JP2517092B2 - Single crystal growth method - Google Patents
Single crystal growth methodInfo
- Publication number
- JP2517092B2 JP2517092B2 JP63331592A JP33159288A JP2517092B2 JP 2517092 B2 JP2517092 B2 JP 2517092B2 JP 63331592 A JP63331592 A JP 63331592A JP 33159288 A JP33159288 A JP 33159288A JP 2517092 B2 JP2517092 B2 JP 2517092B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- crucible
- raw material
- reflector
- crystal growth
- 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 - Fee Related
Links
Landscapes
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は均一性に優れた単結晶を収率良く製造する単
結晶成長方法に関するものである。TECHNICAL FIELD The present invention relates to a single crystal growth method for producing a single crystal excellent in uniformity with high yield.
周期率表第IIIb族、及び第Vb族元素からなる無機化合
物（以下「III−Ｖ族化合物」と言う。）の単結晶、特
にひ化ガリウム、りん化ガリウムの単結晶は、電界効果
トランジスタ、ショットキ・バリア・ダイオード、集積
回路（IC）等の各種半導体素子類の製造に広く用いられ
ている。A single crystal of an inorganic compound (hereinafter referred to as "III-V compound") composed of Group IIIb and Group Vb elements of the periodic table, particularly a single crystal of gallium arsenide or gallium phosphide is a field effect transistor, Widely used in the manufacture of various semiconductor devices such as Schottky barrier diodes and integrated circuits (ICs).
これらの半導体素子の製造に用いられる単結晶は結晶
中の原子配列の乱れである転位が少ないことが必要とさ
れている。The single crystals used for manufacturing these semiconductor elements are required to have few dislocations, which are disordered atomic arrangements in the crystals.
従来、集積回路の基板に用いるIII−Ｖ族化合物、特
にひ化ガリウムの単結晶は三酸化二ほう素を封止剤とし
て用い、第Vb族成分の蒸発を防止する液体封止引き上げ
法、所謂LEC法により成長させるものが使用されてい
た。これは、LEC法によれば不純物の混入が少ないの
で、高純度の結晶が得られるからである。しかしなが
ら、LEC法では引き上げ装置の器壁の冷却、容器内部へ
の高圧の不活性ガスの充填により装置内部に大きい温度
勾配が発生し、液体封止剤中、及び液体封止剤と雰囲気
不活性ガスの界面において単結晶内部に熱応力が生じ、
得られた単結晶の転位密度が高くなるという問題があっ
た。特に、結晶外周部の転位密度が高い領域は基板界面
内に専有する面積が大きいため、外周部における転位密
度の低減化は重要である。Conventionally, a III-V group compound used for a substrate of an integrated circuit, especially a single crystal of gallium arsenide, uses diboron trioxide as a sealing agent, and a so-called liquid sealing pulling method for preventing evaporation of a Vb group component, so-called What was grown by the LEC method was used. This is because according to the LEC method, impurities are less mixed, so that high-purity crystals can be obtained. However, in the LEC method, a large temperature gradient is generated inside the device due to cooling of the vessel wall of the pulling device and filling of high-pressure inert gas into the container, which is inert to the atmosphere inside the liquid sealant and the liquid sealant. Thermal stress occurs inside the single crystal at the gas interface,
There is a problem that the dislocation density of the obtained single crystal becomes high. In particular, a region having a high dislocation density in the outer peripheral portion of the crystal occupies a large area in the interface of the substrate, and therefore it is important to reduce the dislocation density in the outer peripheral portion.
転位密度は、一般に単結晶から切り出したウエハ面を
溶融水酸化カリウム等でエッチングして得られるエッチ
ピットの密度で評価されるが、一般的な用途には５×10
4cm-2以下であることが要求されている。The dislocation density is generally evaluated by the density of etch pits obtained by etching a wafer surface cut from a single crystal with molten potassium hydroxide or the like.
It is required to be 4 cm -2 or less.
第５図は従来の単結晶成長方法を説明するための図
で、不活性ガスを充填した耐圧容器201内において、融
液207を液体封止剤205で封止してルツボ203に入れ、液
体封止剤205と融液207を熱遮蔽板217で覆ったヒータ215
により加熱し、結晶原料融液内、結晶原料融液と封止剤
の界面等を低温度勾配領域にして結晶成長を行ってい
る。FIG. 5 is a diagram for explaining a conventional single crystal growth method. In a pressure resistant container 201 filled with an inert gas, a melt 207 is sealed with a liquid sealant 205 and placed in a crucible 203, A heater 215 in which the sealing agent 205 and the melt 207 are covered with a heat shield plate 217.
The crystal growth is carried out by heating in the crystal raw material melt, the interface between the crystal raw material melt and the sealant, and the like in a low temperature gradient region.
また、転位密度の少ないIII−Ｖ族化合物単結晶を得
るための方法として、ルツボ内の液体封止剤表面にヒー
タを設けて封止剤の加熱温度を高め、結晶原料融液と封
止剤との界面を低温度勾配領域にして結晶成長を行う方
法（特開昭59−116194号公報）も提案されている。Further, as a method for obtaining a III-V group compound single crystal with a low dislocation density, a heater is provided on the surface of the liquid sealant in the crucible to raise the heating temperature of the sealant, and the crystal raw material melt and the sealant are added. A method has also been proposed in which crystal growth is performed in the low temperature gradient region at the interface with (Japanese Patent Laid-Open No. 59-116194).
さらに、長尺のルツボを使用し、種結晶直下にルツボ
の内壁面に接する下方に熱線を反射する反射面を有する
リフレクタを水平に取りつけることにより成長単結晶の
温度勾配を低くする方法（特開昭60−81089号公報）も
提案されている。Further, a method of lowering the temperature gradient of the grown single crystal by using a long crucible and horizontally attaching a reflector having a reflection surface for reflecting heat rays below the seed crystal and in contact with the inner wall surface of the crucible (Japanese Patent Application Laid-Open No. 2000-242242) JP-A-60-81089) has also been proposed.
ところで、GaとAsとをルツボ内に入れ、その上にB2O3
等の液体封止剤を入れてて700〜800℃程度に加熱し、Ga
とAsとを反応させて原料融液を生成する場合、この反応
が急激な発熱反応であるためにAsが液体封止剤を通して
飛散し、これが反射板に付着して反射板の熱反射率が低
下してしまうという問題がある。By the way, Ga and As were put in the crucible, and B 2 O 3 was placed on the crucible.
Add a liquid sealant such as
When As and As are reacted to produce a raw material melt, As is a rapid exothermic reaction, As scatters through the liquid encapsulant, and this adheres to the reflector and the thermal reflectance of the reflector increases. There is a problem that it will decrease.
本発明は上記課題を解決するためのもので、ルツボ内
で原料合成中は反射体を離間させてAsの付着を防ぎ、ま
た付着しても反射体を加熱することにより、Asを揮発さ
せてルツボ内に戻すことにより反射体の反射率低下を防
止し得る単結晶成長方法を提供することを目的とする。The present invention is for solving the above-mentioned problems, while preventing the adhesion of As by separating the reflector during the raw material synthesis in the crucible, and by heating the reflector even if adhered, As is volatilized. It is an object of the present invention to provide a single crystal growth method capable of preventing a decrease in reflectance of a reflector by returning it to the inside of a crucible.
そのために本発明は、不活性ガスを充填した耐圧容器
内に収納されたルツボ内に２種類以上の原料と液体封止
剤を入れて加熱し、原料を反応させて化合物を生成し、
該化合物を融解させた後種結晶により単結晶を成長させ
る方法において、化合物の生成・融解過程では反射板を
ルツボ内の収容物から原料の飛散や不純物が付着しない
程度の距離以上離間させ、その後反射板を下降させて単
結晶を引き上げること、またルツボ内の収容物から原料
の飛散や不純物が付着しない程度の距離以上離間させた
反射板を加熱することを特徴とする。To this end, the present invention puts two or more kinds of raw materials and a liquid sealant in a crucible housed in a pressure vessel filled with an inert gas and heats them to react the raw materials to produce a compound,
In the method of growing a single crystal by melting the compound and then using a seed crystal, in the process of producing and melting the compound, the reflector is separated from the contents in the crucible by a distance not less than the extent that raw materials are not scattered and impurities are not attached, and It is characterized in that the reflecting plate is lowered to pull up the single crystal, and that the reflecting plate is heated from a contained material in the crucible at a distance more than a distance such that the raw material is not scattered and impurities are not attached.
本発明の単結晶成長方法は、ルツボ内で原料合成中は
反射板をルツボ内収容物から離間させ、単結晶を引き上
げるときは反射板を下降させることにより原料の飛散に
よる付着を防止し、また離間させている間は反射板を加
熱することにより付着した原料を揮発させることにより
反射体の反射率低下を防止することが可能となる。The single crystal growth method of the present invention prevents the adhesion due to the scattering of the raw material by separating the reflector from the contents in the crucible during the raw material synthesis in the crucible and lowering the reflector when pulling the single crystal, and It is possible to prevent a decrease in the reflectance of the reflector by heating the reflecting plate during the separation to volatilize the attached raw material.
以下、実施例を図面に基づき説明する。 Embodiments will be described below with reference to the drawings.
第１図〜第４図は本発明の単結晶成長方法を説明する
ための図である。図中、101はルツボ、103は液体封止
剤、105はGa原料、107はAs原料、109は反射板、111はGa
As融液、113は泡である。なお、耐圧容器、ヒータ、熱
遮蔽板等は第５図と同じであるので図示は省略してあ
る。1 to 4 are views for explaining the single crystal growth method of the present invention. In the figure, 101 is a crucible, 103 is a liquid sealant, 105 is a Ga raw material, 107 is an As raw material, 109 is a reflector, and 111 is Ga.
As melt, 113 is foam. The pressure vessel, the heater, the heat shield plate and the like are the same as those in FIG.
第１図において、ルツボ101内にはGa原料105、As原料
107、その上にB2O3液体封止剤103が収容され、図示を省
略したヒータにより加熱されるようになっている。III
−Ｖ族化合物としては、ひ化ガリウム、リン化ガリウ
ム、りん化インジウム、ひ化インジウム、アンチモン化
ガリウム、アンチモン化インジウム等が用いられるので
そのための原料As、Ga、In、Ｐ、Sb等がルツボ内に収容
されて合成される。また液体封止剤に対向して石英製反
射板109が設けられている。勿論石英以外にもBN等不活
性な物質であればよい。In FIG. 1, a Ga raw material 105 and an As raw material are provided in the crucible 101.
107, a B 2 O 3 liquid sealant 103 is housed thereon, and is heated by a heater (not shown). III
As the group V compound, gallium arsenide, gallium phosphide, indium phosphide, indium arsenide, gallium antimonide, indium antimonide, etc. are used. It is housed inside and synthesized. Further, a quartz reflection plate 109 is provided so as to face the liquid sealant. Of course, other than quartz, any inert material such as BN may be used.
このような状態で加熱すると（第２図）、450℃程度
でB2O3が融液状態となり、さらに700〜800℃に加熱する
とGaとAsとが急激に反応する。この反応は発熱反応であ
り、このとき揮発性のAsが飛散する。そのため図示する
ように反射板109はルツボの収容物から所定距離、例え
ば100mm以上離間させておく。こうすることによりAsが
反射体109に到達せず、その結果付着するのを防止する
ことができ、反射率を低下させることはない。なお、第
１図、第２図の状態で反射体109を加熱するようにすれ
ば万一Asが付着してもこれを揮発させることができる。When heated in such a state (Fig. 2), B 2 O 3 becomes a melt state at about 450 ° C, and when heated to 700 to 800 ° C, Ga and As react rapidly. This reaction is an exothermic reaction, and volatile As is scattered at this time. Therefore, as shown in the figure, the reflector 109 is separated from the crucible contents by a predetermined distance, for example, 100 mm or more. By doing so, As does not reach the reflector 109 and as a result it can be prevented from adhering, and the reflectance is not reduced. If the reflector 109 is heated in the state shown in FIGS. 1 and 2, even if As adheres, it can be volatilized.
次に第３図に示すように減圧して原料融液中に溶解し
ている水蒸気、揮発性不純物等を泡113として除去する
泡抜きを行う。この際、泡が激しく発生するので、反射
板に付着すると反射率の低下をきたすため反射板は離間
しておく必要がある。Next, as shown in FIG. 3, the pressure is reduced to remove bubbles such as water vapor and volatile impurities dissolved in the raw material melt as bubbles 113. At this time, bubbles are intensely generated, and if attached to the reflection plate, the reflectance is lowered, so that the reflection plate needs to be separated.
次に、反射板109を下降させてB2O3封止液中に入れ、
必要に応じて再泡抜きを行って結晶成長準備が完了し、
以後は種結晶により単結晶を成長させて引き上げを行う
ことになる。Next, the reflecting plate 109 is lowered and put in the B 2 O 3 sealing liquid,
If necessary, defoaming is performed to complete crystal growth preparation,
After that, a single crystal is grown by the seed crystal and pulled up.
以上のように本発明によれば、原料合成中、及び泡抜
き時には反射板をルツボ収容物から離間させ、単結晶引
き上げ時には反射板を下降させるようにしたので、反射
板に原料の飛散物や不純物が付着するのを防止でき、ま
た反射板自体を加熱することにより反射体に原料や不純
物が付着してもこれを除去することができ、反射体の反
射率の低下を防止することができる。As described above, according to the present invention, during the raw material synthesis and during bubble removal, the reflecting plate is separated from the crucible-containing material, and the reflecting plate is lowered when pulling the single crystal. Impurities can be prevented from adhering, and even if raw materials and impurities adhere to the reflector by heating the reflection plate itself, they can be removed, and a decrease in the reflectance of the reflector can be prevented. .
第１図、第２図、第３図、第４図は本発明の単結晶成長
方法を説明するための図、第５図は従来の単結晶成長方
法を説明するための図である。 101…ルツボ、103…液体封止剤、105…Ga原料、107…As
原料、109…反射板、111…GaAs融液、113…泡。FIG. 1, FIG. 2, FIG. 3, and FIG. 4 are views for explaining the single crystal growth method of the present invention, and FIG. 5 is a view for explaining the conventional single crystal growth method. 101 ... Crucible, 103 ... Liquid sealant, 105 ... Ga raw material, 107 ... As
Raw material, 109 ... Reflector, 111 ... GaAs melt, 113 ... Bubble.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 片野 築 茨城県牛久市東猯穴町1000番地 三菱モ ンサント化成株式会社筑波工場内 (72)発明者 矢島 文和 茨城県牛久市東猯穴町1000番地 三菱モ ンサント化成株式会社筑波工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tsuyoshi Katano Tsuchiba, Ushiku, Ibaraki 1000 No. 1000, Higashihuinaka, Mitsubishi Monsanto Kasei Co., Ltd. Monsanto Kasei Co., Ltd. Tsukuba factory
Claims (2)
れたルツボ内に２種類以上の原料と液体封止剤を入れて
加熱し、原料を反応させて化合物を生成し、該化合物を
融解させた後種結晶により単結晶を成長させる方法にお
いて、化合物の生成・融解過程では反射板をルツボ内の
収容物から原料の飛散や不純物が付着しない程度の距離
以上離間させ、その後反射板を下降させて単結晶を引き
上げることを特徴とする単結晶成長方法。1. A crucible housed in a pressure vessel filled with an inert gas, two or more kinds of raw materials and a liquid sealant are put therein and heated to react the raw materials to produce a compound. In the method of growing a single crystal with a seed crystal after melting, in the process of compound formation and melting, the reflecting plate is separated from the contents in the crucible by a distance not less than the extent that raw materials are not scattered and impurities do not adhere, and then the reflecting plate is A single crystal growth method, which comprises lowering and pulling a single crystal.
が付着しない程度の距離以上離間させた反射板を加熱す
る請求項１記載の単結晶成長方法。2. The method for growing a single crystal according to claim 1, wherein the reflecting plate is heated at a distance from the content of the crucible that is not scattered by the raw material or adhered by impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63331592A JP2517092B2 (en) | 1988-12-28 | 1988-12-28 | Single crystal growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63331592A JP2517092B2 (en) | 1988-12-28 | 1988-12-28 | Single crystal growth method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02175693A JPH02175693A (en) | 1990-07-06 |
| JP2517092B2 true JP2517092B2 (en) | 1996-07-24 |
Family
ID=18245372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63331592A Expired - Fee Related JP2517092B2 (en) | 1988-12-28 | 1988-12-28 | Single crystal growth method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2517092B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118699A (en) * | 1983-11-30 | 1985-06-26 | Sumitomo Electric Ind Ltd | Apparatus for producing callium arsenide single crystal and gallium arsenide single crystal |
-
1988
- 1988-12-28 JP JP63331592A patent/JP2517092B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60118699A (en) * | 1983-11-30 | 1985-06-26 | Sumitomo Electric Ind Ltd | Apparatus for producing callium arsenide single crystal and gallium arsenide single crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02175693A (en) | 1990-07-06 |
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