JPH0814023B2 - High-pressure phase boron nitride vapor phase synthesis method - Google Patents
High-pressure phase boron nitride vapor phase synthesis methodInfo
- Publication number
- JPH0814023B2 JPH0814023B2 JP21796987A JP21796987A JPH0814023B2 JP H0814023 B2 JPH0814023 B2 JP H0814023B2 JP 21796987 A JP21796987 A JP 21796987A JP 21796987 A JP21796987 A JP 21796987A JP H0814023 B2 JPH0814023 B2 JP H0814023B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- substrate
- phase
- boron nitride
- pressure phase
- 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
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- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 〔概要〕 高圧相窒化ホウ素（BN）を気相合成法で連続的に合成
する方法に関し、 高い製膜速度で高品質の高圧相BN膜を気相合成する方
法を提供することを目的とし、 ホウ素原子及び窒素原子をガス構成成分として含有す
る原料ガスを光アーク放電により熱プラズマ化し、得ら
れる熱プラズマを基板上にプラズマジェットとして照射
させて急冷することにより基板上に高圧相窒化ホウ素を
気相成長させることから構成する。Detailed Description [Overview] A method for continuously synthesizing high-pressure phase boron nitride (BN) by a vapor-phase synthesis method, including a method for vapor-phase synthesizing a high-quality high-pressure BN film at a high deposition rate. For the purpose of providing, a raw material gas containing boron atoms and nitrogen atoms as gas constituents is converted into thermal plasma by optical arc discharge, and the resulting thermal plasma is irradiated onto the substrate as a plasma jet and rapidly cooled on the substrate. The vapor-phase growth of high-pressure phase boron nitride is performed.
本発明の高圧相窒化ホウ素（BN）〔立方晶BN（ｃ−B
N）及びウルツ鉱型BN（ｗ−BN）〕の気相合成法、更に
詳しくは、高圧相BNを高い製膜速度で連続的に気相合成
する方法に関する。High pressure phase boron nitride (BN) of the present invention [cubic BN (c-B
N) and wurtzite-type BN (w-BN)], and more specifically to a method for continuously vapor-synthesizing high-pressure phase BN at a high film formation rate.
高圧相BNは熱伝導率及び硬度がダイヤモンドに匹敵す
るほど高く、しかも耐熱性はダイヤモンドより優れてい
るため、高圧相BNを薄膜状に合成できれば、半導体素子
の高密度実装用基板、ヒートシンク及び各種工具の高硬
度コーティング膜などとして広い分野で使用できると期
待されている。The high-pressure phase BN has a thermal conductivity and hardness comparable to that of diamond, and is superior in heat resistance to diamond. Therefore, if the high-pressure phase BN can be synthesized in a thin film, it can be used as a substrate for high-density mounting of semiconductor devices, heat sinks, and various It is expected to be used in a wide range of fields as a high hardness coating film for tools.
従来、高圧相BNの気相合成法としては、IBD法（イオ
ン化蒸着）、IVD法（イオン蒸着併用法）HCD−ARE法
（ホローカソード活性化化成蒸着）等が知られている
が、これらの方法では、得られら高圧相BNにグラファイ
ト構造の低圧相BN（ｈ−BN）や非晶質成分が含まれてし
まい、しかも、製膜速度も１μm/h以下と非常に遅く、
品質、コスト、生産性のいずれの点においても工業的プ
ロセスとしては不十分なものであった。Conventionally, IBD method (ionization vapor deposition), IVD method (ion vapor deposition combined method) HCD-ARE method (hollow cathode activated chemical vapor deposition), etc. are known as vapor phase synthesis methods for high-pressure phase BN. According to the method, the obtained high-pressure phase BN contains a low-pressure phase BN (h-BN) having a graphite structure and an amorphous component, and the film forming rate is very slow at 1 μm / h or less,
It was an insufficient industrial process in terms of quality, cost and productivity.
前述の如く、従来の方法で高圧相BNを合成した場合に
は、得られる窒化ホウ素が品質的に充分でなく、また製
膜速度が非常に遅いという問題があった。As described above, when the high-pressure phase BN is synthesized by the conventional method, there is a problem that the obtained boron nitride is not sufficient in quality and the film forming rate is very slow.
従って、本発明は前記した従来技術の問題点を排除し
て高い製膜速度で高品質の高圧相BN膜を気相合成する方
法を提供することを目的とする。Therefore, it is an object of the present invention to provide a method for vapor phase synthesizing a high-quality high-pressure phase BN film at a high film forming rate while eliminating the above-mentioned problems of the prior art.
本発明に従えば、前記問題点は、ホウ素原子及び窒素
原子をガス構成成分として含有する原料ガスを光アーク
放電により熱プラズマ化し、得られた熱プラズマを基板
上にプラズマジェットとして照射されて急冷することに
より、基板上に高圧相窒化ホウ素を気相成長させること
を特徴とする高圧相窒化ホウ素の気相合成法によって解
決される。According to the present invention, the problem is that a raw material gas containing boron atoms and nitrogen atoms as gas constituents is turned into thermal plasma by optical arc discharge, and the obtained thermal plasma is irradiated onto the substrate as a plasma jet and rapidly cooled. This is solved by a vapor phase synthesis method of high pressure phase boron nitride, which is characterized in that high pressure phase boron nitride is vapor-deposited on a substrate.
以下、添付図面に基づいて本発明を具体的に説明す
る。Hereinafter, the present invention will be specifically described with reference to the accompanying drawings.
第１図は本発明に従って高圧相BNを気相合成する装置
の一例を説明する図面である。FIG. 1 is a view for explaining an example of an apparatus for vapor phase synthesis of high pressure phase BN according to the present invention.
第１図において、１は一般的な大出力レーザ（例えば
炭酸ガスレーザなど）であり、大出力レーザからのレー
ザビーム２を集光レンズ３で集光させて集光コーン12の
先端部に極めて高い光強度を得る。一方、集光コーン12
には、ガス導入口４より原料ガスを大気圧又はそれ以上
の圧力で導入する。この原料ガスは、BNの原料となる、
例えばB2H6などのホウ素の水素化物、BCl3などのホウ素
のハロゲン化物、B2（CH3）６の有機化合物などのホウ
素原子を含むガス及びNH3やN2などの窒素原子を含むガ
スを含有し、更に、好ましくは、反応性を高めるガスと
してH2を含み、またプラズマを安定化させるためのガス
としてAr、Heなどを含む。かかる原料ガス中の各成分の
組成については限定はないが、一般には以下のような組
成（容積％）が好ましい。In FIG. 1, reference numeral 1 is a general high-power laser (for example, a carbon dioxide gas laser), and a laser beam 2 from the high-power laser is condensed by a condenser lens 3 and is extremely high at the tip of the condenser cone 12. Get the light intensity. On the other hand, the condensing cone 12
The raw material gas is introduced through the gas inlet 4 at atmospheric pressure or higher. This source gas is the source of BN,
For example, boron hydrides such as B 2 H 6 ; boron halides such as BCl 3 ; gases containing boron atoms such as B 2 (CH 3 ) 6 organic compounds; and nitrogen atoms such as NH 3 and N 2. It contains a gas, and more preferably contains H 2 as a gas for enhancing the reactivity, and Ar, He and the like as a gas for stabilizing the plasma. The composition of each component in the raw material gas is not limited, but generally the following composition (volume%) is preferable.
Ｂ原子を含むガス 0.01〜 10％ Ｎ原子を含むガス 0.01〜 10％ H2 20 〜100％ Ar又はHe ０ 〜 80％ 上記した原料ガスは、ガス導入口４より導入され、集
光コーン12の先端部で集光されたレーザビーム２によっ
て10000℃以上の高温に加熱され、光アーク放電によっ
て化学的に高い高温熱プラズマとなる。原料ガス流は、
この際の急激な熱膨張によりプラズマジェット７とな
り、水冷プラズマジェットノズル６から噴射される。な
お、集光コーン12の先端部の水冷プラズマジェットノズ
ル６は、ノズルの冷却の目的で冷却水出入口５から冷却
水を流して冷却する。Gas containing B atom 0.01 to 10% Gas containing N atom 0.01 to 10% H 2 20 to 100% Ar or He 0 to 80% The above-mentioned raw material gas is introduced from the gas introduction port 4 to collect the light from the condensing cone 12. It is heated to a high temperature of 10000 ° C. or higher by the laser beam 2 focused at the tip portion, and becomes a chemically high temperature thermal plasma by the light arc discharge. The source gas flow is
The rapid thermal expansion at this time forms a plasma jet 7, which is jetted from a water-cooled plasma jet nozzle 6. The water-cooled plasma jet nozzle 6 at the tip of the condensing cone 12 cools by flowing cooling water from the cooling water inlet / outlet port 5 for the purpose of cooling the nozzle.
ノズル６から噴射されたプラズマジェット７は原料ガ
ス中のBN原料ガスが高密度で分割活性化されており、こ
れが例えば温度500〜1200℃の基板８に衝突すると、熱
プラズマの急冷効果により大量のBN原料ガスが非平衡状
態で高活性化され、基板８上に高い製膜速度で高圧相BN
が気相合成される。基板８には、特に限定はないが、S
i、Al2O3、SiC、Mo、石英ガラスなどを用いることがで
きる。なお、基板８はチャンバー10内の水冷基板ホルダ
９上に置かれ、排ガスは排気系11から排気される。In the plasma jet 7 jetted from the nozzle 6, the BN raw material gas in the raw material gas is divided and activated at a high density, and when this collides with the substrate 8 at a temperature of 500 to 1200 ° C. The BN source gas is highly activated in the non-equilibrium state, and the high-pressure phase BN is formed on the substrate 8 at a high film formation rate.
Are vapor-phase synthesized. The substrate 8 is not particularly limited, but S
i, Al 2 O 3 , SiC, Mo, quartz glass or the like can be used. The substrate 8 is placed on the water-cooled substrate holder 9 in the chamber 10, and the exhaust gas is exhausted from the exhaust system 11.
前記したように、本発明に従えば、非平衡状態で高活
性化されたＢ及びＮを含む原料ガスがプラズマジェット
として基板上に大量供給されるので、高品質の高圧相BN
が高い製膜速度で気相合成することができる。As described above, according to the present invention, a large amount of the source gas containing B and N highly activated in the non-equilibrium state is supplied as a plasma jet onto the substrate, so that the high-quality high-pressure phase BN
It is possible to perform vapor phase synthesis at a high film forming rate.
実施例 以下に本発明の実施例を説明するが、本発明の技術的
範囲を実施例に限定するものではないことはいうまでも
ない。Examples Examples of the present invention will be described below, but it goes without saying that the technical scope of the present invention is not limited to the examples.
光源として、発振波長10.6μｍ、出力20kW及びビーム
径80mmの一般的なフロー型炭酸ガスレーザ１を用い、口
径8mm、f1.5の集光レンズ３を用いたノズル径3mmの光ア
ークプラズマトーチに、Ar5/min、H23/min、B2H61
/min及び、NH31.8/minの原料ガスを流し、プラズマ
ジェット７を発生させた。チャンバー10内の圧力200Tor
rで、ノズルから30mmはなして、水冷基板ホルダ上に30
×30mm、厚さ0.5mmのSi基板８を置き、基板温度が600℃
になるように冷却水流量をコントロールしながら、30
分、BNの合成を行った。As a light source, a general flow type carbon dioxide gas laser 1 having an oscillation wavelength of 10.6 μm, an output of 20 kW and a beam diameter of 80 mm is used, and an optical arc plasma torch having a nozzle diameter of 3 mm and a condenser lens 3 having an aperture of 8 mm and f1.5 is used. Ar 5 / min, H 2 3 / min, B 2 H 6 1
/ min and NH 3 1.8 / min of raw material gas were caused to flow to generate a plasma jet 7. Pressure in chamber 10 200 Tor
At r, release 30 mm from the nozzle and place 30
Place the Si substrate 8 of × 30mm and thickness 0.5mm, and the substrate temperature is 600 ℃.
While controlling the flow rate of the cooling water so that
Min, BN was synthesized.
生成した膜は、厚さ30μｍの無色の膜で、Ｘ線回析及
び赤外分光分析で調べたところ、ｃ−BNのピークのみが
検出された。また、ビッカース硬度を調べたところ荷重
500gで4000〜5000の値を示し、熱伝導率は800W/mKであ
った。The produced film was a colorless film having a thickness of 30 μm, and when examined by X-ray diffraction and infrared spectroscopic analysis, only the peak of c-BN was detected. Also, when the Vickers hardness was examined, the load
It showed a value of 4000 to 5000 at 500 g and a thermal conductivity of 800 W / mK.
本発明によれば、高活性度の光アークプラズマジェッ
トを用いることにより、従来法に比べ低圧相BNが殆ど存
在せず、熱伝導率及び硬度の高い良質の高圧相BNの膜を
高い製膜速度で基板上に気相成長させることができ、品
質、コスト及び生産性の向上が達成できた。According to the present invention, by using a high activity optical arc plasma jet, there is almost no low-pressure phase BN as compared with the conventional method, and a high-quality high-pressure phase BN film with high thermal conductivity and hardness is formed into a high film. Vapor growth was possible on the substrate at a high speed, and improvement in quality, cost and productivity could be achieved.
第１図は本発明に従って高圧相BNを気相合成する装置の
一例を示す説明図である。 第１図において、１……大出力レーザ、２……レーザビ
ーム、３……集光レンズ、４……ガス導入口、５……冷
却水出入口、６……水冷プラズマジェットノズル、７…
…プラズマジェット、８……基板、９……水冷基板ホル
ダ、10……チャンバー、11……排気系、12……集光コー
ンである。FIG. 1 is an explanatory view showing an example of an apparatus for vapor phase synthesis of high pressure phase BN according to the present invention. In FIG. 1, 1 ... Large output laser, 2 ... Laser beam, 3 ... Condenser lens, 4 ... Gas inlet, 5 ... Cooling water inlet, 6 ... Water cooled plasma jet nozzle, 7 ...
… Plasma jet, 8… Substrate, 9… Water-cooled substrate holder, 10… Chamber, 11… Exhaust system, 12… Focusing cone.
Claims (3)
して含有する原料ガスを光アーク放電により熱プラズマ
化し、得られた熱プラズマを基板上にプラズマジェット
として照射させて急冷することにより、基板上に高圧相
窒化ホウ素を気相成長させることを特徴とする高圧相窒
化ホウ素の気相合成法。1. A substrate on which a raw material gas containing boron atoms and nitrogen atoms as gas constituents is converted into thermal plasma by optical arc discharge, and the resulting thermal plasma is irradiated onto the substrate as a plasma jet to be rapidly cooled. A vapor-phase synthesis method of high-pressure phase boron nitride, which comprises vapor-phase growing high-pressure phase boron nitride.
素の水素化物、ハロゲン化物、及び／又は有機ホウ素化
合物を、そして窒素原子含有ガスとしてNH3及び／又はN
2を含み、更に反応性を高めるガスとしてH2を、そして
プラズマの安定化のためにAr及び／又はHeを含む特許請
求の範囲第１項記載の方法。2. The raw material gas is a boron hydride, a halide, and / or an organic boron compound as a boron atom-containing gas, and NH 3 and / or N as a nitrogen atom-containing gas.
2. A method according to claim 1, which contains 2 and further contains H 2 as the gas for increasing the reactivity and Ar and / or He for stabilizing the plasma.
の範囲第１項記載の方法。3. The method according to claim 1, wherein the temperature of the substrate is 500 to 1200 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21796987A JPH0814023B2 (en) | 1987-09-02 | 1987-09-02 | High-pressure phase boron nitride vapor phase synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21796987A JPH0814023B2 (en) | 1987-09-02 | 1987-09-02 | High-pressure phase boron nitride vapor phase synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6462470A JPS6462470A (en) | 1989-03-08 |
| JPH0814023B2 true JPH0814023B2 (en) | 1996-02-14 |
Family
ID=16712571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21796987A Expired - Lifetime JPH0814023B2 (en) | 1987-09-02 | 1987-09-02 | High-pressure phase boron nitride vapor phase synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0814023B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02250969A (en) * | 1989-03-24 | 1990-10-08 | Yukio Ichinose | Production of boron nitride |
| JPH03111573A (en) * | 1989-09-26 | 1991-05-13 | Olympus Optical Co Ltd | Method for synthesizing cubic boron nitride |
| DE102010053214A1 (en) * | 2010-12-03 | 2012-06-06 | Evonik Degussa Gmbh | Process for the hydrogen passivation of semiconductor layers |
-
1987
- 1987-09-02 JP JP21796987A patent/JPH0814023B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6462470A (en) | 1989-03-08 |
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