JPH0351787B2 - - Google Patents
Info
- Publication number
- JPH0351787B2 JPH0351787B2 JP58171217A JP17121783A JPH0351787B2 JP H0351787 B2 JPH0351787 B2 JP H0351787B2 JP 58171217 A JP58171217 A JP 58171217A JP 17121783 A JP17121783 A JP 17121783A JP H0351787 B2 JPH0351787 B2 JP H0351787B2
- Authority
- JP
- Japan
- Prior art keywords
- boron
- substrate
- ions
- ion
- thin film
- 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
- 150000002500 ions Chemical class 0.000 claims description 69
- 239000000758 substrate Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 33
- 239000010409 thin film Substances 0.000 claims description 28
- 230000008020 evaporation Effects 0.000 claims description 25
- 238000001704 evaporation Methods 0.000 claims description 25
- 229910052582 BN Inorganic materials 0.000 claims description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 24
- 125000004429 atom Chemical group 0.000 claims description 15
- 230000001133 acceleration Effects 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 13
- -1 nitrogen atom ions Chemical class 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 239000011195 cermet Substances 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000615 nonconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BGPVFRJUHWVFKM-UHFFFAOYSA-N N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] Chemical compound N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] BGPVFRJUHWVFKM-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 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
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- ZVTQDOIPKNCMAR-UHFFFAOYSA-N sulfanylidene(sulfanylideneboranylsulfanyl)borane Chemical compound S=BSB=S ZVTQDOIPKNCMAR-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
Description
〔発明の技術分野〕
本発明は高硬度窒化ホウ素薄膜の製造方法に関
し、更に詳しくはイオン照射法と蒸着法を組合わ
せて成る、立方晶窒化ホウ素（ｃ−BN）を主体
とした高硬度窒化ホウ素薄膜の製造方法に関す
る。
〔発明の技術的背景とその問題点〕
窒化ホウ素（BN）はセラミツクスの一種で、
近年、非常に注目されている材料の１つである。
このBNには、六方晶系（ｈ−BN）、六方最密
充填系（ｗ−BN）及び立方晶系（ｃ−BN）の
３種類の結晶構造のものが存在する。これらのう
ち、ｃ−BNはダイヤモンドについでその硬度が
高く、電気絶縁体であり、しかもその熱伝導率は
大きく耐摩耗性に優れるという特異な特性を備え
ている。
しかしながら、このｃ−BNは天然には存在せ
ず、現実には、数万気圧、千数百度という高温・
高圧下で、例えばマグネシウムのような触媒を用
いて製造されている。この方法では、粉・粒は製
造できるが、基体の表面を被覆する薄膜として製
造することは極めて困難である。
このため、ｃ−BNは砥石の砥粒としてそのま
ま用いられたり又は焼結して成る切削工具として
用いられているのが現状である。しかし、基体の
表面にｃ−BNの薄膜を形成することができれ
ば、そのことはｃ−BNの有用な特性を生かして
その用途を飛躍的に拡大できる。例えば、保護管
の耐磨耗性保護膜、表面をｃ−BNで被覆した切
削工具、ヒートシンク、半導体素材などである。
一方、薄膜形成は化学蒸着法又は物理蒸着法に
大別でき、とくに、イオンを用いる方法としては
大きく次の３つの方法に分類される。
まず第１は、イオン化された原子を加速後減速
して基体の表面に被着せしめるイオンビームデポ
ジシヨン（Ion beam deposition）法、クラスタ
ーイオンを加速して基体表面に衝突させ一度に多
量の原子を被着せしめるクラスターイオンプレー
テイング（Cluster ion plating）法、イオン化
して加速せしめた希ガスでスパツタした原子を基
体表面に被着せしめるイオンビームスパツタリン
グ（Ion beam sputtering）法などである。
これらの方法の場合、イオン種が持つイオン加
速エネルギーは数eVから高々数十であり、イオ
ン種が基体内に注入されるということはない。そ
れゆえ、これらの方法は成膜技術としては有効で
あるが、しかし形成された薄膜と基体との間の密
着性という点で不充分であり、薄膜が基体から剥
離し易すいという問題がある。
第２の方法はイオン種のイオン加速エネルギー
を数十〜数百keVに高めて行なうイオン注入
（Ion implantation）法である。この方法では、
イオンは基体の内部にまで撃ち込まれ、そこで基
体構成原子と衝突し該基体構成原子との間で準安
定物質を生成して合金又は化合物の層を形成し基
体表面が改質される。この場合、形成された薄膜
と基体との密着性は向上するものの、他方では該
薄膜が準安定物質で構成されているので、例えば
高温になると基体構成原子との反応が進行したり
又は注入イオンの元素それ自体が析出したりして
構造変化をもたらすという問題がある。また、こ
の方法では多量のイオンを注入することが必要で
あるが、短時間での処理を可能にするためには、
大電流のイオン注入装置が不可欠となる。
第３の方法はイオンミキシング（Ion mixing）
法である。この方法は、まず基体表面にある物質
の蒸着膜を形成しておき、ここにイオン化した希
ガスを数百keVのイオン加速エネルギーで照射す
るという方法である。この場合、蒸着原子は照射
イオンとの衝突により反跳して基体内部に侵入し
基体と蒸着膜構成原子との間で新たな層を形成す
る。
この方法は、形成された新たな層と基体との密
着性は良好で、また、高電圧を要するにもかかわ
らずイオン電流はそれほど大きくなくてもよいと
いう利点を有するが、反面、蒸着膜構成原子と基
体構成原子とで形成される新たな層において各原
子の混合比を一定に保持することは非常に困難で
あるという問題を避け得ない。つまり、一定組成
の層形成が困難なのである。
このようなことから、現在までのところ、ｃ−
BNの薄膜を形成するに有効な方法は未だ発表さ
れていない。
〔発明の目的〕
本発明は基体の表面にｃ−BNを主体とする高
硬度のBN薄膜を形成する新規な方法の提供を目
的とする。
〔発明の概要〕
本発明者らは、上記した目的を達成すべく鋭意
研究を重ねた結果、蒸発源とイオン種とに含まれ
るホウ素と窒素との原子比（Ｂ／Ｎ）及びイオン
の加速エネルギーを適宜に調整すれば、基体の表
面にｃ−BNを主体とした薄膜が製造できるとの
事実を見出し本発明を完成するに到つた。
すなわち、本発明方法は、基体上に、ホウ素を
含有する蒸発源を蒸着させ、かつ、その蒸着と同
時又は交互に、イオン源にて生成された加速器に
て加速されたイオン種を照射して、該基体上に該
蒸発源と該イオン種によつて立方晶窒化ホウ素を
主体とした高硬度窒化ホウ素薄膜を生成せしめる
方法であつて、該蒸発源と該イオン種とに含まれ
るホウ素と窒素との原子比（Ｂ／Ｎ）が0.5〜３
であり、かつ、該イオン種のイオン加速エネルギ
ーが該イオン種に含まれているホウ素若しくは窒
素又は不活性ガスの原子当り５〜60keVであるこ
とを特徴とする。
本発明方法にあつて、まず基体としては、セラ
ミツクス、超硬合金、サーメツト又は各種の金属
若しくは合金など何であつてもよく、その材質は
問わない。ただし、基体が電気絶縁体の場合に
は、荷電している場所と荷電していない場所とで
はそこに形成された蒸着膜の特性が異なり膜全体
の特性のバラツキが生じ易くなるので、基体とし
ては電気伝導体であることが好ましい。しかし、
電気絶縁体であつてもその表面に常法により電気
伝導体の薄膜を形成すればよい。
また、Ｂを含有する蒸発源としては、金属Ｂ又
はホウ素化合物（例えばチツ化ホウ素、酸化ホウ
素、硫化ホウ素、アルミニウム若しくはマグネシ
ウム含有の金属ホウ化物）又はこれらの相互固溶
体（例えばＢ−B2O3、BN−B2O3）が用いられ
る。
イオン種としては、所定のイオン加速エネルギ
ーを有するイオン種でＢを含有する蒸発源に作用
してｃ−BNの薄膜を形成するものであればよ
い。具体的には、窒素原子イオン（N+）；窒素原
子イオン（N2 +）；アンモニアイオン（NH3 +）の
ような窒素化合物イオン；ホウ素イオン（B+）；
揮発性ボランのようなホウ化水素イオ（B2H6 +）、
窒化ホウ素イオン（BN+）の如きホウ素化合物
イオン；又は不活性ガスイオン（例えばAc+）の
いずれか１種であることが好ましい。
このようなイオン種は、後述する装置によつて
創生され、質量分析用のマグネトロンを用いて磁
気的に選択されて供給される。
本発明方法では、基体の上にＢを含有する蒸発
源を蒸着させると同時に又はＢを含有する蒸発源
の蒸着膜が形成された後に、上記したイオン種を
照射する。前者の場合には、Ｂを含有する蒸発源
は基体表面に蒸着するとまさにそれと同時に照射
されたイオン種の作用によりそれはBNになりそ
のまま層形成されることになる。また、後者の場
合には、既に蒸着層として存在するＢを含有する
蒸発源の層がそのあとから照射されたイオン種の
作用によりBNに変換される。したがつて、この
後者の場合、Ｂを含有する蒸発源の蒸着層の形成
とイオン照射を交互に反復して行なえば順次BN
層が厚く成長していくことになる。
なお、Ｂを含有する蒸発源としてBNを用いれ
ば、必要とするイオン加速エネルギーが小さくて
すみ、かつ効率よくｃ−BN薄膜を成長させるこ
とができ、そして、イオン種として不活性ガスイ
オンを用いることもできる。
基体表面において、蒸発源とイオン種とに含ま
れるＢとＮとの原子比（Ｂ／Ｎ）が0.5〜３とな
るように制御すること、並びにイオン種のイオン
加速エネルギーを該イオン種に含まれているＢ若
しくはＨ又は不活性ガスの原子当り５〜60keVに
制御することが必要である。
Ｂ／Ｎが0.5より小さい場合には、形成された
薄膜の結晶構造は非晶質又はｈ−BN型となり、
ｃ−BNとはならない。またＢ／Ｎが３より大き
くなると、形成された薄膜は非晶質となる。Ｂ／
Ｎは１〜2.5程度であることがとくに好ましい。
イオン種のイオン加速エネルギーが5keV未満
の場合には、蒸着膜へのイオン種の注入量が減少
してスパツタ現像が支配的となり、また60keVを
超えると基体表面の蒸着層よりも可成り深くイオ
ン種が注入されるので蒸着層にｃ−BNを主体と
する高硬度BNが生成しにくくなり、また、蒸着
層が高温になりすぎてｈ−BNの生成が支配的と
なつてｃ−BNを主体とする高硬度BNが生成し
にくくなる。
本発明方法は、図に例示した装置を用いて次の
ように行なわれる。
まず、イオン化されるべきガス例えばN2はリ
ークバルブ１を経てイオン源２に導入され、ここ
でイオン化されたのち、加速器３で加速されて所
定のイオン加速エネルギーが付与される。イオン
は次に分析マグネツト４に導入され、ここで必要
とするイオン種のみが磁気的に選択されて反応室
５に供給される。
反応室５は真空ポンプ（例えばターボ分子ポン
プ）６によつて10-4Torr以下の高真空に維持さ
れる。基体７は基体ホルダ８に固定され、ここに
上記したイオン種が照射される。照射に際して
は、基体に均一にイオン種を照射するために、収
束レンズ９にイオン種を通過させる。
１０は、基体７の下に配置された蒸着装置であ
る。装置の加熱方法は、電子ビーム加熱、レーザ
線加熱など適宜な方法が用いられる。この中には
Ｂを含有する蒸発源が収容されている。Ｂを含有
する蒸発源の蒸着量及び蒸着速度は、基体ホルダ
８の横に配設した例えば石英板使用の振動型膜厚
計１１によつて測定すればよい。
また、イオン種の原子数、すなわち、イオン電
流は、二次電子追返し電極１２を付設した電流積
算計１３によつて正確に測定することができる。
このような装置において、基体７を所定位置に
セツトし、反応室５内を所定の真空度に保ち、蒸
着装置１０を作動してＢを含有する蒸発源を基体
７に所定量蒸着させ、そこに所定のイオン種を所
定のイオン加速エネルギーで照射すれば、基体表
面にはｃ−BNを主体とする高硬度BNの薄膜が
形成される。
なお、このときＢを含有する蒸発源、イオン種
はいずれも基体の１方向からのみ蒸着又は照射さ
れるので、基体の全表面にｃ−BN主体の高硬度
BN薄膜を形成する場合にはこの基体に回転、揺
動などの運動を与えればよい。
〔発明の実施例〕
実施例 １〜３
図に示した装置を用いて高純度N2ガスをリー
クバルブ１からPIG型イオン源２に導入した。発
生したイオンに加速器３で種々の加速エネルギー
を付与した。このイオンビームを分析マグネツト
４で質量分析しN2 +のみを磁気的に選択した。
他方、基体としてタンタル板を用い、これを基
体ホルダ８にセツトし反応室５内を650／secの
ターボ分子ポンプで１×10-5Torrの真空度に保
持した。
ついで、金属Ｂを収容する電子ビーム蒸着装置
１０を作動して金属Ｂを蒸発させ、N2 +イオンの
照射と同時にタンタル板７の上に蒸着させた。
Ｂの蒸着量、蒸着速度は振動型膜厚計１１で測
定し、N2 +イオンの個数は電流積算計１３で測定
し、Ｂ／Ｎを算出した。
N2 +イオンのイオン加速エネルギーを変え、Ｂ
蒸着量を変化させて薄膜形成を行なつた。その結
果を一括して表に示した。
[Technical Field of the Invention] The present invention relates to a method for manufacturing a high-hardness boron nitride thin film, and more specifically, a high-hardness nitride film mainly composed of cubic boron nitride (c-BN), which is produced by combining an ion irradiation method and a vapor deposition method. The present invention relates to a method for producing a boron thin film. [Technical background of the invention and its problems] Boron nitride (BN) is a type of ceramics.
It is one of the materials that has received much attention in recent years. This BN has three types of crystal structures: hexagonal system (h-BN), hexagonal close-packed system (w-BN), and cubic system (c-BN). Among these, c-BN has the unique characteristics of having the second highest hardness after diamond, being an electrical insulator, and having high thermal conductivity and excellent wear resistance. However, this c-BN does not exist naturally, and in reality, it is exposed to high temperatures of tens of thousands of atmospheres and thousands of hundreds of degrees.
It is produced under high pressure using a catalyst such as magnesium. Although powders and granules can be produced using this method, it is extremely difficult to produce a thin film that covers the surface of a substrate. For this reason, at present, c-BN is used as it is as abrasive grains in grindstones, or as cutting tools made by sintering it. However, if a thin film of c-BN can be formed on the surface of a substrate, the useful properties of c-BN can be utilized to dramatically expand its applications. Examples include wear-resistant protective films for protection tubes, cutting tools whose surfaces are coated with c-BN, heat sinks, semiconductor materials, and the like. On the other hand, thin film formation can be roughly divided into chemical vapor deposition methods and physical vapor deposition methods, and in particular, methods using ions are broadly classified into the following three methods. The first is the ion beam deposition method, in which ionized atoms are accelerated and then decelerated to deposit them on the surface of the substrate.Cluster ions are accelerated and collided with the surface of the substrate, releasing a large number of atoms at once. These include cluster ion plating, in which atoms are deposited, and ion beam sputtering, in which atoms spattered with ionized and accelerated rare gas are deposited on the substrate surface. In these methods, the ion acceleration energy of the ion species ranges from several eV to several tens of volts at most, and the ion species are not implanted into the substrate. Therefore, although these methods are effective as film-forming techniques, they are insufficient in terms of adhesion between the formed thin film and the substrate, and there is a problem that the thin film easily peels off from the substrate. . The second method is an ion implantation method in which the ion acceleration energy of ion species is increased to several tens to hundreds of keV. in this way,
The ions are shot into the interior of the substrate, where they collide with the atoms constituting the substrate and generate a metastable substance with the atoms constituting the substrate to form a layer of an alloy or compound, thereby modifying the surface of the substrate. In this case, although the adhesion between the formed thin film and the substrate is improved, on the other hand, since the thin film is composed of a metastable substance, for example, at high temperatures, reactions with atoms constituting the substrate may proceed or implanted ions may proceed. There is a problem that the elements themselves precipitate and cause structural changes. Additionally, this method requires a large amount of ion implantation, but in order to enable processing in a short time,
A high-current ion implanter is essential. The third method is ion mixing.
It is the law. In this method, a vapor-deposited film of a substance is first formed on the surface of the substrate, and then ionized rare gas is irradiated with ion acceleration energy of several hundred keV. In this case, the vapor-deposited atoms recoil due to collision with the irradiated ions and enter the inside of the substrate, forming a new layer between the substrate and the atoms forming the vapor-deposited film. This method has the advantage that the adhesion between the formed new layer and the substrate is good, and the ion current does not need to be so large despite the high voltage required. The problem cannot be avoided that it is very difficult to maintain a constant mixing ratio of each atom in a new layer formed of the base material and the base constituent atoms. In other words, it is difficult to form a layer with a constant composition. For this reason, up to now, c-
An effective method for forming a BN thin film has not yet been announced. [Object of the Invention] The object of the present invention is to provide a novel method for forming a highly hard BN thin film mainly composed of c-BN on the surface of a substrate. [Summary of the Invention] As a result of extensive research to achieve the above-mentioned object, the present inventors have determined the atomic ratio (B/N) of boron and nitrogen contained in the evaporation source and the ion species and the acceleration of ions. The present invention was completed based on the discovery that a thin film mainly composed of c-BN can be produced on the surface of a substrate by appropriately adjusting the energy. That is, in the method of the present invention, an evaporation source containing boron is deposited on a substrate, and ion species generated in the ion source and accelerated in an accelerator are irradiated simultaneously or alternately with the deposition. , a method of forming a high-hardness boron nitride thin film mainly composed of cubic boron nitride on the substrate by the evaporation source and the ion species, the method comprising: The atomic ratio (B/N) is 0.5 to 3
and the ion acceleration energy of the ion species is 5 to 60 keV per atom of boron, nitrogen, or inert gas contained in the ion species. In the method of the present invention, the substrate may be made of any material, such as ceramics, cemented carbide, cermets, or various metals or alloys, and its material does not matter. However, if the substrate is an electrical insulator, the characteristics of the deposited film will differ between charged and uncharged areas, and variations in the properties of the entire film will likely occur. is preferably an electrical conductor. but,
Even if the material is an electrical insulator, a thin film of an electrical conductor may be formed on its surface by a conventional method. In addition, as an evaporation source containing B, metal B or a boron compound (for example, boron titanide, boron oxide, boron sulfide, metal boride containing aluminum or magnesium) or a mutual solid solution thereof (for example, B-B 2 O 3 , BN-B 2 O 3 ) are used. Any ion species may be used as long as it has a predetermined ion acceleration energy and acts on an evaporation source containing B to form a thin film of c-BN. Specifically, nitrogen atom ions (N + ); nitrogen atom ions (N 2 + ); nitrogen compound ions such as ammonia ions (NH 3 + ); boron ions (B + );
borohydride ions (B 2 H 6 + ), such as volatile borane;
Preferably, the ions are boron compound ions such as boron nitride ions (BN + ); or inert gas ions (eg Ac + ). Such ion species are created by an apparatus to be described later, and are magnetically selected and supplied using a magnetron for mass spectrometry. In the method of the present invention, the above-mentioned ion species are irradiated on the substrate at the same time as the evaporation source containing B is deposited on the substrate or after the evaporation film of the evaporation source containing B is formed. In the former case, when the evaporation source containing B is deposited on the surface of the substrate, it becomes BN and forms a layer as it is due to the action of the ion species irradiated at the same time. In the latter case, the B-containing evaporation source layer already present as a deposited layer is converted into BN by the action of the ion species irradiated thereafter. Therefore, in the latter case, if the formation of the evaporation layer of the B-containing evaporation source and the ion irradiation are repeated alternately, the BN
The layers will grow thicker. Note that if BN is used as an evaporation source containing B, the required ion acceleration energy is small and a c-BN thin film can be grown efficiently, and inert gas ions are used as the ion species. You can also do that. On the substrate surface, the atomic ratio (B/N) of B and N contained in the evaporation source and the ionic species is controlled to be 0.5 to 3, and the ion acceleration energy of the ionic species is contained in the ionic species. It is necessary to control the voltage to 5 to 60 keV per atom of B or H or inert gas. When B/N is smaller than 0.5, the crystal structure of the formed thin film becomes amorphous or h-BN type,
It is not c-BN. Moreover, when B/N becomes larger than 3, the formed thin film becomes amorphous. B/
It is particularly preferable that N be about 1 to 2.5. When the ion acceleration energy of the ion species is less than 5 keV, the amount of ion species implanted into the deposited film decreases and spatter development becomes dominant, and when it exceeds 60 keV, the ions are deposited considerably deeper than the deposited layer on the substrate surface. Because the seeds are injected, it becomes difficult to generate high-hardness BN consisting mainly of c-BN in the deposited layer, and the deposition layer becomes too hot and the formation of h-BN becomes dominant, causing c-BN to form. High hardness BN, which is the main component, becomes difficult to generate. The method of the present invention is carried out as follows using the apparatus illustrated in the figures. First, a gas to be ionized, such as N 2 , is introduced into the ion source 2 via the leak valve 1 and is ionized there, then accelerated by the accelerator 3 and given a predetermined ion acceleration energy. The ions are then introduced into the analysis magnet 4, where only the desired ion species are magnetically selected and supplied to the reaction chamber 5. The reaction chamber 5 is maintained at a high vacuum of 10 -4 Torr or less by a vacuum pump (for example, a turbomolecular pump) 6. The substrate 7 is fixed to a substrate holder 8, and is irradiated with the above-mentioned ion species. During irradiation, the ion species are passed through a converging lens 9 in order to uniformly irradiate the substrate with the ion species. 10 is a vapor deposition device placed under the base 7. As a heating method for the device, an appropriate method such as electron beam heating or laser beam heating is used. This contains an evaporation source containing B. The amount and rate of evaporation of the evaporation source containing B may be measured by a vibrating film thickness meter 11 using, for example, a quartz plate, which is disposed beside the substrate holder 8. Further, the number of atoms of the ion species, that is, the ion current can be accurately measured by a current integrator 13 equipped with a secondary electron repulsion electrode 12. In such an apparatus, the substrate 7 is set at a predetermined position, the interior of the reaction chamber 5 is maintained at a predetermined degree of vacuum, and the evaporation device 10 is operated to deposit a predetermined amount of the evaporation source containing B onto the substrate 7. When a predetermined ion species is irradiated with a predetermined ion acceleration energy, a thin film of high hardness BN mainly composed of c-BN is formed on the substrate surface. At this time, since the evaporation source and the ion species containing B are evaporated or irradiated only from one direction of the substrate, the entire surface of the substrate has a high hardness mainly composed of c-BN.
When forming a BN thin film, it is sufficient to apply motion such as rotation or rocking to this substrate. [Embodiments of the Invention] Examples 1 to 3 High purity N 2 gas was introduced into the PIG type ion source 2 through the leak valve 1 using the apparatus shown in the figure. Various acceleration energies were applied to the generated ions using an accelerator 3. This ion beam was subjected to mass analysis using an analysis magnet 4, and only N 2 + was magnetically selected. On the other hand, a tantalum plate was used as the substrate, which was set in the substrate holder 8, and the inside of the reaction chamber 5 was maintained at a vacuum of 1×10 -5 Torr by a turbo molecular pump at 650/sec. Next, the electron beam evaporator 10 containing the metal B was operated to evaporate the metal B, and the metal B was evaporated onto the tantalum plate 7 at the same time as the N 2 + ion irradiation. The amount of B vapor deposited and the vapor deposition rate were measured with a vibrating film thickness meter 11, and the number of N 2 + ions was measured with a current integrator 13 to calculate B/N. By changing the ion acceleration energy of N 2 + ions, B
Thin films were formed by varying the amount of evaporation. The results are summarized in the table.
本発明方法によれば、基体の表面に有用なｃ−
BNを主体とす高硬度BNの薄膜を形成すること
ができること、そしてその薄膜はイオン照射によ
つて基体との界面で楔効果を有するので密着性に
優れていることなどの点で工業的に資するところ
大である。
According to the method of the present invention, useful c-
It is industrially useful because it is possible to form a thin film of high hardness, mainly composed of BN, and because the thin film has a wedge effect at the interface with the substrate by ion irradiation, it has excellent adhesion. This is a great contribution.
図は本発明方法を行なうに当り好適な装置の１
例を示すものである。
１……リークバルブ、２……イオン源、３……
加速器、４……分析マグネツト、５……反応室、
６……真空ポンプ、７……基体、８……基体ホル
ダ、９……イオン収束レンズ、１０……蒸着装
置、１１……石英板使用の振動型膜厚計、１２…
…二次電子追い返し用電極、１３……電流積算
計。
The figure shows one of the preferred apparatuses for carrying out the method of the present invention.
This is an example. 1...Leak valve, 2...Ion source, 3...
Accelerator, 4... Analysis magnet, 5... Reaction chamber,
6... Vacuum pump, 7... Substrate, 8... Substrate holder, 9... Ion focusing lens, 10... Vapor deposition device, 11... Vibrating film thickness gauge using quartz plate, 12...
...Secondary electron repulsion electrode, 13...Current integrator.
Claims (1)
せ、かつ、その蒸着と同時又は交互に、イオン源
にて生成され加速器にて加速されたイオン種を照
射して、該基体上に該蒸発源と該イオン種とによ
つて立方晶窒化ホウ素を主体とした高硬度窒化ホ
ウ素薄膜を生成せしめる方法であつて、 該蒸発源と該イオン種とに含まれるホウ素と窒
素との原子比（Ｂ／Ｎ）が0.5〜３であり、かつ、
該イオン種のイオン加速エネルギーが該イオン種
に含まれているホウ素若しくは窒素又は不活性ガ
スの原子当り５〜60keVであることを特徴とする
高硬度窒化ホウ素薄膜の製造方法。 ２ 該ホウ素含有の蒸発源が、金属ホウ素、ホウ
素化合物又はこれらの相互固溶体の群から選ばれ
る少なくとも１種である特許請求の範囲第１項記
載の高硬度窒化ホウ素薄膜の製造方法。 ３ 該イオン種が、窒素原子イオン、窒素分子イ
オン、窒素化合物イオン、ホウ素イオン、ホウ素
化合物イオン又は不活性ガスイオンのいずれかで
ある特許請求の範囲第１項記載の高硬度窒化ホウ
素薄膜の製造方法。 ４ 該基体が、超硬合金、サーメツト、セラミツ
クス、又は各種の金属若しくは合金である特許請
求の範囲第１項記載の高硬度窒化ホウ素薄膜の製
造方法。[Scope of Claims] 1. Depositing an evaporation source containing boron on a substrate, and simultaneously or alternately with the deposition, irradiating ion species generated in the ion source and accelerated in an accelerator, A method of forming a high hardness boron nitride thin film mainly composed of cubic boron nitride on the substrate using the evaporation source and the ionic species, the method comprising: boron and nitrogen contained in the evaporation source and the ionic species; The atomic ratio (B/N) is 0.5 to 3, and
A method for producing a highly hard boron nitride thin film, characterized in that the ion acceleration energy of the ion species is 5 to 60 keV per atom of boron, nitrogen, or inert gas contained in the ion species. 2. The method for producing a high hardness boron nitride thin film according to claim 1, wherein the boron-containing evaporation source is at least one selected from the group of metallic boron, boron compounds, or mutual solid solutions thereof. 3. Production of a high hardness boron nitride thin film according to claim 1, wherein the ion species is any one of nitrogen atom ions, nitrogen molecule ions, nitrogen compound ions, boron ions, boron compound ions, or inert gas ions. Method. 4. The method for producing a high hardness boron nitride thin film according to claim 1, wherein the substrate is made of cemented carbide, cermet, ceramics, or various metals or alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58171217A JPS6063372A (en) | 1983-09-19 | 1983-09-19 | Manufacture of thin boron nitride film of high hardness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58171217A JPS6063372A (en) | 1983-09-19 | 1983-09-19 | Manufacture of thin boron nitride film of high hardness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6063372A JPS6063372A (en) | 1985-04-11 |
| JPH0351787B2 true JPH0351787B2 (en) | 1991-08-07 |
Family
ID=15919206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58171217A Granted JPS6063372A (en) | 1983-09-19 | 1983-09-19 | Manufacture of thin boron nitride film of high hardness |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6063372A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152677A (en) * | 1984-01-20 | 1985-08-10 | Sumitomo Electric Ind Ltd | Cubic boron nitride coated hard material and its production |
| JPS61157674A (en) * | 1984-12-29 | 1986-07-17 | Agency Of Ind Science & Technol | Manufacture of high hardness boron nitride film |
| JP2603919B2 (en) * | 1985-10-18 | 1997-04-23 | 日新電機株式会社 | Method for producing boron nitride film containing cubic boron nitride crystal grains |
| JP2593441B2 (en) * | 1986-01-16 | 1997-03-26 | 日新電機株式会社 | High-hardness film-coated tool material and its manufacturing method |
| JPH0742571B2 (en) * | 1986-07-11 | 1995-05-10 | 三菱重工業株式会社 | CBN coating method |
| JPH0819523B2 (en) * | 1986-11-22 | 1996-02-28 | 住友電気工業株式会社 | High hardness boron nitride synthesis method |
| JPH01225767A (en) * | 1988-03-07 | 1989-09-08 | Nissin Electric Co Ltd | Production of silicon nitride film |
| JPH0685962B2 (en) * | 1988-12-07 | 1994-11-02 | 工業技術院長 | Forging die and its manufacturing method |
| JPH02159362A (en) * | 1988-12-13 | 1990-06-19 | Mitsubishi Heavy Ind Ltd | Method and apparatus for production of thin film |
| JP2761026B2 (en) * | 1989-03-31 | 1998-06-04 | 三菱重工業株式会社 | Method for manufacturing boron nitride film |
| DE69021337T2 (en) * | 1989-11-17 | 1996-01-25 | Nissin Electric Co Ltd | A method of forming a boron layer containing boron nitride, a magnetic head, and a method of producing the same. |
| JP2611521B2 (en) * | 1990-09-12 | 1997-05-21 | 日新電機株式会社 | Method of forming boron nitride thin film |
| JP2611522B2 (en) * | 1990-09-12 | 1997-05-21 | 日新電機株式会社 | Method of forming boron nitride thin film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5282699A (en) * | 1975-12-29 | 1977-07-11 | Youichi Murayama | Hard boronnitride c0ating |
-
1983
- 1983-09-19 JP JP58171217A patent/JPS6063372A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5282699A (en) * | 1975-12-29 | 1977-07-11 | Youichi Murayama | Hard boronnitride c0ating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6063372A (en) | 1985-04-11 |
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