JPH07115998B2 - Method for producing silicon carbide single crystal - Google Patents
Method for producing silicon carbide single crystalInfo
- Publication number
- JPH07115998B2 JPH07115998B2 JP62313083A JP31308387A JPH07115998B2 JP H07115998 B2 JPH07115998 B2 JP H07115998B2 JP 62313083 A JP62313083 A JP 62313083A JP 31308387 A JP31308387 A JP 31308387A JP H07115998 B2 JPH07115998 B2 JP H07115998B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- substrate
- sic
- reaction tube
- silicon carbide
- 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 - Lifetime
Links
- 229910010271 silicon carbide Inorganic materials 0.000 title claims description 25
- 239000013078 crystal Substances 0.000 title claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000758 substrate Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 11
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 8
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004886 process control Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は単結晶シリコン基板上に単結晶のβ−炭化珪素
（以下SiCと略）を成長させる方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for growing single crystal β-silicon carbide (hereinafter abbreviated as SiC) on a single crystal silicon substrate.
［従来の技術］ SiCは2.2eVという大きなバンドギャップ及び1000cm2/V
・ｓという大きな電子移動度を持ち、かつｐ型、ｎ型の
制御が容易な半導体である。SiCを用いれば従来のSiやG
aAsなどでは実現不可能な高温動作用の新しい半導体デ
バイスが製作できる。[Prior Art] SiC has a large bandgap of 2.2 eV and 1000 cm 2 / V
A semiconductor having a large electron mobility of s and easily controlling p-type and n-type. With SiC, conventional Si and G
We can manufacture new semiconductor devices for high temperature operation that cannot be realized with aAs.
そこで、近年、シリコン（Si）基板上にβ−SiCを成長
させる方法が種々提案されている。例えばLate News Ab
str.16th Conf.SSDM（1984）には、単結晶Siの上にまず
炭化バッファ層を形成し、その上にSiCをエピタキシャ
ル成長させる方法が提案されている。また、特開昭62−
155512にはトリクロロシランと炭化水素のCVD反応によ
り、Si基板上に直接にβ−SiCをエピタキシャル成長さ
せる方法が提案されている。Therefore, in recent years, various methods for growing β-SiC on a silicon (Si) substrate have been proposed. For example Late News Ab
str.16th Conf.SSDM (1984) proposes a method in which a carbonized buffer layer is first formed on single crystal Si and then SiC is epitaxially grown on the carbonized buffer layer. In addition, JP-A-62-
155512 proposes a method of epitaxially growing β-SiC directly on a Si substrate by a CVD reaction of trichlorosilane and hydrocarbon.
［発明が解決しようとする問題点］ 前者の如く、Si基板上にまず炭化バッファ層を形成する
方法においては、Si基板とβ−SiCとの間に炭化バッフ
ァ層が介在するから、電気的特性に劣る。また、CVD反
応の途中において導入するガスの種類を変えなければな
らないから、プロセスの制御が複雑である。[Problems to be Solved by the Invention] As in the former case, in the method of first forming the carbonization buffer layer on the Si substrate, since the carbonization buffer layer is interposed between the Si substrate and β-SiC, the electrical characteristics Inferior to. In addition, the process control is complicated because the type of gas introduced during the CVD reaction must be changed.
特開昭62−155512の方法では、原料ガスとしてトリクロ
ロシランと炭化水素の複数種類を用いなければならない
から、その混合比の正確な制御が必要となり、プロセス
制御が複雑であると共に、成長速度が小さいという問題
もあった。In the method of Japanese Patent Laid-Open No. 62-155512, it is necessary to use a plurality of types of trichlorosilane and hydrocarbons as a source gas, so accurate control of the mixing ratio is required, process control is complicated, and the growth rate is high. There was also the problem of being small.
［問題点を解決するための手段］ 本発明の炭化珪素単結晶の製造方法は、メチルトリクロ
ルシランを非酸化性のキャリアガスと共に加熱炉内に導
入して熱分解させることにより、HClガスにより表面の
エッチング処理を施したシリコン単結晶基板上に直接に
β−SiCの単結晶を成長させるものである。[Means for Solving Problems] In the method for producing a silicon carbide single crystal of the present invention, methyltrichlorosilane is introduced into a heating furnace together with a non-oxidizing carrier gas to be thermally decomposed, so that the surface is treated with HCl gas. The β-SiC single crystal is grown directly on the silicon single crystal substrate that has been subjected to the etching treatment of.
［作用］ かかる本発明においては、Si基板上に直接にβ−SiCを
成長させることができ、成長速度も速い。また、原料ガ
スもメチルトリクロルシランの１種類のみで良い。[Operation] In the present invention, β-SiC can be grown directly on the Si substrate, and the growth rate is high. Further, the source gas may be only one type of methyltrichlorosilane.
以下本発明の構成について更に詳細に説明する。The structure of the present invention will be described in more detail below.
本発明においてはメチルトリクロルシランはキャリアガ
スと共に加熱炉内に導入されて熱分解される。このメチ
ルトリクロルシランは、常温では液状であるから、飽和
容器（バブラ）中に入れ、キャリアガスを通過させるこ
とにより気化させて必要量を加熱炉内に導入するのが好
適である。In the present invention, methyltrichlorosilane is introduced into a heating furnace together with a carrier gas and thermally decomposed. Since this methyltrichlorosilane is liquid at room temperature, it is preferable to put it in a saturated container (bubbler), vaporize it by passing a carrier gas, and introduce the required amount into the heating furnace.
キャリアガスとしては水素、アルゴン、窒素等の非酸化
性のものが用いられ、これらは１種類のみ用いても良
く、２種類以上を混合して用いても良い。このキャリア
ガスの加熱炉内への導入量は、メチルトリクロルシラン
の1000倍以上とするのが好適である。As the carrier gas, non-oxidizing ones such as hydrogen, argon and nitrogen are used, and these may be used alone or in combination of two or more. The amount of carrier gas introduced into the heating furnace is preferably 1000 times or more that of methyltrichlorosilane.
単結晶Si基板は、通常のSiウエハを用いることができ
る。この単結晶Si基板は、その上にβ−SiCを成長させ
るに先立って、表面を十分に清浄にしておくのが好適で
ある。そのためには、本発明では、β−SiCの成長に先
立って、単結晶Si基板をHClガスでエッチング処理す
る。HClガスにてエッチングする場合、1000〜1100℃程
度の温度下においてHClガスをSi基板1cm2あたり５〜10c
c/min程度流通させ、これを１〜10min程度継続すること
により該Si基板表面を十分に清浄化することができる。A normal Si wafer can be used as the single crystal Si substrate. It is preferable that the surface of this single crystal Si substrate be sufficiently cleaned prior to growing β-SiC on it. For that purpose, in the present invention, the single crystal Si substrate is etched with HCl gas prior to the growth of β-SiC. When etching with HCl gas, 5~10c Si per substrate 1 cm 2 with HCl gas at a temperature of about 1000 to 1100 ° C.
The surface of the Si substrate can be sufficiently cleaned by circulating it for about c / min and continuing this for about 1 to 10 min.
加熱炉としては、石英、アルミナ等耐熱性、耐食性、耐
久性を有する容器とその内部を加熱することができるヒ
ータを備えたものが用いられる。容器は、通常の場合チ
ューブ状とするのが好適であるがその他の形状としても
良い。ヒータとしては抵抗発熱体、誘導加熱コイル、レ
ーザ等各種の加熱方式のものを採用することができる。As the heating furnace, one provided with a container having heat resistance, corrosion resistance, durability such as quartz and alumina and a heater capable of heating the inside thereof is used. Usually, the container is preferably tubular, but may have other shapes. As the heater, various heating methods such as a resistance heating element, an induction heating coil, and a laser can be adopted.
本発明において、β−SiCを成長させるためのメチルト
リクロルシアンの熱分解温度は1200〜1400℃程度が好適
である。この反応時間は、目的とするβ−SiCの膜厚に
より決定される。In the present invention, the thermal decomposition temperature of methyltrichlorcyan for growing β-SiC is preferably about 1200 to 1400 ° C. This reaction time is determined by the desired film thickness of β-SiC.
［実施例］ 以下実施例について説明する。[Examples] Examples will be described below.
実施例１ 第１図に示す装置を用いて単結晶Si基板上にβ−SiCの
単結晶膜を成長させた。なお、第２図は第１図の要部拡
大図、第３図は温度プログラムである。Example 1 A β-SiC single crystal film was grown on a single crystal Si substrate using the apparatus shown in FIG. Note that FIG. 2 is an enlarged view of a main part of FIG. 1, and FIG. 3 is a temperature program.
メチルトリクロルシランはバブラ１中に入れられてお
り、水素ボンベ２から供給される水素ガスが通過される
ことにより石英製反応管３中に供給される。また、石英
製反応管３中にはHClガスがボンベ４から導入可能とさ
れている。石英製反応管３には試料のホルダ５が差し込
まれており、ホルダ５は反応管３の軸線方向に沿って移
動可能である。ホルダ５の先端に単結晶Si基板６が載置
される。反応管３内を加熱するために、本実施例では抵
抗加熱炉７を採用している。反応管３にはゲートバルブ
８が設けられており、反応管３内を抵抗加熱炉７により
所定温度に昇温させたままで試料の出し入れができるよ
うに構成されている。ゲートバルブ８の部分にはロータ
リーポンプ９とベント配管10が接続されている。符号11
はマスフローコントローラを示す。なお、第２図に示す
如くこの抵抗加熱炉７により、反応管３の内部を1300℃
に昇温させてβ−SiCの成長を行なわせた。この反応管
３内部には、第２図に示す如く1300℃の等温帯が約12cm
の長さにわたって存在している。Methyltrichlorosilane is contained in the bubbler 1 and is supplied into the quartz reaction tube 3 by passing the hydrogen gas supplied from the hydrogen cylinder 2. Further, HCl gas can be introduced into the quartz reaction tube 3 from the cylinder 4. A sample holder 5 is inserted into the quartz reaction tube 3, and the holder 5 is movable along the axial direction of the reaction tube 3. The single crystal Si substrate 6 is placed on the tip of the holder 5. In order to heat the inside of the reaction tube 3, a resistance heating furnace 7 is adopted in this embodiment. The reaction tube 3 is provided with a gate valve 8 so that the sample can be taken in and out while the inside of the reaction tube 3 is heated to a predetermined temperature by the resistance heating furnace 7. A rotary pump 9 and a vent pipe 10 are connected to the gate valve 8. Code 11
Indicates a mass flow controller. As shown in FIG. 2, the inside of the reaction tube 3 was heated to 1300 ° C. by the resistance heating furnace 7.
The temperature was raised to β-SiC to grow. Inside this reaction tube 3, an isothermal zone of 1300 ° C is about 12 cm as shown in Fig. 2.
Exists over the length of.
成長方法を次に説明する。ホルダ５の先端にSi基板６を
載せ、まずこのSi基板６が1100℃の領域に位置するよう
にホルダ５を反応管３内に挿入する。そして、HCl流量5
cc/min、水素流量１/min、エッチング時間5minの条件
にてSi基板をエッチング処理してその表面を清浄化し
た。次に、水素を１/minの流量にて5min流し、反応管
３内に残留するHClガスを追い出した。The growth method will be described below. The Si substrate 6 is placed on the tip of the holder 5, and the holder 5 is first inserted into the reaction tube 3 so that the Si substrate 6 is located in the region of 1100 ° C. And the HCl flow rate 5
The surface of the Si substrate was cleaned by etching the Si substrate under the conditions of cc / min, hydrogen flow rate 1 / min, and etching time 5 min. Next, hydrogen was flown at a flow rate of 1 / min for 5 minutes to expel the HCl gas remaining in the reaction tube 3.
次に、Si基板６が反応管３内の1300℃の領域に位置する
ようにホルダ５を反応管３内に差し込んだ。そして、水
素流量１/min、メチルトリクロルシラン流量2cc/mi
n、成長時間10minにてSi基板上にβ−SiCを析出させ
た。10min経過後メチルトリクロルシランの供給を止
め、Si基板６が反応管３内の低温部に位置するようにホ
ルダ５を後退させ、ほぼ室温温度となるまで冷却した後
ゲートバルブ８を開いて試料を取り出した。Next, the holder 5 was inserted into the reaction tube 3 so that the Si substrate 6 was located in the region of 1300 ° C. in the reaction tube 3. Then, the flow rate of hydrogen is 1 / min, the flow rate of methyltrichlorosilane is 2cc / mi.
β-SiC was deposited on the Si substrate at a growth time of 10 min. After the lapse of 10 minutes, the supply of methyltrichlorosilane was stopped, the holder 5 was retracted so that the Si substrate 6 was located at the low temperature part in the reaction tube 3, and the sample was opened by cooling the gate valve 8 until the temperature reached to about room temperature. I took it out.
得られたSi基板上のSiCについて反射電子線回折法（RHE
ED）により結晶性の評価を行なった。その結果、このSi
Cはβ−SiCの単結晶であることが認められた。また、そ
の膜厚は2000Åであり、β−SiCの成長速度は200Å/min
であった。Reflection Electron Diffraction (RHE
The crystallinity was evaluated by ED). As a result, this Si
It was confirmed that C was a single crystal of β-SiC. The film thickness is 2000Å and the growth rate of β-SiC is 200Å / min.
Met.
実施例２ 上記実施例においてメチルトリクロルシランの供給量を
1cc/minとしたこと以外は同様にしてβ−SiCの堆積を行
なわせた。RHEEDの結晶性評価によれば、このβ−SiCは
単結晶であることが認められた。また、得られたβ−Si
Cの膜厚は2000Åであり、成長速度は200Å/minであっ
た。Example 2 In the above example, the amount of methyltrichlorosilane supplied was changed.
Β-SiC was deposited in the same manner except that the rate was 1 cc / min. According to RHEED evaluation of crystallinity, it was confirmed that this β-SiC was a single crystal. In addition, the obtained β-Si
The film thickness of C was 2000Å and the growth rate was 200Å / min.
［効果］ 以上の実施例からも明らかな通り、本発明によればSi基
板上に単結晶β−SiCを直接に成長させることができ
る。この際、原料ガスとしてはメチルトリクロルシラン
を１種類のみで良く、プロセス制御が容易である。[Effect] As is clear from the above examples, according to the present invention, single crystal β-SiC can be directly grown on a Si substrate. At this time, only one type of methyltrichlorosilane may be used as the source gas, and the process control is easy.
第１図は実施例で用いた成長装置の系統図、第２図は第
１図の要部拡大図、第３図は温度プログラムである。 １……バブラ、３……石英製反応管、 ５……ホルダ、６……Si基板、 ７……抵抗加熱炉、８……ゲートバルブ、 ９……ロータリーポンプ。FIG. 1 is a systematic diagram of the growth apparatus used in the examples, FIG. 2 is an enlarged view of a main part of FIG. 1, and FIG. 3 is a temperature program. 1 ... Bubbler, 3 ... Quartz reaction tube, 5 ... Holder, 6 ... Si substrate, 7 ... Resistance heating furnace, 8 ... Gate valve, 9 ... Rotary pump.
Claims (1)
リアガスと共に加熱炉内に導入して熱分解させることに
より、HClガスにより表面のエッチング処理を施したシ
リコン単結晶基板上に直接にβ−炭化珪素の単結晶を成
長させることを特徴とする炭化珪素単結晶の製造方法。1. Methyltrichlorosilane is introduced into a heating furnace together with a non-oxidizing carrier gas to be thermally decomposed, so that β-carbonization is directly carried out on a silicon single crystal substrate whose surface has been subjected to etching treatment with HCl gas. A method for producing a silicon carbide single crystal, which comprises growing a silicon single crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62313083A JPH07115998B2 (en) | 1987-12-10 | 1987-12-10 | Method for producing silicon carbide single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62313083A JPH07115998B2 (en) | 1987-12-10 | 1987-12-10 | Method for producing silicon carbide single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01153600A JPH01153600A (en) | 1989-06-15 |
| JPH07115998B2 true JPH07115998B2 (en) | 1995-12-13 |
Family
ID=18036980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62313083A Expired - Lifetime JPH07115998B2 (en) | 1987-12-10 | 1987-12-10 | Method for producing silicon carbide single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07115998B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117966264B (en) * | 2024-02-02 | 2024-12-13 | 洛阳中硅高科技有限公司 | A method for preparing high-purity silicon carbide by chemical vapor deposition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51116200A (en) * | 1975-04-04 | 1976-10-13 | Showa Denko Kk | Method for formation of uniform and single phase silicon carbide coati ng |
-
1987
- 1987-12-10 JP JP62313083A patent/JPH07115998B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01153600A (en) | 1989-06-15 |
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