窒化珪素被膜作成方法
JPS61253870A (ja) * 1985-05-07 1986-11-11 Hitachi Ltd 光起電力素子
JPS61256735A (ja) * 1985-05-10 1986-11-14 Nec Corp 半導体装置及びその製造方法
JPS62226631A (ja) * 1986-03-28 1987-10-05 Agency Of Ind Science & Technol 絶縁膜形成方法
JPH0376022B2 (ja) * 1986-03-28 1991-12-04 Kogyo Gijutsuin

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DE3364979D1 (en) 1986-09-04
JPH049369B2 (ja) 1992-02-20
EP0104658B1 (en) 1986-07-30
US4495218A (en) 1985-01-22
EP0104658A1 (en) 1984-04-04

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