JP2982332B2 - Vapor growth method - Google Patents
Vapor growth methodInfo
- Publication number
- JP2982332B2 JP2982332B2 JP3032108A JP3210891A JP2982332B2 JP 2982332 B2 JP2982332 B2 JP 2982332B2 JP 3032108 A JP3032108 A JP 3032108A JP 3210891 A JP3210891 A JP 3210891A JP 2982332 B2 JP2982332 B2 JP 2982332B2
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- material inlet
- decomposition temperature
- carrier gas
- growth method
- 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.)
- Expired - Fee Related
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、気相成長方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vapor phase growth method.
【０００２】[0002]
【従来の技術】光デバイスや高速デバイスの作製に用い
られる有機金属気相成長法（ＭＯＶＰＥ法）において
は、急峻なヘテロ接合界面が要求されるため、キャリア
ガスの切り替え等について活発な研究が進められてき
た。近年、反応管内のキャリアガスの流れについてシュ
ミレーションにより解析が進められ（ジャーナル・オブ
・クリスタル・グロース（Ｊｏｕｒｎａｌ ｏｆ Ｃｒ
ｙｓｔａｌ Ｇｒｏｗｔｈ）誌、第１００巻、５４５
頁）、減圧に限らず常圧においても急峻なヘテロ界面が
得られるようになっている（ジャーナル・オブ・アプラ
イド・フィジックス（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌ
ｉｅｄ Ｐｈｙｓｉｃｓ）誌、第６７巻、第１２号、７
５７６頁）。図３に一般的に用いられ反応管形状を示
す。ＭＯＶＰＥ法に用いられる原料はルイス酸、ルイス
塩基にあたるものが多く、付加生成物（アダクト）をつ
くりやすい。特に常圧においては付加生成物が顕著にな
る。そこで図３に示すように各原料の接触を少なくする
ため原料導入口を原料導入口１と原料料導入口２との２
つに分け、半導体結晶基板９近くまで別々に原料を導入
している（ＩＣ−ＭＯＶＰＥ ５、Ａｂｓｔｒａｃｔ
ｓ、８５頁）。また、図中、５はカーボンサセプター、
７は高周波コイル、８は石英製反応管である。2. Description of the Related Art In metal organic chemical vapor deposition (MOVPE) used for manufacturing optical devices and high-speed devices, a steep heterojunction interface is required. I have been. In recent years, the flow of carrier gas in a reaction tube has been analyzed by simulation (Journal of Crystal Growth (Journal of Cr).
ystal Growth), Vol. 100, 545
Page), a steep heterointerface can be obtained not only under reduced pressure but also under normal pressure (Journal of Applied Physics (Journal of Appl.
ied Physics), Vol. 67, No. 12, 7
576). FIG. 3 shows a generally used reaction tube shape. Many of the raw materials used in the MOVPE method correspond to Lewis acids and Lewis bases, so that an addition product (adduct) is easily formed. Particularly at normal pressure, the addition products become remarkable. Therefore, as shown in FIG. 3, in order to reduce the contact between the raw materials, the raw material inlet is connected to the raw material inlet 1 and the raw material inlet 2.
And the raw materials are separately introduced up to the vicinity of the semiconductor crystal substrate 9 (IC-MOVPE 5, Abstract).
s, 85). In the figure, 5 is a carbon susceptor,
7 is a high-frequency coil and 8 is a quartz reaction tube.
【０００３】[0003]
【発明が解決しようとする課題】図３に示す従来より用
いられてきた横型反応管の気相成長装置を用いると、複
数の原料導入口１，２から導入される原料の拡散速度の
差により基板９上の原料濃度に差ができることをシュミ
レーションにより発見した。このことはサセプター５上
に結晶基板９を設置し結晶成長を行なった場合に、結晶
成長速度や結晶成長組成、不純物濃度等に影響を及ぼ
し、均一性の低下を生じさせていた。When the conventional horizontal-type reaction tube vapor phase growth apparatus shown in FIG. 3 is used, the difference in the diffusion rates of the raw materials introduced from the plurality of raw material inlets 1 and 2 is increased. It has been found by simulation that a difference occurs in the concentration of the raw material on the substrate 9. This affects the crystal growth rate, the crystal growth composition, the impurity concentration, and the like when the crystal substrate 9 is placed on the susceptor 5 and crystal growth is performed, resulting in a decrease in uniformity.
【０００４】本発明の目的は、これらの問題点を解決
し、均一な結晶成長が可能な気相成長方法を提供するこ
とにある。An object of the present invention is to solve these problems and to provide a vapor phase growth method capable of uniform crystal growth.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明に係る気相成長方法は、横型反応管で上下に
区切られた複数の原料導入口から分解温度の異なる２種
類以上の原料をガス状物質で結晶基板上に供給する気相
成長方法において、サセプターに近い原料導入口から順
に分解温度の高い原料を導入するものである。In order to achieve the above object, a vapor phase growth method according to the present invention is characterized in that two or more kinds of raw materials having different decomposition temperatures are supplied from a plurality of raw material inlets vertically divided by a horizontal reaction tube. In a vapor phase growth method for supplying a gaseous substance onto a crystal substrate, a raw material having a higher decomposition temperature is sequentially introduced from a raw material inlet close to a susceptor.
【０００６】また、本発明は、分解温度の高い原料を熱
伝導率の高いキャリアガスで導入し、分解温度の低い原
料を熱伝導率の低いキャリアガスで導入するものであ
る。Further, the present invention introduces a raw material having a high decomposition temperature with a carrier gas having a high thermal conductivity and a raw material having a low decomposition temperature with a carrier gas having a low thermal conductivity.
【０００７】[0007]
【作用】図３に示す従来より用いられてきた横型反応管
の気相成長装置を用いて分解温度の異なる原料ガスを導
入する場合、結晶成長速度や結晶成長組成、不純物濃度
等の均一性の低下の原因として以下の点が考えられる。When a raw material gas having a different decomposition temperature is introduced by using a conventional horizontal reaction tube vapor phase growth apparatus shown in FIG. 3, uniformity of the crystal growth rate, crystal growth composition, impurity concentration, etc., is reduced. The following can be considered as causes of the decrease.
【０００８】所定のサセプター温度で基板を加熱し原料
の熱分解反応により結晶成長を行う際に、分解温度の低
い原料は基板の上流で容易に熱分解するため上流で堆積
量が多くなる。一方、分解温度の高い原料は原料の分解
時間が長くなり基板の下流でより多く熱分解するため下
流で堆積量が多くなる。この結晶成長組成の不均一性を
防ぐために分解温度の低い原料の基板までの距離を大き
くし分解速度を遅くするように原料導入順序を決める必
要がある。そこで請求項１の本発明では、サセプターに
近い原料導入口から順に分解温度の高い原料を導入する
ことにより分解速度の差を小さくし、結晶成長組成や膜
厚、不純物濃度等の均一な成長が可能となる方法が得ら
れた。When a substrate is heated at a predetermined susceptor temperature and a crystal is grown by a thermal decomposition reaction of the raw material, the raw material having a low decomposition temperature is easily thermally decomposed upstream of the substrate, so that the amount of deposition is increased upstream. On the other hand, a raw material having a high decomposition temperature has a longer decomposition time and is more thermally decomposed downstream of the substrate, so that the amount of deposition increases downstream. In order to prevent the nonuniformity of the crystal growth composition, it is necessary to determine the order of introducing the raw materials so that the distance of the raw material having a low decomposition temperature to the substrate is increased and the decomposition speed is reduced. Therefore, according to the first aspect of the present invention, the difference in the decomposition rate is reduced by sequentially introducing the raw materials having a high decomposition temperature from the raw material introduction port near the susceptor, and uniform growth of the crystal growth composition, film thickness, impurity concentration, and the like can be achieved. A possible method has been obtained.
【０００９】更に、原料の分解速度の差を小さくするた
め、熱伝導率の違うキャリアガスを用い原料の分解速度
を調整することができる。そこで、請求項２の本発明で
は、分解温度の高い原料を熱伝導率の高いキャリアガス
で導入することにより原料の温度を上げ分解を促進し、
一方、分解温度の低い原料を熱伝導率の低いキャリアガ
スで導入して原料の温度を下げ分解を抑制することによ
り、成長組成や膜厚、不純物濃度等の均一成長が可能と
なる方法が得られた。Further, in order to reduce the difference between the decomposition rates of the raw materials, the decomposition rates of the raw materials can be adjusted by using carrier gases having different thermal conductivities. Therefore, in the present invention of claim 2, by introducing a raw material having a high decomposition temperature with a carrier gas having a high thermal conductivity, the temperature of the raw material is raised to promote decomposition,
On the other hand, by introducing a raw material having a low decomposition temperature with a carrier gas having a low thermal conductivity and lowering the temperature of the raw material to suppress the decomposition, a method that enables uniform growth of the growth composition, film thickness, impurity concentration, and the like is obtained. Was done.
【００１０】[0010]
【実施例】以下、本発明の実施例を図により説明する。BRIEF DESCRIPTION OF THE DRAWINGS FIG.
【００１１】（実施例１）図１は、本発明による気相成
長方法において用いた装置を示す構成図である。実施例
においては、ＩＩＩ−Ｖ族化合物半導体の常圧成長の例
を用いて説明する。(Embodiment 1) FIG. 1 is a configuration diagram showing an apparatus used in a vapor phase growth method according to the present invention. The embodiment will be described using an example of normal pressure growth of a group III-V compound semiconductor.
【００１２】図において、石英製反応管８の中央下部管
壁にカーボンサセプター５が置かれており、その上に２
インチのインジウム・燐（ＩｎＰ）基板６が取り付けら
れている。ＩｎＰ基板６は高周波コイル７により６００
℃に加熱される。原料導入口は上下４段に分かれており
カーボンサセプター５に近い側から原料導入口１、原料
導入口２、原料導入口３、原料導入口４とする。キャリ
アガスを水素（Ｈ2）としたトリエチルガリウム（ＴＥ
Ｇ）、トリメタルインジウム（ＴＭＩ）、アルシン（Ａ
ｓＨ3）、ホスフィン（ＰＨ3）を原料としてＩｎＰに格
子整合するインジウム・ガリウム・砒素・燐（ＩｎＧａ
ＡｓＰ）を成長させる。In the figure, a carbon susceptor 5 is placed on a central lower tube wall of a quartz reaction tube 8, and a carbon susceptor 5 is placed thereon.
An inch indium phosphide (InP) substrate 6 is mounted. The InP substrate 6 is 600
Heat to ° C. The raw material inlet is divided into four upper and lower stages, and the raw material inlet 1, the raw material inlet 2, the raw material inlet 3, and the raw material inlet 4 are arranged from the side closer to the carbon susceptor 5. Triethyl gallium (TE) using hydrogen (H 2 ) as a carrier gas
G), trimetal indium (TMI), arsine (A
sH 3), phosphine (PH 3) and indium gallium arsenide phosphide lattice-matched to InP as a raw material (InGa
Grow AsP).
【００１３】一般的なＩＩＩ−Ｖ族化合物半導体の成長
条件において成長速度はＩＩＩ族原料の供給律則になる
ためカーボンサセプター５の近くからＶ族原料を導入す
る。Ｈ2中のＶ族原料についてはＡｓＨ3の分解温度がＰ
Ｈ3よりも低い。一方、Ｈ2中のＩＩＩ族原料については
ＴＥＧの分解温度がＴＭＩよりも低い。そこで、ＰＨ3
を原料導入口１から、ＡｓＨ3を原料導入口２から、Ｔ
ＭＩを原料導入口３から、ＴＥＧを原料導入口４からそ
れぞれ導入し、反応管圧力７６０Ｔｏｒｒ、キャリアガ
スの流量を各々５ＳＬＭとしてＩｎＧａＡｓＰを成長し
たところ、成長膜厚の面内分布は±５％以下、フォトル
ミネッセンス（ＰＬ）波長の面内分布は±１０ｎｍで成
長膜厚及び組成が均一であることが分かった。Under general III-V compound semiconductor growth conditions, the growth rate is governed by the supply rule of the group III raw material, so that the group V raw material is introduced near the carbon susceptor 5. As for the group V raw material in H 2 , the decomposition temperature of AsH 3 is P
Lower than the H 3. On the other hand, the decomposition temperature of TEG is lower than that of TMI for the group III raw material in H 2 . So PH 3
From the material inlet 1 and AsH 3 from the material inlet 2
MI was introduced from the raw material inlet 3 and TEG was introduced from the raw material inlet 4, and InGaAsP was grown at a reaction tube pressure of 760 Torr and a carrier gas flow rate of 5 SLM. The in-plane distribution of the grown film thickness was ± 5% or less. It was found that the in-plane distribution of the photoluminescence (PL) wavelength was ± 10 nm and the grown film thickness and composition were uniform.
【００１４】一方、原料導入口１からＡｓＨ3を、原料
導入口２からＰＨ3を、原料導入口３からＴＥＧを、原
料導入口４からＴＭＩをそれぞれ導入し、同じ薄膜を成
長したところ、成長膜厚の面内分布は±８％以下、ＰＬ
波長の面内分布は±２０ｎｍであった。On the other hand, AsH 3 was introduced from the material inlet 1, PH 3 was introduced from the material inlet 2, TEG was introduced from the material inlet 3, and TMI was introduced from the material inlet 4, and the same thin film was grown. In-plane distribution of film thickness is ± 8% or less, PL
The in-plane distribution of the wavelength was ± 20 nm.
【００１５】（実施例２） 図２は、本発明の別の気相
成長方法において用いた装置を示す構成図である。図に
おいて、石英製反応管８の中央下部管壁にカーボンサセ
プター５が置かれており、その上に２インチのインジウ
ム・燐（ＩｎＰ）基板６が取り付けられている。ＩｎＰ
基板６は高周波コイル７により６００℃に加熱される。
原料導入口は上下４段に分かれておりカーボンサセプタ
ー５に近い側から原料導入口１、原料導入口２、原料導
入口３、原料導入口４とする。トリエチルガリウム（Ｔ
ＥＧ）、トリメタルインジウム（ＴＭＩ）、アルシン
（ＡｓＨ3）、ホスフィン（ＰＨ3）を原料としてＩｎＰ
に格子整合するインジウム・ガリウム・砒素・燐（Ｉｎ
ＧａＡｓＰ）を成長する。Embodiment 2 FIG. 2 is a configuration diagram showing an apparatus used in another vapor phase growth method of the present invention. In the figure, a carbon susceptor 5 is placed on a central lower tube wall of a quartz reaction tube 8, and a 2-inch indium-phosphorus (InP) substrate 6 is mounted thereon. InP
The substrate 6 is heated to 600 ° C. by the high frequency coil 7.
The raw material inlet is divided into four upper and lower stages, and the raw material inlet 1, the raw material inlet 2, the raw material inlet 3, and the raw material inlet 4 are arranged from the side closer to the carbon susceptor 5. Triethyl gallium (T
EG), trimetal indium (TMI), arsine (AsH 3 ), phosphine (PH 3 )
, Gallium, arsenic, phosphorus (In
GaAsP) is grown.
【００１６】一般的なＩＩＩ−Ｖ族化合物半導体の成長
条件において成長速度はＩＩＩ族原料の供給律則になる
ためカーボンサセプター５の近くからＶ族原料を導入す
る。Ｈ2中のＶ族原料についてはＡｓＨ3の分解温度がＰ
Ｈ3よりも低い。一方、Ｈ2中のＩＩＩ族原料については
ＴＥＧの分解温度がＴＭＩよりも低い。Ｈ2は窒素
（Ｎ2）より約７倍熱伝導率が大きいためキャリアガス
をＨ2からＮ2にすると、キャリアガスの温度が下がり分
解速度が遅くなる。そこで、キャリアガスをＨ2とした
ＰＨ3を原料導入口１から、キャリアガスをＮ2としたＡ
ｓＨ3を原料導入口２から、キャリアガスをＨ2としたＴ
ＭＩを原料導入口３から、キャリアガスをＮ2としたＴ
ＥＧを原料導入口４からそれぞれ導入し、反応管圧力７
６０Ｔｏｒｒ、キャリアガスの流量を各々５ＳＬＭとし
てＩｎＧａＡｓＰを成長したところ、成長膜厚の面内分
布は±５％以下、ＰＬ波長の面内分布は±５ｎｍで成長
膜厚及び組成が均一であることが分かった。Under general growth conditions for a group III-V compound semiconductor, the growth rate is governed by the supply rule of the group III material, so that a group V material is introduced near the carbon susceptor 5. As for the group V raw material in H 2 , the decomposition temperature of AsH 3 is P
Lower than the H 3. On the other hand, the decomposition temperature of TEG is lower than that of TMI for the group III raw material in H 2 . Since H 2 has a thermal conductivity approximately seven times greater than that of nitrogen (N 2 ), when the carrier gas is changed from H 2 to N 2 , the temperature of the carrier gas decreases and the decomposition rate decreases. Therefore, the carrier gas from the raw material inlet 1 a PH 3 that the H 2, A of the carrier gas was N 2
sH 3 from the material inlet 2 and T as carrier gas H 2
MI from the material inlet 3 and T as carrier gas N 2
EG was introduced from the raw material introduction port 4 respectively, and the reaction tube pressure 7
When InGaAsP was grown at 60 Torr with a carrier gas flow rate of 5 SLM, the in-plane distribution of the grown film thickness was ± 5% or less and the in-plane distribution of the PL wavelength was ± 5 nm, and the grown film thickness and composition were uniform. Do you get it.
【００１７】[0017]
【発明の効果】以上説明したように、本発明によれば、
横型反応管で上下に区切られた複数の原料導入口から分
解温度の異なる２種類以上の原料をガス状物質で結晶基
板上に供給する気相成長方法において、サセプターに近
い原料導入口から順に分解温度の高い原料を導入する方
法により及び分解温度の高い原料を熱伝導率の高いキャ
リアガスで分解温度の低い原料を熱伝導率低いキャリア
ガスで導入する方法により、結晶膜厚および組成が均一
な結晶成長ができる効果がある。As described above, according to the present invention,
In a vapor phase growth method in which two or more kinds of raw materials having different decomposition temperatures are supplied as gaseous substances onto a crystal substrate from a plurality of raw material inlets vertically separated by a horizontal reaction tube, the raw material is sequentially decomposed from a raw material inlet close to a susceptor. The method of introducing a raw material having a high temperature and a method of introducing a raw material having a high decomposition temperature with a carrier gas having a high thermal conductivity and a method of introducing a raw material having a low decomposition temperature with a carrier gas having a low thermal conductivity have uniform crystal film thickness and composition. This has the effect of allowing crystal growth.
【図１】本発明による結晶成長方法の実施例１の構成を
示す図である。FIG. 1 is a diagram showing a configuration of a first embodiment of a crystal growth method according to the present invention.
【図２】本発明による結晶成長方法の実施例２の構成を
示す図である。FIG. 2 is a diagram showing a configuration of a second embodiment of the crystal growth method according to the present invention.
【図３】従来の反応管形状を示す図である。FIG. 3 is a diagram showing a conventional reaction tube shape.
１ 原料導入口 ２ 原料導入口 ３ 原料導入口 ４ 原料導入口 ５ カーボンサセプター ６ ＩｎＰ基板 ７ 高周波コイル ８ 石英製反応管 ９ 半導体結晶基板 REFERENCE SIGNS LIST 1 raw material inlet 2 raw material inlet 3 raw material inlet 4 raw material inlet 5 carbon susceptor 6 InP substrate 7 high frequency coil 8 quartz reaction tube 9 semiconductor crystal substrate
Claims (2)
料導入口から分解温度の異なる２種類以上の原料をガス
状物質で結晶基板上に供給する気相成長方法において、
サセプターに近い原料導入口から順に分解温度の高い原
料を導入することを特徴とする気相成長方法。1. A vapor-phase growth method for supplying two or more kinds of raw materials having different decomposition temperatures from a plurality of raw material inlets vertically separated by a horizontal reaction tube onto a crystal substrate as a gaseous substance,
A vapor phase growth method characterized by introducing raw materials having a higher decomposition temperature in order from a raw material inlet close to a susceptor.
ャリアガスで導入し、分解温度の低い原料を熱伝導率の
低いキャリアガスで導入することを特徴とする請求項１
に記載の気相成長方法。2. The method according to claim 1, wherein a raw material having a high decomposition temperature is introduced with a carrier gas having a high thermal conductivity, and a raw material having a low decomposition temperature is introduced with a carrier gas having a low thermal conductivity.
3. The vapor phase growth method according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3032108A JP2982332B2 (en) | 1991-01-31 | 1991-01-31 | Vapor growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3032108A JP2982332B2 (en) | 1991-01-31 | 1991-01-31 | Vapor growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04254491A JPH04254491A (en) | 1992-09-09 |
| JP2982332B2 true JP2982332B2 (en) | 1999-11-22 |
Family
ID=12349702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3032108A Expired - Fee Related JP2982332B2 (en) | 1991-01-31 | 1991-01-31 | Vapor growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2982332B2 (en) |
-
1991
- 1991-01-31 JP JP3032108A patent/JP2982332B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04254491A (en) | 1992-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3239622B2 (en) | Method of forming semiconductor thin film | |
| Tokunaga et al. | Growth condition dependence of Mg-doped GaN film grown by horizontal atmospheric MOCVD system with three layered laminar flow gas injection | |
| JP2982332B2 (en) | Vapor growth method | |
| JP2768023B2 (en) | Vapor growth method | |
| JP2712910B2 (en) | Vapor growth method | |
| JPH0754802B2 (en) | Vapor growth method of GaAs thin film | |
| JP2827736B2 (en) | Vapor growth method | |
| JPH0817160B2 (en) | Vapor growth method | |
| JP2687862B2 (en) | Method of forming compound semiconductor thin film | |
| EP0477374B1 (en) | Process for growing semiconductor crystal | |
| JP3141628B2 (en) | Compound semiconductor device and method of manufacturing the same | |
| JPH01261818A (en) | Method of vapor growth of high-resistance algaas mixed crystal | |
| JP2646966B2 (en) | Method for growing thin film of III-V compound semiconductor | |
| JPH06132227A (en) | Vapor growth method | |
| JPH01206618A (en) | Organic metal vapor growth method | |
| JP2982333B2 (en) | Vapor growth method | |
| JPH10242062A (en) | Method of growing semiconductor thin film | |
| JPH0748478B2 (en) | Vapor phase growth equipment | |
| JPH04254492A (en) | Vapor growth method | |
| JPS62270493A (en) | Vapor growth of iii-v compound semiconductor | |
| JPH0722344A (en) | Vapor growth method | |
| JPH03145718A (en) | Vapor epitaxial growth method | |
| JPH03232221A (en) | Vapor growth method for compound semiconductor | |
| JPS647487B2 (en) | ||
| JPH0483332A (en) | Growth method of compound semiconductor crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080924 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |