JPH0442898A - Crystal growth of compound semiconductor - Google Patents
Crystal growth of compound semiconductorInfo
- Publication number
- JPH0442898A JPH0442898A JP14446990A JP14446990A JPH0442898A JP H0442898 A JPH0442898 A JP H0442898A JP 14446990 A JP14446990 A JP 14446990A JP 14446990 A JP14446990 A JP 14446990A JP H0442898 A JPH0442898 A JP H0442898A
- Authority
- JP
- Japan
- Prior art keywords
- plane
- crystal
- compound semiconductor
- substrate
- compound
- 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
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 31
- 239000004065 semiconductor Substances 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 12
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical group [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims abstract description 4
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims abstract 2
- 239000011777 magnesium Substances 0.000 claims description 11
- 238000000927 vapour-phase epitaxy Methods 0.000 claims description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000002109 crystal growth method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QBJCZLXULXFYCK-UHFFFAOYSA-N magnesium;cyclopenta-1,3-diene Chemical compound [Mg+2].C1C=CC=[C-]1.C1C=CC=[C-]1 QBJCZLXULXFYCK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、マグネシウム元素をドープした閃亜鉛鉱型ｍ
−ｖ族化合物半導体を有機金属気相成長法で結晶成長さ
せる方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a zinc blende type m
-Relates to a method for growing crystals of group V compound semiconductors by metal-organic vapor phase epitaxy.
（従来の技術）
有機金属気相成長法（ＯＭＶＰＥ法）は、有機金属化合
物と金属水素化物を、反応炉中で熱分解させることによ
り、基板上に薄膜の単結晶を成長させる方法である。こ
の方法は、超薄膜の多層構造の形成が容易であり、量産
性も高いので、化合物半導体を用いたヘテロ接合デバイ
ス用基板の作製に用いられている。ヘテロ接合デバイス
の中でもＨＢＴ（ヘテロ・バイポーラ・トランジスタ）
は超高速で動作するため、盛んに開発されている。ＩＩ
ＢＴの構造は第３図に示すように、ｎ−ＧａＡｓのコレ
クタ、ｐＧａＡｓのベース、ｎ−Ａ ｌＧａＡｓのエミ
ッタから構成されている。ｌ’ｌＢＴの特性は、ベース
層のキャリア密度が高いほど、高い特性が得られる。従
来、ＯＭＶＰＥ法ではｐ型ドーパントとしてＺｎが用い
られていたが、Ｚｎは拡散係数が大きいため、成長中に
ベース領域からエミッタ領域に拡散してしまい、急峻な
ｐｎ接合を得ることができないという問題があった。(Prior Art) Organometallic vapor phase epitaxy (OMVPE) is a method of growing a thin single crystal film on a substrate by thermally decomposing an organometallic compound and a metal hydride in a reactor. This method facilitates the formation of an ultra-thin multilayer structure and is highly suitable for mass production, so it is used for manufacturing substrates for heterojunction devices using compound semiconductors. Among heterojunction devices, HBT (hetero bipolar transistor)
is being actively developed because it operates at extremely high speeds. II
As shown in FIG. 3, the structure of the BT is composed of an n-GaAs collector, a pGaAs base, and an n-AlGaAs emitter. The higher the carrier density of the base layer, the better the characteristics of l'lBT can be obtained. Conventionally, Zn has been used as a p-type dopant in the OMVPE method, but since Zn has a large diffusion coefficient, it diffuses from the base region to the emitter region during growth, making it impossible to obtain a steep p-n junction. was there.
ＭＢＥ法では、ｌＸｌ０”ｃｉ−’程度まで高密度にド
ーピングすることが可能で、かつ、拡散係数の小さなり
ｅが一般的に用いられているが、ＯＭＶＰｆｉ法では安
全件の問題から、Ｂｅを用いることは困難である。In the MBE method, it is possible to dope at a high density of about l It is difficult to use.
そのため、ｚｎに比べて拡散係数が５桁小さいＭｇのド
ーピングが検討されている。Ｍｇの原料としては、ビス
シクロペンタジェニルマグ不シウム（ＣｐｔＭｇ）又ハ
ビスメチルシクロペンタジエニルマグネシウム（ＬＣｐ
Ｊｇ）が用いられる。これらの原料は、液体又は固体の
有機金属であり、キャリアガスである水素によって、化
合物半導体の原料である有機金属と金属水素化物と共に
反応管に導入され、基板上で熱分解され、結晶中に取り
込まれる。Therefore, doping with Mg, which has a diffusion coefficient five orders of magnitude smaller than that of zn, is being considered. As a raw material for Mg, biscyclopentadienylmagnesium (CptMg) or habismethylcyclopentadienylmagnesium (LCp
Jg) is used. These raw materials are liquid or solid organic metals, and are introduced into a reaction tube together with organic metals and metal hydrides, which are the raw materials for compound semiconductors, using hydrogen as a carrier gas, and are thermally decomposed on the substrate, forming crystals. It is captured.
第４図は、有機金属気相成長法により、Ｍｇドープ化合
物半導体結晶を成長させる装置の概念図である。予め、
反応管を減圧し、化合物半導体の■族原料は水素ガスに
よって反応管に導入され、■族原料は水素化物ガスの形
で導入される。これらの原料は、過熱された基板上で熱
分解され、基板上に化合物半導体結晶を成長する。この
化合物半導体中にｐ型の層を形成するには、予め排気管
に流していた口原料を含んだ水素ガスを、ノマルブＡヲ
閉シ、バルブＢを開（ことによって、反応管中に導入し
、所定の厚さのＰ層を成長しブ１、バルブＢを閉じ、バ
ルブＡを開いてＭｇ原料ガスを反応管から排気管へ切り
替えることにより行われる。FIG. 4 is a conceptual diagram of an apparatus for growing Mg-doped compound semiconductor crystals by metal organic vapor phase epitaxy. In advance,
The pressure in the reaction tube is reduced, and the Group 1 raw material of the compound semiconductor is introduced into the reaction tube by hydrogen gas, and the Group 1 raw material is introduced in the form of hydride gas. These raw materials are thermally decomposed on a heated substrate to grow compound semiconductor crystals on the substrate. In order to form a p-type layer in this compound semiconductor, hydrogen gas containing raw material, which had been previously flowed into the exhaust pipe, was introduced into the reaction tube by closing normal valve A and opening valve B. Then, a P layer of a predetermined thickness is grown, valves 1 and B are closed, and valve A is opened to switch the Mg source gas from the reaction pipe to the exhaust pipe.
（発明が解決しようとする課題）
上記のＯＭＶ’ＰＥ法でＭｇドープＧａＡｓ層を成長す
るときに、基板の（１００）面から隣接する（１１０）
面へ２度傾けた基板上にＭｇドープＧａＡｓを成長して
いるが、ｌＸｌ０”ｃ■−３以上のドーピングを行うと
結晶表面が劣化するという問題があった（例えば、Ｊｏ
ｕｒ＋ａｌ ｏｒＥｌｅｃｔｏｎｉｃｓ Ｍａｔｅｒｉ
ａｌｓ、 Ｖｏｌ、 １２． Ｎｏ、 ３． ｐ、 ５
０７〜５２４）。(Problem to be Solved by the Invention) When growing an Mg-doped GaAs layer by the above OMV'PE method, the (110) layer adjacent to the (100) plane of the substrate
Mg-doped GaAs is grown on a substrate tilted at 2 degrees to the plane, but there is a problem that the crystal surface deteriorates when doping more than lXl0''c■-3 (for example, Jo
ur+al orElectronics Materi
als, Vol, 12. No, 3. p, 5
07-524).
本発明は、上記の問題を解消して、１０”ｃ＋ｎ−’以
上のマグネシウム元素をドーピングする場合においても
、結晶表面が平坦な閃亜鉛鉱型■−■族化合物半導体単
結晶を結晶成長可能な方法を提供しようとするものであ
る。The present invention solves the above problems and makes it possible to grow a zincblende type ■-■ group compound semiconductor single crystal with a flat crystal surface even when doping with a magnesium element of 10"c+n-' or more. It is intended to provide a method.
（課題を解決するための手段）
本発明は、マグネシウム元素をドープした閃亜鉛鉱型■
−■族化合物半導体を有機金属気相成長法で結晶成長さ
せる方法において、同一結晶構造を有する基板を（１０
０）面から隣接する（ＩＩＩ）Ａ面又は（１１１）８面
に０．５度以上傾けて結晶成長させることを特徴とする
化合物半導体の結晶成長方法である。なお、上記基板の
傾きの好ましい上限は、約１０度である。(Means for Solving the Problems) The present invention provides zinc blende doped with magnesium element.
- In a method of growing crystals of a group compound semiconductor by metal-organic vapor phase epitaxy, a substrate having the same crystal structure (10
This is a compound semiconductor crystal growth method characterized by growing a crystal at an angle of 0.5 degrees or more from the 0) plane to the adjacent (III)A plane or (111)8 plane. Note that the preferable upper limit of the inclination of the substrate is about 10 degrees.
本発明の結晶成長方法に好適な化合物半導体としては、
ＧａＡｓ、 ＡｌＧａＡｓ、 ＩｎＰ、 Ｇａ１ｎＡｓ
などを挙げることができる。Compound semiconductors suitable for the crystal growth method of the present invention include:
GaAs, AlGaAs, InP, Ga1nAs
etc. can be mentioned.
（作用）
ＯＭＶＰＥ法においては、上記の文献に示されるように
、Ｍｇ原料の供給量の２乗に比例してドーピングされる
が、約２Ｘ１０’″Ｃ１−３で飽和する。このように、
正孔密度が飽和する原因としては、通常の（１１０）面
又は（１００）面から隣接する（＋１０）面へ傾けた基
板上に成長する方法では、２ＸＩＯ”Ｃｍ−３以上の口
原子が結晶中に取り込まれても、結晶格子上に配置され
ずに晶格子間に位置し、正孔を供給するアクセプタとし
て機能しないためと考えられる。(Function) In the OMVPE method, as shown in the above-mentioned literature, doping is carried out in proportion to the square of the supply amount of the Mg raw material, but it is saturated at about 2X10'''C1-3.In this way,
The reason why the hole density is saturated is that in the method of growing on a substrate tilted from the normal (110) plane or (100) plane to the adjacent (+10) plane, the hole atoms of 2XIO"Cm-3 or more are crystallized. This is thought to be because even if they are incorporated into the crystal lattice, they are not placed on the crystal lattice but are located between the crystal lattices and do not function as acceptors that supply holes.
そこで、本発明者らは、基板面を傾ける方位を隣接の（
Ｉｌｌ）面に変更し、傾ける角度も０．５度以上、好ま
しくは０．５〜ＩＯ度の範囲で調節したところ、ｌ×１
０ＩＩｌｃＩ１１−３以上のＭｇドーピングを行っても
平坦なエピタキシャル表面を得ることができた。これは
、■族原子の格子位置にＭｇ原子が位置しやすくなり、
格子間に位置するＭｇ原子が減少するため、異常成長の
発生が抑制され、ＩＸＩ（１”ｃｍ−３以上の、１１ｇ
ドーピングを行っても表面が劣化しないものと考えられ
る。Therefore, the present inventors decided to change the direction in which the substrate surface is tilted to the adjacent (
Ill) surface and adjusted the inclination angle to 0.5 degrees or more, preferably in the range of 0.5 to IO degrees, and the result was 1 x 1
A flat epitaxial surface could be obtained even with Mg doping of 0IIlcI11-3 or higher. This makes it easier for Mg atoms to be located in the lattice positions of group ■ atoms,
Since the number of Mg atoms located in the interstitial space is reduced, the occurrence of abnormal growth is suppressed, and
It is considered that the surface does not deteriorate even if doping is performed.
（実施例１）
予め反応管内にＡｓ原料のアルシン（＾５Ｈ３）ガスを
流した状態で、（１００）面から隣接した（ＩＩＩ）Ａ
面へ２度傾けたＧａＡｓ基板と、比較のために（１００
）面から隣接した（＋１０）Ａ面へ２度傾けたＧａＡｓ
基板を、同時に反応管内に設置し、温度６５０°Ｃまで
加熱した後、予め排気管へ流しておいたＣｐｙＭｇを毎
分６０ｍ１で反応管内に導入した。１０分後に、Ｃａ原
料のＴＭＧａを毎分７ｎ＋Ｉで反応管へ導入して、毎時
２μｍの成長速度でＧａＡｓの成長を始めた。９０分後
、ＴＭＧａとＣｐｔＭｇを排気管に切り替え、基板温度
を室温に戻し成長を終了した。(Example 1) With arsine (^5H3) gas as the As raw material flowing in the reaction tube in advance, adjacent (III) A from the (100) plane
For comparison, a GaAs substrate tilted 2 degrees to the plane (100
) plane tilted 2 degrees to the adjacent (+10) A plane
The substrate was placed in the reaction tube at the same time and heated to a temperature of 650° C., and then CpyMg, which had been flowed into the exhaust pipe in advance, was introduced into the reaction tube at a rate of 60 ml per minute. After 10 minutes, TMGa, which is a Ca raw material, was introduced into the reaction tube at a rate of 7n+I per minute, and the growth of GaAs was started at a growth rate of 2 μm per hour. After 90 minutes, TMGa and CptMg were switched to the exhaust pipe, and the substrate temperature was returned to room temperature to complete the growth.
第１図及び第２図は、上記実施例及び比較例の２種類の
ＧａＡｓ基板上に成長したＭｇドープＧａＡｓエピタキ
シャル層の表面をノマルスキイ式光学顕微鏡を用いて倍
率１０００倍で撮影した結晶構造の顕微鏡写真である。Figures 1 and 2 are micrographs showing the crystal structure of the surfaces of the Mg-doped GaAs epitaxial layers grown on the two types of GaAs substrates of the above examples and comparative examples, taken using a Nomarski optical microscope at a magnification of 1000 times. It's a photo.
第１図は、本発明とは関係のない表面欠陥による中央の
キズを除いて、エピタキシャル表面が鏡面であるのに対
し、第２図は、エピタキシャル表面が劣化していること
が分かる。In FIG. 1, the epitaxial surface is a mirror surface except for a central scratch due to a surface defect unrelated to the present invention, whereas in FIG. 2, it can be seen that the epitaxial surface has deteriorated.
（実施例２）
実施例１の成長条件において、基板を（１００）面から
隣接（ＩＩＩ）Ａ面へ７度傾け、その他の成長条件を同
じにしてＭｇドープＧａＡｓエピタ牛シャル層を成長さ
せたところ、エピタキシャル表面は実施例１と同様に鏡
面であり、劣化は見られなかった。(Example 2) Under the growth conditions of Example 1, the substrate was tilted by 7 degrees from the (100) plane to the adjacent (III)A plane, and an Mg-doped GaAs epitaxial layer was grown under the same growth conditions as in Example 1. However, the epitaxial surface was a mirror surface as in Example 1, and no deterioration was observed.
（発明の効果）
本発明は、上記の構成を採用し、基板の傾きを調節する
ことにより、１Ｇ”ａｍ−’以上のマグネシウム元素を
ドーピングする場合においても、結晶表面が平坦な閃亜
鉛鉱型■−■族化合物半導体単結晶を得ることができる
ようになった。(Effects of the Invention) The present invention adopts the above structure and adjusts the inclination of the substrate to achieve a zinc blende type crystal with a flat crystal surface even when doping with magnesium element of 1 G"am-" or more. It has become possible to obtain single crystals of ■-■ group compound semiconductors.
第１図並びに第２図は、本発明の実施例１並びに比較例
で得たＧａＡｓエピタキシャル層の表面を撮影した結晶
構造の顕微鏡写真、第３図は、ＨＢＴの断面模式図、第
４図は、ＯＭＶＰＥ装置の概念図である。
第１図
第２図Figures 1 and 2 are micrographs of the crystal structure of the surface of the GaAs epitaxial layer obtained in Example 1 and Comparative Example of the present invention, Figure 3 is a schematic cross-sectional view of HBT, and Figure 4 is , is a conceptual diagram of an OMVPE device. Figure 1 Figure 2
Claims (2)
Ｖ族化合物半導体を有機金属気相成長法で結晶成長させ
る方法において、同一結晶構造を有する基板を（１００
）面から隣接する（１１１）Ａ面又は（１１１）Ｂ面に
０．５度以上傾けて結晶成長させることを特徴とする化
合物半導体の結晶成長方法。(1) Zinc blende type III doped with magnesium element
In a method for growing crystals of group V compound semiconductors by metal-organic vapor phase epitaxy, a substrate having the same crystal structure is grown (100
) A crystal growth method for a compound semiconductor, characterized in that the crystal is grown at an angle of 0.5 degrees or more from the (111)A plane or (111)B plane to the adjacent (111)A plane or (111)B plane.
ＩｎＰ及びＧａＩｎＡｓからなる群より選ばれる１種類
以上の化合物半導体である請求項（１）記載の化合物半
導体の結晶成長方法。(2) The above compound semiconductor is GaAs, AlGaAs,
2. The method for growing compound semiconductor crystals according to claim 1, wherein the compound semiconductor is one or more compound semiconductors selected from the group consisting of InP and GaInAs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14446990A JP2870989B2 (en) | 1990-06-04 | 1990-06-04 | Compound semiconductor crystal growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14446990A JP2870989B2 (en) | 1990-06-04 | 1990-06-04 | Compound semiconductor crystal growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0442898A true JPH0442898A (en) | 1992-02-13 |
| JP2870989B2 JP2870989B2 (en) | 1999-03-17 |
Family
ID=15363010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14446990A Expired - Lifetime JP2870989B2 (en) | 1990-06-04 | 1990-06-04 | Compound semiconductor crystal growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2870989B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994016459A1 (en) * | 1993-01-13 | 1994-07-21 | Sumitomo Chemical Company, Limited | Semiconductor expitaxial substrate |
| JPH076971A (en) * | 1993-01-25 | 1995-01-10 | Ohio Aerospace Inst | Synthetic semiconductor and its controlled doping |
| US5709745A (en) * | 1993-01-25 | 1998-01-20 | Ohio Aerospace Institute | Compound semi-conductors and controlled doping thereof |
-
1990
- 1990-06-04 JP JP14446990A patent/JP2870989B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994016459A1 (en) * | 1993-01-13 | 1994-07-21 | Sumitomo Chemical Company, Limited | Semiconductor expitaxial substrate |
| JPH076971A (en) * | 1993-01-25 | 1995-01-10 | Ohio Aerospace Inst | Synthetic semiconductor and its controlled doping |
| US5709745A (en) * | 1993-01-25 | 1998-01-20 | Ohio Aerospace Institute | Compound semi-conductors and controlled doping thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2870989B2 (en) | 1999-03-17 |
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