JPH01296613A - ３−ｖ族化合物半導体の気相成長方法 - Google Patents
３−ｖ族化合物半導体の気相成長方法Info
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- JPH01296613A JPH01296613A JP12589188A JP12589188A JPH01296613A JP H01296613 A JPH01296613 A JP H01296613A JP 12589188 A JP12589188 A JP 12589188A JP 12589188 A JP12589188 A JP 12589188A JP H01296613 A JPH01296613 A JP H01296613A
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- 238000001947 vapour-phase growth Methods 0.000 claims description 12
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- 229910000070 arsenic hydride Inorganic materials 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010453 quartz Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
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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。
め要約のデータは記録されません。
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は■−Ｖ族化合物半導体の気相成長方法に関し、
ざらに詳しくは一度に多数枚の大面積基板上に高均一に
■−ｖ族化合物半導体およびその混晶の極薄膜を効率良
く形成することのできる■−Ｖ族化合物半導体の気相成
長方法に関するものである。
ざらに詳しくは一度に多数枚の大面積基板上に高均一に
■−ｖ族化合物半導体およびその混晶の極薄膜を効率良
く形成することのできる■−Ｖ族化合物半導体の気相成
長方法に関するものである。
［従来の技術］
■−ｖ族化合物半導体のエピタキシャル成長層は発光ダ
イオード、レーザダイオードなどの光デバイスや、ＦＥ
Ｔなどの高速デバイス等に広く応用されている。さらに
最近では、デバイス性能を向上させるために数〜数十へ
の薄膜半導体を積み重ねた構造が要求されている。例え
ば、量子井戸構造を持つレーザダイオードでは、駆動電
流の低減や温度特性の向上、また発撮波長の短波長化が
可能である。また二次元電子ガスを利用したＦＥＴなど
は、高速低雑音デバイスとして期待されている。
イオード、レーザダイオードなどの光デバイスや、ＦＥ
Ｔなどの高速デバイス等に広く応用されている。さらに
最近では、デバイス性能を向上させるために数〜数十へ
の薄膜半導体を積み重ねた構造が要求されている。例え
ば、量子井戸構造を持つレーザダイオードでは、駆動電
流の低減や温度特性の向上、また発撮波長の短波長化が
可能である。また二次元電子ガスを利用したＦＥＴなど
は、高速低雑音デバイスとして期待されている。
これらの薄膜エピタキシャル成長法として、従来は有機
金属気相成長法（ＭＯＣＶＤ法）やハロゲン輸送法など
のガスを用いる気相成長法（ＶＰＥ法）が知られ、供給
ガスの量、成長温度および成長時間等の精密な制御によ
り膜厚をコントロールしていた。また高真空中で元素の
ビームを飛ばして成長を行う分子線エピタキシャル成長
法（ＭＢＥ法〉は比較的厚さ制御か容易な成長法として
知られているが、やはり分子線強度や成長温度、時間等
の精密な制御が必要でおった。
金属気相成長法（ＭＯＣＶＤ法）やハロゲン輸送法など
のガスを用いる気相成長法（ＶＰＥ法）が知られ、供給
ガスの量、成長温度および成長時間等の精密な制御によ
り膜厚をコントロールしていた。また高真空中で元素の
ビームを飛ばして成長を行う分子線エピタキシャル成長
法（ＭＢＥ法〉は比較的厚さ制御か容易な成長法として
知られているが、やはり分子線強度や成長温度、時間等
の精密な制御が必要でおった。
これを改良したのが、近年、スントラ（Ｔ。
５ｕｎｔｏｒａ）らによって報告された原子層エピタキ
シャル成長法（ＡＬＥ法）で、第１６回置体素子・材料
コンファレンス予稿集（Ｔ、５ｕｎｔｏｒａ、 Ｅｘｔ
ｅｎｄｅｄＡｂｓｔｒａｃｔ ｏｆ ｔｈｅ １６ｔｈ
Ｃｏｎｆｅｒｅｎｃｅ ｏｎ ５ｏｌｉｄＳｔａｔｅ
Ｄｅｖｉｃｅｓ ａｎｄ ト１ａｔｅｒｉａｌ
ｓ、Ｋｏｂｅ、１９８４．ｐｐ、６４７−６５０＞に説
明されているように、化合物半導体の（１４成元素、あ
るいはその元素を含むガスを交互に供給して１原子層お
るいは１分子層ずつ吸着させると共に反応させ、全体と
して所望の厚さの化合物半導体を成長させる方法である
。この方法は、ｍ族および■族原料を交互に供給する操
作の繰返しの数によって成長膜厚が決まり、原料の供給
分圧にほとんどよらないため、容易に単原子層レベルで
急峻な界面を持つ移置薄膜構造を成長することができる
。さらに多数の基板上に均一に成長できるため、量産技
術として大きな利点を持っている。
シャル成長法（ＡＬＥ法）で、第１６回置体素子・材料
コンファレンス予稿集（Ｔ、５ｕｎｔｏｒａ、 Ｅｘｔ
ｅｎｄｅｄＡｂｓｔｒａｃｔ ｏｆ ｔｈｅ １６ｔｈ
Ｃｏｎｆｅｒｅｎｃｅ ｏｎ ５ｏｌｉｄＳｔａｔｅ
Ｄｅｖｉｃｅｓ ａｎｄ ト１ａｔｅｒｉａｌ
ｓ、Ｋｏｂｅ、１９８４．ｐｐ、６４７−６５０＞に説
明されているように、化合物半導体の（１４成元素、あ
るいはその元素を含むガスを交互に供給して１原子層お
るいは１分子層ずつ吸着させると共に反応させ、全体と
して所望の厚さの化合物半導体を成長させる方法である
。この方法は、ｍ族および■族原料を交互に供給する操
作の繰返しの数によって成長膜厚が決まり、原料の供給
分圧にほとんどよらないため、容易に単原子層レベルで
急峻な界面を持つ移置薄膜構造を成長することができる
。さらに多数の基板上に均一に成長できるため、量産技
術として大きな利点を持っている。
ところで、ガスを交互に切り換えて基板上に供給する方
法としては、通常は基板を反応容器中に固定し、それぞ
れの原料ガス供給ライン中に配設されたバルブを交互に
切り換えることによって行う。バルブを交互に切り換え
て原子層エピタキシセル成長を行うために従来用いられ
てきた気相成長装置による成長方法の一例として、■族
有機金属原料とＶ酸水素化物原料を用いる有機金属気相
成長装置（ＭＯＣＶＤ装置）による気相成長方法につい
て以下に説明する。
法としては、通常は基板を反応容器中に固定し、それぞ
れの原料ガス供給ライン中に配設されたバルブを交互に
切り換えることによって行う。バルブを交互に切り換え
て原子層エピタキシセル成長を行うために従来用いられ
てきた気相成長装置による成長方法の一例として、■族
有機金属原料とＶ酸水素化物原料を用いる有機金属気相
成長装置（ＭＯＣＶＤ装置）による気相成長方法につい
て以下に説明する。
第４図はＭＯＣＶＤ装置の一例を示す概略構成図である
。通常、常温で液体である第１の■族有機金屈原料４１
０、また固体である第２の■族有機金属原料４１１は適
度の蒸気圧を持つ一定の温度に保たれており、流量制御
装置４１３で制御されたキャリアガスでこれをバブルす
るかまたは近傍を通ずことによって気化し、輸送する。
。通常、常温で液体である第１の■族有機金屈原料４１
０、また固体である第２の■族有機金属原料４１１は適
度の蒸気圧を持つ一定の温度に保たれており、流量制御
装置４１３で制御されたキャリアガスでこれをバブルす
るかまたは近傍を通ずことによって気化し、輸送する。
そして例えばバルブ４１７を開くことによって第１の■
族有機金属原料４１０を反応容器４１に導入し、またバ
ルブ４１７を閉じ、バルブ４１８を開くことによって直
接排気系へ流すことができる。Ｖ族水索化物原料４９に
ついても同様で、バルブ４１５を開くことによって反応
容器４１に導入し、またバルブ４１５を閉じ、バルブ４
１６を開くことによって直接排気系へ流すことができる
。なお図中、４６はカーボンサセプタ、４７は基板結晶
、４８は高周波コイルである。
族有機金属原料４１０を反応容器４１に導入し、またバ
ルブ４１７を閉じ、バルブ４１８を開くことによって直
接排気系へ流すことができる。Ｖ族水索化物原料４９に
ついても同様で、バルブ４１５を開くことによって反応
容器４１に導入し、またバルブ４１５を閉じ、バルブ４
１６を開くことによって直接排気系へ流すことができる
。なお図中、４６はカーボンサセプタ、４７は基板結晶
、４８は高周波コイルである。
従来はこのような装置を用い、一方の原料を反応容器に
導入している間はもう一方の原料は直接排気系に流すと
いう操作を切り換えることによって、ｍ族およびＶ族原
料を交互に反応容器に導入し、原子層エピタキシセル成
長を行っていた。
導入している間はもう一方の原料は直接排気系に流すと
いう操作を切り換えることによって、ｍ族およびＶ族原
料を交互に反応容器に導入し、原子層エピタキシセル成
長を行っていた。
［発明か解決しようとする課題］
上記のような気相成長装置を用いて原子層エピタキシャ
ル成長を行う場合においては、ｍ族および■族原料を交
互に供給する操作の繰返しの数によって成長膜厚が決ま
り、原料の供給分圧にほとんどよらないため、１つの反
応容器中の多数の基板上に均一な膜を成長でき、量産技
術として大きな利点を持っている。
ル成長を行う場合においては、ｍ族および■族原料を交
互に供給する操作の繰返しの数によって成長膜厚が決ま
り、原料の供給分圧にほとんどよらないため、１つの反
応容器中の多数の基板上に均一な膜を成長でき、量産技
術として大きな利点を持っている。
しかしながら、反面、通常の連続成長法とは異なり、ｍ
族およびＶ族原料ガス供給時間がそれぞれ別に必要であ
る。ざらに加えてガスの切り換え動作のためのバルブの
オン、オフに要する時間と配管中を原料ガスがパルス的
に流れる時に生じるパルスの゛′立上がりパ′立下がり
″に要する時間をみこんだパージ時間が必要になる。
族およびＶ族原料ガス供給時間がそれぞれ別に必要であ
る。ざらに加えてガスの切り換え動作のためのバルブの
オン、オフに要する時間と配管中を原料ガスがパルス的
に流れる時に生じるパルスの゛′立上がりパ′立下がり
″に要する時間をみこんだパージ時間が必要になる。
バルブのオン、オフに要する時間は高圧エアー動作式の
バルブを用いた場合には極めて短く問題にはならない。
バルブを用いた場合には極めて短く問題にはならない。
しかし、原料ガス流の″立上がりパ″立下がり″に要す
る時間としては、バルブから反応容器までの配管の長さ
や途中のガス溜まりの有無、ガス流速や反応容器の容積
などに依存するが、短くてコンマ数秒から長いときは数
秒以上必要でおると思われる。
る時間としては、バルブから反応容器までの配管の長さ
や途中のガス溜まりの有無、ガス流速や反応容器の容積
などに依存するが、短くてコンマ数秒から長いときは数
秒以上必要でおると思われる。
そのため原子層エピタキシャル成長を行う場合にはｍ族
およびＶ族原料を交互に供給する操作の間に通常パージ
時間を設け、合計４つのステップを１つのサイクルとし
て、これを繰返すことによって成長を行う。
およびＶ族原料を交互に供給する操作の間に通常パージ
時間を設け、合計４つのステップを１つのサイクルとし
て、これを繰返すことによって成長を行う。
従って、通常のＭＯＣＶＤ法の場合には■族原料の供給
時間がそのまま成長時間に相当していたのに比べると、
３ステップ分余計に成長時間が長く必要なことになる。
時間がそのまま成長時間に相当していたのに比べると、
３ステップ分余計に成長時間が長く必要なことになる。
すなわち、もし１つの反応容器で一度に処理できる基板
の枚数がＭＯＣＶＤ法でもＡＬＥ法でも同じであるなら
ば、単位時間あたりに処理できる基板の枚数はＡＬＥ法
の方が成長時間が長く必要な分だけ少なくなり、処理効
率が悪くなる。さらに反応容器に一方の原料ガスを導入
しているステップ以外の３ステップ間は、その原料は直
接排気系に捨てて″おくため、原料利用効率が低く、極
めて無駄が多い。
の枚数がＭＯＣＶＤ法でもＡＬＥ法でも同じであるなら
ば、単位時間あたりに処理できる基板の枚数はＡＬＥ法
の方が成長時間が長く必要な分だけ少なくなり、処理効
率が悪くなる。さらに反応容器に一方の原料ガスを導入
しているステップ以外の３ステップ間は、その原料は直
接排気系に捨てて″おくため、原料利用効率が低く、極
めて無駄が多い。
本発明の目的はこのような従来技術の欠点を克服し、−
度に多数枚の大面積基板上に、効率良く高均一に■−Ｖ
族化合物半導体およびその混晶の極薄膜を形成すること
のできる■−ｖ族化合物半導体の気相成長方法を提供す
ることにある。
度に多数枚の大面積基板上に、効率良く高均一に■−Ｖ
族化合物半導体およびその混晶の極薄膜を形成すること
のできる■−ｖ族化合物半導体の気相成長方法を提供す
ることにある。
「課題を解決するための手段］
本発明は、■族元素とＶ族元素とをそれぞれ交互にエピ
タキシャル成長室に導入し、該成長室内の基板結晶上に
供給してなる■−ｖ族化合物半導体の気相成長方法にお
いて、エピタキシャル成長室は内部に基板結晶が保持さ
れた独立の反応部を複数有すると共に、各原料ガスは該
複数の反応部に所定時間ずつ順次供給されることを特徴
とする■−Ｖ族化合物半導体の気相成長方法である。
タキシャル成長室に導入し、該成長室内の基板結晶上に
供給してなる■−ｖ族化合物半導体の気相成長方法にお
いて、エピタキシャル成長室は内部に基板結晶が保持さ
れた独立の反応部を複数有すると共に、各原料ガスは該
複数の反応部に所定時間ずつ順次供給されることを特徴
とする■−Ｖ族化合物半導体の気相成長方法である。
［作用］
反応容器に一方の原料ガスを導入しているステップ以外
の３ステップ間に、その原料を直接排気系に“捨てて″
おくために生じる原料利用の無駄をなくし、単位時間あ
たりに処理できる基板の枚数を増やすためには、反応容
器を１つではなく複数用意し、今まで直接排気系に捨て
てパおいた分の原料ガスもその間は他の反応容器に供給
し、そこでも成長を行うようにすれば良い。それぞれの
原料供給ラインからの原料ガスはバルブの開閉によって
所定時間ずつ順次繰返して複数の反応部へ供給する。
の３ステップ間に、その原料を直接排気系に“捨てて″
おくために生じる原料利用の無駄をなくし、単位時間あ
たりに処理できる基板の枚数を増やすためには、反応容
器を１つではなく複数用意し、今まで直接排気系に捨て
てパおいた分の原料ガスもその間は他の反応容器に供給
し、そこでも成長を行うようにすれば良い。それぞれの
原料供給ラインからの原料ガスはバルブの開閉によって
所定時間ずつ順次繰返して複数の反応部へ供給する。
ここで、まず■族およびＶ族それぞれ１種類ずつの原料
を用いて２元化合物を成長する場合について考えてみる
。その場合、原料の無駄を全くなくすためには、■族有
機金属原料の供給時間ｔ （１１１とＶ族水素化物原料
の供給時間ｔ （Ｖｌが、ｔ ｌＩ［ｌｌ＝ ｔ ｆＶ
ｌ＝ ｔ １ ・・・（１）と等しく
、１サイクルの長さをｔｓ、反応容器の数をＮとすると
、 Ｎ＝ｔＳ／ｊ＋≧２ ・・・（２）となる
必要がある。ｍ族原料のパージ時間ｔ Ｄ ｆｌａｉｌ
とＶ族原料のパージ時間ｔ ｌ） （Ｖｌの和は、１Ｄ
（ｎｌｌ＋ｊｌ）（Ｖ］＝１：１Ｘ （Ｎ ２＞・・
・ （３）トする。ｔ ｐ ｆｌ）とｔ ｐ （Ｖｌの
比率は任意に選ぶことができる。ｉＳ／１１＝２のとき
には原料の無駄なしではパージ時間はとれない。もしｔ
（ｍｌとｔ ？Ｖｌが等しくない場合、例えばｔ ｔ
■ｔ≧ｔ ＩＶＩの場合、ｔ ｓ ＝ ｔ（Ｉｌｌｌｘ
Ｎとなりｔ （１１１１−ｔ （Ｖｌの時間はＶ族原
料を無駄に捨てることになる。以下無駄が出ない場合に
ついて表−１にまとめて示す。
を用いて２元化合物を成長する場合について考えてみる
。その場合、原料の無駄を全くなくすためには、■族有
機金属原料の供給時間ｔ （１１１とＶ族水素化物原料
の供給時間ｔ （Ｖｌが、ｔ ｌＩ［ｌｌ＝ ｔ ｆＶ
ｌ＝ ｔ １ ・・・（１）と等しく
、１サイクルの長さをｔｓ、反応容器の数をＮとすると
、 Ｎ＝ｔＳ／ｊ＋≧２ ・・・（２）となる
必要がある。ｍ族原料のパージ時間ｔ Ｄ ｆｌａｉｌ
とＶ族原料のパージ時間ｔ ｌ） （Ｖｌの和は、１Ｄ
（ｎｌｌ＋ｊｌ）（Ｖ］＝１：１Ｘ （Ｎ ２＞・・
・ （３）トする。ｔ ｐ ｆｌ）とｔ ｐ （Ｖｌの
比率は任意に選ぶことができる。ｉＳ／１１＝２のとき
には原料の無駄なしではパージ時間はとれない。もしｔ
（ｍｌとｔ ？Ｖｌが等しくない場合、例えばｔ ｔ
■ｔ≧ｔ ＩＶＩの場合、ｔ ｓ ＝ ｔ（Ｉｌｌｌｘ
Ｎとなりｔ （１１１１−ｔ （Ｖｌの時間はＶ族原
料を無駄に捨てることになる。以下無駄が出ない場合に
ついて表−１にまとめて示す。
（以下余白）
表−１
上記の例では１つの反応容器で処理できる基板 ′の枚
数が同じなら１バツチあたりの処理能力では反応容器の
数が多い程大きく、しかし１バツチ成長するのにかかる
時間はこれに比例して長くなる。
数が同じなら１バツチあたりの処理能力では反応容器の
数が多い程大きく、しかし１バツチ成長するのにかかる
時間はこれに比例して長くなる。
従って単位時間あたりの処理能力で見るとすべて同じで
ある。
ある。
また反応容器の数が多い程パージ時間は長く取れる。ど
うしても短時間に厚い膜が必要な場合でも、反応容器の
数は１つより２つの方が良い。１バツチ成長するのにか
かる時間は反応容器の数が１つでも２つでも同じである
のに対して、処理能力は２つの方が２倍、また、たとえ
多少無駄を出してパージ時間を設けた場合でも無駄にな
る量は反応容器の数が２つの時の方がはるかに少なくて
すむ。
うしても短時間に厚い膜が必要な場合でも、反応容器の
数は１つより２つの方が良い。１バツチ成長するのにか
かる時間は反応容器の数が１つでも２つでも同じである
のに対して、処理能力は２つの方が２倍、また、たとえ
多少無駄を出してパージ時間を設けた場合でも無駄にな
る量は反応容器の数が２つの時の方がはるかに少なくて
すむ。
次に混晶を成長する場合について考えてみる。
この場合、目的の混晶組成が得られるような比率でそれ
ぞれ■族原料同士、Ｖ族原料同士を混ば゛合わせておい
て供給する場合、すなわち組成については通常の成長と
同じくアナログ的な制御を行う場合には、２元化合物と
まったく同じ方法で効率良く成長することができる。
ぞれ■族原料同士、Ｖ族原料同士を混ば゛合わせておい
て供給する場合、すなわち組成については通常の成長と
同じくアナログ的な制御を行う場合には、２元化合物と
まったく同じ方法で効率良く成長することができる。
これに対して混晶組成についても原子層エピタキシャル
成長法の特徴でおるデジタル的な制御を行いたい場合、
すなわち単分子層レベルの超格子構造を持ったいわゆる
配列混晶を成長したい場合には、２元化合物と同じ方法
ではガスの種類を換えている間の分は原料が無駄になる
。もちろん２元化合物での考え方を拡張することで配列
混晶の成長でも原料の無駄をなくすことができ、以下に
示しておくが、装置か複雑になり、あまり現実的な方法
ではない。
成長法の特徴でおるデジタル的な制御を行いたい場合、
すなわち単分子層レベルの超格子構造を持ったいわゆる
配列混晶を成長したい場合には、２元化合物と同じ方法
ではガスの種類を換えている間の分は原料が無駄になる
。もちろん２元化合物での考え方を拡張することで配列
混晶の成長でも原料の無駄をなくすことができ、以下に
示しておくが、装置か複雑になり、あまり現実的な方法
ではない。
いま、例えば■族、Ｖ族それぞれ２つの構成元素からな
る４元混晶としてｌｌ１１ｘＩ２１−ｘＶｌ、ｙＶ ２
ｉ−ｙを考える。これらの各組成は、整数ｎ。
る４元混晶としてｌｌ１１ｘＩ２１−ｘＶｌ、ｙＶ ２
ｉ−ｙを考える。これらの各組成は、整数ｎ。
ｍ、 ｈ、 ｋを使ってそれぞれＸ＝ ｎ／（ｎ４ｍ）
、１−Ｘ＝ｍ／（ｎ４ｍ）、Ｖ＝ ｈ／（ｈ＋ｋ）、
１−Ｖ＝ ｋ／（ｈ十ｋ）と表すことができ、ｎ、 ｍ
、 ｈ、 ｋのなかで例えばｎが最小でおったとする。
、１−Ｘ＝ｍ／（ｎ４ｍ）、Ｖ＝ ｈ／（ｈ＋ｋ）、
１−Ｖ＝ ｋ／（ｈ十ｋ）と表すことができ、ｎ、 ｍ
、 ｈ、 ｋのなかで例えばｎが最小でおったとする。
その場合、全く原料の無駄なく成長を行うためには、
１十ｍ＝ｈ＋ｋ
・・・ （４）ｔ ｆｌｌｌｌ＝ ｔ （Ｖ］＝
ｔ １ ・・・（５）が成り立
ち、反応容器の数は、 Ｎ ＝ （（ｎ４ｍ）／ｎ）Ｘ （ｔ ｓ／ ｔ １）
≧（（ｎ４ｍ）／ｎ） ｘ ２・・・（６） を満タシ、原料■１、■２、Ｖｌ、ｖ２についてそれぞ
れｎ、 ｍ、 ｈ、 ｋ個の原料供給ラインを用意する
必要がある。ただしｔＳ／１１＝２のときには原料の無
駄なしではパージ時間はとれない。
・・・ （４）ｔ ｆｌｌｌｌ＝ ｔ （Ｖ］＝
ｔ １ ・・・（５）が成り立
ち、反応容器の数は、 Ｎ ＝ （（ｎ４ｍ）／ｎ）Ｘ （ｔ ｓ／ ｔ １）
≧（（ｎ４ｍ）／ｎ） ｘ ２・・・（６） を満タシ、原料■１、■２、Ｖｌ、ｖ２についてそれぞ
れｎ、 ｍ、 ｈ、 ｋ個の原料供給ラインを用意する
必要がある。ただしｔＳ／１１＝２のときには原料の無
駄なしではパージ時間はとれない。
例えば、Ｉｎ□、４ Ｇａ□、６ Ａｓ□、２ＰＯ，８
を成長したい場合は、ｎ＝２、ｍ＝３、ｈ＝１、ｋ＝４
、ｎ＋＋＋＋＝ｈ＋に＝５と考えれば良く、ｈ＝ １が
最少ｒＩｒｌ。
を成長したい場合は、ｎ＝２、ｍ＝３、ｈ＝１、ｋ＝４
、ｎ＋＋＋＋＝ｈ＋に＝５と考えれば良く、ｈ＝ １が
最少ｒＩｒｌ。
Ｇａ、 Ａｓ、 Ｐの原料ラインをそれぞれ２，３，
１゜４本と、１０以上の反応容器を用意して、例えば、
Ｉｎ（１） −Ａｓ（１） →Ｉｎ（２） −＊Ｐ（１
）−Ｇａ（１） →Ｐ（２）→Ｇａ（２） →Ｐ（３）
→Ｇａ（３） →Ｐ（４）のように順次時間をずらして
供給すれば良い。
１゜４本と、１０以上の反応容器を用意して、例えば、
Ｉｎ（１） −Ａｓ（１） →Ｉｎ（２） −＊Ｐ（１
）−Ｇａ（１） →Ｐ（２）→Ｇａ（２） →Ｐ（３）
→Ｇａ（３） →Ｐ（４）のように順次時間をずらして
供給すれば良い。
最も単純な混晶、例えば■族元素について、Ｉｎ□、５
Ｇａｏ、５ Ａｓのような均等な組成比を持つような
場合は、ｎ＝１ 、ｍ＝１ 、ｎ＋ｍ＝２ テｈ＋に＝
２ ＋ Ｏ＝ ２と考えれば良く、ＩｎとＧａの原料ラ
インとＡｓの原料ラインについては２つの、計４本の原
料ラインに対して４つ以上の反応容器を用意すれば良い
、ということになる。もしパージ時間を１ ／ ２ Ｘ
ｔ ｊずつとるならば反応容器の数を３／２倍にすれ
ば良い。
Ｇａｏ、５ Ａｓのような均等な組成比を持つような
場合は、ｎ＝１ 、ｍ＝１ 、ｎ＋ｍ＝２ テｈ＋に＝
２ ＋ Ｏ＝ ２と考えれば良く、ＩｎとＧａの原料ラ
インとＡｓの原料ラインについては２つの、計４本の原
料ラインに対して４つ以上の反応容器を用意すれば良い
、ということになる。もしパージ時間を１ ／ ２ Ｘ
ｔ ｊずつとるならば反応容器の数を３／２倍にすれ
ば良い。
以上のように、基板結晶を保持した独立の反応部を複数
有し、■族およびＶ族原料供給ラインが該複数の反応部
のすへでにそれぞれ独立したバルブを介して接続されて
いる成長装置を用い、それぞれの原料供給ラインからの
原料ガスをバルブの開閉によって一定時間ずつ順次繰返
して複数の反応部へ供給すれば、−度に多数枚の大面積
基板上に高均一の■−Ｖ族化合物半導体およびその混晶
の極薄膜を効率良く形成する■−ｖ族化合物半導体気相
成長方法を実現できる。
有し、■族およびＶ族原料供給ラインが該複数の反応部
のすへでにそれぞれ独立したバルブを介して接続されて
いる成長装置を用い、それぞれの原料供給ラインからの
原料ガスをバルブの開閉によって一定時間ずつ順次繰返
して複数の反応部へ供給すれば、−度に多数枚の大面積
基板上に高均一の■−Ｖ族化合物半導体およびその混晶
の極薄膜を効率良く形成する■−ｖ族化合物半導体気相
成長方法を実現できる。
［実施例］
以下、本発明の実施例について図面を参照して詳細に説
明する。なお、本実施例では■族有機金属原料とＶ族水
素化物原料を用いる有機金属気相成長法（ＭＯＣＶＤ法
）を基礎とした原子層エピタキシャル成長法（ＡＬＥ法
）に本発明を適用した場合について説明する。
明する。なお、本実施例では■族有機金属原料とＶ族水
素化物原料を用いる有機金属気相成長法（ＭＯＣＶＤ法
）を基礎とした原子層エピタキシャル成長法（ＡＬＥ法
）に本発明を適用した場合について説明する。
実施例１
第１図に示す４つの独立した反応容器を持つ横型ＭＯＣ
ＶＤ装置を用いてＧａＡｓ基板上へのＧａＡｓ成長を行
った。
ＶＤ装置を用いてＧａＡｓ基板上へのＧａＡｓ成長を行
った。
石英容器（エピタキシャル成長室）５の中に４つの独立
した反応容器（反応部）１〜４かあり、この４つの反応
容器それぞれの中に、複数の基板結晶７が載置されたカ
ーボンサセプタ６がある。
した反応容器（反応部）１〜４かあり、この４つの反応
容器それぞれの中に、複数の基板結晶７が載置されたカ
ーボンサセプタ６がある。
該カーボンサセプタ６は石英容器５の外側に巻回された
高周波コイル８によって加熱されるようになっている。
高周波コイル８によって加熱されるようになっている。
また９〜２０はガス導入系統で、９，１０および１１は
原料ガスを発生する、それぞれＡｓＨ３ガスボンべ、Ｄ
ＥＧａＣｉバブラおよびＤ旧ｎｃ１２容器であり、１２
はキレリアとなるＨ２ガスである。それぞれのガス流量
は流量制御装置１３によって制御される。１４〜２０は
バルブで、バルブ１５ａを開くことによって、Ｖ族水素
化物原料９を反応容器１に導入し、同様に１５ｂ、 １
５Ｃ，１５ｄを開くことによって反応容器２゜３．４に
それぞれ導入することができる。またバルブ１５ａ〜１
５ｄはすべて閉じ、バルブ１６を開くことによって直接
排気系へ流すことができる。■族有機金属原料、例えば
ＤＥＧａｌｌ、ｅｌＯについても同様で、バルブ１７ａ
を開くことによって反応容器１に導入し、同様に１７ｂ
、 １７ｃ、 １７ｄを開くことによって反応容器２，
３．４にそれぞれ導入することができる。
原料ガスを発生する、それぞれＡｓＨ３ガスボンべ、Ｄ
ＥＧａＣｉバブラおよびＤ旧ｎｃ１２容器であり、１２
はキレリアとなるＨ２ガスである。それぞれのガス流量
は流量制御装置１３によって制御される。１４〜２０は
バルブで、バルブ１５ａを開くことによって、Ｖ族水素
化物原料９を反応容器１に導入し、同様に１５ｂ、 １
５Ｃ，１５ｄを開くことによって反応容器２゜３．４に
それぞれ導入することができる。またバルブ１５ａ〜１
５ｄはすべて閉じ、バルブ１６を開くことによって直接
排気系へ流すことができる。■族有機金属原料、例えば
ＤＥＧａｌｌ、ｅｌＯについても同様で、バルブ１７ａ
を開くことによって反応容器１に導入し、同様に１７ｂ
、 １７ｃ、 １７ｄを開くことによって反応容器２，
３．４にそれぞれ導入することができる。
またバルブ１７ａ〜１７ｄはすべて閉じ、バルブ１８を
開くことによって直接排気系へ流すことができる。
開くことによって直接排気系へ流すことができる。
以上のように構成された横型ＭＯＣＶＤ装置を用い、次
のようにしてＧａＡｓ成長を行った。
のようにしてＧａＡｓ成長を行った。
４つの反応容器１〜４の中のカーボンサセプタ６上に３
枚ずつ計１２枚の３インチＧａＡＳ基板７を置き、それ
ぞれの反応容器１〜４にキャリアガスとしての１１２を
９！／ｍｉｎずつ流しておく。コイル８による高周波加
熱によってカーボンサセプタ６上のＧａＡｓ基板７を５
００°ＣにＩＪＯ熱し、このときすべての反応容器内に
それぞれ１Ｔｏｒｒの分圧のＡｓＨ３を供給しておいた
。
枚ずつ計１２枚の３インチＧａＡＳ基板７を置き、それ
ぞれの反応容器１〜４にキャリアガスとしての１１２を
９！／ｍｉｎずつ流しておく。コイル８による高周波加
熱によってカーボンサセプタ６上のＧａＡｓ基板７を５
００°ＣにＩＪＯ熱し、このときすべての反応容器内に
それぞれ１Ｔｏｒｒの分圧のＡｓＨ３を供給しておいた
。
しかる後に、まず反応容器１のＡ Ｓ Ｈ３の供給を停
止し、１秒経過後、５ ｘ １Ｏ−２Ｔｏｒｒの分圧の
ＤＥＧａ（Ｊを１秒間供給した。このあと原料無供給時
間を１秒とり、そのあと’ｌ 丁ｏｒｒの分圧のＡｓＨ
３を１秒間供給した。この４秒間の操作を４０００回繰
返した。反応容器２〜４についても１と同様に、１秒間
のＤＥＧａ（ｉの供給と１秒間のＡｓＨ３の供給を、１
秒の原料無供給時間を挟んで４０００回繰返した。
止し、１秒経過後、５ ｘ １Ｏ−２Ｔｏｒｒの分圧の
ＤＥＧａ（Ｊを１秒間供給した。このあと原料無供給時
間を１秒とり、そのあと’ｌ 丁ｏｒｒの分圧のＡｓＨ
３を１秒間供給した。この４秒間の操作を４０００回繰
返した。反応容器２〜４についても１と同様に、１秒間
のＤＥＧａ（ｉの供給と１秒間のＡｓＨ３の供給を、１
秒の原料無供給時間を挟んで４０００回繰返した。
この時、第２図に示すフローシーケンスに従って、ＤＥ
ＧａＣｌおよびＡｓＨ３はそれぞれ反応容器１から順に
時間をずらして２，３．４と切り換えて供給し、そして
再び１に戻って同じ＜２．３．４というように繰返し、
切り換えて供給した。
ＧａＣｌおよびＡｓＨ３はそれぞれ反応容器１から順に
時間をずらして２，３．４と切り換えて供給し、そして
再び１に戻って同じ＜２．３．４というように繰返し、
切り換えて供給した。
ＤＥＧａｌを原料とした原子層エピタキシャル成長（Ａ
ＬＥ＞では、ＤＥＧａＣＪの分解物であルＧａ（、（が
まずＡｓ面上に単層吸着し、次いで供給されたＡｓＨ３
とこれが反応して１分子層のＧａＡｓ層が成長すると考
えられる。この実施例の装置では最大分圧５×１Ｏ−２
ＴＯｒｒまでの叶Ｇａαの供給が可能であり、これを１
秒間供給して十分に単層弁の吸着が可能な基板の面積、
すなわちここでは直径３インチのＧａＡｓ基板での枚数
で３枚までが限界であった。しかし本実施例のように４
つの反応容器を用意し、ＤＥＧａ（、ｅおよびＡｓｈを
それぞれ反応容器１から順に時間をずらして２，３．４
と切り換えて供給することで、反応容器が１つの時には
直接排気系に無駄に捨てておいた分の０ＥＧａＣ１原料
をすべて利用し、同じ時間で４倍の１２枚の基板に一度
に成長することが可能であった。
ＬＥ＞では、ＤＥＧａＣＪの分解物であルＧａ（、（が
まずＡｓ面上に単層吸着し、次いで供給されたＡｓＨ３
とこれが反応して１分子層のＧａＡｓ層が成長すると考
えられる。この実施例の装置では最大分圧５×１Ｏ−２
ＴＯｒｒまでの叶Ｇａαの供給が可能であり、これを１
秒間供給して十分に単層弁の吸着が可能な基板の面積、
すなわちここでは直径３インチのＧａＡｓ基板での枚数
で３枚までが限界であった。しかし本実施例のように４
つの反応容器を用意し、ＤＥＧａ（、ｅおよびＡｓｈを
それぞれ反応容器１から順に時間をずらして２，３．４
と切り換えて供給することで、反応容器が１つの時には
直接排気系に無駄に捨てておいた分の０ＥＧａＣ１原料
をすべて利用し、同じ時間で４倍の１２枚の基板に一度
に成長することが可能であった。
実施例２
３つの独立した反応容器を持つ装置を用いてＧａＡｓ基
板上へのＧａＡｓ成長を行った。これは第１図に示した
４つの独立した反応容器をもつ横型ＭＯＣＶＤ装置で４
番目の反応容器のみを使わない場合に相当するため、こ
こでは同じく第１図の装置を用いて成長した。
板上へのＧａＡｓ成長を行った。これは第１図に示した
４つの独立した反応容器をもつ横型ＭＯＣＶＤ装置で４
番目の反応容器のみを使わない場合に相当するため、こ
こでは同じく第１図の装置を用いて成長した。
３つの反応容器１〜３の中のカーボンサセプタ６上に３
枚ずつ計９枚の３インチＧａＡｓ基板７を置き、それぞ
れの反応容器１〜３にキャリアガスとしてのＨ２を９Ｌ
’ｍｉｎずつ流しておく。コイル已による高周波加熱に
よってカーボンサセプタ６上のＧａＡｓ基板７を５００
’Ｃに加熱し、このとぎすべての反応容器内にそれぞれ
’ｌ Ｔｏｒｒの分圧のＡｓＨ３を供給しておいた。
枚ずつ計９枚の３インチＧａＡｓ基板７を置き、それぞ
れの反応容器１〜３にキャリアガスとしてのＨ２を９Ｌ
’ｍｉｎずつ流しておく。コイル已による高周波加熱に
よってカーボンサセプタ６上のＧａＡｓ基板７を５００
’Ｃに加熱し、このとぎすべての反応容器内にそれぞれ
’ｌ Ｔｏｒｒの分圧のＡｓＨ３を供給しておいた。
しかる後に、まず反応容器１のＡｓＨ３の供給を停止し
、０．５秒経過後、５ Ｘ １Ｏ−２Ｔｏｒｒの分圧の
０ＥＧａ団を１秒間供給した。このあと原料無供給時間
を０．５秒とり、そのあと’ｌ ＴＯｒｒの分圧のＡｓ
ｔ１３を１秒間供給した。この３秒間の操作を４０００
回繰返した。反応容器２〜３についても１と同様に、１
秒間のＤＥＧａαの供給と１秒間のＡｓＨ３の供給を、
０．５秒の原料無供給時間を挟んで４０００回繰返した
。
、０．５秒経過後、５ Ｘ １Ｏ−２Ｔｏｒｒの分圧の
０ＥＧａ団を１秒間供給した。このあと原料無供給時間
を０．５秒とり、そのあと’ｌ ＴＯｒｒの分圧のＡｓ
ｔ１３を１秒間供給した。この３秒間の操作を４０００
回繰返した。反応容器２〜３についても１と同様に、１
秒間のＤＥＧａαの供給と１秒間のＡｓＨ３の供給を、
０．５秒の原料無供給時間を挟んで４０００回繰返した
。
この時、第３図に示すフローシーケンスに従って、ＤＥ
ＧａＣｉおよびＡｓＨ３はそれぞれ反応容器１から順に
時間をずらして２，３と切り換えて供給し、そして再び
１に戻って同じく２，３というように繰返し、切り換え
て供給した。
ＧａＣｉおよびＡｓＨ３はそれぞれ反応容器１から順に
時間をずらして２，３と切り換えて供給し、そして再び
１に戻って同じく２，３というように繰返し、切り換え
て供給した。
本実施例のように３つの反応容器を用いた場合も、ＤＥ
Ｇａ（ｉ原料をすべて利用し、反応容器が１つの時と比
べて同じ時間で３倍の９枚の基板に一度に成長すること
が可能であった。−度に処理できる基板の枚数は４つの
反応容器を用いる実施例１の場合と比べると３／４と減
るが、しかしパージ時間は半分に減らけるため、その分
同じ膜厚を得るのに必要な時間は３／４に減ってより高
速で成長できる。
Ｇａ（ｉ原料をすべて利用し、反応容器が１つの時と比
べて同じ時間で３倍の９枚の基板に一度に成長すること
が可能であった。−度に処理できる基板の枚数は４つの
反応容器を用いる実施例１の場合と比べると３／４と減
るが、しかしパージ時間は半分に減らけるため、その分
同じ膜厚を得るのに必要な時間は３／４に減ってより高
速で成長できる。
以上、ＤＥＧａＣＪ！、とＡｓＨ３を用いたＧａＡｓの
成長を例に説明したが、第１図に示す装置を用いて、Ｄ
ＥＧａｌ、Ｉ２＋ ＤＨｌｎＣｌとＡｓＨ３の交互供給
によるＩｎＧａＡｓ混晶を上記と同様にして成長させる
ことかできた。
成長を例に説明したが、第１図に示す装置を用いて、Ｄ
ＥＧａｌ、Ｉ２＋ ＤＨｌｎＣｌとＡｓＨ３の交互供給
によるＩｎＧａＡｓ混晶を上記と同様にして成長させる
ことかできた。
本発明の方法に適用しうる■族およびＶ族原料としては
、基本的にガスとして供給可能であればよい。例えば叶
ＭＣ１とＡｓＨ３を用いたＭＡＳの成長や、Ｄ旧ｎｃｊ
２とＰ［１３を用いたＩｎＰの成長にも本発明を適用す
ることができる。また、■族有機金属原料としては塩素
との結合を持たないＴトＩＧ、 ＴＥＧ等でもよい。
、基本的にガスとして供給可能であればよい。例えば叶
ＭＣ１とＡｓＨ３を用いたＭＡＳの成長や、Ｄ旧ｎｃｊ
２とＰ［１３を用いたＩｎＰの成長にも本発明を適用す
ることができる。また、■族有機金属原料としては塩素
との結合を持たないＴトＩＧ、 ＴＥＧ等でもよい。
さらに■族原料としてはＧａ（１３等の無機原料を用い
てもよく、逆にＶ族水素化物原料をＴＥＡｓ等のＶ族有
機金属原料に代えてもよい。また、気相成長装置として
は常圧装置を用いたが減圧装置でも同様の効果か期待で
きる。
てもよく、逆にＶ族水素化物原料をＴＥＡｓ等のＶ族有
機金属原料に代えてもよい。また、気相成長装置として
は常圧装置を用いたが減圧装置でも同様の効果か期待で
きる。
［発明の効果］
以上説明したように、本発明の方法によれば、エピタキ
シャル成長室に複数の反応部を設け、各反応部に順次原
料ガスを供給することにより、−度に多数枚の基板上に
■−ｖ族化合物半導体の超薄膜を形成することができる
と共に、従来のように原料ガスを排気系に′捨てて″お
く必要がないので、原料利用効率が高くなり、無駄を省
くことができる。
シャル成長室に複数の反応部を設け、各反応部に順次原
料ガスを供給することにより、−度に多数枚の基板上に
■−ｖ族化合物半導体の超薄膜を形成することができる
と共に、従来のように原料ガスを排気系に′捨てて″お
く必要がないので、原料利用効率が高くなり、無駄を省
くことができる。
第１図は本発明の方法を実施するための装置の一例を示
す構成図、第２図および第３図はそれぞれ実施例１およ
び実施例２におけるガスのフローシーケンスを示す図、
第４図は従来技術を説明するためのＭＯＣＶＤ装置の一
例を示す構成図でおる。 １〜４，４１・・・反応容器 ５・・・石英容器６
．４６・・・カーボンサセプタ ７，４７・・・基板結
晶８．４８・・・高周波コイル ９・・・ＡｓＨ３
ボンベ１Ｏ−ＤＥＧａＣｉバブラ １ｌ−Ｄ）
ｆＩｎＣ１容器１２、４１２・・・１１２ガス １３．４１３・・・流量制御装置
す構成図、第２図および第３図はそれぞれ実施例１およ
び実施例２におけるガスのフローシーケンスを示す図、
第４図は従来技術を説明するためのＭＯＣＶＤ装置の一
例を示す構成図でおる。 １〜４，４１・・・反応容器 ５・・・石英容器６
．４６・・・カーボンサセプタ ７，４７・・・基板結
晶８．４８・・・高周波コイル ９・・・ＡｓＨ３
ボンベ１Ｏ−ＤＥＧａＣｉバブラ １ｌ−Ｄ）
ｆＩｎＣ１容器１２、４１２・・・１１２ガス １３．４１３・・・流量制御装置
Claims (1)
- （１）ＩＩＩ族元素とＶ族元素とをそれぞれ交互にエピ
タキシャル成長室に導入し、該成長室内の基板結晶上に
供給してなるＩＩＩ−Ｖ族化合物半導体の気相成長方法
において、エピタキシャル成長室は内部に基板結晶が保
持された独立の反応部を複数有すると共に、各原料ガス
は該複数の反応部に所定時間ずつ順次供給されることを
特徴とするＩＩＩ−Ｖ族化合物半導体の気相成長方法。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12589188A JPH01296613A (ja) | 1988-05-25 | 1988-05-25 | ３−ｖ族化合物半導体の気相成長方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12589188A JPH01296613A (ja) | 1988-05-25 | 1988-05-25 | ３−ｖ族化合物半導体の気相成長方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01296613A true JPH01296613A (ja) | 1989-11-30 |
Family
ID=14921476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12589188A Pending JPH01296613A (ja) | 1988-05-25 | 1988-05-25 | ３−ｖ族化合物半導体の気相成長方法 |
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|---|---|
| JP (1) | JPH01296613A (ja) |
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