JPS63230598A - Method for growing gaas single crystal - Google Patents
Method for growing gaas single crystalInfo
- Publication number
- JPS63230598A JPS63230598A JP6170287A JP6170287A JPS63230598A JP S63230598 A JPS63230598 A JP S63230598A JP 6170287 A JP6170287 A JP 6170287A JP 6170287 A JP6170287 A JP 6170287A JP S63230598 A JPS63230598 A JP S63230598A
- Authority
- JP
- Japan
- Prior art keywords
- gaas
- single crystal
- reaction tube
- boat
- quartz
- 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
- 239000013078 crystal Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 10
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 28
- 239000010453 quartz Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000011109 contamination Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 Sc2Og Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高純度Ｇ ａ Ａ ｓ結晶の成長方法、特にＳ
ｔの汚染のない直接合成法ＧａＡｓ単結晶の成長方法に
関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for growing high-purity GaAs crystals, especially S
This invention relates to a method for growing GaAs single crystals by direct synthesis without contamination.
、従来、直接合成法によるＧａＡｓ単結晶の成長方法は
゛、第３図（ａ）に示すように反応管４の一方の側にＡ
ｓ５を置き、他方の側にＧａ２とＧａＡｓ種結晶６を入
れた石英ボート３を置いたのち反応管４を封止し、次に
図（ｂ）に示すように反応管４のＡｓ５を約６１０℃に
、Ｇａ２を約１２５０℃に室温から昇温してＧａＡｓメ
ルト８を形成したのちに、図（Ｃ）のようにこのＧａＡ
ｓメルト８を１２３８℃まで徐冷用してＧａＡｓ単結晶
７を成長していた。In the conventional method of growing GaAs single crystals by direct synthesis method, as shown in FIG. 3(a), A
After placing the quartz boat 3 containing Ga2 and GaAs seed crystal 6 on the other side, the reaction tube 4 was sealed, and then the As5 in the reaction tube 4 was heated to about 610 nm as shown in Figure (b). After heating Ga2 from room temperature to about 1250°C to form a GaAs melt 8, the GaAs melt 8 was formed as shown in Figure (C).
The GaAs single crystal 7 was grown by slowly cooling the s-melt 8 to 1238°C.
この直接合成法は簡単な手順で単結晶を成長できる利点
があるが、上述した従来の直接合成法は石英ボートにＧ
ａを室温で入れたのち約１２５０℃まで昇温しなければ
ならないので
４Ｇａ＋３Ｓｉ０２−＋３Ｓｉ＋２Ｇａ２Ｏ３なる反応
を生じてしまい、その結果、石英ボートから溶出したＳ
ｔのＧａ中への混入を避けられない欠点を有していた。This direct synthesis method has the advantage of being able to grow single crystals in a simple procedure, but the conventional direct synthesis method described above
Since it is necessary to raise the temperature to approximately 1250℃ after adding a at room temperature, a reaction of 4Ga + 3Si02- + 3Si + 2Ga2O3 occurs, and as a result, the S eluted from the quartz boat
This had the disadvantage that it was impossible to avoid mixing of t into Ga.
従って、このようなＧａを使ってＧａＡｓ成長をおこな
ったＧａＡｓ単結晶には１０１６ｃｍ−３程度のＳｉが
残留してしまうというＳｉの汚染問題があった。Therefore, there is a problem of Si contamination in which about 1016 cm-3 of Si remains in GaAs single crystals grown using Ga.
本発明によれば、ＧａとＡｓとを直接に合成してなるＧ
ａ Ａ ｓ単結晶の成長方法において、室温から１５
００℃の温度範囲でＧａ２Ｏ３形成の自由エネルギーよ
りさらに卑なる自由エネルギーを有する固体様の酸化物
膜を内表面に被着した石英ボートを用いてＧａとＡｓの
直接合成をおこなわせてＧａＡｓメルトを形成する工程
と、このＧａＡｓメルトからＧａＡｓ単結晶を成長する
工程とを含むＧａＡｓ単結晶成長方法が得られる。According to the present invention, G formed by directly synthesizing Ga and As
In the method of growing a A s single crystal, from room temperature to 15
GaAs melt was produced by directly synthesizing Ga and As using a quartz boat whose inner surface was coated with a solid-like oxide film that had a free energy lower than that of Ga2O3 formation in the temperature range of 00°C. A method for growing a GaAs single crystal is obtained, which includes the steps of forming a GaAs single crystal and growing a GaAs single crystal from the GaAs melt.
第２図は本発明の詳細な説明するための図で横軸に温度
を、縦軸に酸化物形成の自由エネルギーを示したもので
ある。５ｉ０２形成の自由エネルギーの温度曲線２１は
、約９６７〜９７６℃以下の温度ではＧａ２Ｏｇ形成の
自由エネルギーの温度曲線２２より常に正に大きい（す
なわち貴）のでＧａと５ｉ０２の反応を自然に生じてし
まうが、Ｇａ２Ｏ３の温度曲線２２より常に負に大きい
（すなわち卑）ような、たとえばＣｒ２Ｏ３の温度曲線
２３をもつ酸化物膜が５ｉ０２とＧａとの間に存在する
ならば、ＧａとＣｒ２Ｏ３の反応は生じないのでＧａと
５ｉ０２の反応を防止できることになる。このようにＣ
ｒ２Ｏ３膜はＧａと５ｉ０２の反応を防ぐ役割を果す。FIG. 2 is a diagram for explaining the present invention in detail, in which the horizontal axis shows temperature and the vertical axis shows free energy of oxide formation. The temperature curve 21 of the free energy of 5i02 formation is always positively larger (i.e. nobler) than the temperature curve 22 of the free energy of Ga2Og formation at temperatures below about 967 to 976°C, so that the reaction between Ga and 5i02 naturally occurs. However, if an oxide film exists between 5i02 and Ga that has a temperature curve 23 of Cr2O3 that is always more negative (that is, less noble) than the temperature curve 22 of Ga2O3, the reaction between Ga and Cr2O3 will occur. Therefore, the reaction between Ga and 5i02 can be prevented. In this way C
The r2O3 film plays a role in preventing the reaction between Ga and 5i02.
本発明は上記の自由エネルギーの差を利用して石英ボー
トとＧａの反応を防止すると云う極めて簡単であるが新
規な考えに基づいてなされたものである。The present invention is based on the extremely simple but novel idea of preventing the reaction between quartz boats and Ga by utilizing the above-mentioned free energy difference.
第１図は本発明の第１の実施例を説明するための図で、
ＧａＡｓ結晶炉結晶面図を示している。FIG. 1 is a diagram for explaining the first embodiment of the present invention,
A crystal plane diagram of a GaAs crystal furnace is shown.
図（ａ）には電子銃蒸着法で厚さ０．５μｍのＣｒ２Ｏ
ｇ膜１を被着した石英ボート３にＧ ａＡｓ種結晶６と
Ｇ ａ ２を入れて石英反応管４の一方の側に置き、他
方の側にＡｓ５を置いて石英反応管４を封止した様子を
示す。図（ｂ）はＧａ２側を１２５０℃に、ＡｓＳ側を
６１０℃に加熱してＡｓ蒸気９をＧａ２に溶かし込んで
ＧａＡｓメルト８を形成した様子を示す、そして図（ｃ
）では、Ｇ ａ Ａ ｓメルト８をＡｓ５側がら１２３
８℃に冷却しながら種付けをおこないＧ ａ Ａ ｓ単
結晶７を成長した様子を示す。Ｇａ２は石英反応管４と
全く接していないので、反応管からのＳＬ汚染はない。Figure (a) shows Cr2O with a thickness of 0.5 μm by electron gun evaporation method.
GaAs seed crystal 6 and Ga 2 were placed in a quartz boat 3 coated with G film 1 and placed on one side of the quartz reaction tube 4, and As 5 was placed on the other side to seal the quartz reaction tube 4. Show the situation. Figure (b) shows how GaAs melt 8 is formed by heating the Ga2 side to 1250°C and the AsS side to 610°C to melt As vapor 9 into Ga2, and Figure (c)
), G a As melt 8 from As5 side 123
This figure shows how a Ga As single crystal 7 was grown by seeding while cooling to 8°C. Since Ga2 is not in contact with the quartz reaction tube 4 at all, there is no SL contamination from the reaction tube.
さらに、Ｃｒ２Ｏｇ膜は厚さ０．５μｍ程度′に薄いの
で、本発明の製法によってもボートを透して結晶成長の
様子を観察できる。Furthermore, since the Cr2Og film is as thin as about 0.5 μm, the crystal growth can be observed through the boat using the manufacturing method of the present invention.
このように本実施例によれば、石英ボートがＣｒ２Ｏ３
膜に覆われているのでＧａと５ｉ０２との反応が阻止さ
れ、成長させたＧａＡｓ単結晶がＳｔで汚染されない。In this way, according to this embodiment, the quartz boat is Cr2O3
Since it is covered with a film, the reaction between Ga and 5i02 is inhibited, and the grown GaAs single crystal is not contaminated with St.
次に本発明の第２の実施例を説明する。第１の実施例と
の違いは第２図の２４に示した自由エネルギーの温度曲
線を有するＡｌ２Ｏ，膜をＣｒ２Ｏ３膜の代りに用いた
点、及びこのＡｌ２Ｏ３膜をスパッタリング（ｓｐｕｔ
ｔｅｒｉｎｇ）蒸着法で０．３７１ｍの厚さに被着した
点で、第１の実施例と同様にＧａＡｓ単結晶を成長でき
る。この実施例の場合は大面積にわたって均一に蒸着で
きる利点がある。Next, a second embodiment of the present invention will be described. The difference from the first embodiment is that an Al2O film having the free energy temperature curve shown at 24 in FIG. 2 was used instead of the Cr2O3 film, and this Al2O3 film was sputtered.
A GaAs single crystal can be grown in the same manner as in the first embodiment, in that it is deposited to a thickness of 0.371 m by the evaporation method (tering). This embodiment has the advantage that it can be deposited uniformly over a large area.
以上の実施例において、Ｃｒ２Ｏ３膜やＡｌ２Ｏ、膜な
どは石英反応管やボートの前処理としておこなう１３５
０〜１５００℃の高温ベーキングに十分に耐えることが
でき、またＢ２Ｏ３と違って固体であるので成長中にＧ
ａ Ａ Ｓメルト上に浮遊してしまうことも無い。In the above examples, the Cr2O3 film, Al2O film, etc. are performed as a pretreatment for the quartz reaction tube or boat135
It can withstand high temperature baking from 0 to 1500℃, and unlike B2O3, it is solid, so G
aAS There is no possibility of it floating on the melt.
なお、本発明の実施例においては、ボート成長法による
結晶成長について説明したが、Ｌ Ｅ Ｃ（Ｌｉｑｕｉ
ｄ Ｅｎｃａｐｓｕｌａｔｅｄ Ｃｚｃｈｒａｌｓｋｉ
）法によってもおこない得る。またＣｒ２Ｏ３ 、Ａ１
２Ｏｇの他にＨｆＯ２、Ｓｃ２Ｏｇ 、Ｌａ２Ｏ３ 、
Ｔａ２Ｏ５ 。In addition, in the examples of the present invention, crystal growth by boat growth method was explained, but L E C (Liqui
d Encapsulated Czchralski
) It can also be done by law. Also Cr2O3, A1
In addition to 2Og, HfO2, Sc2Og, La2O3,
Ta2O5.
Ｔｈ０２ 、ＺｒＯ２でも本発明の効果を得ることがで
きる。The effects of the present invention can also be obtained with Th02 and ZrO2.
第１図（ａ）、（ｂ）、（ｃ）は本発明の実施例を説明
するための工程断面図、第２図は本発明の詳細な説明す
るための酸化物形成の自由エネルギ一温度依存性を示し
た図、第３図（ａ）。
（ｂ）、（ｃ）は従来の直接合成法による単結晶成長方
法を説明するための工程断面図である。
１−Ｃｒ２ ｏ３ｐｌＡ、２−Ｇ ａ、３・・・石英ボ
ート、４・・・石゛英反応管、５・・・Ａｓ、６・・・
ＧａＡｓ種結晶、７・・・ＧａＡｓ単結晶、８・・・Ｇ
ａＡｓメルト、９・・・Ａｓ蒸気。
１１ 面
育２回゛
温度（°Ｃ）
ｆｉ３ 目FIGS. 1(a), (b), and (c) are process cross-sectional views for explaining embodiments of the present invention, and FIG. 2 is a diagram showing the free energy and temperature of oxide formation for explaining the details of the present invention. A diagram showing the dependence, FIG. 3(a). (b) and (c) are process cross-sectional views for explaining a single crystal growth method using a conventional direct synthesis method. 1-Cr2 o3plA, 2-Ga, 3...Quartz boat, 4...Quartz reaction tube, 5...As, 6...
GaAs seed crystal, 7...GaAs single crystal, 8...G
aAs melt, 9... As vapor. 11 Surface education twice゛Temperature (°C) fi3
Claims (1)
自由エネルギーよりさらに卑なる自由エネルギーを有す
る固体様の酸化物膜を内表面に被着した石英ボートを用
いてＧａとＡｓの直接合成をおこなわせてＧａＡｓメル
トを形成する工程と、該ＧａＡｓメルトからＧａＡｓ単
結晶を成長する工程とを含むことを特徴とするＧａＡｓ
単結晶の成長方法。GaAs is produced by directly synthesizing Ga and As using a quartz boat coated with a solid-like oxide film on its inner surface, which has a free energy lower than that of Ga_2O_3 in the temperature range from room temperature to 1500°C. GaAs characterized by comprising the steps of forming a melt and growing a GaAs single crystal from the GaAs melt.
How to grow single crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6170287A JPS63230598A (en) | 1987-03-16 | 1987-03-16 | Method for growing gaas single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6170287A JPS63230598A (en) | 1987-03-16 | 1987-03-16 | Method for growing gaas single crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63230598A true JPS63230598A (en) | 1988-09-27 |
Family
ID=13178837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6170287A Pending JPS63230598A (en) | 1987-03-16 | 1987-03-16 | Method for growing gaas single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63230598A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03122097A (en) * | 1989-09-14 | 1991-05-24 | Akzo Nv | Preparation of single crystal ii-vi group or iii-v group compound and product made of it |
-
1987
- 1987-03-16 JP JP6170287A patent/JPS63230598A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03122097A (en) * | 1989-09-14 | 1991-05-24 | Akzo Nv | Preparation of single crystal ii-vi group or iii-v group compound and product made of it |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3655439A (en) | Method of producing thin layer components with at least one insulating intermediate layer | |
| US4365588A (en) | Fixture for VPE reactor | |
| JPS6021959B2 (en) | Method for manufacturing a layer with a surface composition of Hg↓1-xCdxTe | |
| JPS63230598A (en) | Method for growing gaas single crystal | |
| JPS6050759B2 (en) | ZnSe epitaxial growth method and growth apparatus | |
| JPS6210274A (en) | Method and device for vapor phase synthesis | |
| JPS63206397A (en) | Crucible for growth of gaas crystal | |
| US3740261A (en) | Modified czochralski grown spinel substrate by solid state diffusion | |
| JPS63206395A (en) | Method for growing gaas single crystal | |
| JPS6163591A (en) | Installation for production of single crystal of compound semiconductor | |
| JPS59107998A (en) | Crystal growth method | |
| JPS6246074B2 (en) | ||
| JPS61198789A (en) | Continuous manufacture of optical semiconductor element | |
| JPS62145736A (en) | Liquid phase epitaxial growth | |
| JPS623408Y2 (en) | ||
| JPS61184813A (en) | Manufacture of substrate for semiconductor device | |
| JPS6076119A (en) | Compound semiconductor crystal growing apparatus | |
| JPS63185897A (en) | Producing apparatus of iii-v group compound crystal | |
| JPS6439018A (en) | Intermetallic compound semiconductor thin film and manufacture thereof | |
| JPH04299822A (en) | Semiconductor wafer and manufacture thereof | |
| JPS62119939A (en) | Insulating substrate for semiconductor | |
| JPS5973500A (en) | Preparation of compound semiconductor | |
| JPS60218851A (en) | Manufacture of semiconductor device | |
| JPS57194519A (en) | Method of crystal growth | |
| JPS61174192A (en) | Method for growing crystal |