JPS623408Y2 - - Google Patents
Info
- Publication number
- JPS623408Y2 JPS623408Y2 JP1982084742U JP8474282U JPS623408Y2 JP S623408 Y2 JPS623408 Y2 JP S623408Y2 JP 1982084742 U JP1982084742 U JP 1982084742U JP 8474282 U JP8474282 U JP 8474282U JP S623408 Y2 JPS623408 Y2 JP S623408Y2
- Authority
- JP
- Japan
- Prior art keywords
- crucible
- container
- gallium arsenide
- quartz
- melt
- 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
- 239000013078 crystal Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 18
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 4
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 20
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 20
- 239000010453 quartz Substances 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910005540 GaP Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Description
【考案の詳細な説明】
本考案は融解温度で高い蒸気圧を示す元素を含
す化合物半導体の合成や単結晶の製造において、
所望材料の融液ないし所望材料を含す溶液を入れ
る結晶製造用るつぼに関するものである。[Detailed description of the invention] This invention is useful in the synthesis of compound semiconductors containing elements that exhibit high vapor pressure at melting temperatures and in the production of single crystals.
The present invention relates to a crucible for crystal production into which a melt of a desired material or a solution containing the desired material is placed.
ガリウムヒ素を代表とする−族化合物半導
体やシリコンはその特異な電気的特性を活かして
多種の半導体素子用基板材料として用いられてい
る。半導体材料を半導体素子用基板として用いる
ためには所定の不純物を導入し、または導入せ
ず、所望の比抵抗に制御する必要がある。このた
めには、所定不純物以外の不純物（以後残留不純
物と呼ぶ）の当該結晶中への混入を可能なかぎり
減らすことが重要である。半導体材料の製造にお
いては、所望材料の融液あるいは所望材料を含む
溶液を収納する容器からのこれらへの残留不純物
混入が第一に問題となる。このため従来より種々
の材質、構造の容器が考えられている。これら
は、例えば、石英、カーボン、アルミナ、窒化ホ
ウ素、窒化ケイ素あるいは石英ないしカーボン容
器内壁に炭化ケイ素、窒化ケイ素、三酸化ホウ素
を被覆したもの等がある。しかし工業的には経済
性、容器材質の純度の面から主に石英容器が用い
られている。現在工業的に多量生産されている。 BACKGROUND ART - Group compound semiconductors, typified by gallium arsenide, and silicon are used as substrate materials for various semiconductor devices, taking advantage of their unique electrical properties. In order to use a semiconductor material as a substrate for a semiconductor element, it is necessary to control the resistivity to a desired level by introducing or not introducing certain impurities. For this purpose, it is important to reduce as much as possible the incorporation of impurities other than predetermined impurities (hereinafter referred to as residual impurities) into the crystal. In the production of semiconductor materials, the primary problem is the contamination of a melt of a desired material or a solution containing a desired material with residual impurities from a container containing the material. For this reason, containers made of various materials and structures have been considered. These include, for example, quartz, carbon, alumina, boron nitride, silicon nitride, or those in which the inner wall of a quartz or carbon container is coated with silicon carbide, silicon nitride, or boron trioxide. However, industrially, quartz containers are mainly used from the viewpoint of economy and purity of the container material. Currently, it is industrially produced in large quantities.
ガリウムリン、インジウムリン、ガリウムヒ素
等の化合物半導体材料の合成や結晶製造には石英
容器が使用されているが、石英容器には石英と液
相半導体材料との反応により石英の構成元素であ
るシリコンと酸素が液相半導体材料中に溶け込む
結果、半導体材料中にはシリコンおよび酸素が残
留不純物として混入しており、これら残留不純物
が素子特性の劣化を生起したり、所望比抵抗結晶
の製造を困難にしているという欠点がある。また
ガリウムヒ素の合成や結晶製造においては、特に
シリコンの混入を防止する必要があるため、近年
高純度で化学的安定性に優れた熱分解法による窒
化ボロン（PBN）容器が用いられているが、非常
に高価である、ボロンが多量に混入する、という
欠点がある。一方、三酸化ホウ素（B2O3）は現在
化合物半導体の液体封止引き上げ法による単結晶
成長法において、高蒸気圧成分の蒸発を抑止する
カプセル剤として用いられている化学的に非常に
安定なガラス状物質であるが、軟化点が約450℃
と低いために半導体材料の合成や結晶製造用容器
としては用いることができないという欠点があ
る。 Quartz containers are used to synthesize and produce crystals of compound semiconductor materials such as gallium phosphide, indium phosphide, and gallium arsenide. As a result, silicon and oxygen are mixed into the semiconductor material as residual impurities, and these residual impurities cause deterioration of device characteristics and make it difficult to manufacture the desired resistivity crystal. It has the disadvantage of being. In addition, in the synthesis and crystal manufacturing of gallium arsenide, it is especially necessary to prevent the contamination of silicon, so in recent years boron nitride (PBN) containers made using the pyrolysis method, which are highly pure and have excellent chemical stability, have been used. , it has the disadvantages of being very expensive and containing a large amount of boron. On the other hand, boron trioxide (B 2 O 3 ) is currently used as an encapsulant to suppress the evaporation of high vapor pressure components in the single crystal growth method using the liquid confinement pulling method for compound semiconductors. It is a glassy substance with a softening point of approximately 450℃.
It has the disadvantage that it cannot be used as a container for synthesizing semiconductor materials or producing crystals because of its low temperature.
本考案は上記の事情に着目してなされたもの
で、その目的とするところは、半導体材料の合成
や結晶製造を行なうに際し、高純度の合成多結晶
および単結晶を安価に製造するためのるつぼを提
供することにある。 The present invention was developed in light of the above circumstances, and its purpose is to provide a crucible for manufacturing high-purity synthetic polycrystals and single crystals at low cost when synthesizing semiconductor materials and manufacturing crystals. Our goal is to provide the following.
従つて、本考案による液体封止法結晶製造用る
つぼは、石英あるいは窒化ボロン容器等を外周容
器とし、三酸化ホウ素を主成分とする物質により
形成された容器を内部容器とする二重構造を特徴
とするものである。 Therefore, the crucible for producing crystals using the liquid sealing method according to the present invention has a double structure in which the outer container is a quartz or boron nitride container, and the inner container is a container made of a substance whose main component is boron trioxide. This is a characteristic feature.
以下、本考案による液体封止法結晶製造用るつ
ぼの実施例を説明する。第１図及び第２図は直接
合成液体封止（Liquid Encapsulated
Czochralski：LEC）法によるガリウムヒ素の合
成および単結晶製造に適用した際の本考案による
容器の概略断面図であり、第１図は合成段階、第
２図は単結晶製造段階を示すものである。図中、
１は三酸化ホウ素（B2O3）から成る（内部）るつ
ぼ、２は石英るつぼ、３はカプセル剤（B2O3）、
４はガリウム容液、５はヒ素、６はカーボンサセ
プター、７はガリウムヒ素単結晶、８はガリウム
ヒ素融液である。このような容器によりガリウム
ヒ素を合成し、さらに単結晶を成長させるには、
容器１，２内を加熱し、ガリウム溶液４と共にヒ
素５及びカプセル剤３を溶融してガリウムヒ素融
液８を合成させる。ガリウムヒ素融液８を合成し
た後、第２図に示すように種結晶（図示せず）を
前記ガリウムヒ素融液に接触させてガリウムヒ素
単結晶７を形成せしめる。 Hereinafter, embodiments of the crucible for producing crystals using the liquid sealing method according to the present invention will be described. Figures 1 and 2 show direct synthetic liquid encapsulation.
These are schematic cross-sectional views of the container according to the present invention when applied to the synthesis and single crystal production of gallium arsenide by the Czochralski (LEC) method, with Fig. 1 showing the synthesis stage and Fig. 2 showing the single crystal production stage. . In the figure,
1 is an (internal) crucible made of boron trioxide (B 2 O 3 ), 2 is a quartz crucible, 3 is a capsule (B 2 O 3 ),
4 is a gallium liquid, 5 is arsenic, 6 is a carbon susceptor, 7 is a gallium arsenide single crystal, and 8 is a gallium arsenide melt. To synthesize gallium arsenide and grow a single crystal using such a container,
The insides of the containers 1 and 2 are heated to melt the arsenic 5 and the capsule 3 together with the gallium solution 4 to synthesize a gallium arsenide melt 8. After synthesizing the gallium arsenide melt 8, a seed crystal (not shown) is brought into contact with the gallium arsenide melt to form a gallium arsenide single crystal 7, as shown in FIG.
これらの過程において、ガリウムヒ素結晶中で
浅いドナーレベルを作る不純物であるシリコン
（特にMESFETをイオンインプランテーシヨン技
術で作成するための半絶縁性結晶としては極力混
入を避けなければならない不純物である）は、ガ
リウムヒ素融液８の合成初期（室温）から合成完
了時（約1250℃）までガリウム溶液
（Ga1-XAsX；Ｘ＝０〜0.5）が直接石英るつぼ２
に接触することがないので、ガリウムヒ素単結晶
中に混入することはなくなる。即ち、従来のよう
に石英るつぼを用いる方法ではガリウム溶液と石
英の反応性が高いため、シリコンの混入を防止す
ることは困難であつたが、本考案による容器によ
れば、室温〜約450℃までは内部るつぼ１が、そ
れ以上の温度では、内部るつぼであるB2O3るつ
ぼ１及びカプセル剤であるB2O3３が融解し３′の
領域ガリウム溶液４あるいはガリウムヒ素融液８
の周囲を覆い石英るつぼ２と溶（融）液との接触
を防止するのである。 In these processes, silicon is an impurity that creates a shallow donor level in the gallium arsenide crystal (this is an impurity that must be avoided as much as possible especially for semi-insulating crystals used to create MESFETs using ion implantation technology). ), the gallium solution (Ga 1-X As
Since the gallium arsenide does not come into contact with the gallium arsenide single crystal, it will not be mixed into the gallium arsenide single crystal. That is, in the conventional method using a quartz crucible, it was difficult to prevent silicon from being mixed in due to the high reactivity of the gallium solution and quartz, but with the container of the present invention, the temperature range from room temperature to approximately 450°C At higher temperatures, the internal crucible B 2 O 3 crucible 1 and the capsule B 2 O 3 3 melt and form the gallium solution 4 or the gallium arsenide melt 8 in the region 3'.
This prevents contact between the quartz crucible 2 and the melt.
内部るつぼ１の厚さを２mmとし、上記の手順に
従つてガリウムヒ素単結晶を製造し、質量分析法
により不純物分析を行なつた結果、シリコン濃度
は1014at／cm3以下となつており、従来法による混
入量1015〜1016at／cm3と比較して大巾な高純度化
が達成された。また、石英るつぼ２のかわりに
PBNるつぼを使用して同様に結晶の製造、不純物
分析を行なつた結果、ボロン濃度は1015at／cm3以
下となり、従来法による混入量約1016at／cm3と比
較して約1/10に減少した。 The thickness of the internal crucible 1 was set to 2 mm, a gallium arsenide single crystal was produced according to the above procedure, and impurity analysis was performed using mass spectrometry. As a result, the silicon concentration was 10 14 at/cm 3 or less. , a significantly higher degree of purity was achieved compared to the conventional method, which had a contamination amount of 10 15 to 10 16 at/cm 3 . Also, instead of quartz crucible 2
As a result of similarly producing crystals and analyzing impurities using a PBN crucible, the boron concentration was less than 10 15 at/cm 3 , which was about 1% compared to the contamination amount of about 10 16 at/cm 3 by the conventional method. /10.
以上の実施例においては直接合成LEC法によ
るガリウムヒ素の合成および結晶製造について行
なつたが、本考案によるるつぼは以上説明した主
旨から、他の半導体材料の合成や結晶製造方法に
おいて高純度結晶を安価に得ることのできる容器
として利用することができる。 In the above embodiments, the synthesis and crystal production of gallium arsenide by the direct synthesis LEC method was carried out, but based on the purpose explained above, the crucible according to the present invention can be used to synthesize high purity crystals in the synthesis of other semiconductor materials and crystal production methods. It can be used as a container that can be obtained at low cost.
以上説明したように、B2O3Cから成るるつぼを
内部容器として用い、石英あるいはPBNるつぼを
外周容器として用いることにより、半導体材料の
溶（融）液は化学的に非常に安定なB2O3とのみ
接触し、石英等の容器との接触を避けることがで
きるから、本考案のるつぼには高純度の半導体材
料および単結晶を得ることができるという利点が
ある。 As explained above, by using a crucible made of B 2 O 3 C as the inner container and a quartz or PBN crucible as the outer container, the molten liquid of the semiconductor material is made of B 2 which is chemically very stable. The crucible of the present invention has the advantage of being able to obtain high-purity semiconductor materials and single crystals, since it contacts only O 3 and avoids contact with containers such as quartz.
また、本考案のるつぼは、外周容器と内部容器
が別々に製造されて、外周容器の内側に内部容器
が納められるので、従来の外周容器の内側に三酸
化ホウ素が被覆・密着されて製造されていたるつ
ぼの製造歩留りが、外周容器の石英等の材料と三
酸化ホウ素の熱膨張係数が大きく異なるため低か
つたのを改善することができる。 In addition, in the crucible of the present invention, the outer container and the inner container are manufactured separately, and the inner container is housed inside the outer container, so boron trioxide is coated and adhered to the inside of the conventional outer container. It is possible to improve the low production yield of crucibles due to the large difference in thermal expansion coefficient between boron trioxide and the material such as quartz for the outer container.
第１図及び第２図は本考案による液体封止法結
晶製造用るつぼの実施例の概略断面図である。
１……三酸化ホウ素るつぼ、２……石英るつ
ぼ、３……カプセル剤、４……ガリウム溶液、５
……ヒ素、６……カーボンサセプター、７……ガ
リウムヒ素単結晶、８……ガリウムヒ素融液。
1 and 2 are schematic cross-sectional views of an embodiment of a crucible for producing crystals using a liquid sealing method according to the present invention. 1...Boron trioxide crucible, 2...Quartz crucible, 3...Capsule, 4...Gallium solution, 5
...Arsenic, 6...Carbon susceptor, 7...Gallium arsenide single crystal, 8...Gallium arsenide melt.
Claims (1)
質により形成された内部容器を、該外周容器の内
側に配置して二重構造の容器としたことを特徴と
する液体封止法結晶製造用るつぼ。 A liquid sealing method for producing crystals, characterized in that an inner container made of a material made of boron trioxide, which is different from the outer container, is arranged inside the outer container to form a double-structured container. Crucible.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8474282U JPS59463U (en) | 1982-06-09 | 1982-06-09 | Crucible for liquid sealing crystal production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8474282U JPS59463U (en) | 1982-06-09 | 1982-06-09 | Crucible for liquid sealing crystal production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59463U JPS59463U (en) | 1984-01-05 |
| JPS623408Y2 true JPS623408Y2 (en) | 1987-01-26 |
Family
ID=30214710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8474282U Granted JPS59463U (en) | 1982-06-09 | 1982-06-09 | Crucible for liquid sealing crystal production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59463U (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116756A (en) * | 1984-04-27 | 1986-01-24 | テイ−・エム・シ−・コ−ポレイシヨン | Ski binding |
-
1982
- 1982-06-09 JP JP8474282U patent/JPS59463U/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116756A (en) * | 1984-04-27 | 1986-01-24 | テイ−・エム・シ−・コ−ポレイシヨン | Ski binding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59463U (en) | 1984-01-05 |
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