JPS63206397A - Crucible for growth of gaas crystal - Google Patents
Crucible for growth of gaas crystalInfo
- Publication number
- JPS63206397A JPS63206397A JP3817987A JP3817987A JPS63206397A JP S63206397 A JPS63206397 A JP S63206397A JP 3817987 A JP3817987 A JP 3817987A JP 3817987 A JP3817987 A JP 3817987A JP S63206397 A JPS63206397 A JP S63206397A
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- gaas
- quartz
- free energy
- concentration
- 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 11
- 239000010453 quartz Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 abstract description 2
- 229910004369 ThO2 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
Landscapes
- Glass Melting And Manufacturing (AREA)
- 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ＧａＡｓ成長に用いる坩堝に関し、特にＧａや
ＧａＡｓメルトを収容するための石英製の坩堝の構造に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a crucible used for GaAs growth, and particularly to the structure of a quartz crucible for accommodating Ga or GaAs melt.
従来、この種の坩堝は、たとえば第４図の断面図に示す
ようなり２０，１２を用いたチョクラルスキー法用の坩
堝１１にＧａとＡｓを入れて約１２５０℃に昇温しＧａ
Ａｓメルト（＋ｎｅｌｔ）９を形成し、あるいは第５図
に示すようなボート成長法用の坩堝１４にＧａ５を入れ
て約１２５０℃に昇温し約６１０℃のＡｓ４の蒸気と反
応させてＧａＡｓメルトを形成し、このようなＧａＡｇ
メルトを１２３８℃以下に冷却してＧａＡｓ単結晶やＧ
ａＡｓ多結晶を成長する目的に使用されている。Conventionally, this type of crucible has been used, for example, as shown in the cross-sectional view of FIG.
Form an As melt (+nelt) 9, or place Ga5 in a boat growth crucible 14 as shown in FIG. and such GaAg
The melt is cooled to below 1238°C to form GaAs single crystals and G
It is used for the purpose of growing aAs polycrystals.
従来の坩堝の材料としては、１５００℃程度の高温でも
変形せず、しかも不純物の少ない石英やパイロリティッ
ク窒化ボロンを用いてきた。しかし、石英は加工が容易
でしかも安価な特長を有するが、約９６７〜９７６℃以
下の温度ではＧａと石英との反応により石英中のＳｉが
Ｇａ中に不純物として溶出してしまう欠点があり、一方
、パイロリティック窒化ボロンはＧａとの反応が無いも
のの非常に高価で、しかも加工し難いという問題があっ
た。Conventional materials for crucibles include quartz and pyrolytic boron nitride, which do not deform even at high temperatures of about 1500° C. and contain few impurities. However, although quartz has the advantage of being easy to process and being inexpensive, it has the disadvantage that at temperatures below about 967-976°C, Si in the quartz is eluted into the Ga as an impurity due to the reaction between Ga and quartz. On the other hand, although pyrolytic boron nitride does not react with Ga, it is very expensive and difficult to process.
そこで、Ｇａと石英との反応を防止すべく石英表面に液
体酸化物であるＢ２Ｏ３を塗ってＧａが石英と直接に接
触しない方法も試みられたが、Ｂ２Ｏ３は液体でしかも
ＧａＡｓメルトより軽いためにＢ２０．がＧａＡｓメル
ト上に浮き上がってしまい目的の効果を得ることはでき
ないでいた。Therefore, in order to prevent the reaction between Ga and quartz, an attempt was made to coat the quartz surface with B2O3, a liquid oxide, so that Ga would not come into direct contact with the quartz, but since B2O3 is a liquid and lighter than GaAs melt, B20. floated on top of the GaAs melt, making it impossible to obtain the desired effect.
本発明によれば、ＧａＡｓ結晶成長用に少なくともＧａ
を入れて使用する石英の坩堝において、室温から１５０
０℃の温度範囲で固体で且つ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酸化物
膜を石英坩堝のすくなくとも内表面に被着してなる新規
な坩゛堝を得ることができる。According to the present invention, at least Ga
In a quartz crucible used with
A novel crucible can be obtained in which an oxide film that is solid in the temperature range of 0° C. and has a free energy lower than that of Ga2O3 is deposited on at least the inner surface of the quartz crucible.
第３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ている。FIG. 3 is a diagram for explaining the present invention in detail, with the horizontal axis representing temperature and the vertical axis representing free energy of oxide formation.
この図はＧａ２Ｏ３形成の自由エネルギーの温度曲線３
１が５ｉ０２形成の自由エネルギーの温度曲線３２より
９６７〜９７６℃以下で負に大きく（すなわち卑）なっ
ているが、２つの温度曲線３１と３２が交差する温度以
下でＧａと石英が接触すると
４ Ｇａ＋ ３５ｉｏ２−＋ ２ Ｇａ２０ｇ ＋ ３
Ｓｉなる反応が自然に生じてしまうことを示している
。一方、Ｃ，２０，やＨ，０２形成の自由エネルギーの
温度曲線３３．３４はＧａ２０ｇの温度曲線３１より図
の温度範囲でさらに卑であるので、ＧａがＣｒ２Ｏ３や
Ｈｒ０２と直接に接していてもＧａと石英のような反応
を生じることはない、すなわち、ＧａＡｓ結晶成長に必
要な室温から約１５００℃の温度範囲で固体であって、
しかもＧａ２０Ｂ形成の自由エネルギーより常に卑なる
自由エネルギーを有するような酸化物膜を石英坩堝の内
表面に被着しておくならば、酸化物膜とＧａとは全く反
応しないので、Ｇａと石英の反応を阻止することができ
る０本発明はこの原理を用いたものである。This figure shows the temperature curve 3 of the free energy of Ga2O3 formation.
1 is negatively larger (i.e., less noble) than the free energy temperature curve 32 of 5i02 formation below 967 to 976°C, but when Ga and quartz come into contact at a temperature below the intersection of the two temperature curves 31 and 32, 4 Ga+ 35io2-+ 2 Ga20g + 3
This shows that the Si reaction occurs naturally. On the other hand, the free energy temperature curves 33 and 34 for the formation of C,20, and H,02 are more noble than the temperature curve 31 for 20 g of Ga in the temperature range shown, so even if Ga is in direct contact with Cr2O3 or Hr02, It does not react like Ga and quartz, that is, it is solid in the temperature range from room temperature to about 1500°C, which is necessary for GaAs crystal growth,
Moreover, if an oxide film whose free energy is always baser than the free energy of Ga20B formation is deposited on the inner surface of the quartz crucible, the oxide film and Ga will not react at all. The present invention uses this principle to prevent the reaction.
第１図は本発明の一実施例の断面図である。 FIG. 1 is a sectional view of an embodiment of the present invention.
本実施例の石英坩堝１の内表面には、Ｃ，２０３をター
ゲットとした真空スパッタリング蒸着法で厚さ約０．５
μｍの、Ｃ，２０，膜２が被着されている。第２図はこ
の石英坩堝１を用いてＧａＡｇ多結晶を製作する状態を
示している。第２図（ａ）は、Ｇａを入れた石英坩堝１
を石英製反応管３の一方の側に置き、他方の側にＡｓ４
を置いて反応管を封止し、次にＧ＆の入った坩堝を１２
５０℃にＡｓを６１０℃に加熱して坩堝内でＧａＡｓメ
ルト９を形成した様子を示す、第２図（ｂ）は坩堝内で
（ｉａＡｓメルト９を１２３８℃以下に冷却して得たＧ
ａＡｓ多結晶６の断面図を示す、 ＧａＡｓ単結晶を得
るには、第２図（ａ）でＧａＡｓの種結晶をあらかじめ
設けておけばよい。The inner surface of the quartz crucible 1 of this example was coated with C,203 to a thickness of approximately 0.5 cm using a vacuum sputtering method as a target.
A C,20, membrane 2 of .mu.m is deposited. FIG. 2 shows the state in which GaAg polycrystals are produced using this quartz crucible 1. Figure 2 (a) shows quartz crucible 1 containing Ga.
was placed on one side of the quartz reaction tube 3, and As4 was placed on the other side.
to seal the reaction tube, and then place the crucible containing G &
Figure 2(b) shows the state in which GaAs melt 9 was formed in a crucible by heating As to 610°C at 50°C.
A cross-sectional view of an aAs polycrystal 6 is shown. To obtain a GaAs single crystal, a GaAs seed crystal may be provided in advance as shown in FIG. 2(a).
なお、石英反応管とＧａは直接に接していないので石英
反応管とＧａとの反応は無く、石英反応管からのＳ１汚
染はない。また、石英坩堝のすくなくと６内表面に被着
するＣｒ２Ｏ３は厚さがせいぜい１μｍ以下の１膜であ
るので石英坩堝の有する透明さを失うことはなく、結晶
成長の様子を観察するさまたげにならない、さらに、Ｃ
，２Ｑ、膜などの酸化物膜は坩堝の前処理としておこな
う１３５０〜１５００℃のベーキングに充分に耐えられ
るような固体状のものであるので実用的に問題はない。Note that since the quartz reaction tube and Ga are not in direct contact, there is no reaction between the quartz reaction tube and Ga, and there is no S1 contamination from the quartz reaction tube. In addition, since the Cr2O3 that adheres to at least the inner surface of the quartz crucible is a single film with a thickness of at most 1 μm or less, the transparency of the quartz crucible is not lost, and it does not obstruct observation of crystal growth. , furthermore, C
, 2Q, and the like are in a solid state that can sufficiently withstand baking at 1350 to 1500 DEG C. as a pretreatment for the crucible, so there is no practical problem.
なお、本発明の実施例ではＣｒ２Ｏ３を例に説明をおこ
なってきたが、Ｃｒ２Ｏ３の他にＡ ｌ ２０ ｇ ｒ
Ｈｒ ０２ ｒＬａ２０３ ＋ ｌ＋ａ２０ｓ ｌ
Ｔａ２０５１ Ｔｈ０２ ＋ ＺｒＯ２でも同様の効果
を得ることは言うまでもない。In the embodiments of the present invention, Cr2O3 has been explained as an example, but in addition to Cr2O3, Al 20 gr
Hr 02 rLa203 + l+a20s l
Needless to say, similar effects can be obtained with Ta2051 Th02 + ZrO2.
以上説明したように本発明は、加工の容易な石英坩堝の
内表面にＧａ２Ｏ３形成の自由エネルギーより卑なる自
由エネルギーを有し且つ固体のＣｒ２Ｏ５＋ Ｆ４ｔ（
ｈなどの酸化膜を被着することにより、Ｇａと坩堝の反
応を容易に防止できる効果がある０本発明の坩堝を用い
てＧａＡｓメルトを形成しＧａＡｓ多結晶を製作した場
合のＧａＡｓ多結晶中の８１濃度は二次イオン質量分析
法の検出限界３Ｘ１０ ”ａｍ″″以下であった。従来
の坩堝を使用した場合のＳｉ濃度の１／１０以下に低減
できている。As explained above, the present invention provides solid Cr2O5+ F4t(
By depositing an oxide film such as h, it is effective to easily prevent the reaction between Ga and the crucible. The 81 concentration was below the detection limit of 3×10 ``am'''' for secondary ion mass spectrometry.The Si concentration could be reduced to 1/10 or less of the Si concentration when using a conventional crucible.
またＧａＡｓメルトと坩堝の反応がないので本発明の坩
堝は再利用できる特徴がある。Furthermore, since there is no reaction between the GaAs melt and the crucible, the crucible of the present invention has the characteristic of being reusable.
第１図は本発明の一実施例の断面図、第２図（ａ）、（
ｂ）は本発明の坩堝を用いてＧａＡｓ多結晶を製作する
状態を示す断面図、第３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ーの温度曲線図、第４図
、第５図は従来の坩堝とその使われ方を示した断面図で
ある。
１・・・石英坩堝、２・・・Ｃｒ２Ｏ３膜、３・・・石
英反応ＧａＡｓインゴット。
（ｂ）
＄ １ 菌
芽 ２ＴｆＪ
井 ３ 図
Ｔ（’Ｃ）
茅 ４ 固
一￥ｆ Ｓ 図FIG. 1 is a sectional view of an embodiment of the present invention, FIG. 2(a), (
b) is a cross-sectional view showing the production of GaAs polycrystal using the crucible of the present invention; FIG. 3 is a temperature curve diagram of the free energy of oxide formation for detailed explanation of the present invention; FIG. FIG. 5 is a sectional view showing a conventional crucible and how it is used. 1... Quartz crucible, 2... Cr2O3 film, 3... Quartz reaction GaAs ingot. (b) $ 1 Bacterial bud 2TfJ Well 3 Diagram T ('C) Chiga 4 Koichi ￥f S Diagram
Claims (1)
石英の坩堝において、室温から１５００℃の温度範囲で
固体で且つＧａ＿２Ｏ＿３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酸化物膜を前記石英
坩堝のすくなくとも内表面に被着してなることを特徴と
するＧａＡｓ結晶成長用坩堝。In a quartz crucible containing at least Ga for GaAs crystal growth, an oxide film that is solid in the temperature range from room temperature to 1500° C. and has a free energy lower than the free energy of forming Ga_2O_3 is at least added to the quartz crucible. A crucible for growing GaAs crystals, characterized in that the crucible is coated on the inner surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3817987A JPS63206397A (en) | 1987-02-20 | 1987-02-20 | Crucible for growth of gaas crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3817987A JPS63206397A (en) | 1987-02-20 | 1987-02-20 | Crucible for growth of gaas crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63206397A true JPS63206397A (en) | 1988-08-25 |
Family
ID=12518159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3817987A Pending JPS63206397A (en) | 1987-02-20 | 1987-02-20 | Crucible for growth of gaas crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63206397A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040732A1 (en) * | 2000-11-15 | 2002-05-23 | G.T. Equipment Technologies Inc. | A protective layer for quartz crucibles used for silicon crystallization |
| EP1495155A1 (en) * | 2002-03-21 | 2005-01-12 | Lam Research Corporation | Low contamination components for semiconductor processing apparatus and methods for making components |
-
1987
- 1987-02-20 JP JP3817987A patent/JPS63206397A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040732A1 (en) * | 2000-11-15 | 2002-05-23 | G.T. Equipment Technologies Inc. | A protective layer for quartz crucibles used for silicon crystallization |
| US6479108B2 (en) * | 2000-11-15 | 2002-11-12 | G.T. Equipment Technologies, Inc. | Protective layer for quartz crucibles used for silicon crystallization |
| EP1495155A1 (en) * | 2002-03-21 | 2005-01-12 | Lam Research Corporation | Low contamination components for semiconductor processing apparatus and methods for making components |
| US8318327B2 (en) | 2002-03-21 | 2012-11-27 | Lam Research Corporation | Low contamination components for semiconductor processing apparatus and methods for making components |
| US8935990B2 (en) | 2002-03-21 | 2015-01-20 | Lam Research Corporation | Low contamination components for semiconductor processing apparatus and methods for making components |
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