JPS59103329A - Vapor growth of compound semiconductor layer - Google Patents
Vapor growth of compound semiconductor layerInfo
- Publication number
- JPS59103329A JPS59103329A JP21277082A JP21277082A JPS59103329A JP S59103329 A JPS59103329 A JP S59103329A JP 21277082 A JP21277082 A JP 21277082A JP 21277082 A JP21277082 A JP 21277082A JP S59103329 A JPS59103329 A JP S59103329A
- Authority
- JP
- Japan
- Prior art keywords
- crystal
- compound semiconductor
- gas
- vessel
- reaction tube
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- 239000012495 reaction gas Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 238000001947 vapour-phase growth Methods 0.000 claims description 5
- -1 aluminum organic compound Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000010453 quartz Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 abstract description 3
- 108010085603 SFLLRNPND Proteins 0.000 abstract description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910000070 arsenic hydride Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000004804 winding Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 101100215641 Aeromonas salmonicida ash3 gene Proteins 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000134884 Ericales Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241001354491 Lasthenia californica Species 0.000 description 1
- 241000700560 Molluscum contagiosum virus Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02387—Group 13/15 materials
- H01L21/02395—Arsenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02543—Phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/02546—Arsenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Semiconductor Lasers (AREA)
Abstract
Description
【発明の詳細な説明】
（ａ） 発明の技術分野
本発明は化合物半導体層の気相成長方法、特にガリウム
・アルミニウム・砒素（ＧａＡ／Ａｓ ） 、インジウ
ム・アルミニウム・燐（ＩｎＡ／Ｐ ）等のアルミニウ
ム（Ａ／）を含む化合物半導体の有機金属熱分解気相成
長方法（Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｃａ
ｌＶａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ ；以下ＭＯＣＶ
Ｄ法と略称する）の改善に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field of the Invention The present invention relates to a method for vapor phase growth of compound semiconductor layers, particularly gallium-aluminum-arsenic (GaA/As), indium-aluminum-phosphorus (InA/P), etc. Metal organic chemical vapor phase growth method for compound semiconductors containing aluminum (A/)
lVapor Deposition;hereinafter referred to as MOCV
(abbreviated as D method).
（ｂ） 技術の背景 光応用計測制御、光通信その他の種々の産業。(b) Technology background Optical applied measurement control, optical communication and other various industries.
民生分野における光を情報信号媒体に用いる技術におい
て、半導体レーザ、発光ダイオード等の半導体発光装置
及びフォトダイオード等の半導体受光装置は最も重要で
基本的な泡成要素である。In the technology of using light as an information signal medium in the consumer field, semiconductor light emitting devices such as semiconductor lasers and light emitting diodes, and semiconductor light receiving devices such as photodiodes are the most important and basic foam forming elements.
これらの半導体発光装置は主として化合物半導体によっ
て構成され、半導体受光装置についても例えば波長０．
７乃至ｌ〔μｍ〕程度以上の帯域のために化合物半導体
受光装置の開発・実用化が推進されている。These semiconductor light emitting devices are mainly composed of compound semiconductors, and the semiconductor light receiving devices are also made of, for example, wavelengths of 0.
The development and practical use of compound semiconductor photodetectors for a band of about 7 to 1 [μm] or more is being promoted.
他方、情報処理装置等の能力の一層の向上のために、シ
リコン（Ｓｌ）よりキャリアの移動度が遥に大きい化合
物半導体を用いて、半導体装置の高速化、低消費電力化
を推進する努力が重ねられている。On the other hand, in order to further improve the performance of information processing devices, efforts are being made to promote higher speed and lower power consumption of semiconductor devices by using compound semiconductors, which have a much higher carrier mobility than silicon (Sl). They are stacked on top of each other.
以上述べたレーザ、フォトダイオード及びトランジスタ
等に用いられる化合物半導体は現在■−Ｖ族化合物が主
体をなし１例えばガリウム・砒素（ＧａＡＳ）、インジ
ウム・燐（ＩｎＰ）等の二元化合物結晶及びガリウム・
アルミニウム・砒素（ＧａＡＡＡｓ）、 インジウム・
ガリウム・砒素・惧（ＩｎＧａＡｓＰ ）等の三元以上
の化合物混晶なとである。The compound semiconductors used in the lasers, photodiodes, transistors, etc. mentioned above are currently mainly composed of -V group compounds.
Aluminum/arsenic (GaAAAs), indium/
It is a mixed crystal of ternary or higher compounds such as gallium, arsenic, and (InGaAsP).
光半導体装置及び高電子移動度電界効果トランジスタ等
においては、一般に組成金界にしかつ結晶格子の整合が
可能な化合物半導体を選択してこれを化合物半導体基板
上に積層成長させ、これらの成長層に所要の機能を有す
る領域が形成されている。従ってこれらの化合物半導体
装置の特性及び信頼性は前記成長層に大きく依存してい
る。In optical semiconductor devices and high electron mobility field effect transistors, etc., compound semiconductors that have a composition of gold fields and whose crystal lattice can be matched are generally selected and grown in layers on a compound semiconductor substrate. A region having the required function is formed. Therefore, the characteristics and reliability of these compound semiconductor devices largely depend on the growth layer.
（Ｃ） 従来技術と問題点
化合物半導体の結晶成長方法としては、液相成長法、化
学気相成長法（化学輸送法；以下ＣＶＤ法と略称する）
、有機金属熱分解気相成長法（ＭＯＣＶＤ法）及び分子
線成長法などが既に行なわれている。(C) Conventional technology and problems Crystal growth methods for compound semiconductors include liquid phase growth method and chemical vapor deposition method (chemical transport method; hereinafter abbreviated as CVD method).
, metal organic pyrolysis vapor deposition (MOCVD), and molecular beam growth have already been used.
成長させる化合物半導体の組成にアルミニウム（Ａｌり
が含まれる場合には、従来行なわれている前記各成長方
法は何れも困難が伴なっている。When aluminum is included in the composition of the compound semiconductor to be grown, each of the conventional growth methods described above is accompanied by difficulties.
ＱａＡｓ−ＧａＡｌＡｓ系の半導体レーザ及び発光ダイ
オード等の光半導体装置のＧａＡＡＡｓ ｎの成長には
従来液相成長法が最も多く行なわれている。Conventionally, the liquid phase growth method has been most commonly used to grow GaAAASn for optical semiconductor devices such as QaAs-GaAlAs semiconductor lasers and light emitting diodes.
しかしながら成長溶液組成のうちＡＩ濃度は特に希薄な
ために、結晶成長中に成長層近傍で溶液のＡｌ濃度不足
を生じる。これは溶液中のＡｌの自己拡散と対流によっ
て補われるが、成長速度が太きいとき、又は成長層を厚
く形成するときには成長層のＡ１組成比の減少が避けら
れない。However, since the Al concentration in the growth solution composition is particularly dilute, an insufficient Al concentration in the solution occurs near the growth layer during crystal growth. This is compensated for by self-diffusion and convection of Al in the solution, but when the growth rate is high or the growth layer is formed thick, a decrease in the Al composition ratio of the growth layer is unavoidable.
また塩素（（Ｊ）化合物が原料とされるＣＶＤ法によっ
てＧａＡｌＡｓを成長させることを試みるならば、 Ａ
ｌが石英反応管に析出するなどして制御良く良質のＧａ
ＡＩＡＳ結晶を得ることは不可能である。Furthermore, if we attempt to grow GaAlAs by the CVD method using chlorine ((J) compounds as raw materials, A
Good quality Ga is produced in a well-controlled manner, such as by precipitation of l in a quartz reaction tube.
It is not possible to obtain AIAS crystals.
このＣＶＤ法に対して、 ｒｖｉｏ ＣＶＤ法において
は例えばトリメチルガリウム（（ＣＨ３）５Ｇａ）、
トリメチルアルミニウム（（ＣＨ３）３Ａｌ）などの
有機金属材料とハイドライドアルシン（ＡＳＩ（３）と
を水素（Ｈ２）をキャリアとして適量混合して反応管に
送υ、結晶を成長させる基板近傍において加熱分解する
ことによってＧａＡＪＡｓ結晶の成長を可能にしている
。In contrast to this CVD method, in the rvio CVD method, for example, trimethyl gallium ((CH3)5Ga),
An appropriate amount of organometallic material such as trimethylaluminum ((CH3)3Al) and hydride arsine (ASI(3)) are mixed together using hydrogen (H2) as a carrier, sent to a reaction tube, and thermally decomposed near the substrate where crystals are grown. This makes it possible to grow GaAJAs crystals.
しかしながら従来のＭＯＣＶＤ法で成長させだＧａＡｎ
ＡＳ結晶を用いる半導体レーザ等の光半導体装置は、液
相成長法で成長させたＧａＡｌＡＳ 結晶を用いる光半
導体装置に比較して発光効率が大幅に低く、かつＭＯＣ
ＶＤ法によるＧａＡ６ＡＳ結晶はキャリアの濃度及び移
動度が液相成長結晶に比較して大幅に低下していること
が知られている。However, GaAn grown by conventional MOCVD method
Optical semiconductor devices such as semiconductor lasers that use AS crystals have significantly lower luminous efficiency than optical semiconductor devices that use GaAlAS crystals grown by liquid phase growth, and are
It is known that the carrier concentration and mobility of GaA6AS crystals produced by the VD method are significantly lower than those of liquid phase grown crystals.
これらの特性劣化は、 ＭＯＣＶＤ 法において有機
金属材料やＡ８Ｈ３等のキャリアとして多量に用いられ
る水素（Ｈ２）ガス等に含まれ、或いは装置内に残留す
る酸素（０２）、水蒸気（Ｈ２Ｏ）或いは酸化炭素（Ｃ
Ｏ）等によってＡ７が酸化されて。These characteristic deteriorations are caused by hydrogen (H2) gas, which is used in large quantities as a carrier for organometallic materials and A8H3 in the MOCVD method, or by oxygen (02), water vapor (H2O), or carbon oxides remaining in the device. (C
A7 is oxidized by O) etc.
ＧａＡｌＡｓ 結晶中に多量の深いキャリア捕獲率位が
６入されることに起因すると考えられる。このＡｌ酸化
に対処するために、既にＭＯＣＶＤ装置要望されている
。This is thought to be due to the large number of deep carrier trapping sites in the GaAlAs crystal. In order to deal with this Al oxidation, MOCVD equipment is already in demand.
（ｄ） 発明の目的
本発明は、有機金属熱分解気相成長方法（ＭＯＣＶＤ法
）によって成長させたアルミニウム（Ａ４）を含む化合
物半導体結晶内のアルミニウム（Ａ４）酸化物等による
キャリア捕獲単位の形成を阻止してその特性を改善する
ことを目的とする。(d) Purpose of the Invention The present invention relates to the formation of carrier trapping units by aluminum (A4) oxide, etc. in a compound semiconductor crystal containing aluminum (A4) grown by a metal organic pyrolysis vapor deposition method (MOCVD method). The purpose is to prevent this and improve its characteristics.
（ｅ） 発明の構成
本発明の前記目的は、アルミニウムを含む化合物半導体
層を、アルミニウム有機化合物ガスを含む反応ガスの熱
分解によって被処理基板上に生成する方法において、前
記反応ガス中に酸素との反応速度がアルミニウムよりも
大なるマグネシウムを１（ｐｐｍ）以下添加することに
より達成される。(e) Structure of the Invention The object of the present invention is to provide a method for producing a compound semiconductor layer containing aluminum on a substrate to be processed by thermal decomposition of a reaction gas containing an aluminum organic compound gas. This can be achieved by adding 1 (ppm) or less of magnesium, which has a higher reaction rate than aluminum.
Ａｌを含む化合物半導体結晶例えばＧａＡ／Ａｓ結晶の
成長において反応ガス中の微量の酸素及び酸素化合物が
大きい障害要因となるのは、Ａｌが例えばＱａに比較し
て化学的に甚だ活発であって容易に酸化さｎるためであ
る。−！たＧａＡｌＡｓ結晶内にＡＡ酸化物によってギ
ヤリア捕獲単位が形成されるのは、酸素が微量であるた
めにＡｌの酸化がＡ４０等の不飽和酸化物の生成状態に
止まることによると考えられる。The reason why trace amounts of oxygen and oxygen compounds in the reaction gas become a major hindrance in the growth of compound semiconductor crystals containing Al, such as GaA/As crystals, is because Al is chemically extremely active compared to, for example, Qa. This is because it is oxidized to n. -! The reason why gearia capture units are formed by AA oxides in the GaAlAs crystals is thought to be because the oxidation of Al remains in the state of producing unsaturated oxides such as A40 due to the trace amount of oxygen.
本発明においては、酸素との結合エネルギーがＡＡより
大きい２価金属であるマグネシウム（Ｍｇ ）を反応カ
ス中に導入することによってＡ ７ 酸化物の生成が阻
止され、かつこれに代って生成される酸化マグネシウム
（ＭｇＯ）は電子的に２ 皿した化合物であり、ＧａＡ
ｌＡｓ等の半導体結晶内に混入した場合にも′屯気的に
不活性であるためにキャリア捕獲準位が形成されない。In the present invention, by introducing magnesium (Mg), which is a divalent metal whose bonding energy with oxygen is larger than that of AA, into the reaction residue, the production of A 7 oxide is inhibited, and the A 7 oxide is produced in its place. Magnesium oxide (MgO) is an electronically double compound, and GaA
Even when mixed into a semiconductor crystal such as lAs, carrier trapping levels are not formed because it is generally inactive.
キャリア捕獲準位の形成を阻止するためのマグネシウム
（Ｍｇ）の反応ガスへの添加量は１（ｐｐｍｌ以下例え
ば１０（ｐｐｂ）乃至数１００ （ｐｐｂ）程度の微量
にて足りる。The amount of magnesium (Mg) added to the reaction gas to prevent the formation of carrier trapping levels may be as small as 1 ppml or less, for example, about 10 ppb to several 100 ppb.
しかしながら形成されるＡｌを含む半導体結晶にｐ型の
導電性を与えることが必要である場合には、添加量を適
量に増加してＭｇをアクセプタ不純物とすることが容易
に可能である。However, if it is necessary to impart p-type conductivity to the formed semiconductor crystal containing Al, it is easily possible to appropriately increase the amount of addition and use Mg as an acceptor impurity.
また反対に形成されるＡＩＪ’ｅ含む半導体結晶にｎ型
の導気型を与えることが必要である場合には。Conversely, if it is necessary to provide n-type conductivity to the semiconductor crystal containing AIJ'e formed.
ドナー不純物とともに微量のＭｇを反応ガス中に添加す
ることによって、キャリア捕獲準位の形成が阻止された
ｎ型半啓体結晶が形成される。By adding a small amount of Mg to the reaction gas together with a donor impurity, an n-type half-envelope crystal in which the formation of carrier trapping levels is prevented is formed.
（【）発明の実施例
以下本発明を実施例により図面全参照して具体的に説明
する。([) Embodiments of the Invention The present invention will be specifically described below by way of embodiments with reference to all the drawings.
図はＧａＡｓ基板上にＧａＡＡＡｓ結晶を成長せしめる
本発明の実施状況を模式的に示す。図において、１は（
ＣＨ３１＋Ａｌを収容したバブラー、２は（Ｃ’Ｈ３）
３Ｇａ 全収容したバブラー、収容容器３にＨ２＋収容
容器４にＡＳＨ３、収容容器５に）Ｉ２Ｓがそれぞれ収
容される。６は金属マグネシウム。The figure schematically shows the implementation of the present invention in which a GaAAAs crystal is grown on a GaAs substrate. In the figure, 1 is (
Bubbler containing CH31+Al, 2 is (C'H3)
A fully accommodated 3Ga bubbler, H2 in the container 3, ASH3 in the container 4, and I2S in the container 5 are stored, respectively. 6 is metallic magnesium.
７は石英反応管、８はヒーター、９はトラップ。7 is a quartz reaction tube, 8 is a heater, and 9 is a trap.
１０は例えばパラジウム（Ｐｄ）拡散膜を用いたＨ２精
製装置、１１は流量制仙Ｉ装置？Ｎｉ、１２はパルプ。For example, 10 is an H2 purification device using a palladium (Pd) diffusion membrane, and 11 is a flow rate control I device? Ni, 12 is pulp.
１３はフィルタ、１４は石英反応管、１５はその排気孔
、１６は例えば炭化群Ｘ（ＳｉＣ）によって形成された
基台、１７はＧａＡｌＡｓ結晶を成長させる被処理Ｇａ
Ａｓ基板、１８は高周波コイルを示す。なお、金属マグ
ネシウム６、石英反応管７゜ヒーター８及びトラップ９
が本実施例において従来技術によるｒｌｌｏ ＣＶＤ
法に新たに付加された部分である。づ・た本装置のリー
クばＩ Ｘ ｉ Ｏ＝ ［の−３／ ａｔｍｒＩｎ ”
〕以下と充分に高い気密度にされている。13 is a filter, 14 is a quartz reaction tube, 15 is an exhaust hole thereof, 16 is a base made of, for example, carbon group X (SiC), and 17 is a Ga to be treated for growing a GaAlAs crystal
As substrate, 18 indicates a high frequency coil. In addition, metal magnesium 6, quartz reaction tube 7° heater 8 and trap 9
In this example, rllo CVD according to the prior art
This is a new part of the law. If there is a leak in this device,
] The airtightness is sufficiently high as below.
このような気相成長装賢を用い、収容容器５からのｉ■
２ｓ”Ｘ停止してノンドープ状態のＣ，ａ Ｏ，７ＡＡ
０．３Ａｓ結晶をＧ ａ Ａ ｓ基板１７上に成長さ−
ＩＪ’−る本発明（７）’ＪＩＭａ例ニｈいて、従来技
術と同様にトリメデルガリウム（（ＣＨ３）３Ｇａ）、
）リメチルアルミニウム（（ＣＨ３） ３ＡＡ ）及
びＡＳＨ３とキャリアとしてＩ−Ｉ ２３００（’（、
〕に加熱された純度９９．９９９９（２）以上の金属マ
グネシウム（Ｍｇ）６に接触させることによって１反応
ガス中にｔｏｏ（ｐｐｂ）程度にマグネシウム（Ｍｇ）
蒸気を含有させて石英反応管１４に導き、成長温度約７
３０〔℃〕としてＱａＯ，７ＡｌＯ，３Ａ ｓ結晶を成
長させる。このＭｇ蒸気の含有率は反応ガス中の酸素（
０２）の含有率のほぼ２倍に相当する。Using such a vapor phase growth system, i■
2s”X stopped and non-doped C, a O, 7AA
A 0.3As crystal is grown on the GaAs substrate 17.
According to the present invention (7)'JIMa example, trimedergallium ((CH3)3Ga),
) remethylaluminum ((CH3) 3AA) and ASH3 and I-I 2300('(,
] Magnesium (Mg) is added to about too (ppb) in one reaction gas by contacting with metallic magnesium (Mg) 6 of purity 99.9999 (2) or higher heated to
Steam is introduced into the quartz reaction tube 14, and the growth temperature is about 7.
QaO, 7AlO, 3As crystals are grown at 30[° C.]. The content of this Mg vapor is determined by the oxygen (
This corresponds to approximately twice the content rate of 02).
ここに得られたＧａ Ｏ，７Ａｌｊ ０．３Ａｓ結晶は
、正孔濃度約ｌＸｌ０ ［ｍ ：］ｌ移動度３５０
乃至４００Ｃｃｍ”／Ｖ ｓｅａ：） テアル。The GaO,7Alj0.3As crystal obtained here has a hole concentration of about lXl0 [m:]l mobility of 350
〜400Ccm''/V sea:) Theal.
比較試料として１本実施例の特つとする金属マグネシウ
ム６に反応ガスを接触させることなく。A comparative sample was prepared without contacting the metal magnesium 6, which is a special feature of this example, with a reactive gas.
従来技術によって一同一温度で成長さぜたＱａｏ、７Ａ
１０．３Ａｓ結晶は抵抗率１０７乃至１０９ 〔Ω・副
〕を示して、正孔濃度、移動度を前記実施例と同様に測
定することは不可能である。Qao, 7A grown at the same temperature by conventional technology
The 10.3As crystal exhibits a resistivity of 107 to 109 [Ω·sub], making it impossible to measure the hole concentration and mobility in the same manner as in the previous example.
寸た第二の比較試料として前記比較試料の成長温度を７
９０ Ｃ’Ｃ）に高めた場合にも、抵抗率１０ 乃至１
０ 〔Ω・副〕程度、正孔儂度約ｌＸｌ０ （副 〕
、移動［１００乃至２００（ｃｒｌ ／ Ｖ−ｓｅｅ）
のＧａ０．７ＡＩｊＯ，３Ａｓ結晶が得られるに止まり
、この比較試料と前記本発明の実施例とについてホトル
ミネセンス強度を比較するならば。As a second comparative sample, the growth temperature of the comparative sample was set to 7.
Even when the resistivity is increased to 90 C'C), the resistivity is 10 to 1.
0 [Ω・minor] degree, hole intensity approximately lXl0 (minor)
, movement [100 to 200 (crl/V-see)
However, if we compare the photoluminescence intensity of this comparative sample and the example of the present invention.
前記実施例は約１００倍以上の強度を示して両者の間に
は大幅な差がある。The strength of the above example is approximately 100 times higher, and there is a large difference between the two.
前記本発明の実施例について得られたＱａ ＡＳ結晶の
正孔濃度及び移動ｖ１を、同一装置によって成長させた
ｉを含有しないＧａＡｓ 結晶の正孔ざ′ｉ度約１Ｘ
ｌ０ （ｃｍ ｌｔ移動度約４ｏ ｏｃｃｒｌ／Ｖ
、 ｓｅａ ’）と比較したところ２本発明によれば
、 Ａｌ酸化物によるキャリア捕獲準位の形成が充分に
阻止され、かつＰ、１ｇ ｅ化物によってＡＩ３酸化物
に代る障害も発生しかい。The hole concentration and migration v1 of the Qa AS crystal obtained in the example of the present invention are compared with the hole concentration and migration v1 of the i-free GaAs crystal grown by the same apparatus, about 1X.
l0 (cm lt mobility approximately 4o occrl/V
, sea'), according to the present invention, the formation of carrier trapping levels by Al oxide is sufficiently prevented, and the P, 1ge oxide does not cause any disturbance in place of the Al3 oxide.
また前記実施例は本発明を明確にするためにＧａＡｌＡ
ｓ結晶をノンドープ状襲としているが。In addition, the above embodiments are based on GaAlA in order to clarify the present invention.
Although the s crystal is treated as non-doped.
先に述べた如くマグネシウム（Ｍｇ ）をｐ型不純物と
し、或いはｎ型不純物と共にＭｇヲ用いてそれぞれｐ型
或いはｎ型の酸素による特性省化力■１止された良質の
Ａｎ’を含む化合物半導体結晶を得ることができる。As mentioned above, by using magnesium (Mg) as a p-type impurity or by using Mg together with an n-type impurity, a compound semiconductor containing high-quality An' with reduced characteristics due to p-type or n-type oxygen is produced. Crystals can be obtained.
更に前記実施例はＧａＡｌＡｓ結晶を形成しているが１
本発明は例えばＩｎＡ／Ａｓ、ＩｎＡＩＰ等のＧａ又は
Ａｓ以外の組成を含むＡｄ化化合物等導体結晶成長に適
用して同様の効果を得ることができる。Furthermore, although the above embodiment forms a GaAlAs crystal, 1
The present invention can be applied to the growth of conductor crystals such as Ad compounds containing compositions other than Ga or As, such as InA/As and InAIP, to obtain similar effects.
（ｇ） 発明の効果
以上説明した如く本発明によれば、有機金屓熱分解気相
成長法によって、従来重大な問題であった酸素の影響が
阻止されて光半導体装置等に適する良質のアルミニウム
（Ａ７）を含む化合物半導体結晶を成長させることがで
きる。(g) Effects of the Invention As explained above, according to the present invention, the influence of oxygen, which has been a serious problem in the past, is prevented by the organic metal pyrolysis vapor phase growth method, and high quality aluminum suitable for optical semiconductor devices, etc. can be produced. A compound semiconductor crystal containing (A7) can be grown.
またキャリアガスを増加することが可能となり成長する
結晶の均質性が向上する等の効果を有しIt also has the effect of increasing the amount of carrier gas and improving the homogeneity of the growing crystal.
図はＧａＡＡＡｓ 結晶成長の実施例を示す模式図で
ある。
１：ｌにおいて、１は（ＣＨ３）３ＡＡを収容したバブ
ラー＋ ２ ＋ｉ （ＣＨ３） ３ Ｇ ａを収容し
たバブラー、３ｉ”ｔ： Ｈ２Ｍ、容容器、４はＡ Ｓ
ｆ（３収容容器、５はＨ２Ｓ収容容器、６は金属Ｍｇ
、７は石英反応管、８はヒーター、９はトラップ、ｉｏ
はＨ２精製装置。
１１は流量制御装置、１４は石英反応管、１６は基台＋
１７ ＩＩ Ｇａ’Ａｓ 基板を示す。The figure is a schematic diagram showing an example of GaAAAs crystal growth. In 1:l, 1 is a bubbler containing (CH3)3AA + 2 +i (CH3)3G a bubbler, 3i"t: H2M, container, 4 is A S
f (3 storage container, 5 is H2S storage container, 6 is metal Mg
, 7 is a quartz reaction tube, 8 is a heater, 9 is a trap, io
is an H2 purification device. 11 is a flow rate control device, 14 is a quartz reaction tube, 16 is a base +
17 II Ga'As substrate is shown.
Claims (1)
機化合物ガスを含む反応ガスの熱分解によって被処理基
板上に生成する方法にかいて、前記反応ガス中に、マグ
ネシウムを１ （ｐｐｍ）以下添加することを特徴とす
る化合物半導体層の気相成長方法。A method for producing a compound semiconductor layer containing aluminum on a substrate to be processed by thermal decomposition of a reaction gas containing an aluminum organic compound gas, characterized in that 1 (ppm) or less of magnesium is added to the reaction gas. A method for vapor phase growth of a compound semiconductor layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21277082A JPS59103329A (en) | 1982-12-06 | 1982-12-06 | Vapor growth of compound semiconductor layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21277082A JPS59103329A (en) | 1982-12-06 | 1982-12-06 | Vapor growth of compound semiconductor layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59103329A true JPS59103329A (en) | 1984-06-14 |
Family
ID=16628106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21277082A Pending JPS59103329A (en) | 1982-12-06 | 1982-12-06 | Vapor growth of compound semiconductor layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59103329A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866198A (en) * | 1992-06-17 | 1999-02-02 | Kabushiki Kaisha Toshiba | Method of fabricating a compound semiconductor having a plurality of layers using a flow compensation technique |
-
1982
- 1982-12-06 JP JP21277082A patent/JPS59103329A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| JAPAN J.APPL PHYS * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866198A (en) * | 1992-06-17 | 1999-02-02 | Kabushiki Kaisha Toshiba | Method of fabricating a compound semiconductor having a plurality of layers using a flow compensation technique |
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