JPS63239923A - Organic metal chemical vapor growth method and apparatus thereof - Google Patents
Organic metal chemical vapor growth method and apparatus thereofInfo
- Publication number
- JPS63239923A JPS63239923A JP7181987A JP7181987A JPS63239923A JP S63239923 A JPS63239923 A JP S63239923A JP 7181987 A JP7181987 A JP 7181987A JP 7181987 A JP7181987 A JP 7181987A JP S63239923 A JPS63239923 A JP S63239923A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor crystal
- compound semiconductor
- organic metal
- gas
- supplied
- 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
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 7
- 239000000126 substance Substances 0.000 title abstract 2
- 239000004065 semiconductor Substances 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 11
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 7
- 239000007769 metal material Substances 0.000 claims abstract 4
- 125000002524 organometallic group Chemical group 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000004678 hydrides Chemical class 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 13
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 241000700560 Molluscum contagiosum virus Species 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は半導体基体上に化合物半導体結晶を成長させ
る有機金属化学気相成長方法及びその装置に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an organometallic chemical vapor deposition method and apparatus for growing compound semiconductor crystals on a semiconductor substrate.
（従来の技術）
従来、この種の有機金属化学気相成長方法及びその装置
は文献ジャーナルオツアプライドフィジツクス（Ｊｏｕ
ｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ ）
Ｖｏｌ、 ５８（８） 、 １９８５−１０−１５ 、
り−Ｐａ Ｒ３１−Ｒ５５に記載さ、れ、有機金属と
ハイＰライドガスを原料とし水素をキャリアガスとする
方式が用いられている。以下に図面を用いて詳しく説明
する。第２図は従来の有機金属気相成長（以下ＭＯＣＶ
Ｄという）装置の概略図である。通常半導体基板１を反
応管２１内の回転可能なカーデンサセゾタ２２上に設置
し、カーボンサセグタ２２はＲＦ（高周波）コイル２３
による高周波誘導加熱で昇温し、化学気相成長させる化
合物半導体結晶を構成する元素を含む原料ガス等を導入
口２４より導入し、排気口２５よシ排気することによっ
て、基板表面の反応により化合物半導体結晶を成長させ
ている。以下はＧａＡｓを成長する材料の例としてＩｎ
Ｐを成長する場合のＭＯＣＶＤ装置とＭＯＣＶＤ成長過
程について述べる。原料としては、トリメチルインジウ
ム（ＴＭＩｎ。(Prior Art) Conventionally, this type of organometallic chemical vapor deposition method and its apparatus have been described in the literature journal Otsu Applied Physics.
rnal of Applied Physics)
Vol, 58(8), 1985-10-15,
A method is used in which an organic metal and a high P-ride gas are used as raw materials and hydrogen is used as a carrier gas. This will be explained in detail below using the drawings. Figure 2 shows conventional metal organic chemical vapor deposition (hereinafter referred to as MOCV).
FIG. Normally, the semiconductor substrate 1 is placed on a rotatable capacitor sesegrator 22 in a reaction tube 21, and the carbon sussegrator 22 is equipped with an RF (high frequency) coil 23.
A raw material gas containing elements constituting a compound semiconductor crystal to be heated by high-frequency induction heating and chemically vapor-phase grown is introduced from the inlet 24 and exhausted through the exhaust port 25, thereby forming a compound by a reaction on the substrate surface. Growing semiconductor crystals. The following is an example of a material for growing GaAs.
The MOCVD apparatus and MOCVD growth process for growing P will be described. The raw material is trimethylindium (TMIn.
（ＣＨ３）３Ｉｎ ）とホスフィン（ＰＨ３）が用いら
れ、キャリアガスである水素と一緒にガスの導入口２４
より反応管２Ｉに導入される。成長は加熱した基板表面
上で次のような反応過程で行われる。最初に基板表面に
ＴＭＩｎが吸着し、次いでＰＨ，が基板上でＰＩ（、→
ＰＨ２＋Ｈ
ＰＨ２→ＰＨ＋Ｈ
と什解し
ＣＨｓＩｎ” ＋ ＰＨ−ＩｎＰ ＋ ＣＦ（４↑とな
る過程で成長する。この際有機金属のＣはＰＨ３よシ分
解したＨ＊との反応によりＣＨ４となり結晶内に取り込
まれないようにしである。そのため低カーボン濃度を実
現するために〔ｖ〕／〔■〕モル比を高くしなければな
らず通常１００以上を用いん（Ｔ、Ｋａｍｉ ｊｏｈ＋
Ｈ−Ｔａｋａｎｏ ＆ Ｍ、 ５ａｋｕｔａ、Ｊ、 Ｃ
ｒｙｓｔ。(CH3)3In) and phosphine (PH3) are used together with hydrogen as a carrier gas at the gas inlet 24.
is introduced into the reaction tube 2I. Growth takes place on the heated substrate surface through the following reaction process. First, TMIn is adsorbed on the substrate surface, and then PH, is PI(, →
PH2 + H PH2 → PH + H Growth occurs in the process of CHsIn" + PH-InP + CF (4↑). At this time, organic metal C reacts with PH3 and decomposed H* to become CH4 and is incorporated into the crystal. Therefore, in order to achieve a low carbon concentration, the [v]/[■] molar ratio must be high, and usually a value of 100 or more is used (T, Kami joh +
H-Takano & M, 5akuta, J, C
ryst.
Ｇｒｏｗｔｈ ６７ 、１４４−１４６ （１９８４）
）。Growth 67, 144-146 (1984)
).
（発明が解決しようとする問題点）
しかしながら、上記のＭＯＣＶＤ方法及びその装置では
、Ｃ（炭素）の結晶内への取り込みを少なくするために
多量のホスフィ／のような■族ハイＰライドガスを原料
として用いなければならず■コスト的に高くなること■
危険ガスの多量使用■分解したリン、セ素による装置の
汚染などの欠点があった。(Problems to be Solved by the Invention) However, in the above-mentioned MOCVD method and apparatus, a large amount of Group III high Pride gas such as phosphine is used as a raw material in order to reduce the incorporation of C (carbon) into the crystal. It must be used as
There were disadvantages such as the use of large amounts of dangerous gas and the contamination of the equipment by decomposed phosphorus and selenium.
本発明の目的は少量の■族ハイドライドガスを原料とし
て用い、Ｃの取り込みの少ない高品質半導体結晶を成゛
長させるＭＯＣＶＤ方法及びその装置を提供するもので
ある。An object of the present invention is to provide an MOCVD method and apparatus for growing high-quality semiconductor crystals with low carbon uptake using a small amount of Group 1 hydride gas as a raw material.
（問題点を解決するための手段）
この発明は前記問題点を解決するために、半導体気体上
に化合物半導体結晶を有機金属化学気相成長させるに際
し、前記化合物半導体結晶を構成する一元素を含む有機
金属材料ガスを供給し、前記化合物半導体結晶を構成す
る他の元素を含む原料ガスを供給し、キャリアガスとし
て水素ラジカルを供給して成長させるものであり、また
、その装置として前記化合物半導体結晶を構成する一元
素を含む有機金属材料ガス源と、前記化合物半導体結晶
を構成する他の元素を含む原料ガス源と、キャリアガス
としての水素ラジカルを発生させる水素ラジカル発生装
置とを設けたものである。(Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention provides a method for organic metal chemical vapor deposition of a compound semiconductor crystal on a semiconductor gas, including one element constituting the compound semiconductor crystal. The compound semiconductor crystal is grown by supplying an organometallic material gas, a raw material gas containing other elements constituting the compound semiconductor crystal, and supplying hydrogen radicals as a carrier gas. An organometallic material gas source containing one element constituting the compound semiconductor crystal, a raw material gas source containing another element constituting the compound semiconductor crystal, and a hydrogen radical generator that generates hydrogen radicals as a carrier gas. be.
（作用）
以上のように本発明によれば、水素ラジカルをキャリア
ガスとして用いているので、化合物半導体結晶を構成す
る他の元素を含む少量の原料ガス（■族ハイドライドガ
ス）でも、ＭＯＣＶＤ方法でＣの取り込みの少ない結晶
成長が可能となる。(Function) As described above, according to the present invention, since hydrogen radicals are used as a carrier gas, even a small amount of raw material gas (group Ⅰ hydride gas) containing other elements constituting a compound semiconductor crystal can be used in the MOCVD method. Crystal growth with less C uptake becomes possible.
（実施例）
第１図はこの発明の詳細な説明するだめのＭＯＣＶＤ
ｍ置概略断面図であシ、以下図面を用いて説明する。こ
の装置においては、基板１をチェンバー（反応管）２内
の基板ホルダ３に取り付け、加熱は基板ヒータ４による
抵抗加熱方式で６００〜８００℃程度に加熱する。チェ
ンバ２内はパックグラウドとして〜１０−’Ｔｏｒｒ
程度に排気し、化学気相成長させる化合物半導体結晶
の構成元素であるＩｎとＰはそれぞれ、有機金属材料導
入口５よりＴＭＩｎとして供給し、ＰＨ３をＰＨ３導入
口６より供給する。ＰＨ，はヒータ２によシ９００℃程
度まで加熱してもよい。さらに、キャリアガスとして、
水素ラジカルを含む水素を供給している。この実施例で
はラジカル発生の方法として、プラズマ源８とメツシー
電極９の組合せを用いている。プラズマ源８にＨ２ガス
を導入し、水素イオン（Ｈ＋）と水素ラジカル（Ｈ＊）
を生成する。次いでメツシー電極９で水素イオンを除去
し、水素ラジカルのみが基板１に到達するようにする。(Example) Fig. 1 is a detailed explanation of the present invention.
This is a schematic cross-sectional view at 30 m, and will be explained below using the drawings. In this apparatus, a substrate 1 is attached to a substrate holder 3 in a chamber (reaction tube) 2, and heated to about 600 to 800° C. by a resistance heating method using a substrate heater 4. The inside of chamber 2 is ~10-'Torr as a pack ground.
In and P, which are the constituent elements of the compound semiconductor crystal to be grown by chemical vapor deposition, are respectively supplied as TMIn from the organometallic material inlet 5, and PH3 is supplied from the PH3 inlet 6. PH, may be heated to about 900° C. by the heater 2. Furthermore, as a carrier gas,
It supplies hydrogen containing hydrogen radicals. In this embodiment, a combination of a plasma source 8 and a mesh electrode 9 is used as a method of generating radicals. Introducing H2 gas into the plasma source 8, hydrogen ions (H+) and hydrogen radicals (H*)
generate. Next, hydrogen ions are removed by a mesh electrode 9 so that only hydrogen radicals reach the substrate 1.
この結果［”ＰＨ３］ ／［ＴＭＩｎ］のモル比を１０
０以下にしても顕著なＣの取り込みを生じない。それは
、ＰＨ３が分解して生じるＨ−、Ｈ＊以外にＨ＊が加わ
るためである。As a result, the molar ratio of [”PH3] / [TMIn] was set to 10
Even if it is set to 0 or less, no significant C uptake occurs. This is because H* is added in addition to H- and H* produced by decomposition of PH3.
尚、本発明の実施例ではＩｎＰを成長する一方法を示し
ているにすぎず原料ガスの組合せにより他の化合物の成
長も可能である。Note that the embodiments of the present invention merely show one method for growing InP, and other compounds can also be grown by combining raw material gases.
この方法はＧａＡｓ 、 ＧａＰ 、 ＩｎＡｓ 、
ＺｎＳ 、 Ｚｎ５ｅ 。This method is applicable to GaAs, GaP, InAs,
ZnS, Zn5e.
ＣｄＳ 、 ＣｄＳｅ等の化合物とその混晶のＭＯＣＶ
Ｄ成長に可能となる。MOCV of compounds such as CdS and CdSe and their mixed crystals
D. It becomes possible to grow.
（発明の効果）
以上詳細に説明したように、本発明によれば化合物半導
体結晶をＭＯＣＶＤ成長させるに際し、この化合物半導
体結晶を構成する一元素を含む有機金属材料ガスを供給
し、他の元素を含む原料ガスを供給し、さらに水素ラジ
カルをキャリアガスとして供給しているので、少量の■
族ノ・イドライドがスでもＣの取り込みの少ない良質な
化合物半導体結晶成長が可能となる。この方法はＭＯＣ
ＶＤ成長全般に応用できる。(Effects of the Invention) As described above in detail, according to the present invention, when growing a compound semiconductor crystal by MOCVD, an organometallic material gas containing one element constituting the compound semiconductor crystal is supplied, and another element is grown. Since the raw material gas containing hydrogen radicals is supplied as a carrier gas, a small amount of ■
It is possible to grow high-quality compound semiconductor crystals with less C incorporation even when the group hydrides are sulfur. This method is MOC
It can be applied to general VD growth.
第１図は本発明の詳細な説明するだめのＭＯＣＶＤ装置
の概略断面図であり、第２図は従来のＭＯＣＶＤ装置の
概略図である。
１・・・基板、２・・・チェンバー、３・・・基板ホル
ダ、４・・・基板ヒータ、５・・・有機金属材料導入口
、６・・・ＰＨ，導入口、７・・・ヒータ、８・・・プ
ラズマ源、９・・・メツシュ電極、１０・・・液体チッ
素。
特許出願人 沖電気工業株式会社
Ｍｏｃｖｏｔ＞Ｒｆ、、賂１！１１１（失方５イ？’ｊ
）第１図
＜’Ｂｃｒ＋ＭＯｃｖｏｉ置、尤天＊ａ第２図FIG. 1 is a schematic cross-sectional view of an MOCVD apparatus for which the present invention will not be explained in detail, and FIG. 2 is a schematic view of a conventional MOCVD apparatus. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Chamber, 3... Substrate holder, 4... Substrate heater, 5... Organometallic material introduction port, 6... PH, introduction port, 7... Heater , 8... plasma source, 9... mesh electrode, 10... liquid nitrogen. Patent applicant: Oki Electric Industry Co., Ltd.
) Fig. 1
Claims (1)
相成長させるに際し、 前記化合物半導体結晶を構成する一元素を含む有機金属
材料ガスを供給し、 前記化合物半導体結晶を構成する他の元素を含む原料ガ
スを供給し、 キャリアガスとして水素ラジカルを供給して成長させる
ことを特徴とする有機金属化学気相成長方法。 ２）半導体気体上に化合物半導体結晶を有機金属化学気
相成長させる装置において、 前記化合物半導体結晶を構成する一元素を含む有機金属
材料ガス源と、 前記化合物半導体結晶を構成する他の元素を含む原料ガ
ス源と、 キャリアガスとしての水素ラジカルを発生させる水素ラ
ジカル発生装置とを備えてなることを特徴とする有機金
属化学気相成長装置。[Claims] 1) When performing organometallic chemical vapor deposition of a compound semiconductor crystal on a semiconductor gas, supplying an organometallic material gas containing one element constituting the compound semiconductor crystal, and forming the compound semiconductor crystal. An organometallic chemical vapor deposition method characterized by supplying a raw material gas containing other elements such as 2) An apparatus for organic metal chemical vapor deposition of a compound semiconductor crystal on a semiconductor gas, comprising: an organic metal material gas source containing one element constituting the compound semiconductor crystal; and another element constituting the compound semiconductor crystal. An organometallic chemical vapor deposition apparatus comprising a raw material gas source and a hydrogen radical generator that generates hydrogen radicals as a carrier gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62071819A JPH0626186B2 (en) | 1987-03-27 | 1987-03-27 | Metal-organic chemical vapor deposition method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62071819A JPH0626186B2 (en) | 1987-03-27 | 1987-03-27 | Metal-organic chemical vapor deposition method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63239923A true JPS63239923A (en) | 1988-10-05 |
| JPH0626186B2 JPH0626186B2 (en) | 1994-04-06 |
Family
ID=13471543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62071819A Expired - Lifetime JPH0626186B2 (en) | 1987-03-27 | 1987-03-27 | Metal-organic chemical vapor deposition method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0626186B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61168229A (en) * | 1985-01-21 | 1986-07-29 | Fujitsu Ltd | Apparatus for vapor growth |
| JPS6261321A (en) * | 1985-09-11 | 1987-03-18 | Sharp Corp | Manufacture of iii-v compound semiconductor and device thereof |
| JPS62172714A (en) * | 1986-01-25 | 1987-07-29 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of compound semiconductor thin film |
| JPS62229823A (en) * | 1986-03-29 | 1987-10-08 | Nippon Telegr & Teleph Corp <Ntt> | Method of growing added compound semiconductor crystal |
| JPS63221611A (en) * | 1987-03-11 | 1988-09-14 | Oki Electric Ind Co Ltd | Method and apparatus for metal organic chemical vapor deposition |
-
1987
- 1987-03-27 JP JP62071819A patent/JPH0626186B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61168229A (en) * | 1985-01-21 | 1986-07-29 | Fujitsu Ltd | Apparatus for vapor growth |
| JPS6261321A (en) * | 1985-09-11 | 1987-03-18 | Sharp Corp | Manufacture of iii-v compound semiconductor and device thereof |
| JPS62172714A (en) * | 1986-01-25 | 1987-07-29 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of compound semiconductor thin film |
| JPS62229823A (en) * | 1986-03-29 | 1987-10-08 | Nippon Telegr & Teleph Corp <Ntt> | Method of growing added compound semiconductor crystal |
| JPS63221611A (en) * | 1987-03-11 | 1988-09-14 | Oki Electric Ind Co Ltd | Method and apparatus for metal organic chemical vapor deposition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0626186B2 (en) | 1994-04-06 |
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