JPH035051B2 - - Google Patents
Info
- Publication number
- JPH035051B2 JPH035051B2 JP7497685A JP7497685A JPH035051B2 JP H035051 B2 JPH035051 B2 JP H035051B2 JP 7497685 A JP7497685 A JP 7497685A JP 7497685 A JP7497685 A JP 7497685A JP H035051 B2 JPH035051 B2 JP H035051B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- growth
- gaas substrate
- chamber
- gaas
- 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
Links
- 239000000758 substrate Substances 0.000 claims abstract description 79
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 51
- 239000004065 semiconductor Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- 229910052733 gallium Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007872 degassing Methods 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910000673 Indium arsenide Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000005219 brazing Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 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
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- 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
- H01L21/02656—Special treatments
- H01L21/02658—Pretreatments
- H01L21/02661—In-situ cleaning
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
- Semiconductor Lasers (AREA)
Abstract
Description
【発明の詳細な説明】
＜技術分野＞
本発明は、700nｍ未満に発光波長を有するＰ
（リン）化合物半導体をGaAs基板上に成長させ
て発光半導体素子を高精細度に製作する上で極め
て有効な分子線エピタキシヤル成長方法を用いた
半導体素子の製造方法に関するものである。Detailed Description of the Invention <Technical Field> The present invention provides P
The present invention relates to a method of manufacturing a semiconductor device using a molecular beam epitaxial growth method, which is extremely effective in growing a (phosphorus) compound semiconductor on a GaAs substrate and manufacturing a light emitting semiconductor device with high definition.
＜従来技術とその問題点＞
近年の情報化社会の進展には著しいものがあ
り、その中にあつて半導体レーザや発光ダイオー
ド等の発光デバイスを基礎とした光通信、光デイ
スク等の光情報処理技術は目ざましい発展を遂げ
ている。このような情況下において可視域に発光
波長を有する発光デバイスへのニーズが急速に高
まつており、特に可視半導体レーザへの期待は大
きい。現在、780nｍに発振波長を有するGaAlAs
系半導体レーザがコンパクトデイスクおよびビデ
オデイスク用光源として実用化されているが、よ
り多くの情報量を扱うためには集光後のスポツト
径をより小さくする必要があり、そのためにより
短波長に発振波長を有する半導体レーザが必要と
なつている。<Prior art and its problems> There has been remarkable progress in the information society in recent years, and among these are optical communications based on light-emitting devices such as semiconductor lasers and light-emitting diodes, and optical information processing such as optical disks. Technology is making remarkable progress. Under these circumstances, the need for light-emitting devices having emission wavelengths in the visible range is rapidly increasing, and expectations are particularly high for visible semiconductor lasers. Currently, GaAlAs has an oscillation wavelength of 780 nm.
Semiconductor lasers have been put into practical use as light sources for compact discs and video discs, but in order to handle a larger amount of information, it is necessary to make the spot diameter after condensing the light smaller. There is a growing need for semiconductor lasers with
このような短波長域に相当するエネルギーギヤ
ツプを有する半導体材料としてGaAs基板に格子
整合する（AlxGa1-X）yIn11-YＰが注目されてい
る。 As a semiconductor material having an energy gap corresponding to such a short wavelength region, (Al x Ga 1-X ) y In 11-Y P, which is lattice-matched to a GaAs substrate, is attracting attention.
この材料は従来の液相エピタキシヤル成長法
（LPE法）では成長が困難であるため、最近、分
子線エピタキシヤル成長法（MBE法）あるいは
有機金属を用いた気相成長法（MO−CVD法）
を導入した成長法の研究開発が活発になつてい
る。特に、MBE法は急峻なヘテロ接合界面を得
ることができるため、通常のダブルヘテロ接合半
導体レーザばかりでなく量子井戸半導体レーザ
（Quantum Well Laser：略してQWレーザ）へ
の発展も考えられる非常に有望な成長法である。 Since this material is difficult to grow using the conventional liquid phase epitaxial growth method (LPE method), it has recently been developed using molecular beam epitaxial growth method (MBE method) or metal-organic vapor phase epitaxy method (MO-CVD method). )
Research and development of growth methods that introduce In particular, since the MBE method can obtain a steep heterojunction interface, it is very promising and can be used not only for ordinary double heterojunction semiconductor lasers but also for quantum well semiconductor lasers (QW lasers). This is a great way to grow.
しかしながら、従来の分子線エピタキシヤル装
置（MBE装置）でGaAs基板上にＰ（リン）化合
物半導体を成長させる場合、予め大気中で基板の
保護用に形成したGaAsの自然酸化膜を除去する
ために、成長室中でAs分子線を照射しながら基
板を加熱する方法が採られていた（H.Ashahi、
Y.Kawamura，and H.Nagai、J.Appl、Phys.
vol.53（1982）、p4928）。この方法はGaAs基板上
にAlGaAsのようなAs化合物半導体を成長させる
場合に一般的に行なわれている方法である。 However, when growing P (phosphorus) compound semiconductors on GaAs substrates using conventional molecular beam epitaxial equipment (MBE equipment), it is necessary to remove the natural oxide film of GaAs that has been formed in advance to protect the substrate in the atmosphere. , a method was adopted in which the substrate was heated while irradiating As molecular beams in the growth chamber (H.Ashahi,
Y. Kawamura, and H. Nagai, J. Appl, Phys.
vol.53 (1982), p4928). This method is commonly used when growing As compound semiconductors such as AlGaAs on GaAs substrates.
しかしながら、この方法でＰ化合物半導体を成
長させる場合に、本来成長に不必要なAsを成長
室に持ち込むことを余儀なくされ、好ましくな
い。もしAsがＰ化合物中に１％程度でも取り込
まれると大きな格子定数変化を生じて良質の半導
体結晶を得ることはできないが、上記GaAs酸化
膜除去工程中10-4〜10-5torrと極めて高い圧力を
もつAs分子線強度を短時間に下げることは不可
能であり、工程に長時間を要するだけでなく一度
Asを用いた成長室中でＰ系化合物半導体を成長
するため本質的にAsによる汚染を避けることが
できない。一方、Ｐ（リン）分子線を照射しなが
らGaAs基板を加熱してGaAs基板上の酸化膜を
除去する方法も考えられるが、Asに比べてＰの
蒸気圧は極めて高いため、10-5torr以下のＰ圧で
はGaAs酸化膜の通常の蒸気温度である約580℃
ではほとんど効果がなく、また強いＰ分子線を照
射した場合でもAsの蒸発を生じて基板表面が
GaAsPに交換されることが考えられ好ましくな
い。 However, when growing a P compound semiconductor using this method, it is unavoidable to introduce As, which is essentially unnecessary for growth, into the growth chamber, which is not preferable. If even 1% of As is incorporated into the P compound, a large change in lattice constant will occur, making it impossible to obtain a high-quality semiconductor crystal.However, during the GaAs oxide film removal process mentioned above, the concentration is extremely high at 10 -4 to 10 -5 torr. It is impossible to reduce the As molecular beam intensity under pressure in a short time, and not only does the process take a long time, but also
Since P-based compound semiconductors are grown in a growth chamber using As, contamination by As is essentially unavoidable. On the other hand, it is possible to remove the oxide film on the GaAs substrate by heating the GaAs substrate while irradiating it with a P (phosphorous) molecular beam, but since the vapor pressure of P is extremely high compared to As, the vapor pressure is 10 -5 torr. At P pressure below, the normal vapor temperature of GaAs oxide film is about 580℃.
This has almost no effect, and even if a strong P molecular beam is irradiated, As will evaporate and the substrate surface will be damaged.
This is not desirable as it may be replaced with GaAsP.
第２図は従来の分子線エピタキシヤル成長装置
を示すブロツク構成図である。結晶成長用基板を
試料導入室１へ挿入し、真空にした後基板加熱室
２へ基板を搬送する。この基板加熱室２で基板を
適当な温度に加熱し、基板表面の吸着物等をガス
出しする。ガス出しの完了した基板を成長室４へ
搬送し、ここで基板上にエピタキシヤル層を成長
させる。各室１，２，４間はゲートバルブ５，
７，８により仕切られている。 FIG. 2 is a block diagram showing a conventional molecular beam epitaxial growth apparatus. A substrate for crystal growth is inserted into the sample introduction chamber 1, and after evacuating it, the substrate is transferred to the substrate heating chamber 2. The substrate is heated to an appropriate temperature in the substrate heating chamber 2, and adsorbed substances on the surface of the substrate are gassed out. After the gas release is completed, the substrate is transferred to the growth chamber 4, where an epitaxial layer is grown on the substrate. Gate valve 5 between each chamber 1, 2, and 4,
It is divided by 7 and 8.
MBE法は、成長用原料を蒸気とし、ノズルか
ら分子流として高真空状態の成長室４内へ流出さ
せることによつて基板上へエピタキシヤル層を成
長させる方法である。成長室４にはクヌードセ
ン・セルと称される分子流生成管が適当数配設さ
れており、このセルの一部に設けた小孔から蒸気
物質が分子流として流出される。この流出レート
を各セル間で制御することによつて２成分あるい
は多成分系の化合物薄膜を成長させることができ
る。正確にエピタキシヤル成長を行なうためには
成長室４内を超高真空に保持しかつ数ｎｍ／分程
度のゆつくりした成長速度となるように成分物質
の流出レートを制御し、各成分の基板への付着確
率を成分物質の特性な合わせて設定することが必
要となる。このようなMBE法を用いてGaAs系
成長用基板上にＰ化合物を成長させる場合、上述
した問題点があり、実際には良質の結晶層を具備
する化合物半導体発光素子を得ることは困難であ
つた。 The MBE method is a method of growing an epitaxial layer on a substrate by using a vapor as a growth material and flowing it as a molecular stream from a nozzle into a growth chamber 4 in a high vacuum state. A suitable number of molecular flow generating tubes called Knudsen cells are disposed in the growth chamber 4, and a vapor substance flows out as a molecular flow from a small hole provided in a part of the cell. By controlling this outflow rate between cells, a two-component or multi-component compound thin film can be grown. In order to accurately perform epitaxial growth, the inside of the growth chamber 4 is maintained at an ultra-high vacuum, and the outflow rate of the component substances is controlled to a slow growth rate of several nanometers per minute. It is necessary to set the probability of adhesion to the material taking into account the characteristics of the component substances. When growing a P compound on a GaAs-based growth substrate using such an MBE method, there are the above-mentioned problems, and it is actually difficult to obtain a compound semiconductor light-emitting device with a high-quality crystal layer. Ta.
＜発明の目的＞
本発明は上述の問題に鑑み、GaAs基板の上に
Asの汚染なく良質のＰ化合物半導体を分子線エ
ピタキシヤル成長させることにより700nｍ未満
に発光波長を有する半導体発光素子を作製するこ
とのできる製造技術を提供することを目的として
いる。<Object of the invention> In view of the above-mentioned problems, the present invention provides a
The object of the present invention is to provide a manufacturing technique that can produce a semiconductor light-emitting device having an emission wavelength of less than 700 nm by molecular beam epitaxial growth of a high-quality P compound semiconductor without As contamination.
＜実施例＞
第１図は本発明の一実施例の説明に供する分子
線エピタキシヤル装置の要部構成図である。この
装置は従来の分子線エピタキシヤル装置の成長室
４と基板加熱室２の間に新たな前処理室３を設け
た構成となつており各室２，３，４間は搬送系に
より超高真空中で自在にGaAs基板を搬送するこ
とができるように構成されている。また、搬送時
以外は各室間はゲートバルブ５，６，７により隔
離されている。前処理室３には基板加熱用ホルダ
ーとAsセルが設けられている。<Example> FIG. 1 is a diagram showing the main part of a molecular beam epitaxial apparatus for explaining an example of the present invention. This equipment has a new pre-processing chamber 3 between the growth chamber 4 and substrate heating chamber 2 of the conventional molecular beam epitaxial equipment, and the ultra-high temperature between each chamber 2, 3, and 4 is It is constructed so that GaAs substrates can be freely transported in vacuum. Further, each chamber is isolated by gate valves 5, 6, and 7 except during transportation. The pretreatment chamber 3 is provided with a substrate heating holder and an As cell.
Ｐ化合物半導体層を成長形成するための結晶成
長基板として、硫酸系エツチヤントでエツチング
後、純水中で表面に自然酸化膜を形成したGaAs
基板を用い、該GaAs基板をIn（インジウム）の
ロウ材でMo（モリブデン）ブロツクに貼り付け、
バルブ８を開いて試料導入室１へ挿入する。バル
ブ８を閉じて試料導入室１を10-8〜10-9torrに真
空引きした後、バルブ５を開いてGaAs基板を基
板加熱室２へ搬送しバルブ５を閉じる。次に基板
加熱室２で徐々にGaAs基板を400℃まで加熱す
る。加熱初期にはGaAs基板、Inロウ材及びMo
ブロツクからのガス放出により真空度が落ちるが
30〜60分の加熱により約10-10torrの真空度が得
られる。この超高真空下でGaAs基板に吸着して
いた不純物やガス分子等を除去される。このよう
にして初期のガス出しを終了したGaAs基板を基
板加熱室２からゲートバルブ６を介して前処理室
３に移し、約10-6〜10-5torrのAs4分子線をAsセ
ルより照射しながら徐々に約600℃まで加熱し、
約10分経過した後As4分子線の照射を持続しなが
らGaAs基板温度200℃以下まで下げる。この段
階でGaAs基板表面に形成されていた酸化膜は完
全に除去され清浄なGaAs基板表面が得られる。
前処理室３には液体窒素シユラウドを取り付ける
ことにより比較的蒸気圧の高いAsを効率良く排
気することができる。この段階で、AsがGaAs基
板上に堆積することがあつても、後のエピタキシ
ヤル成長開始前の基板加熱時に完全に蒸発するた
め問題はなく、逆に前処理室３から成長室４へ
GaAs基板を搬送する際に考えられる残留ガスの
基板表面への付着に対する保護膜となるため、む
しろ基板温度を下げてもAs分子線を照射して積
極的にAsをGaAs基板に堆積させる方が良い。前
処理室３からゲートバルブ７を介して成長室４に
搬送されたGaAs基板にＰ分子線を照射しながら
成長可能な温度（例えば500℃）まで加熱して必
要な族分子線即ち本実施例ではIn、Al及びGa
を照射しGaAs基板上に（AlXGa1-X）YIn1-YＰ層の
エピタキシヤル成長を開始する。成長は比較的低
温から開始しGaAs基板表面からのAs脱離等に起
因する劣化をできるだけ防止し、成長が始まつて
から最適の基板温度（例えば600℃）まで徐々に
増加させると良質の結晶が得られる。 As a crystal growth substrate for growing a P compound semiconductor layer, GaAs was etched with a sulfuric acid-based etchant and a natural oxide film was formed on the surface in pure water.
Using a substrate, the GaAs substrate is attached to a Mo (molybdenum) block using In (indium) brazing material,
Open the valve 8 and insert the sample into the sample introduction chamber 1. After closing the valve 8 and evacuating the sample introduction chamber 1 to 10 -8 to 10 -9 torr, the valve 5 is opened to transfer the GaAs substrate to the substrate heating chamber 2, and the valve 5 is closed. Next, the GaAs substrate is gradually heated to 400° C. in the substrate heating chamber 2. At the initial stage of heating, the GaAs substrate, In brazing material and Mo
The degree of vacuum decreases due to gas release from the block.
A vacuum level of approximately 10 -10 torr is obtained by heating for 30 to 60 minutes. Impurities and gas molecules adsorbed on the GaAs substrate are removed under this ultra-high vacuum. The GaAs substrate, which has undergone initial gas release in this way, is transferred from the substrate heating chamber 2 to the pretreatment chamber 3 via the gate valve 6, and an As 4 molecule beam of about 10 -6 to 10 -5 torr is applied from the As cell. Gradually heat to approximately 600℃ while irradiating.
After approximately 10 minutes, the temperature of the GaAs substrate is lowered to below 200°C while continuing irradiation with the As 4 molecular beam. At this stage, the oxide film formed on the GaAs substrate surface is completely removed, resulting in a clean GaAs substrate surface.
By installing a liquid nitrogen shroud in the pretreatment chamber 3, As having a relatively high vapor pressure can be efficiently exhausted. Even if As may be deposited on the GaAs substrate at this stage, there is no problem because it will completely evaporate when the substrate is heated before the start of epitaxial growth.
It is better to actively deposit As on the GaAs substrate by irradiating it with an As molecular beam even if the substrate temperature is lowered, since this will act as a protective film against the adhesion of residual gas to the substrate surface when the GaAs substrate is transported. good. The GaAs substrate transferred from the pretreatment chamber 3 to the growth chamber 4 via the gate valve 7 is irradiated with a P molecular beam and heated to a temperature that allows growth (for example, 500° C.) to generate the necessary group molecular beam, that is, the present example. In, Al and Ga
irradiation to start epitaxial growth of a (Al x Ga 1-x ) Y In 1-Y P layer on the GaAs substrate. Growth starts at a relatively low temperature to prevent deterioration caused by As desorption from the GaAs substrate surface as much as possible, and then gradually increases the substrate temperature to the optimal substrate temperature (e.g. 600°C) after growth begins, resulting in good quality crystals. is obtained.
以上によりGaAs基板上にGaAlInPのエピタキ
シヤル成長層が得られる。GaAlInP層に光電変
換用ｐ−ｎ接合を形成し電極を設けることにより
短波長の発光を出力する半導体発光素子が作製さ
れる。また（AlXGa1-X）YIn1-YＰ層の混晶比ｘ、
ｙを適当に設定してレーザ発振用活性層とこれに
ヘテロ接合界面を介して接合するクラツド層とを
有する多層結晶構造のダブルヘテロ接合半導体レ
ーザ素子とすることもできる。 Through the above steps, an epitaxially grown layer of GaAlInP is obtained on the GaAs substrate. By forming a p-n junction for photoelectric conversion in the GaAlInP layer and providing electrodes, a semiconductor light emitting device that outputs short wavelength light is manufactured. Also, (Al x Ga 1-X ) Y In 1-Y P layer mixed crystal ratio x,
By appropriately setting y, a double heterojunction semiconductor laser device having a multilayer crystal structure having a laser oscillation active layer and a cladding layer bonded to the active layer via a heterojunction interface can be obtained.
第３図は本発明の他の実施例の説明に供する分
子線エピタキシヤル装置の構成図である。この構
成では試料導入室１と試料取出室１２をゲートバ
ルブ２１，２５を介して両端に連結した試料搬送
室１１に基板加熱室２、前処理室３、成長室４が
並列にそれぞれゲートバルブ２２，２３，２４を
介して取り付けられている。従つてそれぞれの真
空室２，３，４間のGaAs基板搬送は試料搬送室
１１を通して行うことになる。また、この構成で
は成長後の基板は試料取出室１２より大気中へ取
り出せるため、基板の輸送が一方向となり連続的
に多数の基板に成長を行う場合に適している。 FIG. 3 is a block diagram of a molecular beam epitaxial apparatus for explaining another embodiment of the present invention. In this configuration, a substrate heating chamber 2, a pretreatment chamber 3, and a growth chamber 4 are connected in parallel to a sample transfer chamber 11, in which a sample introduction chamber 1 and a sample extraction chamber 12 are connected at both ends via gate valves 21 and 25, respectively. , 23, 24. Therefore, the GaAs substrate is transferred between the respective vacuum chambers 2, 3, and 4 through the sample transfer chamber 11. In addition, in this configuration, the substrate after growth can be taken out into the atmosphere from the sample extraction chamber 12, so the substrate transport is unidirectional and is suitable for the case where a large number of substrates are continuously grown.
上記同様に酸化膜の形成されたGaAs基板をIn
ロウ材でMoブロツクに貼り付け、ゲートバルブ
２６を開いて試料導入室１へ挿入し、真空引きし
た後ゲートバルブ２１，２２を開いて基板加熱室
２へ搬送する。基板加熱室２で加熱ガス出しした
GaAs基板を試料搬送室１１へ取り出し、ゲート
バルブ２３を開いて隣の前処理室３へ移送する。
前処理室３でAsセルよりAs4分子線を照射しなが
らGaAs基板を600℃迄加熱し10分経過後200℃迄
降温する。この前処理によつてGaAs基板表面よ
り酸化膜を完全に除去する。酸化膜の除去された
GaAs基板は再度試料搬送室１１へ取り出され、
ゲートバルブ２４より成長室４内へ挿入される。
この成長室４内でセルより分子流がGaAs基板上
に照射され、GaAlInPのエピタキシヤル層が成
長形成される。 In the same way as above, a GaAs substrate with an oxide film formed is
It is pasted on a Mo block with brazing material, the gate valve 26 is opened, the sample is inserted into the sample introduction chamber 1, and after evacuation, the gate valves 21 and 22 are opened and the sample is transferred to the substrate heating chamber 2. Heating gas was released in substrate heating chamber 2.
The GaAs substrate is taken out to the sample transfer chamber 11, the gate valve 23 is opened, and the GaAs substrate is transferred to the adjacent pretreatment chamber 3.
In the pretreatment chamber 3, the GaAs substrate is heated to 600°C while being irradiated with an As 4 molecular beam from an As cell, and after 10 minutes, the temperature is lowered to 200°C. This pretreatment completely removes the oxide film from the surface of the GaAs substrate. oxide film removed
The GaAs substrate is taken out again to the sample transfer chamber 11,
It is inserted into the growth chamber 4 through the gate valve 24.
In this growth chamber 4, a molecular stream is irradiated from the cell onto the GaAs substrate, and an epitaxial layer of GaAlInP is grown.
以上の実施例では前処理室３にAsセルのみを
装備した成長装置を用いていたが、更にGaセル
を取り付けてGaAsの成長を可能とし、酸化膜を
除去した後にGa分子線を照射してGaAsバツフア
層を成長してから成長室へ搬送し上記と同様の工
程で成長を行うようにすることもできる。この方
法を用いればバルク基板より更に結晶性の良いエ
ピタキシヤル層を成長させることができるという
利点がある。 In the above example, a growth apparatus equipped with only an As cell in the pretreatment chamber 3 was used, but a Ga cell was also attached to enable the growth of GaAs, and after the oxide film was removed, Ga molecular beams were irradiated. It is also possible to grow the GaAs buffer layer, then transport it to the growth chamber and grow it in the same steps as above. This method has the advantage that it is possible to grow an epitaxial layer with better crystallinity than that of a bulk substrate.
また、更に別の方法として前処理室３にInセル
を具設し、CaAs基板を自然酸化膜を除去した後
In分子線を照射して薄いInAs層を形成し、これ
を保護膜としてGaAs基板を成長室４へ搬送す
る。成長室４では上記と同様にＰ分子線を照射し
て基板温度を上げていくと450〜500℃程度で
InAs層が蒸発し清浄なGaAs基板表面が得られ
る。この上に例えばInとGaの分子線を同時に照
射してInGaPの成長を開始させることができる。
InAs保護膜の利点としては、、InAsとGaAsは大
きな格子不整合があるため50〜100Åの薄層の場
合には２次元成長をせず３次元的な島を伴つて表
面が凹凸形状をなして成長する。従つて、
RHEEDにより成長前に基板表面の観測を行いな
がら基板を加熱すると、InAsが残つている間は
スポツト状のRHEEDパターンがみられるが、
InAsが完全除去されるとGaAs表面の平坦性を反
映してストリーク状のRHEEDパターンとなるた
め成長開始の時期を決めるのに極めて都合が良
い。 In addition, as yet another method, an In cell is installed in the pretreatment chamber 3, and after removing the natural oxide film from the CaAs substrate,
A thin InAs layer is formed by irradiation with an In molecular beam, and the GaAs substrate is transported to the growth chamber 4 using this as a protective film. In growth chamber 4, the substrate temperature was raised to about 450-500℃ by irradiating the P molecular beam in the same manner as above.
The InAs layer evaporates and a clean GaAs substrate surface is obtained. For example, the growth of InGaP can be started by simultaneously irradiating In and Ga molecular beams onto this.
The advantage of the InAs protective film is that since InAs and GaAs have a large lattice mismatch, a thin layer of 50 to 100 Å will not grow two-dimensionally and will have an uneven surface with three-dimensional islands. grow up. Therefore,
When the substrate is heated while observing the substrate surface before growth using RHEED, a spot-like RHEED pattern can be seen while InAs remains.
When InAs is completely removed, a streak-like RHEED pattern reflects the flatness of the GaAs surface, which is extremely convenient for determining the timing of growth initiation.
＜発明の効果＞
以上詳説したように本発明を用いれば成長前に
GaAs基板表面を劣化させることなくその上に
InGaPあるいはInGaAlPのような700nｍ以下に
発光波長を有する半導体を分子線エピタキシヤル
成長することが可能となり、He−Neガスレーザ
より短波長の発振が可能なInGaAlP系半導体発
光素子あるいは半導体レーザの実用化への道が開
かれる。<Effects of the invention> As explained in detail above, if the present invention is used, the
onto the GaAs substrate surface without deteriorating it.
It has become possible to grow semiconductors with emission wavelengths below 700 nm, such as InGaP or InGaAlP, by molecular beam epitaxial growth, leading to the practical use of InGaAlP-based semiconductor light-emitting devices or semiconductor lasers that can oscillate at shorter wavelengths than He-Ne gas lasers. The way will be opened.
また、本発明の製造方法はＰ系半導体の成長室
にAsを持ち込まない装置構成をとつているため、
長期の製造を行なつてもＰとAsの相互汚染を起
こすことがなく、製造装置として、長期間安定し
た再現性を保持することが可能である。 Furthermore, since the manufacturing method of the present invention has an equipment configuration that does not introduce As into the P-based semiconductor growth chamber,
Even during long-term production, there is no mutual contamination between P and As, and the production equipment can maintain stable reproducibility over a long period of time.
第１図は本発明の一実施例の説明に供する分子
線エピタキシヤル装置の構成図である。第２図は
従来の分子線エピタキシヤル装置の構成図であ
る。第３図は本発明の他の実施例の説明に供する
分子線エピタキシヤル装置の構成図である。
１……試料導入室、２……基板加熱室、３……
前処理室、４……成長室、５，６，７，８……ゲ
ートバルブ、１１……試料搬送室、１２……試料
取出室。
FIG. 1 is a block diagram of a molecular beam epitaxial apparatus used to explain one embodiment of the present invention. FIG. 2 is a block diagram of a conventional molecular beam epitaxial apparatus. FIG. 3 is a block diagram of a molecular beam epitaxial apparatus for explaining another embodiment of the present invention. 1...Sample introduction chamber, 2...Substrate heating chamber, 3...
Pretreatment chamber, 4...Growth chamber, 5, 6, 7, 8...Gate valve, 11...Sample transport chamber, 12...Sample extraction chamber.
Claims (1)
ツフア層を分子線エピタキシヤル成長させる工程
と、 上記前処理室に連結された成長室で上記GaAs
バツフア層上にＰ化合物半導体層を分子線エピタ
キシヤル成長させる工程と、 を含んでなることを特徴とする半導体素子の製造
方法。[Claims] 1. A step of molecular beam epitaxial growth of a GaAs buffer layer on a GaAs-based growth substrate in a pretreatment chamber;
A method for manufacturing a semiconductor device, comprising the steps of: growing a P compound semiconductor layer on a buffer layer by molecular beam epitaxial growth.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7497685A JPS61232608A (en) | 1985-04-08 | 1985-04-08 | Manufacture of semiconductor element |
| US06/843,146 US4824518A (en) | 1985-03-29 | 1986-03-24 | Method for the production of semiconductor devices |
| FR868604353A FR2579824B1 (en) | 1985-03-29 | 1986-03-26 | METHOD AND APPARATUS FOR MANUFACTURING SEMICONDUCTOR DEVICES USING EPITAXIAL MOLECULAR BEAM TREATMENT |
| GB08607458A GB2174542B (en) | 1985-03-29 | 1986-03-26 | A method and apparatus for the production of semiconductor devices |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7497685A JPS61232608A (en) | 1985-04-08 | 1985-04-08 | Manufacture of semiconductor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61232608A JPS61232608A (en) | 1986-10-16 |
| JPH035051B2 true JPH035051B2 (en) | 1991-01-24 |
Family
ID=13562825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7497685A Granted JPS61232608A (en) | 1985-03-29 | 1985-04-08 | Manufacture of semiconductor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61232608A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61289621A (en) * | 1985-06-18 | 1986-12-19 | Kokusai Denshin Denwa Co Ltd <Kdd> | Molecular beam epitaxial growth |
| JPS6273705A (en) * | 1985-09-27 | 1987-04-04 | Anelva Corp | Method and apparatus for forming protective film of clean substrate in forming molecular beam epitaxially grown layer |
| JP5107076B2 (en) * | 2008-02-01 | 2012-12-26 | Ｊｘ日鉱日石金属株式会社 | Method for surface treatment of semiconductor substrate |
-
1985
- 1985-04-08 JP JP7497685A patent/JPS61232608A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61232608A (en) | 1986-10-16 |
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