JPS63123892A - Boat for growth of ii-vi compound single crystal - Google Patents

Boat for growth of ii-vi compound single crystal

Info

Publication number
JPS63123892A
JPS63123892A JP27056386A JP27056386A JPS63123892A JP S63123892 A JPS63123892 A JP S63123892A JP 27056386 A JP27056386 A JP 27056386A JP 27056386 A JP27056386 A JP 27056386A JP S63123892 A JPS63123892 A JP S63123892A
Authority
JP
Japan
Prior art keywords
boat
single crystal
growth
compound single
carbon film
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.)
Granted
Application number
JP27056386A
Other languages
Japanese (ja)
Other versions
JPH0712998B2 (en
Inventor
Takeshi Miyazaki
健史 宮崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP27056386A priority Critical patent/JPH0712998B2/en
Publication of JPS63123892A publication Critical patent/JPS63123892A/en
Publication of JPH0712998B2 publication Critical patent/JPH0712998B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

PURPOSE:To provided the titled boat for the growth of a II-VI compound single crystal, having roughened inner surface coated with a carbon layer and effective in preventing the generation of bubbles between the wall of the boat and the grown signal crystal. CONSTITUTION:The inner surface of a boat 1 for the growth of a II-VI compound single crystal is blasted with coarse metal particles, sand, abrasive, etc., to form a roughened surface 2 having a roughness of 1-100mum on the inner surface. The boat 1 is put into a reaction vessel optionally after degreasing, cleaning, etching, etc., degassed in vacuum and heated at 1,000-1,200 deg.C. A carbon source such as benzene is introduced into the reaction vessel and thermally decomposed to deposit a carbon film 3 on the inner surface of the boat.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 この発明は■−■族化合物単結晶成長用ボートに関する
。さらに詳細には、三温度水平ブリッジマン法によりI
I−VI族化合物単結晶を製造する際に使用される単結
晶成長用ボートに関する。
DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a boat for growing single crystals of ■-■ group compounds. More specifically, I
The present invention relates to a boat for single crystal growth used in producing single crystals of Group I-VI compounds.

〈従来技術及び発明が解決しようとする問題点〉従来か
らII−VI族化合物単結晶を製造する方法として種々
の方法が用いられており、そのような方法の一つとして
、三温度水平ブリッジマン法が知られている。上記の三
温度水平ブリッジマン法では、封管反応容器が細管を有
する隔壁により隔てられており、単結晶原料が収容され
た単結晶成長用ボートと、蒸気圧制御物質がそれぞれに
収容されている。この反応容器を、三段階の温度分布を
育する炉内に、該ボートが最高温側、蒸気圧制御物質が
最低温側となるように配設し、該ボート内の単結晶原料
を溶融させた後、炉または前記ボートを適当な速度で移
動させて単結晶を成長させる。この際、蒸気圧制御物質
を加熱蒸発させ、反応容器内の蒸気圧を制御することに
より、成長単結晶の組成制御が行なわれる。
<Prior Art and Problems to be Solved by the Invention> Various methods have been used to produce II-VI group compound single crystals, and one such method is the three-temperature horizontal Bridgman method. The law is known. In the three-temperature horizontal Bridgman method described above, a sealed tube reaction vessel is separated by a partition wall having a thin tube, and a single crystal growth boat containing a single crystal raw material and a vapor pressure control substance are respectively housed. . This reaction vessel is placed in a furnace that develops a three-stage temperature distribution so that the boat is on the highest temperature side and the vapor pressure control substance is on the lowest temperature side, and the single crystal raw material in the boat is melted. After that, the furnace or the boat is moved at an appropriate speed to grow a single crystal. At this time, the composition of the grown single crystal is controlled by heating and vaporizing the vapor pressure controlling substance and controlling the vapor pressure within the reaction vessel.

上記の三温度水平ブリッジマン法に使用される単結晶成
長用ボートとしては、従来、石英製ボート、p−BNや
石英製のボートにカーボンコートがされたもの等が使用
されている。
As the boat for single crystal growth used in the above-mentioned three-temperature horizontal Bridgman method, a boat made of quartz, a boat made of p-BN or quartz coated with carbon, etc. are conventionally used.

しかし、上記石英製のボートを使用した場合、ボートの
石英と単結晶原料、例えばCdTeとが反応し、得られ
たII−Vl族化合物単結晶中に不純物としてケイ素が
混入するという問題がある。
However, when the boat made of quartz is used, there is a problem in that the quartz in the boat reacts with a single crystal raw material, such as CdTe, and silicon is mixed as an impurity into the resulting II-Vl group compound single crystal.

また、石英やp−BN製のボートにカーボンコートがさ
れたものにあっては、単結晶原料との反応は抑制できる
が、成長単結晶とボート壁面との間に気孔が生じ易く、
エッチピット密度(以下、EPDと称する)が大きくな
る等、単結晶が十分に成長しないという問題がある。
In addition, if a boat made of quartz or p-BN is coated with carbon, the reaction with the single crystal raw material can be suppressed, but pores are likely to form between the growing single crystal and the boat wall.
There is a problem that the single crystal does not grow sufficiently, such as an increase in etch pit density (hereinafter referred to as EPD).

く目 的〉 この発明は上記問題点に鑑みてなされたものであり、上
記気孔の発生が防止できると共に高品質の単結晶が得ら
れるII−VI族化合物単結晶成長用ボートを提供する
ことを目的とする。
Purpose This invention has been made in view of the above-mentioned problems, and an object thereof is to provide a boat for growing a single crystal of a group II-VI compound, which can prevent the formation of pores and obtain a high-quality single crystal. purpose.

く問題を解決するための手段及び作用〉上記の問題点を
解決すべくなされた、この発明のII−Vl族化合物単
結晶成長用ボートは、該ボートの内面が粗面に形成され
ていると共に該粗面がカーボン膜で被覆されていること
を特徴とするものである。
Means and operation for solving the above problems> The boat for single crystal growth of II-Vl group compounds of the present invention, which was made to solve the above problems, has a rough inner surface and The rough surface is coated with a carbon film.

この発明は、上記の構成よりなり、ボートの内面が粗面
とされ、粗面をつたわってガスが放出されるので、成長
単結晶とボート壁面との間に気孔が発生するのを防止す
ることができる。またカーボン膜により被覆されている
ので、ボートと単結晶原料との反応が防止できる。
This invention has the above-mentioned structure, and the inner surface of the boat is made rough, and gas is released through the rough surface, so that it is possible to prevent the formation of pores between the growing single crystal and the boat wall. I can do it. Furthermore, since it is coated with a carbon film, reaction between the boat and the single crystal raw material can be prevented.

なお、n−vt族化合物単結晶とししては、例えば、C
d T e s Cd S s Cd S e SZ 
n S e sZnSSHgSeSHgTe等の2元系
単結晶、CdZnS、ZnSSe、HgCdTe等の多
元系混晶等のII−Vl族化合物単結晶が挙げられる。
Note that as the n-vt group compound single crystal, for example, C
d T e s Cd S s Cd S e SZ
Examples include II-Vl group compound single crystals such as binary single crystals such as nSe sZnSSHgSeSHgTe, and multicomponent mixed crystals such as CdZnS, ZnSSe, and HgCdTe.

〈実施例〉 以下、実施例を示す添附図面に基づいて詳細に説明する
。   ゛ 添付図面は、この発明にかかる単結晶成長用ボートの一
実施例の横断面概念図であり、石英等の材質よりなる単
結晶成長用ボート(1)の内面が粗面(2)に形成され
ており、該粗面(2)はカーボン膜(3)により被覆さ
れている。
<Examples> Hereinafter, examples will be described in detail based on the accompanying drawings showing examples.゛The attached drawing is a cross-sectional conceptual diagram of an embodiment of a boat for single crystal growth according to the present invention, in which the inner surface of the boat for single crystal growth (1) made of a material such as quartz is formed into a rough surface (2). The rough surface (2) is covered with a carbon film (3).

上記ボート内面を14面に形成する手段としては、慣用
の手段のいずれも使用できるが、ボート内面に、金属粗
粒、砂、研磨材等を吹き付けて粗面を形成する、いわゆ
るサンドブラスト加工、ショツトブラスト加工、ショッ
トピーニング加工等と称される方法が好ましい。形成さ
れる粗面の粗さは、特に限定されないが、1〜100μ
m、好ましくは10〜50μ■程度とされる。粗面の粗
さが上記範囲より細いと気孔発生防止効果が少なく、ま
た粗いと粗面の形成が困難である。
Any of the conventional means can be used to form the inner surface of the boat into 14 surfaces, but so-called sandblasting or short processing, in which coarse metal particles, sand, abrasive material, etc. are sprayed onto the inner surface of the boat to form a rough surface, can be used. Methods called blasting, shot peening, etc. are preferred. The roughness of the formed rough surface is not particularly limited, but is 1 to 100μ.
m, preferably about 10 to 50 μm. If the roughness of the roughened surface is finer than the above range, the effect of preventing the generation of pores will be low, and if it is rough, it will be difficult to form a roughened surface.

上記で形成された粗面を被覆するカーボン膜は慣用の方
法で形成され、例えば、高温(例えば、1000〜12
00℃)の真空または不活性ガス中で、ベンゼン、メタ
ン等の炭化水素類、四塩化炭素等のハロゲン化炭化水素
類などを熱分解させ、カーボン膜を析出、形成させるこ
とにより行われる。形成されるカーボン膜の膜厚は、炭
化水素類等の炭素源の導入量により調整されるが、薄す
ぎるとボートと単結晶原料との反応が生ずる場合があり
、また厚すぎると剥離をもたらす場合があるので、粗面
の粗さ、II−Vl族化合物の種類等に応じて適宜選択
される。
The carbon film covering the rough surface formed above is formed by a conventional method, for example, at a high temperature (e.g.
This is carried out by thermally decomposing hydrocarbons such as benzene and methane, halogenated hydrocarbons such as carbon tetrachloride, etc. in a vacuum or inert gas at a temperature (00°C) to precipitate and form a carbon film. The thickness of the carbon film formed is adjusted by the amount of carbon source such as hydrocarbons introduced, but if it is too thin, a reaction may occur between the boat and the single crystal raw material, and if it is too thick, it may cause peeling. Therefore, it is selected appropriately depending on the roughness of the rough surface, the type of II-Vl group compound, etc.

なお、この発明のボートの形状および材質は、特に限定
されず、従来慣用の形状および材質のものが用いられ、
またその使用方法も従来のボートと同様に使用される。
The shape and material of the boat of the present invention are not particularly limited, and conventional shapes and materials may be used.
It is also used in the same way as a conventional boat.

次に、この発明の■−■族化合物単結晶成長用ボートの
製造方法の一例の概略を説明する。まず、従来慣用に用
いられている石英、p−BN等からなる単結晶成長用ボ
ートの内面を前記の手段により加工して所望の粗さの粗
面を形成する。次いで、必要に応じて脱脂、洗浄、エツ
チング等を行なった後、上記粗面が形成されたボートを
反応容器内に配設し、真空脱気および加熱したのち、反
応容器内にベンゼン等の炭素源を導入して熱分解させ、
カーボン膜を析出させることにより、この発明の単結晶
成長用ボートが得られる。
Next, an outline of an example of a method for manufacturing a boat for growing single crystals of group (1)-(2) compounds of the present invention will be explained. First, the inner surface of a conventional single crystal growth boat made of quartz, p-BN, etc. is processed by the above-mentioned means to form a rough surface with a desired roughness. Next, after degreasing, washing, etching, etc. as necessary, the boat with the rough surface is placed in a reaction vessel, vacuum degassed and heated, and carbon such as benzene is added to the reaction vessel. Introducing a source to cause thermal decomposition,
By depositing a carbon film, the single crystal growth boat of the present invention can be obtained.

なお、上記の粗面の形成およびカーボン膜による被覆処
理は、ボート内面の全面に行なってもよいし、また単結
晶原料に接触する部分だけに行なってもよい。
Note that the above-described rough surface formation and carbon film coating treatment may be performed on the entire inner surface of the boat, or may be performed only on the portion that comes into contact with the single crystal raw material.

さらに、例えば、ボートの一端に単結晶の成長を開始さ
せる種子結晶を保持するための棚部を設ける等、適宜設
計変更することができる。
Furthermore, the design can be modified as appropriate, for example, by providing a shelf at one end of the boat for holding a seed crystal for starting the growth of a single crystal.

以下、試験例および比較例をもって、この発明をより詳
細に説明する。
This invention will be explained in more detail below using test examples and comparative examples.

試験例および比較例 高純度石英にて作製された単結晶成長用ボートの内面に
、粗さが30μm程度のサンドブラスト加工を行った後
、脱指、洗浄および王水によるエツチングを行った。上
記処理がされたボートを反応槽に設置し、10−6To
rrの真空度とし1100℃に加熱した後、高純度ベン
ゼンを導入してカーボン膜による被覆を行い、本発明の
単結晶成長用ボートを作製した。上記で得られたボート
を用いて、純度99.9999%のCdTeを原料とし
て三温度水平ブリッジマン法によりCdTe単結晶を成
長させた。単結晶成長条件として、高温部1100℃、
中間温度部1050℃、低温部815℃および結晶成長
速度3+n/hr、とした。得られた単結晶の性状およ
びEPDの測定結果を表に示す。
Test Examples and Comparative Examples The inner surface of a single-crystal growth boat made of high-purity quartz was sandblasted to a roughness of about 30 μm, and then subjected to finger removal, washing, and etching with aqua regia. The boat treated above was placed in a reaction tank, and 10-6To
After heating to 1100° C. with a vacuum degree of rr, high purity benzene was introduced and coating with a carbon film was performed to produce a boat for single crystal growth of the present invention. Using the boat obtained above, a CdTe single crystal was grown by the three-temperature horizontal Bridgman method using CdTe with a purity of 99.9999% as a raw material. As single crystal growth conditions, high temperature part 1100℃,
The intermediate temperature part was 1050°C, the low temperature part was 815°C, and the crystal growth rate was 3+n/hr. The properties of the obtained single crystal and the EPD measurement results are shown in the table.

一方、比較例として、内面が無処理の石英ボート(比較
例1)、カーボンコーティング処理のみの石英ボート(
比較例2)およびサンドブラスト処理のみの石英ボート
(比較例3)を用い、上記試験例と同様にしてCdTe
単結晶を成長させた。
On the other hand, as comparative examples, a quartz boat with an untreated inner surface (comparative example 1), a quartz boat with only carbon coating treatment (
Comparative Example 2) and a quartz boat subjected only to sandblasting (Comparative Example 3)
Grown single crystals.

得られた単結晶の性状およびEPDの測定結果を併せて
表に示した。
The properties of the obtained single crystal and the EPD measurement results are also shown in the table.

(以下余白) 上記試験例および比較例から明らかなように、本発明に
かかるボートを用いて得られた単結晶は、気孔の発生が
見られず、またEPDも少なく優れた特性を有するのに
対し、比較例1〜3で得られた単結晶は、ボートとの反
応や気孔の発生が見られ、EPDも大きな値を示した。
(Left below) As is clear from the above test examples and comparative examples, the single crystal obtained using the boat according to the present invention has excellent properties, with no pores and less EPD. On the other hand, in the single crystals obtained in Comparative Examples 1 to 3, reactions with boats and generation of pores were observed, and the EPD also showed large values.

く効果〉 以上のように、この発明のIf−Vl族化合物単結晶成
長用ボートによれば、ボート内面が粗面に形成され、さ
らにカーボン膜による被覆がなされているので、ボート
壁面と成長単結晶との間の気孔の発生を防止できると共
に結晶性がよくなるので歩留まりおよび品質の向上を図
ることができる。
Effect> As described above, according to the If-Vl group compound single crystal growth boat of the present invention, the inner surface of the boat is formed into a rough surface and is further coated with a carbon film, so that the boat wall surface and the growth crystal are Since the generation of pores between crystals can be prevented and crystallinity is improved, yield and quality can be improved.

また、粗面が形成されることにより被覆されたカーボン
膜の剥離強度が大きくなり、カーボン膜が剥がれにくく
なるので、ボートと原料との反応による不純物の混入を
未然に防止することができ、高品質の単結晶が得られる
という特有の効果を奏する。
In addition, the peel strength of the coated carbon film increases due to the formation of a rough surface, making it difficult for the carbon film to peel off, making it possible to prevent impurities from being mixed in due to the reaction between the boat and the raw material. It has the unique effect of producing high-quality single crystals.

【図面の簡単な説明】[Brief explanation of the drawing]

添付図面は、この発明にかかる単結晶成長用ボートの一
実施例の横断面概念図である。 (1)・・・・・・単結晶成長用ボート (2)・・・
・・・粗面■・・・・・・カーボン膜
The accompanying drawing is a conceptual cross-sectional view of an embodiment of a boat for single crystal growth according to the present invention. (1)・・・Single crystal growth boat (2)・・・
・・・Rough surface■・・・Carbon film

Claims (1)

【特許請求の範囲】 1、三温度水平ブリッジマン法に用いられるII−VI族化
合物単結晶成長用ボートにおいて、 上記ボートの内面が粗面に形成されていると共に該粗面
がカーボン膜で被覆されていることを特徴とするII−V
I族化合物単結晶成長用ボート。 2、II−VI族化合物単結晶がCdTeである上記特許請
求の範囲第1項記載のII−VI族化合物単結晶成長用ボー
ト。
[Claims] 1. In a boat for growing a single crystal of a group II-VI compound used in the three-temperature horizontal Bridgman method, the inner surface of the boat is formed into a rough surface, and the rough surface is coated with a carbon film. II-V characterized by being
Boat for single crystal growth of Group I compounds. 2. A boat for growing a II-VI group compound single crystal according to claim 1, wherein the II-VI group compound single crystal is CdTe.
JP27056386A 1986-11-13 1986-11-13 <II>-<VI> Group compound single crystal growth boat Expired - Lifetime JPH0712998B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27056386A JPH0712998B2 (en) 1986-11-13 1986-11-13 <II>-<VI> Group compound single crystal growth boat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27056386A JPH0712998B2 (en) 1986-11-13 1986-11-13 <II>-<VI> Group compound single crystal growth boat

Publications (2)

Publication Number Publication Date
JPS63123892A true JPS63123892A (en) 1988-05-27
JPH0712998B2 JPH0712998B2 (en) 1995-02-15

Family

ID=17487904

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27056386A Expired - Lifetime JPH0712998B2 (en) 1986-11-13 1986-11-13 <II>-<VI> Group compound single crystal growth boat

Country Status (1)

Country Link
JP (1) JPH0712998B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0704891A1 (en) * 1994-09-30 1996-04-03 Shin-Etsu Handotai Company Limited Quartz glass jig for heat-treating semiconductor wafers and method for producing same
US6287381B1 (en) * 1991-08-22 2001-09-11 Raytheon Company Crystal growth process for large area GaAs with controllable resistivity and infrared window/dome with EMI-EMP protection formed therefrom
US6706205B2 (en) * 1999-06-28 2004-03-16 General Electric Company Semiconductor processing article
JP2006348965A (en) * 2005-06-13 2006-12-28 Myotoku Ltd Multitubular piping device, and multitubular piping attachment manifold
KR100677908B1 (en) * 2005-05-24 2007-02-05 (주)하나기술 Crucible for the evaporation apparatus of organic material and Evaporation apparatus of organic material used it

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6287381B1 (en) * 1991-08-22 2001-09-11 Raytheon Company Crystal growth process for large area GaAs with controllable resistivity and infrared window/dome with EMI-EMP protection formed therefrom
EP0704891A1 (en) * 1994-09-30 1996-04-03 Shin-Etsu Handotai Company Limited Quartz glass jig for heat-treating semiconductor wafers and method for producing same
US6425168B1 (en) * 1994-09-30 2002-07-30 Shin-Etsu Handotai Co., Ltd. Quartz glass jig for heat-treating semiconductor wafers and method for producing same
US6706205B2 (en) * 1999-06-28 2004-03-16 General Electric Company Semiconductor processing article
KR100677908B1 (en) * 2005-05-24 2007-02-05 (주)하나기술 Crucible for the evaporation apparatus of organic material and Evaporation apparatus of organic material used it
JP2006348965A (en) * 2005-06-13 2006-12-28 Myotoku Ltd Multitubular piping device, and multitubular piping attachment manifold

Also Published As

Publication number Publication date
JPH0712998B2 (en) 1995-02-15

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