JPS62205277A - Method for synthesizing high-hardness boron nitride - Google Patents
Method for synthesizing high-hardness boron nitrideInfo
- Publication number
- JPS62205277A JPS62205277A JP4546286A JP4546286A JPS62205277A JP S62205277 A JPS62205277 A JP S62205277A JP 4546286 A JP4546286 A JP 4546286A JP 4546286 A JP4546286 A JP 4546286A JP S62205277 A JPS62205277 A JP S62205277A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- boron nitride
- atom
- containing gas
- hydrogen
- 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
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 44
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 27
- 239000007789 gas Substances 0.000 claims abstract description 69
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000008246 gaseous mixture Substances 0.000 abstract 4
- 238000005520 cutting process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 B5N3& Inorganic materials 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- AOPJVJYWEDDOBI-UHFFFAOYSA-N azanylidynephosphane Chemical compound P#N AOPJVJYWEDDOBI-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 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、非常に高硬度を有するのみならず、熱伝導率
にとみ、化学的に安定で、加えてダイヤモンドとは異な
り、鉄族金し４に対する耐性（（も優れることから、切
削工具、耐摩工具などの工具材料、さらにはヒートシン
クなどの１１ｙ子材料とし、で用いられている立方晶窒
化ホウ素ケ、気相より基材表面に析出させる方法に関す
るイ、のである。[Detailed Description of the Invention] [Industrial Application Field] The present invention not only has extremely high hardness, but also has high thermal conductivity and is chemically stable. Due to its excellent resistance to corrosion, it is used as a material for tools such as cutting tools and wear-resistant tools, and even for heat sinks. This is about how to do it.
立方晶窒化ホウ素の製造方法として、従来、例えば下記
の■〜■の方法等が知られていた。Conventionally, methods for producing cubic boron nitride have been known, such as the following methods (1) to (2).
■ 特公昭ＡＯ−１８１２６２号公報に示されるように
、ホウ素を含有する蒸発林からｗ体上にホウ素分を蒸着
させると共に、少なくとも窒素を含むイオン種を発生せ
しめるイオン発生源から基体上に該イオン種を照射して
、該基体上に窒化ホウ素を生成させる窒化ホウ素膜の製
造方法。■ As shown in Japanese Patent Publication No. AO-181262, boron is deposited on the substrate from an evaporation forest containing boron, and at the same time, the ions are deposited on the substrate from an ion source that generates ionic species containing at least nitrogen. A method for producing a boron nitride film, comprising irradiating a seed to produce boron nitride on the substrate.
■ ジャーナル オプ マテリアルス サイエンス レ
ターズ（、Ｔｏｕｒｎａｌ ｏｆ ｍａｔｅｒｉａｌａ
ａｃｉａｎｃｅ ｘｅｔｔｅｒｓ ）、Ｊ（１９８５）
５１〜５４頁、に示されるように、Ｈｚ十Ｎｚプラズマ
によるボロンの化学輸送を行うことにより、立方晶窒化
ホウ素を生成する方法。■ Journal of Materials Science Letters (, Journal of Materials Science Letters)
aciance xetters), J. (1985).
As shown in pages 51 to 54, a method for producing cubic boron nitride by chemically transporting boron using Hz-10Nz plasma.
■ ８ｇ９回イオン工学シンポジウム（１９８５年、東
京）議事録、「イオ／源とイオンを基礎とした応用技術
」、に示されるように、ＨＯＤガンでボロンを蒸発させ
ながら、ホローアノードからＮａｋイオン化して基板に
放射し、基板には高周波を印加して、セルフバイアス効
果を持たせて立方晶窒化ホウ素を生成する方法。■ As shown in the proceedings of the 8g 9th Ion Engineering Symposium (Tokyo, 1985), ``Ion/source and applied technology based on ions'', Nak ionization was performed from the hollow anode while boron was evaporated with a HOD gun. A method of generating cubic boron nitride by applying high frequency waves to the substrate and creating a self-bias effect.
〔発明が解決しようとする問題点〕
しかしながら、前記■の方法は、イオンビームを発生す
る装置及びその集束装置が高価であることが欠截である
。[Problems to be Solved by the Invention] However, the above-mentioned method (1) is lacking in that the ion beam generating device and its focusing device are expensive.
前記（力の方法は、プラズマエネルギー密度が大きい為
、Ｓｐ’結号がうまく働かず、欠陥準位を多く有する欠
点を有している。The aforementioned (force method) has the disadvantage that the Sp' bond does not work well because the plasma energy density is high, and that it has many defect levels.
前記■の方法は、■の方法と同じく、イオンビームを発
生する装置及びその集束装置が高価でちることと、不活
性ガスの原子が析出した立方晶窒化ホウ素に取り込まれ
る、という欠点を有する。Like method (2), method (2) has the disadvantages that the ion beam generating device and its focusing device are expensive and expensive, and that atoms of the inert gas are incorporated into the precipitated cubic boron nitride.
本発明の目的は、化学気相析出法において、反応ガスの
濃度及びその比率、加熱温度、反応系の圧力、などの合
成条件を独立して可変することが容易であり、それらの
合成条件を可変することにより、前記した従来法■〜■
の問題点を解決し、基板表面に立方晶窒化ホウ素を析出
する新規な方法を提案するところにδる。An object of the present invention is to easily and independently vary synthesis conditions such as the concentration and ratio of reaction gases, heating temperature, and pressure of the reaction system in a chemical vapor deposition method. By varying the above conventional methods ■～■
We propose a new method for depositing cubic boron nitride on the surface of a substrate by solving these problems.
本発明はホウ素原子含有ガス、窒素原子含有ガスおよび
水素からなる混合ガスを、マイクロ波無極放電中を通過
させた後、３００〜１３００℃に加熱した基板表面に導
入することにより、該混合ガスを熱分解、反応させ、上
記基板表面に窒化ホウ素を析出させることを特徴とする
高硬度窒化ホウ素の合成方法である。In the present invention, a mixed gas consisting of a boron atom-containing gas, a nitrogen atom-containing gas, and hydrogen is passed through a microwave non-polar discharge, and then introduced onto the surface of a substrate heated to 300 to 1300°C. This is a method for synthesizing high hardness boron nitride, which is characterized by thermal decomposition and reaction to precipitate boron nitride on the surface of the substrate.
また本発明のＷ、２の発明は、水素ガスをマイクロ波無
極放電中を通過させた後に、ホウ素原子含有ガスおよび
窒素原子含有ガスと混合し、該混合ガスを３００〜１３
００℃に加熱した基板表面に導入することにより、該混
合ガスを熱分解、反応させ、上記基板表面に窒化ホウ素
を析出させることを特徴とする高硬度窒化ホウ素の合成
方法に関する。In addition, in the invention of W, 2 of the present invention, after passing hydrogen gas through a microwave non-polar discharge, it is mixed with a boron atom-containing gas and a nitrogen atom-containing gas, and the mixed gas is
The present invention relates to a method for synthesizing high-hardness boron nitride, which comprises introducing the mixed gas onto the surface of a substrate heated to 00° C. to cause the mixed gas to thermally decompose and react, thereby depositing boron nitride on the surface of the substrate.
上記＃４１および第２の発明における特に好ましい実施
態様としては、ホウ素原子含有ガス、窒素原子含有ガス
および水素の混合ガスの混合比率を、
ホウ素原子含有ガス／水索回１００〜１１００１、窒素
原子含有ガス／ 水素−１００〜（１００１、の範囲と
することが挙げられる。As a particularly preferred embodiment of the above #41 and the second invention, the mixing ratio of the mixed gas of the boron atom-containing gas, the nitrogen atom-containing gas, and hydrogen is set such that the boron atom-containing gas/water line ratio is 100 to 11001, and the nitrogen atom-containing Gas/Hydrogen may be in the range of -100 to (1001).
本発明は、励起状態のホウ素原子含有ガスと励起状態の
窒素ガスとを、励起もしくは原子状態の水素の存在下、
加熱された基板表面で熱分解・反応させて、これにより
生成した立方晶窒化ホウ素を該基板上に析出せしめる方
法であり、原料ガス及び水素を励起もしくは原子状態と
するには、これらのガスをマイクロ波無極放電中を通過
させることによる。これにはまず水素ガスをマイクロ波
無極放電中に通過せしめた後、ホウ素原子含有ガス及び
窒素原子含有ガスと混合してもよいし、またはホウ素原
子含有ガス及び窒素原子含有ガスと水素ガスを混合した
後、マイクロ波無極放電中を通過せしめてもよい。The present invention combines an excited boron atom-containing gas and an excited nitrogen gas in the presence of excited or atomic hydrogen.
This method involves thermal decomposition and reaction on the surface of a heated substrate, and the resulting cubic boron nitride is deposited on the substrate. By passing microwaves through a polarless discharge. For this, hydrogen gas may first be passed through a microwave polarless discharge and then mixed with a boron atom-containing gas and a nitrogen atom-containing gas, or the boron atom-containing gas and nitrogen atom-containing gas may be mixed with hydrogen gas. After that, it may be passed through microwave non-polar discharge.
いずれの方法によっても、励起状態のホウ素原子含有ガ
ス及び窒素原子含有ガス、励起状態又は原子状態の水素
を生成することができる。前者の場合には、励起された
水素の作用でホウ素原子、窒素原子も励起される。Any of the methods can produce a boron atom-containing gas and a nitrogen atom-containing gas in an excited state, and hydrogen in an excited state or an atomic state. In the former case, boron atoms and nitrogen atoms are also excited by the action of excited hydrogen.
本発明においては、安定に放電を持続させるため、マイ
クロ波無極放電を採用することが好ましい。直流放電の
場合は、電極を利用するため長時間連続しての放電の発
生は困難である。In the present invention, it is preferable to employ microwave nonpolar discharge in order to sustain stable discharge. In the case of direct current discharge, since electrodes are used, it is difficult to generate continuous discharge for a long time.
また、数千ＭＨｚ以下の周波数による無極放電の発生は
系の圧力に強く依存する。従ってマイクロ波無極放電は
系の圧力への依存度を軽減することができる。Furthermore, the occurrence of nonpolar discharge at a frequency of several thousand MHz or less strongly depends on the pressure of the system. Therefore, microwave non-polar discharge can reduce the dependence on system pressure.
無極放電を発生する管内の圧力は、放電安定を維持する
ために、０．０５ Ｔｏｒｒ〜４００Ｔｏｒｒの範囲が
好ましい。The pressure inside the tube that generates the non-polar discharge is preferably in the range of 0.05 Torr to 400 Torr in order to maintain discharge stability.
次にこれらの気体を加熱された基板表面に導入すると、
この励起状態のホウ素原子含有ガス及び窒素原子含有ガ
スが加熱された基板表面で熱分解した時に、遊離ホウ素
原子及び遊離窒素原子に互いにＳ？結合を起すのに充分
な反応エネルギーを供給する。Next, when these gases are introduced onto the heated substrate surface,
When this excited state boron atom-containing gas and nitrogen atom-containing gas are thermally decomposed on the heated substrate surface, free boron atoms and free nitrogen atoms are mutually converted into S? Provides sufficient reaction energy to cause bonding.
また、励起状態または原子状態の水素は、非立方晶窒化
ホウ素を成長させる原因となるｓｌ混成軌道を持った核
と反応し、これをｓｐ結合に変換あるいは、水素化ホウ
素、窒化水素を生成し、高硬度窒化ホウ素の成長する面
の清浄化の作用をする。In addition, hydrogen in an excited or atomic state reacts with a nucleus with an sl hybrid orbital, which causes the growth of non-cubic boron nitride, converting it into an sp bond or producing boron hydride or hydrogen nitride. , has the effect of cleaning the surface on which the high hardness boron nitride grows.
ホウ素原子含有ガスとして、例えば迅へ。For example, as a boron atom-containing gas.
Ｂｅ／３ 、 ＢＢｒ３ 、 Ｂ５Ｎ３＆等が挙げられ
、又、窒素原子含有ガスとして、例えばＮｚ 、Ｎｕｔ
、等が挙げられる。Examples include Be/3, BBr3, B5N3&, and nitrogen atom-containing gases include, for example, Nz, Nut
, etc.
使用する混合ガスのホウ素原子含有ガス及び慴素原子含
有ガスと水素ガスと混合比率は広い範囲に変更し得るも
ので、ホウ素原子含有ガス／水素ガス＝ｍ１００〜０．
００１、窒素原子含有ガス／水素ガス−１００〜（１０
０１の範囲が好ましい。上記夫々の比率が１００１以下
の時は、ホウ素原子含有ガス及び窒素原子含有ガスが希
釈されすぎているため、基板上ｌＣ窒化ホウ素膜が成膜
しにくくなる。また上記夫々の比率が１００以上の時は
、水素ガスがほとんど含まれないため、高硬度窒化ホウ
素の清浄面の作用がされにくく、高硬度窒化ホウ素が得
にくい。The mixing ratio of the boron atom-containing gas and hydrogen atom-containing gas to the hydrogen gas in the mixed gas used can be varied within a wide range, and boron atom-containing gas/hydrogen gas = m100 to 0.
001, nitrogen atom-containing gas/hydrogen gas-100~(10
A range of 01 is preferred. When each of the above ratios is 1001 or less, the boron atom-containing gas and the nitrogen atom-containing gas are too diluted, making it difficult to form an 1C boron nitride film on the substrate. Further, when each of the above ratios is 100 or more, hydrogen gas is hardly contained, so that the cleaning surface effect of high hardness boron nitride is difficult to be performed, and it is difficult to obtain high hardness boron nitride.
基板温度は、析出した立方晶窒化ホウ素から窒素が抜け
、非立方晶窒化ホウ素に転移する現象を防止し、また励
起状態のホウ素原子含有ガス及び窒素原子含有ガスを熱
分解を起すのに必要な温度であることを必要とするので
、３００〜１３００℃であることが好ましい。The substrate temperature is set at a temperature necessary to prevent nitrogen from leaving the deposited cubic boron nitride and transform into non-cubic boron nitride, and to thermally decompose the excited boron atom-containing gas and nitrogen atom-containing gas. The temperature is preferably 300 to 1300°C.
次に本発明の方法を図を参照して具体的に説明する。第
１図及び第２図は本発明により高硬度窒化ホウ素を合成
する実施態様を示す図であって、第１図及び第２図にお
いて１は、ホウ素原子含有ガス及び窒素原子含有ガス供
給装置、２は水素ガス供給装置、３はウェーブガイド、
４はマイクロ波発振器、５は反応室、６は排気装置、７
は基板、８は基板支持台、９は抵抗加熱炉、１０，１１
．１２はコック、１５は排気口を示す。Next, the method of the present invention will be specifically explained with reference to the drawings. 1 and 2 are diagrams showing an embodiment of synthesizing high-hardness boron nitride according to the present invention, and in FIGS. 1 and 2, 1 indicates a boron atom-containing gas and a nitrogen atom-containing gas supply device, 2 is a hydrogen gas supply device, 3 is a wave guide,
4 is a microwave oscillator, 5 is a reaction chamber, 6 is an exhaust device, 7
is a substrate, 8 is a substrate support stand, 9 is a resistance heating furnace, 10, 11
．． 12 is a cock, and 15 is an exhaust port.
第１図は、ガス供給装置１及び２からの全反応ガスと混
合して反応室５に導入し、マイクロ波無極放電中に通過
させた後、基板７の天面に導入し反応させる方法の例で
あり、第２図は水素ガスのみをマイクロ波無極放電中に
通過させ、その後にガス供給装置ｆ １からホウ素原子
含有ガス及び窒素原子含有ガスと混合して反応室５へ導
入する方法の例でおる。Figure 1 shows a method in which the mixture is mixed with all the reaction gases from gas supply devices 1 and 2, introduced into the reaction chamber 5, passed through the microwave during polarless discharge, and then introduced onto the top surface of the substrate 7 for reaction. As an example, FIG. 2 shows a method in which only hydrogen gas is passed through a microwave non-polar discharge, and then mixed with a boron atom-containing gas and a nitrogen atom-containing gas from the gas supply device f1 and introduced into the reaction chamber 5. I'll give you an example.
第１図の方法では、マイクロ波放電中に基板７が存在し
ているので、マイクロ波プラズマの強度により基板温度
を変えうるが、第２図の方法では、基板７はマイクロ波
プラズマ外に存在しているので、抵抗加熱炉９により基
板？加熱する。In the method shown in Fig. 1, the substrate 7 is present during the microwave discharge, so the substrate temperature can be changed depending on the intensity of the microwave plasma, but in the method shown in Fig. 2, the substrate 7 is present outside the microwave plasma. So, is the substrate heated by the resistance heating furnace 9? Heat.
実施例１゜
Ｆｉ１図の構成に従い、本発明による窒化ホウ素の合成
を行った。基板としてはモリブデン？用い、反応ガスと
しては、ジボランガス、窒素ガス及び水素ガスを用いた
。Example 1 Boron nitride according to the present invention was synthesized according to the configuration shown in Fig. 1°Fi1. Molybdenum for the substrate? Diborane gas, nitrogen gas, and hydrogen gas were used as reaction gases.
排気装置を作動し反応系を減圧にした。次にジボランガ
ス、窒素ガス、水素ガスをそれぞれ、Ｉ ＣＣ／ ｍｉ
ｎ 、 ４ ＣＣ／ ｍｉｎ 、 １００ ＣＣ／ ｍ
ｉｎ流した。その時の反応系圧力は５０ Ｔｏｒｒ
とした。The exhaust system was activated to reduce the pressure in the reaction system. Next, diborane gas, nitrogen gas, and hydrogen gas were each
n, 4 CC/min, 100 CC/m
I ran it in. The reaction system pressure at that time was 50 Torr.
And so.
次に基板温度を７００℃に上昇すると共に、２、４５
ＧＨｚのマイクロ波発振器によって無極放電を発生し、
５時間反応を続けたところ、基板表面に２μ？ルの厚さ
の窒化ホウ素膜？付出させることができた。これをＸ線
回折しｆｃところ（１゜１．１）パターンが現ｆ１．た
ので、立方晶窒化ホウ素と同定できだ。Next, the substrate temperature was raised to 700°C, and
A GHz microwave oscillator generates a non-polar discharge,
When the reaction continued for 5 hours, 2μ? A boron nitride film with a thickness of 1.5 mm? I was able to get him to submit it. This was subjected to X-ray diffraction, and the fc (1° 1.1) pattern was found to be the current f1. Therefore, it could be identified as cubic boron nitride.
実施例Ｚ
′″ＪＹ、１図の杯！成に従い、シリコンウェハーを基
板として、本発明（てよる窒化ホウ九の合成を行った。Example Z'''JY, according to the method shown in Fig. 1, the synthesis of phosphorous nitride according to the present invention was carried out using a silicon wafer as a substrate.
操作子ｊＩは実施例１と同様で、反応ガス条件はジボラ
ンガス２ ＣＣ／ ｍｉｎ 、アンモニア１０ ｃＣ／
ｍｉｎ 、水嵩ガス５０ＣＣ／ｍｉｎ、反応系圧力２
０ Ｔｒ＞ｒｒ とした。基板温度７００℃とし、７
、、．４５ ＧＨｚのマイクロ波発振器で無極放電？発
生し、４時間析出を行ったところ、基板表面に約１．５
μ慣の厚さの立方晶窒化ホウ素膜を得た。The operator jI was the same as in Example 1, and the reaction gas conditions were diborane gas 2 CC/min and ammonia 10 cC/min.
min, water bulk gas 50CC/min, reaction system pressure 2
0 Tr>rr. The substrate temperature is 700℃, and
,,． Polarless discharge with a 45 GHz microwave oscillator? After 4 hours of precipitation, about 1.5
A cubic boron nitride film with a thickness of μm was obtained.
実施例乙
第１図の構成に従い、シリコーンウェハーを基板として
、本発明による窒化ホウ素の合成を行った。操作手順は
実施例１と同様とし、反応ガス条件は、塩化ホウ素ガス
１ｏｃ／ｍｉｎ、窒素ガス２ｅｃ／ｍｉｎ、水素ガス１
００ｃ／ｍｉｎ、反応系圧力４１’ｌ Ｔｏｒｒ と
Ｉ７た。基板ＦｎｌｌＪｆ ７０’ ℃、２、、、 Ａ
５ ｔｌＨｚマイクロ波発振器によるマイクＩ］波無
極放屯、析出時間５時間で、基叛表面各・□こ厚さ２μ
青の立方晶窒化ホウ素１漠金得た、３実施例４゜
第２図の構成に従い、シリコーンウェーバー・全基板と
し２、本発明によＺ）窒化ホウ素の合成を行った。４ず
、排気装置を作動し、反応系を減圧にする。続いて、水
素ガスケ１００仁／ ｍｉｎのｉｔで供給すると共に、
反応系圧力’；＜ ２０ ＴｏｒｒＫ調整した。２．
Ａ ５ ＧＨｚのマイクロ波発振器Ｖこより無極放電を
発生し、この中？通過した水素ガスを反応室へと導入し
た。次に基板温度全７００℃に上昇させると共（１ｃ１
ジボランガス２Ｃｒ、 ／ ｍｉｎ及びアンモニア１
０ Ｅ ／ ｍｉｎを供給し、前記の無極放電中を通過
してきた水素と混合して加熱基板表面に導入した。５時
間反応を続けたところ、基板表面ＩＣ厚さ１μｍの高硬
度窒化ホウ素膜が析出した。これをＸＨ回折したところ
、立方晶窒化ホウ素と同定できた。Example B According to the structure shown in FIG. 1, boron nitride was synthesized according to the present invention using a silicone wafer as a substrate. The operating procedure was the same as in Example 1, and the reaction gas conditions were boron chloride gas 1 oc/min, nitrogen gas 2 ec/min, and hydrogen gas 1 oc/min.
The reaction system pressure was 41'l Torr and I7. Substrate FnllJf 70'℃, 2,, A
Microphone I using a 5 tlHz microwave oscillator] Waveless radiation, deposition time 5 hours, thickness of each □ on the substrate surface 2μ
Blue cubic boron nitride was obtained.Example 4 According to the structure shown in FIG. 2, silicone Weber was used as the entire substrate.Z) Boron nitride was synthesized according to the present invention. 4. First, operate the exhaust system to reduce the pressure in the reaction system. Next, hydrogen gas was supplied at a rate of 100 liters/min, and
Reaction system pressure was adjusted to <20 TorrK. 2.
A 5 GHz microwave oscillator V generates a non-polar discharge, and inside this? The hydrogen gas that passed through was introduced into the reaction chamber. Next, the total substrate temperature was raised to 700°C (1c1
Diborane gas 2Cr, / min and ammonia 1
0 E/min was supplied, and the hydrogen was mixed with the hydrogen that had passed through the non-polar discharge and introduced onto the surface of the heated substrate. When the reaction was continued for 5 hours, a highly hard boron nitride film with a thickness of 1 μm was deposited on the substrate surface. When this was subjected to XH diffraction, it was identified as cubic boron nitride.
以上の実施例１〜４において、立方晶窒化ホウ素（ＯＢ
Ｎ ）が作製できたので、これらの条件を用いて、チッ
プにコーティングを行い、切削テストを行った。尚、比
較として、コーティングと行っていないチップ及びＣＶ
Ｄ法を用いてＡ ｔ２０３ のコーティングを行った
チップの切削テストも行った（比較例２及び１）。In the above Examples 1 to 4, cubic boron nitride (OB
N) was successfully produced, a chip was coated using these conditions and a cutting test was performed. For comparison, chips with and without coating and CV
Cutting tests were also conducted on chips coated with A t203 using method D (Comparative Examples 2 and 1).
使用するチップは、材質がｗＣＣ超超硬合金型溝基準で
９．５％Ｃ０１１２％Ｔｉｅ、６％ＴａＣおよび残余Ｗ
Ｃ）である’ｒＮＭＧ ５５２の切削チップを用いた。The material of the tip used is wCC cemented carbide type groove reference, 9.5% CO, 12% Tie, 6% TaC, and the remainder W.
C) 'rNMG 552 cutting tip was used.
実施例１〜４の条件で作製する立方晶窒化ホウ素コーテ
ィング層、及び比較例１で作製するＡ ｅ２ｏ３ コ
ーティング層の厚みは４μ悔と統一し九チップの切削テ
ストの条件を表１に示す。The thickness of the cubic boron nitride coating layer produced under the conditions of Examples 1 to 4 and the Ae2o3 coating layer produced in Comparative Example 1 were unified to 4μ, and the conditions of the nine-chip cutting test are shown in Table 1.
表１ ［ 表２に切削テストの結果と示す。Table 1 [ Table 2 shows the results of the cutting test.
表 ２
以上のように本発明による立方晶窒化ホウ素を被覆層と
してチップに使用した場合、従来品のＡ ｌ、Ｏ，破り
、及び破覆なしのものに比し耐摩耗性に優れており、こ
の結果からも本発明の効果は明らかである。Table 2 As shown above, when the cubic boron nitride according to the present invention is used as a coating layer on a chip, it has excellent wear resistance compared to the conventional product without Al, O, breakage, or breakage. The effects of the present invention are clear from this result as well.
本発明は耐熱衝撃性、熱伝導性、硬度、耐摩耗性及び高
温での鉄襄金鵠に対する耐性にも優？２る、立方晶窒化
ホウ素を、可変な合成条件（（より気相から析出できる
新規な方法である。このように合成条件が可変であるの
で、本発明の方法は切削部材、耐摩耗部材、耐熱部材等
の立方晶窒化ホウ素被株形成に用いて、非常に有利で、
ｂる。The present invention also has excellent thermal shock resistance, thermal conductivity, hardness, abrasion resistance, and resistance to iron lint at high temperatures. 2. This is a new method that allows cubic boron nitride to be precipitated from the gas phase under variable synthesis conditions.Since the synthesis conditions are variable in this way, the method of the present invention can be used for cutting materials, wear-resistant materials, Very advantageous when used to form cubic boron nitride stocks for heat-resistant parts, etc.
bl.
本発明方法により得られる立方晶窒化ホウ素は、耐熱衝
撃性、熱伝導性、硬度及びＭ＃耗性並びに高温での鉄族
金−に対する耐性ｒこも優れているため、切削部材、耐
摩耗部材及び耐熱部材の被覆膜として利用して、多大の
効果を有する。The cubic boron nitride obtained by the method of the present invention has excellent thermal shock resistance, thermal conductivity, hardness, M# wear resistance, and resistance to iron group metals at high temperatures, so it can be used in cutting parts, wear-resistant parts, etc. It has great effects when used as a coating film for heat-resistant members.
第１図及び第２図は本発明の実１包、態様を概Ｂ各訣、
明する断面図である。Figures 1 and 2 show one packet of the present invention, each aspect of which is shown in detail.
FIG.
Claims (3)
素からなる混合ガスを、マイクロ波無極放電中を通過さ
せた後、３００〜１３００℃に加熱した基板表面に導入
することにより、該混合ガスを熱分解、反応させ、上記
基板表面に窒化ホウ素を析出させることを特徴とする高
硬度窒化ホウ素の合成方法。(1) A mixed gas consisting of a boron atom-containing gas, a nitrogen atom-containing gas, and hydrogen is passed through a microwave non-polar discharge, and then introduced onto the substrate surface heated to 300 to 1300°C. A method for synthesizing high hardness boron nitride, which comprises pyrolyzing and reacting to precipitate boron nitride on the surface of the substrate.
に、ホウ素原子含有ガスおよび窒素原子含有ガスと混合
し、該混合ガスを３００〜１３００℃に加熱した基板表
面に導入することにより、該混合ガスを熱分解、反応さ
せ、上記基板表面に窒化ホウ素を析出させることを特徴
とする高硬度窒化ホウ素の合成方法。(2) After hydrogen gas passes through a microwave non-polar discharge, it is mixed with a boron atom-containing gas and a nitrogen atom-containing gas, and the mixed gas is introduced onto the substrate surface heated to 300 to 1300°C. A method for synthesizing high hardness boron nitride, which comprises pyrolyzing and reacting a mixed gas to deposit boron nitride on the surface of the substrate.
素の混合ガスの混合比率が、 ホウ素原子含有ガス／水素＝１００〜０．００１窒素原
子含有ガス／水素＝１００〜０．００１の範囲である特
許請求の範囲第（１）項又は第（２）項に記載される高
硬度窒化ホウ素の合成方法。(3) The mixing ratio of the mixed gas of boron atom-containing gas, nitrogen atom-containing gas, and hydrogen is in the range of boron atom-containing gas/hydrogen = 100 to 0.001 and nitrogen atom-containing gas/hydrogen = 100 to 0.001. A method for synthesizing high hardness boron nitride as set forth in claim (1) or (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4546286A JPS62205277A (en) | 1986-03-04 | 1986-03-04 | Method for synthesizing high-hardness boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4546286A JPS62205277A (en) | 1986-03-04 | 1986-03-04 | Method for synthesizing high-hardness boron nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62205277A true JPS62205277A (en) | 1987-09-09 |
Family
ID=12720030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4546286A Pending JPS62205277A (en) | 1986-03-04 | 1986-03-04 | Method for synthesizing high-hardness boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62205277A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018074418A1 (en) * | 2016-10-19 | 2018-04-26 | 国立大学法人名古屋大学 | cBN MOLDING AND METHOD FOR MANUFACTURING cBN FILM |
-
1986
- 1986-03-04 JP JP4546286A patent/JPS62205277A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018074418A1 (en) * | 2016-10-19 | 2018-04-26 | 国立大学法人名古屋大学 | cBN MOLDING AND METHOD FOR MANUFACTURING cBN FILM |
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