JPH02250969A - Production of boron nitride - Google Patents
Production of boron nitrideInfo
- Publication number
- JPH02250969A JPH02250969A JP7324289A JP7324289A JPH02250969A JP H02250969 A JPH02250969 A JP H02250969A JP 7324289 A JP7324289 A JP 7324289A JP 7324289 A JP7324289 A JP 7324289A JP H02250969 A JPH02250969 A JP H02250969A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- plasma
- gas
- cvd method
- production
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 17
- 229910052582 BN Inorganic materials 0.000 title claims description 16
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 B2H6 Chemical class 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はいわゆるＣＶＤ法による窒化ほう素の製造法に
関する。この窒化ほう素（ＢＮ）は立方耐食、耐磨耗性
被覆材、切削材などに利用される。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing boron nitride by a so-called CVD method. This boron nitride (BN) is used for cubic corrosion-resistant, wear-resistant coating materials, cutting materials, etc.
ＢＮには軟らかい六方晶窒化ほう素（以下ｈ−ＢＮとい
う）と高硬度なｃ−ＢＮがある。BN includes soft hexagonal boron nitride (hereinafter referred to as h-BN) and highly hard c-BN.
ｃ−ＢＮはｈ−ＢＮを高温、高圧処理して得る方法が古
くから行われているが、近年はほう素含有化合物からＣ
ＶＤ法による製法も提案されている。c-BN has long been obtained by processing h-BN at high temperature and high pressure, but in recent years, c-BN has been obtained by processing h-BN from boron-containing compounds.
A manufacturing method using the VD method has also been proposed.
ＣＶＤ法として従来知られている方法は原料としてポロ
アミノポリマー、ボラン、ジボラン、テトラボラン、Ｂ
ＣＩ ３．Ｂ５Ｎ５Ｈ，などが知られ、またＣＶＤ法と
してはマイクロ波、高周波、アーク放電、熱フイラメン
ト法などが知られている（特開昭６０−８１００９ 、
同６２−１８４８６９、同８２−４０３７６ 、同（ｔ
ｏ −５８７４、同８１−１７４３７８、同６３−１９
９８７１）。The method conventionally known as the CVD method uses polyamino polymer, borane, diborane, tetraborane, B
CI 3. B5N5H, etc. are known, and microwave, high frequency, arc discharge, hot filament methods, etc. are known as CVD methods (Japanese Patent Laid-Open No. 60-81009,
62-184869, 82-40376, (t
o -5874, 81-174378, 63-19
9871).
ＣＶＤ法によりＢＮを製造する場合、重要なことはｃ−
ＢＮの含有量を高めること、及びＢＮの生成速度を上げ
ること、その他原料化合物の毒性がないことや取り易い
ことである。When producing BN by the CVD method, the important thing is that c-
Increasing the content of BN, increasing the production rate of BN, and making the raw material compounds non-toxic and easy to remove.
前記した従来法では最も問題になるのはＢＨの生成速度
が低いことである。その他毒性のある原料を用いている
もの、特殊な装置を用いるためにコストが高くなるもの
などがある。The biggest problem with the conventional method described above is that the BH production rate is low. Others use toxic raw materials or require special equipment, resulting in high costs.
本発明の目的は特別な原料や装置を用いることなく、比
較的ｃ−ＢＮ含有率の高いＢＮを高速度で得ることにあ
る。An object of the present invention is to obtain BN with a relatively high c-BN content at high speed without using special raw materials or equipment.
本発明者はＣＶＤ法のＢＮ製法として従来試みられなか
ったプラズマジェット法が前記目的に対して極めて有効
であることを発見した。プラズマジェットは通常ＤＣ（
直流）であるがＡＣ（交流）も可能である。The inventors of the present invention have discovered that the plasma jet method, which has not been tried before as a CVD method for producing BN, is extremely effective for the above purpose. Plasma jet is usually DC (
Direct current), but AC (alternating current) is also possible.
本発明で使用される原料化合物となるほう素、窒素源は
特に制限なく、ＢとＮを含む化合物、例えば８３Ｎ３Ｈ
６、ポロアミノポリマーやＢ含有化合物とＮ含有化合物
の混合物、例えばＢ２Ｈ６とＮＨＨＢＯとＮＨ３などを
用いることができる。またＮＨに代ってＮ２とＮ２の混
合ガスでもよい。これらの中では原料の導入やガス圧の
調整のし昌さなどから、気体化合物である８ ２ Ｈ８
が好ましい。The boron and nitrogen sources used as raw material compounds used in the present invention are not particularly limited, and compounds containing B and N, such as 83N3H
6. Polyamino polymers or mixtures of B-containing compounds and N-containing compounds, such as B2H6, NHHBO, and NH3, can be used. Further, a mixed gas of N2 and N2 may be used instead of NH. Among these, 8 2 H8 is a gaseous compound due to the ease of introducing raw materials and adjusting gas pressure.
is preferred.
プラズマジェットを発生させるにはこれらの原料化合物
の外、プラズマ発生を容易にするためにＨｅ 、 Ａ
ｒ 、Ｈ２Ｉ Ｎ ２ガスなどが混合される。To generate a plasma jet, in addition to these raw material compounds, He and A are used to facilitate plasma generation.
r, H2IN2 gas, etc. are mixed.
その割合は一般的に混合ガス総量に対し、Ｂ源化合物と
窒素源化合物が１〜９９容量％が適し、残部がＨ２、Ａ
、等になる。この場合の全ガス圧は０．５〜６７ｋＰ
ａが適当である。In general, it is suitable that the proportion of B source compound and nitrogen source compound is 1 to 99% by volume with respect to the total amount of mixed gas, and the balance is H2 and A.
, etc. The total gas pressure in this case is 0.5 to 67kP
a is appropriate.
次に図面に基づいて具体的に本発明を説明する。Next, the present invention will be specifically explained based on the drawings.
図１は本発明を実施するための装置の１例で、１はセラ
ミック製管で内面に石英管２がはめ込まれている。３は
陰極でタングステンが好ましい。FIG. 1 shows an example of a device for carrying out the present invention, in which 1 is a ceramic tube with a quartz tube 2 fitted inside. 3 is a cathode, preferably made of tungsten.
その他黒鉛、Ｍｏ、Ｔａｔども用いることができる。４
は陽極で同じくタングステンが好ましいが、その他黒鉛
、Ｍｏ、Ｔａなども用いることができる。５は基体のｉ
Ｆｉである基板で８１ 、 Ｗ、 Ｍｏ 。Other materials such as graphite, Mo, and Tat can also be used. 4
Similarly, tungsten is preferable for the anode, but other materials such as graphite, Mo, and Ta can also be used. 5 is i of the base
81 on a substrate that is Fi, W, Mo.
Ｔａなどの金属、ＳｉＣ焼結体などのセラミ・ツク、超
硬合金チップ、その他サーメットなど殆んど制限なく使
用できる。その形状は板状、湾曲状など特に制限はない
。６は直流電源、８は原料ガスの導入口である。Metals such as Ta, ceramics such as SiC sintered bodies, cemented carbide chips, and other cermets can be used without any restrictions. The shape is not particularly limited, such as a plate shape or a curved shape. 6 is a DC power supply, and 8 is an inlet for raw material gas.
電極３と４の間でアークが発生し、ガスがプラズマ化す
る。このときプラズマの温度が５０００〜２００００
”Ｋにもなるので、ガスが急激に膨脂し、プラズマジェ
ット流７が形成される。電極４と基板５の距離は５〜５
０龍位が好ましい。基板温度は２００〜７００℃が適当
で、好ましくは５００〜７００℃である。必要ならばこ
れらの温度にするために基板に温度制御装置を設ける。An arc is generated between electrodes 3 and 4, and the gas turns into plasma. At this time, the temperature of the plasma is 5,000 to 20,000.
``K, so the gas rapidly expands and a plasma jet flow 7 is formed.The distance between the electrode 4 and the substrate 5 is 5 to 5.
0 dragon rank is preferred. The substrate temperature is suitably 200 to 700°C, preferably 500 to 700°C. A temperature control device is provided on the substrate to achieve these temperatures if necessary.
本発明の方法で基板への堆積速度は１分間に厚さで平均
約１００ｍ、最大で３００虜に達し、ＢＮの膜が形成さ
れる。このＢＮ膜巾のｃ−ＢＮ含有率は一般的には３０
〜４０重量％である。In the method of the present invention, the deposition rate on the substrate reaches an average thickness of about 100 m per minute and a maximum of 300 m, and a BN film is formed. The c-BN content of this BN film width is generally 30
~40% by weight.
従来、公知のプラズマＣＶＤ法では原料の供給を多くす
るとｃ−ＢＮ含有率が下がり、優れたＢＨ膜をつくるこ
とが困難であったが、本発明によるプラズマジェット法
では高速のジェット流が形成され、従って原料の供給速
度が大となるが、それにも拘らず、その理由は定かでは
ないがＣ−ＢＮの含有率下がらないという意外な結果が
わかった。Conventionally, in the known plasma CVD method, when the supply of raw materials was increased, the c-BN content decreased, making it difficult to create an excellent BH film, but in the plasma jet method of the present invention, a high-speed jet stream was formed. Therefore, although the feed rate of the raw material increases, the unexpected result was found that the C-BN content did not decrease, although the reason for this is not clear.
図１に装置を用い実験した。原料 ガスはＢ２Ｈ６（０
，７容量％）、ＮＨ（０，７容量％） 、Ｎ２（８８，
８容量％）、Ａｒ（３０容量％）の混合ガスを用いた。An experiment was conducted using the apparatus shown in Figure 1. The raw material gas is B2H6 (0
, 7% by volume), NH (0.7% by volume), N2 (88,
A mixed gas of 8% by volume) and Ar (30% by volume) was used.
Ａ「はアークの安定のために用いるものである。A is used to stabilize the arc.
石英管２は内周の径３．９ｃａ、長さ１５（！０１であ
る。混合ガスはガス導入口より１３ｋＰａで２０Ｉ／分
を供給した。なお、図示してないが、図１の装置は１３
ｋＰａに減圧しであるケース内に収められている。The quartz tube 2 has an inner diameter of 3.9 ca and a length of 15 (!01). The mixed gas was supplied from the gas inlet at 13 kPa and 20 I/min.Although not shown, the device in Fig. 1 13
It is housed in a case with a reduced pressure of kPa.
タングステン電極３．４間に直流電源６から電圧５５０
ｖを印加してアークを発生させた。出力は５．５ｋｗで
ある。基板温度は約７００℃とした。電極と基板間の距
離は約２０ｍ１１ｍである。基板にはＳｉウェハーを用
いた。Voltage 550 from DC power supply 6 between tungsten electrodes 3 and 4
v was applied to generate an arc. The output is 5.5kw. The substrate temperature was approximately 700°C. The distance between the electrode and the substrate is approximately 20m11m. A Si wafer was used as the substrate.
この条件で５分間実験したところ、基板５にＢＮが堆積
し、中心部が厚くなっていたが平均して約５００ｔｍの
膜となった。これを赤外分光により分析したところｃ−
ＢＮとｈ−ＢＮ混在したものであることがわかり、ｃ−
ＢＨの含有率は３０重量％であった。When an experiment was conducted under these conditions for 5 minutes, BN was deposited on the substrate 5, and the film was about 500 tm thick on average, although it was thick at the center. When this was analyzed by infrared spectroscopy, c-
It turns out that it is a mixture of BN and h-BN, and c-
The BH content was 30% by weight.
本発明によれば従来法に比較して格段に早い速度でＢＮ
膜が形成でき、しかもそのｃ−ＢＮ含有率も従来に較べ
て遜色ない。According to the present invention, BN can be generated at a much faster speed than the conventional method.
A film can be formed, and its c-BN content is comparable to that of conventional methods.
ｃ−ＢＮは熱電導度が島いので、放熱基板として利用で
き、またｃ−ＢＮは高硬度であり、これに潤滑性のｈ−
ＢＮが混在しているので、基材に被覆して摺動部材とし
ても優れた効果を発揮する。Since c-BN has a low thermal conductivity, it can be used as a heat dissipation substrate. Also, c-BN has high hardness and has lubricating properties.
Since BN is mixed therein, it exhibits an excellent effect when coated on a base material and used as a sliding member.
さらにステンレスやセラミック材に被覆して切削材とし
たり、或いは膜を粉砕し、ｃ−ＢＮを分離してｃ−ＢＮ
の粉粒体砥粒としての利用も可能である。Furthermore, it can be coated on stainless steel or ceramic material to be used as a cutting material, or the film can be crushed to separate c-BN.
It is also possible to use it as a powder abrasive grain.
図１は本発明方法を実施するための装置の１例を示す概
略断面図である。
３．４・・・電極 ５・・・基板
７・・・プラズマジェット流
特許出願人 −ノ瀬 幸 雄FIG. 1 is a schematic cross-sectional view showing one example of an apparatus for carrying out the method of the present invention. 3.4... Electrode 5... Substrate 7... Plasma jet flow patent applicant - Yukio Nose
Claims (2)
化ほう素を製造する方法において、ＣＶＤ法としてプラ
ズマジェット法を用いることを特徴とする方法。(1) A method for producing boron nitride on a substrate from a boron source and a nitrogen source by a CVD method, characterized in that a plasma jet method is used as the CVD method.
３を用いる請求項１の方法。(2) B_2H_6 and NH_ as boron source and nitrogen source
3. The method of claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7324289A JPH02250969A (en) | 1989-03-24 | 1989-03-24 | Production of boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7324289A JPH02250969A (en) | 1989-03-24 | 1989-03-24 | Production of boron nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02250969A true JPH02250969A (en) | 1990-10-08 |
Family
ID=13512517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7324289A Pending JPH02250969A (en) | 1989-03-24 | 1989-03-24 | Production of boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02250969A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04235283A (en) * | 1990-12-31 | 1992-08-24 | Semiconductor Energy Lab Co Ltd | Apparatus and method for forming coating film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277767A (en) * | 1987-05-11 | 1988-11-15 | Fujitsu Ltd | Method for synthesizing high-pressure phase boron nitride in gaseous phase |
| JPS6462471A (en) * | 1987-09-03 | 1989-03-08 | Fujitsu Ltd | Vapor phase synthesis method for high pressure-phase boron nitride |
| JPS6462470A (en) * | 1987-09-02 | 1989-03-08 | Fujitsu Ltd | Vapor synthesis method for high-pressure phase boron nitride |
| JPH01201481A (en) * | 1987-10-13 | 1989-08-14 | Fujitsu Ltd | Method and apparatus for vapor phase synthesis of high-pressure phase boron nitride |
-
1989
- 1989-03-24 JP JP7324289A patent/JPH02250969A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277767A (en) * | 1987-05-11 | 1988-11-15 | Fujitsu Ltd | Method for synthesizing high-pressure phase boron nitride in gaseous phase |
| JPS6462470A (en) * | 1987-09-02 | 1989-03-08 | Fujitsu Ltd | Vapor synthesis method for high-pressure phase boron nitride |
| JPS6462471A (en) * | 1987-09-03 | 1989-03-08 | Fujitsu Ltd | Vapor phase synthesis method for high pressure-phase boron nitride |
| JPH01201481A (en) * | 1987-10-13 | 1989-08-14 | Fujitsu Ltd | Method and apparatus for vapor phase synthesis of high-pressure phase boron nitride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04235283A (en) * | 1990-12-31 | 1992-08-24 | Semiconductor Energy Lab Co Ltd | Apparatus and method for forming coating film |
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