JPH01119673A - Method for synthesizing high-hardness boron nitride - Google Patents
Method for synthesizing high-hardness boron nitrideInfo
- Publication number
- JPH01119673A JPH01119673A JP27342787A JP27342787A JPH01119673A JP H01119673 A JPH01119673 A JP H01119673A JP 27342787 A JP27342787 A JP 27342787A JP 27342787 A JP27342787 A JP 27342787A JP H01119673 A JPH01119673 A JP H01119673A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- boron nitride
- containing gas
- atom
- boron
- 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 description 40
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 22
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910052796 boron Inorganic materials 0.000 claims abstract description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 41
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 22
- 230000005855 radiation Effects 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- -1 iron group metals Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 125000004429 atom Chemical group 0.000 abstract description 2
- 229910015844 BCl3 Inorganic materials 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 102100033312 Alpha-2-macroglobulin Human genes 0.000 description 1
- 101710187168 Alpha-2-macroglobulin Proteins 0.000 description 1
- 101710136034 Alpha-2-macroglobulin homolog Proteins 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
- C04B35/5831—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride based on cubic boron nitrides or Wurtzitic boron nitrides, including crystal structure transformation of powder
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- 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
鉄族金属に対する耐性にも優れることから、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
電子材料として用いられている立方晶電化ホウ素を、気
相より基材表面に析出させる方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention not only has extremely high hardness, but also has excellent thermal conductivity, is chemically stable, and, unlike diamond, has resistance to iron group metals. It is also excellent in cutting tools,
The present invention relates to a method for depositing cubic electrified boron, which is used as tool materials such as wear-resistant tools and electronic materials such as heat sinks, on the surface of a substrate from a gas phase.
立方晶窒化ホウ素の製造方法として、従来、例えば下記
の■〜■の方法等が仰られていた。As methods for producing cubic boron nitride, for example, the following methods (1) to (2) have been conventionally used.
■ 特公昭６０−１８１２６２号公報に示されるように
、ホウＸを含有する蒸発源から基体上にホク索分を蒸Ｎ
させると共に、少なくとも窒素を含めイオンａｔを発生
せしめるイオン発生源から基体上に該イオンａ’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０
■ ［ジャーナル オブ マテリアル サイエンス
レターズ（Ｊｏｕｒｎａｌ ｏｆ ｍａｔ、ｅｒｉａｌ
ｓｃｉｅｎｃｅ １ｅｔｔｅｒｓ ）、４（１９８５）
５１〜５４頁」に示されるように、Ｈ，＋Ｎ、プラズマ
によるボロンの化学輸送を行うことによ仄立方晶窒化ホ
ウ素全生成する方法０
■ （第９＠イオン工学（Ｉｏｎ ５ｏｕｒｃｅ Ｉｏ
ｎＡａａｉｓｔｅａ Ｔｅｃｈｎｏｌｏｇｙ ）シンポ
ジウム（１９８５年２束累）議事録、「イオン源とイオ
ンを基礎とした応用技術」〕に示されるように、）ＩＣ
Ｄカンでボロンを蒸発させながら、ホローアノードから
Ｎｚ ｔ−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／＜イアス効果金持たせて立方晶窒
化ホウ素を生成する方法。■ As shown in Japanese Patent Publication No. Sho 60-181262, phosphorus is evaporated onto a substrate from an evaporation source containing boro
[Journal of Materials Science] [Journal of Materials Science]
Letters (Journal of mat,erial
Science 1etters), 4 (1985)
As shown in ``Pages 51-54'', a method for completely producing cubic boron nitride by chemically transporting boron using H, +N, and plasma 0.
As shown in the proceedings of the nAaaistea Technology Symposium (1985 2nd Edition), "Ion Sources and Ion-Based Application Technologies", the ) IC
A method of generating cubic boron nitride by evaporating boron with a D-can, ionizing Nz t- from a hollow anode and emitting it to a substrate, and applying high frequency to the substrate to create a self/<Iass effect.
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点でるる。However, method (2) has a drawback in that the ion beam generating device and its focusing device are expensive.
前記■の方法は、烏出力のＲＦプラズマ金成膜に利用し
ているために、反応系からの不純物が混入しやすい。Since the above-mentioned method (2) is utilized for RF plasma gold film formation at high power, impurities from the reaction system are likely to be mixed in.
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あることと、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 that the atoms of the inert gas are incorporated into the precipitated cubic boron nitride.
本発明はこのような現状に鑑みてなされたもので、耐熱
衝撃性、熱伝導性、硬度、耐摩耗性及び高温での鉄族金
属に対する耐性に優れた立方晶窒化ホウ素を気相から析
出させることのできる新規な合成法を提案することを目
的とするものでめる。The present invention was made in view of the current situation, and is a method of precipitating cubic boron nitride from the gas phase, which has excellent thermal shock resistance, thermal conductivity, hardness, wear resistance, and resistance to iron group metals at high temperatures. The purpose of this paper is to propose a new synthetic method that can
〔問題点を解決するための手段及び作用〕本発明者らは
、高強度な立方晶窒化ホウ素を合成するにめたｐ１ホウ
素及び窒素が互にＢｐ！結合を生じうるに充分な励起状
態となるエネルギーを与える方法につ諭て鋭意研究の結
果、熱電子放射材による加熱と直流プラズマ放電さらに
高周波プラズマを印加という励起手段の併用が好適であ
ることを見出した０
本発明は化学気相析出法による窒化ホウ素の合成法にお
いて、ホウ素原子含有ガス及び窒素原子含有ガスを別個
に反応系内に導入し、該反応系内の支持台に設置した基
材を熱電子放射材によジ加熱する一方、熱電子放射材と
該支持台の間に直流放電を起すと共に高周波プラズマを
該基材に印加することにｘ９基材上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法であ
る。[Means and effects for solving the problem] The present inventors have discovered that p1 boron and nitrogen are mutually Bp! in order to synthesize high-strength cubic boron nitride. As a result of intensive research on methods of applying energy to create an excited state sufficient to cause bonding, we found that a combination of excitation methods such as heating with a thermionic emitter, direct current plasma discharge, and application of high-frequency plasma is suitable. Found 0 The present invention relates to a method for synthesizing boron nitride by chemical vapor deposition, in which a boron atom-containing gas and a nitrogen atom-containing gas are separately introduced into a reaction system, and a substrate is placed on a support in the reaction system. is heated by a thermionic radiation material, while causing a direct current discharge between the thermionic radiation material and the support base, and applying high frequency plasma to the substrate to precipitate boron nitride on the x9 substrate. This is a method for synthesizing high hardness boron nitride.
本発明の特に好ましい実施態様としては、加熱された基
材の温度が３００〜２０００℃である上記方法およびホ
ウ素原子含有ガス中のホウ素原子数と窒素原子含有ガス
中の窒素原子数との比Ｂ／Ｎがα０００１〜１００００
の範囲内である上記方法が挙げられる。Particularly preferred embodiments of the present invention include the above method in which the temperature of the heated base material is 300 to 2000°C, and the ratio B of the number of boron atoms in the boron atom-containing gas to the number of nitrogen atoms in the nitrogen atom-containing gas. /N is α0001~10000
Examples include the above-mentioned methods that fall within the scope of.
以下、図面を参照して本発明全具体的に説明する。Hereinafter, the present invention will be fully explained in detail with reference to the drawings.
第１１は本発明の実施態様を示す概略の断面図であって
、ホウ素原子含有ガス供給装置１及び窒素原子含有ガス
供給装［２からそれぞれ供給てれる、ホウ素原子含有ガ
スと窒素原子含有ガスは％混合されることなく別々に反
応炉４に供給される。このとき反応炉４内の基材支持台
６上に載置した基材５を、図示の位置にある熱電子放射
材３によってカロ熱しておくと共に、該熱電子放射材３
と基板支持台６の間で、直流電源７により直流放ｔｔ発
生させる０さらに高周波電源８．ＲＦコイル１０によす
゛基材５に高周波プラズマ金印加する。これによシ原料
ガスは励起され、立方晶窒化ホウ素が基材表面に析出す
る。なお、第１図中の９は熱′電子放射材加熱電源、１
１は排気装置、１２は排気口である。11 is a schematic cross-sectional view showing an embodiment of the present invention, in which the boron atom-containing gas and the nitrogen atom-containing gas are respectively supplied from the boron atom-containing gas supply device 1 and the nitrogen atom-containing gas supply device [2]. % are separately supplied to the reactor 4 without being mixed. At this time, the base material 5 placed on the base material support stand 6 in the reactor 4 is heated by the thermionic emitter 3 located at the position shown in the figure, and the thermionic emitter 3
and the substrate support table 6, a DC power supply 7 generates a DC discharge tt, and a high frequency power supply 8. High frequency plasma gold is applied to the base material 5 using the RF coil 10 . As a result, the raw material gas is excited, and cubic boron nitride is deposited on the surface of the substrate. In addition, 9 in FIG. 1 is a thermal electron emitting material heating power source, 1
1 is an exhaust device, and 12 is an exhaust port.
本発明はこのようにまずホウ素原子含有ガスと窒素原子
含有ガスを別々に反応系に導入する。In this way, the present invention first separately introduces a boron atom-containing gas and a nitrogen atom-containing gas into a reaction system.
このようにホウ素原子含有ガスと窒素原子含有ガスを別
々にプラズマ発生領域に導入することにニジ、立方晶雪
化ホウ素の生成全防止できる。By introducing the boron atom-containing gas and the nitrogen atom-containing gas separately into the plasma generation region in this way, the formation of cubic boron snow can be completely prevented.
なおホウ素原子含有ガス導入口、窒素原子含有ガス導入
口の一方、又は両方をプラズマ発生領域内に位置してお
く。熱電子放射材で基材を加熱すると共に、該熱電子放
射材と基材支持台の間に直流放電全印加することにより
、熱電子放射材から分離した熱電子が基板表面方向に加
速され、基板表面をより活性化できる。窒素原子含有ガ
ス供給口のごく近傍に熱電子放射材を位置することによ
れば窒素原子含有ガスを活性化してお（ことができる。Note that one or both of the boron atom-containing gas inlet and the nitrogen atom-containing gas inlet are located within the plasma generation region. By heating the base material with the thermionic emission material and applying a full direct current discharge between the thermionic emission material and the base material support, thermionic electrons separated from the thermionic emission material are accelerated in the direction of the substrate surface, The substrate surface can be further activated. By placing the thermionic radiation material in close proximity to the nitrogen atom-containing gas supply port, the nitrogen atom-containing gas can be activated.
そして基材周辺全体にＲＦ’プラズマ金印加することに
よシ、励起状のホウ素原子及び励起状の窒素原子を生ぜ
しめ、これ等の励起状のホウ素原子と窒素原子との間に
ＳＰ＝結合を生ぜしめ、これによって加熱された基材表
面に立方晶窒化ホウ素を生成できる。By applying RF' plasma gold to the entire periphery of the base material, excited boron atoms and excited nitrogen atoms are generated, and SP=bonds are formed between these excited boron atoms and nitrogen atoms. This allows cubic boron nitride to be produced on the surface of the heated substrate.
本発明において原料ガスとするホウ素原子含有ガスとし
ては、例えば、Ｂ２Ｈ４、ＢＯ２、ＢＢｒ３等が挙げら
れ、窒素原子含有ガスとしては−例えばＮ、 、 ＮＨ
３等が挙げられる。またこれ等のガスにＮ２やＡｒ等の
不活性ガス全添加してもよい〇ホウ素原子含有ガス中の
ホウ素原子数及び窒素原子含有ガス中の窒素原子数比Ｂ
／ Ｎはα０００１〜１００００の範囲内が好ましい
。In the present invention, the boron atom-containing gas used as the raw material gas includes, for example, B2H4, BO2, BBr3, etc., and the nitrogen atom-containing gas includes - for example, N, , NH
3rd prize is mentioned. Also, an inert gas such as N2 or Ar may be completely added to these gases. Ratio of the number of boron atoms in the boron atom-containing gas and the number of nitrogen atoms in the nitrogen atom-containing gas B
/N is preferably within the range of α0001 to 10000.
Ｂ ／ Ｎが［１０００１未満では非晶質状の窒化ホウ
素膜が析出されやすく、−万Ｂ ／ Ｎが１００００を
越えるとホウ素が過剰となり、非晶質状のホウ素が形成
されやすいので好ましくない。また、反応室内の圧力は
、プラズマを安定に生ぜしめるために、α０１〜１００
ＴｏｒｒＯ範囲とすることが好ましい。If B/N is less than 10,001, an amorphous boron nitride film is likely to be deposited, and if -10,000 B/N exceeds 10,000, boron becomes excessive and amorphous boron is likely to be formed, which is not preferable. In addition, the pressure in the reaction chamber is set at α01 to 100 in order to stably generate plasma.
It is preferable to set it in the TorrO range.
基材を加熱する熱電子放射材としては高温に耐えられる
タングステンフィラメント、トリウム含有タングステン
フィラメントが挙げられる。Examples of thermionic radiation materials that heat the base material include tungsten filaments and thorium-containing tungsten filaments that can withstand high temperatures.
また、基材を加熱する手段としてヒーターを付は加えて
も良い。基材温度は３００−２０００℃の範囲にするの
が好ましく、３００℃未満では立方晶窒化ホウ素を基材
上に析出せしめるエネルギーに不足し、２０００℃を越
えると、析出する窒化ホウ素膜から窒素が抜は出て、非
立方晶窒化ホウ素となり好ましくない。Further, a heater may be added as a means for heating the base material. The substrate temperature is preferably in the range of 300-2000°C. If it is less than 300°C, there is insufficient energy to deposit cubic boron nitride on the substrate, and if it exceeds 2000°C, nitrogen will be removed from the precipitated boron nitride film. This is undesirable because it becomes non-cubic boron nitride.
原料のホウ素原子含有ガス、窒素原子含有ガス全励起・
活性化するための直流放電及ヒＲＦプラズマの出力は、
それぞれ１００Ｗ以上でるることが好ましい。１００Ｗ
未満では原料ガスの励起するためには出力不足となる。Total excitation of boron atom-containing gas and nitrogen atom-containing gas as raw materials
The output of DC discharge and RF plasma for activation is:
It is preferable that each output power is 100 W or more. 100W
If it is less than that, the output will be insufficient to excite the source gas.
第２図に本発明の別の実施態様を示す０この例では、基
材５は熱電子放射材３と基材支持台６を加熱するヒータ
の両方で加熱される。第２図において第１図と共通符号
の部分は第１図のものと同じ全意味している。Another embodiment of the invention is shown in FIG. 2. In this example, the substrate 5 is heated by both the thermionic emitter 3 and a heater that heats the substrate support 6. In FIG. 2, parts having the same reference numerals as those in FIG. 1 have the same meanings as in FIG.
実施例１
第１図の装置構成で、本発明によシＣ−８１’ｉ基材と
して高硬度窒化ホウ素膜を合成して被覆した。ホウ素原
子含有ガスとしてＢＣ／４’ｉｉ ２５ω／ ｗｉｎ
、窒素原子含有ガスとしてＮ２ を５０ＣＩ−／ｍｉｎ
ヲ、夫々別個に反応室に流して、反応室内圧力は５ Ｔ
Ｏｒｒ ＩＩＣ調整した。熱電子放射材としてタングス
テンフィラメントを使用してその温度’（ｚ２０００℃
とし、基板温度は８００℃とした。直流放電パワー全１
００Ｗ、ＲＦパワー３００Ｗに設定した。この条件で５
時開成膜全行った。その結果、Ｃ−３ｉ基材表面に膜厚
４μｍの窒化ホウ素膜が析出した。この膜をｘ森回折法
により評価したところ、２θ＝ ４３．３ Ｃ付近に鋭
いピークを検出したので、鉄膜は立方晶窒化ホウ素であ
ると同足できた。Example 1 Using the apparatus configuration shown in FIG. 1, a high hardness boron nitride film was synthesized and coated as a C-81'i base material according to the present invention. BC/4'ii 25ω/win as boron atom-containing gas
, 50CI-/min of N2 as nitrogen atom-containing gas
ヲ, each is flowed into the reaction chamber separately, and the pressure in the reaction chamber is 5 T.
Orr IIC adjusted. Using a tungsten filament as a thermionic emitter, its temperature' (z2000℃
The substrate temperature was 800°C. DC discharge power total 1
00W, and the RF power was set to 300W. 5 under this condition
All depositions were performed intermittently. As a result, a boron nitride film with a thickness of 4 μm was deposited on the surface of the C-3i substrate. When this film was evaluated by the x-Mori diffraction method, a sharp peak was detected near 2θ = 43.3 C, so it was concluded that the iron film was cubic boron nitride.
実施例２
第２図の装置構成で本発明によジ、モリブデン板を基材
として高硬度窒化ホウ素膜全合成した。ホウ素原子含有
ガスとしてＢ＊Ｈｓ Ｗ ／ ｍｉｎ、窒素原子含有ガ
スとしてＮ２を１５ Ｗ ／ ｍｉｎ流した。反応室内
圧力Ｉ Ｑ Ｔｏｒｒ、熱電子放射材はトリウム含有タ
ングステンフィラメント２２００℃、ヒータ温度９５０
℃とし、直流放電出力１５０Ｗ％ＲＦ出力２５０Ｗ’ｚ
印加し、１時間５０分の間気相合成を続けた。その結果
、モリブデン基材表面に膜厚五５μｍの窒化ホウ素膜が
析出し、これをレーザラマン公党法により分析評価した
ところ、１０５５ ｃｍ−’及び１３１０ ｃｍ−”付
近に鋭いピークを検出したので、立方晶窒化ホウ累であ
ると同定できた。Example 2 A high hardness boron nitride film was totally synthesized using a molybdenum plate as a base material according to the present invention using the apparatus configuration shown in FIG. B*Hs W/min was flowed as the boron atom-containing gas, and N2 was flowed at 15 W/min as the nitrogen atom-containing gas. The pressure in the reaction chamber is IQ Torr, the thermionic emitting material is a thorium-containing tungsten filament at 2200°C, and the heater temperature is 950°C.
℃, DC discharge output 150W% RF output 250W'z
The gas phase synthesis was continued for 1 hour and 50 minutes. As a result, a boron nitride film with a thickness of 55 μm was deposited on the surface of the molybdenum base material, and when this was analyzed and evaluated using the laser Raman method, sharp peaks were detected near 1055 cm and 1310 cm. It was identified as cubic boron nitride.
比較例１
第１図の装置構成で、Ｃ−８１を基材として窒化ホウ素
膜を台底したが、比較例として熱電子放射材と基板支持
台の間の直流放電印加を行わなかった。ホウ素原子含有
ガスとしてＢＣｔ３ｔ−１ｃｃ ／ ｍｉｎ 、窒素原
子含有ガスとしてＮＨ３を３０ｃｃ ／ ｍ１ｎ流し、
反応室内圧力は８ ＴＯｒｒに調整した。熱電子放射材
としてはメンタルフィラメントを用い、フィラメント温
度を２１００℃とした。ＲＦ出力は２５０Ｗ印加し、２
時間の成膜を行なった。その結果、Ｃ−８１基材表面に
膜厚２μｍの窒化ホウ素膜が析出し、これｔ−Ｘ線回折
により評価し、たところ、２θ＝２６７°及び４＆゛３
° 付近にピークを検出し、立方晶窒化ホウ素及び六方
晶窒化ホウ素の混合物でるると同定できた。Comparative Example 1 In the apparatus configuration shown in FIG. 1, C-81 was used as the base material and a boron nitride film was used as the base, but as a comparative example, no direct current discharge was applied between the thermionic emitter and the substrate support. BCt3t-1cc/min as a boron atom-containing gas and NH3 as a nitrogen atom-containing gas at 30cc/m1n,
The pressure inside the reaction chamber was adjusted to 8 TOrr. A mental filament was used as the thermionic emission material, and the filament temperature was set at 2100°C. RF output is 250W applied, 2
Film formation was performed for hours. As a result, a boron nitride film with a thickness of 2 μm was deposited on the surface of the C-81 substrate, and this was evaluated by t-X-ray diffraction, and it was found that 2θ = 267° and 4&゛3
A peak was detected near °, and it was identified as a mixture of cubic boron nitride and hexagonal boron nitride.
以上の実施例１．２及び比較例１の条件で窒化ホウ素膜
が得られたので、この条件を利用して切削工具に被覆形
成を行なって被覆部品と１夫々について切削テスト１表
１の条件で行った。Since a boron nitride film was obtained under the conditions of Example 1.2 and Comparative Example 1 above, coating was formed on a cutting tool using these conditions, and a cutting test was performed on each coated part under the conditions shown in Table 1. I went there.
また比較のために、ＣＶＤ法によりＡｔ２０．コーティ
ングを行ったチップ及び無被徨のチップについても同様
にテストをした。なお被覆はすべて３μｍ厚嘔に純−し
た。表２に切削テスト結果をまとめて示す。表２の中の
ＯＢＮは立方晶窒化ホウ素、ｈＢＮは六方晶窒化ホウ素
を意味する。For comparison, At20. The coated chip and the uncoated chip were also tested in the same way. All coatings were pure to a thickness of 3 μm. Table 2 summarizes the cutting test results. In Table 2, OBN means cubic boron nitride, and hBN means hexagonal boron nitride.
表 １
茨 ２
表２の結果は窒化ホウ素特に本発明による立方晶窒化ホ
ウ素を被徨層として切削工具に使用した場合、耐摩耗性
に優れていることが明らかに示しておシ、本発明の有効
性を証明している。Table 1 Thorn 2 The results in Table 2 clearly show that boron nitride, especially the cubic boron nitride according to the present invention, has excellent wear resistance when used as a stuck layer in a cutting tool. It has proven its effectiveness.
実施例３．比較例４及び５
第１図の装置を用いて、本発明によりＰ種類硬合金チッ
プ（’Ｉ’ＥＧＮ ２２０４０８ ）に立方晶窒化ホウ
素（ｃＢＮ）’Ｉｉ被榎した。被覆条件は、原料力Ｘ
： ＢＩＨｓ ３００ ｃｒ−／ ｍｉｎ ｂ Ｎ
Ｈ３６０Ｃ１−／ ｍ１ｎｘＲＦプラズマ出カニ２ｓＯ
Ｗ、直流放電出カニ１５０Ｗ、熱電子放射材温度：２０
００℃、圧カニ Ｉ Ｑ Ｔｏｒｒ、基材温度：８３０
℃、であり、膜厚３μｍとした（実施ガ５）。Example 3. Comparative Examples 4 and 5 Using the apparatus shown in FIG. 1, a P-type hard alloy chip ('I'EGN 220408) was subjected to cubic boron nitride (cBN) 'Ii according to the present invention. The coating conditions are raw material power
: BIHs 300 cr-/ min b N
H360C1-/m1nxRF plasma output crab 2sO
W, DC discharge crab 150W, thermionic radiation material temperature: 20
00℃, pressure crab IQ Torr, substrate temperature: 830
℃, and the film thickness was 3 μm (Example 5).
実施例３と同じチップにＣＶＤ法によｐ ＴｉＣｔ−３
μｍ厚さに被覆した（比較ＩＡＵ４）。TiCt-3 was deposited on the same chip as in Example 3 by the CVD method.
Coated to a μm thickness (comparison IAU4).
以上で得た実施例３、比較例４のチップと、全く被覆し
ないままのＴＥＧＮ ２２０４０８チップ全比較例５
として用いて、鋼旋削における耐摩耗特注をテストした
０被削材は８０Ｍ４１５、切削速度は２５０ ｍ／ ｍ
ｉｎ ％切込み［１１ｗ＋、送りα１■／ｒθＶである
。結果を第３図の図表に示すが、イが本発明品、口が比
較例４のＴｉＣコートチップ、ハがコーティング無しチ
ップである。Chips of Example 3 and Comparative Example 4 obtained above and TEGN 220408 chip with no coating at all Comparative Example 5
The work material was 80M415, and the cutting speed was 250 m/m.
in% depth of cut [11w+, feed α1■/rθV. The results are shown in the diagram of FIG. 3, where A is the product of the present invention, A is the TiC-coated chip of Comparative Example 4, and C is the uncoated chip.
ＷＪｓ図から明らかなように、本発明にょるｃＢＮコー
トチップが耐摩耗性において最も優れている。As is clear from the WJs diagram, the cBN coated chip according to the present invention has the best wear resistance.
実施？ｌＪ ４ 、比較例６〜８
第１図の装置を用いて、本発明によりに棟超硬合金チッ
プ（ＴＰＭＮ ２２０４０８ ）に（！ Ｂ Ｎ ｆ、
Ｈ被覆した０被覆条件は、原料ガス：ＢＣ２３２５ｃｃ
／ｍｉｎ、 Ｎｌ： １０ ｃｃ／ｍｉｎ、 ＲＦプラ
ズマ出カニ３５０Ｗ％直流放電出カニ１００Ｗ、圧カニ
１０Ｔｏｒｒ 、熱電子放射材の温度２１００℃、基
材＠度：９００℃であり、膜厚４μｍが得られた（実施
例４）。implementation? lJ 4 , Comparative Examples 6 to 8 Using the apparatus shown in FIG.
The 0 coating conditions for H coating are: Raw material gas: BC2325cc
/min, Nl: 10 cc/min, RF plasma output crab 350W%, DC discharge crab 100W, pressure crab 10 Torr, temperature of thermionic emission material 2100℃, base material @ degree: 900℃, and a film thickness of 4 μm was obtained. (Example 4).
実施例４と同じチップにイオンブレーティング法によ５
ＴｉＮを４μｍ厚さに被覆した〆（比較例６）。ｌ丑
１、ＣＶＤ法によりＡｔ２０３ ｆ ４Ａｍ厚さに被覆
した（比較例７）。5 was applied to the same chip as in Example 4 by the ion blating method.
TiN was coated to a thickness of 4 μm (Comparative Example 6). It was coated with At203 f 4 Am thick by CVD method (Comparative Example 7).
以上で得た実施例４、比較例６，７の被覆チップと、全
く被覆しないままのＴＰＭＮ ２２０４０Ｂチツプを比
較例８として用いて、鋳鉄旋削における欠損特性をテス
トした。被剛材はＦｅ１２、切削速度３００ｍ／ｍｉｎ
、切込みα２籠、送夕α２ ｍ ／ ｒｅｖである。な
お衝撃は１周に４このＵ＃ｌ′？を有する被剛材とした
。結果を第４図の図表に示すが、本発明のｃＢＮコーテ
ィングチップが比較例６〜Ｂのものより格段に優れてい
ることがわかる。Using the coated chips of Example 4 and Comparative Examples 6 and 7 obtained above, and the completely uncoated TPMN 22040B chip as Comparative Example 8, the chipping characteristics in cast iron turning were tested. The rigid material is Fe12, the cutting speed is 300m/min
, depth of cut α2, and sending height α2 m/rev. In addition, the impact is 4 U#l' in one lap? The material to be stiffened was The results are shown in the diagram of FIG. 4, and it can be seen that the cBN-coated chips of the present invention are significantly superior to those of Comparative Examples 6-B.
以上説明したように、本発明は耐熱衝撃性。 As explained above, the present invention has thermal shock resistance.
熱伝尋性、硬度、耐摩耗注及び高温での鉄族金属に対す
る耐性に優れる立方晶窒化ホウ素全気相から析出できる
新規な合成法でるる。本発明によシ合成した高硬度窒化
ホウ素膜を切削部材。A novel synthesis method that allows cubic boron nitride to be precipitated from the entire gas phase, which has excellent thermal conductivity, hardness, wear resistance, and resistance to iron group metals at high temperatures. A cutting member made of a high hardness boron nitride film synthesized according to the present invention.
耐摩耗部材等の被覆として利用すると、非常に切削特性
に優れた部材を得ることができる。When used as a coating for wear-resistant members, etc., members with extremely excellent cutting properties can be obtained.
第１図及び第２図はいずれも本発明の高硬度窒化ホウ素
の合成法の実施態様を示す概略図であり、第３図及び第
４図は本発明品と比較品、従来品の旋削における特性試
験結果金示した図表であって、第３図は鋼旋削における
耐摩耗特注、第４図は鋳鉄旋削における欠損特性金示す
。Fig. 1 and Fig. 2 are both schematic diagrams showing an embodiment of the high-hardness boron nitride synthesis method of the present invention, and Fig. 3 and Fig. 4 are diagrams showing the lathes of the inventive product, comparative product, and conventional product. Figure 3 shows the wear resistance custom made for turning steel, and Figure 4 shows the defect characteristics for turning cast iron.
Claims (3)
て、ホウ素原子含有ガス及び窒素原子含有ガスを別個に
反応系内に導入し、該反応系内の支持台に設置した基材
を熱電子放射材により加熱する一方、熱電子放射材と該
支持台の間に直流放電を起すと共に高周波プラズマを該
基材に印加することにより基材上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法。(1) In a method for synthesizing boron nitride by chemical vapor deposition, a boron atom-containing gas and a nitrogen atom-containing gas are separately introduced into a reaction system, and a substrate placed on a support in the reaction system is heated by thermionic electrons. High hardness characterized by depositing boron nitride on the base material by heating with a radiant material, generating a direct current discharge between the thermionic radiation material and the support, and applying high frequency plasma to the base material. Synthesis method of boron nitride.
る特許請求の範囲第１項記載の高硬度窒化ホウ素の合成
法。(2) The method for synthesizing high hardness boron nitride according to claim 1, wherein the temperature of the heated base material is 300 to 2000°C.
含有ガス中の窒素原子数との比Ｂ／Ｎが０．０００１〜
１００００の範囲内である特許請求の範囲第１又は２項
記載の高硬度窒化ホウ素の合成法。(3) The ratio B/N of the number of boron atoms in the boron atom-containing gas to the number of nitrogen atoms in the nitrogen atom-containing gas is 0.0001 to
The method for synthesizing high hardness boron nitride according to claim 1 or 2, wherein the hardness is within the range of 10,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27342787A JPH01119673A (en) | 1987-10-30 | 1987-10-30 | Method for synthesizing high-hardness boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27342787A JPH01119673A (en) | 1987-10-30 | 1987-10-30 | Method for synthesizing high-hardness boron nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01119673A true JPH01119673A (en) | 1989-05-11 |
Family
ID=17527748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27342787A Pending JPH01119673A (en) | 1987-10-30 | 1987-10-30 | Method for synthesizing high-hardness boron nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01119673A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463901A (en) * | 1991-09-27 | 1995-11-07 | Sumitomo Electric Industries, Ltd. | Stacked piezoelectric surface acoustic wave device with a boron nitride layer in the stack |
-
1987
- 1987-10-30 JP JP27342787A patent/JPH01119673A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463901A (en) * | 1991-09-27 | 1995-11-07 | Sumitomo Electric Industries, Ltd. | Stacked piezoelectric surface acoustic wave device with a boron nitride layer in the stack |
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