JPH02236269A - Formation of boron nitride film - Google Patents
Formation of boron nitride filmInfo
- Publication number
- JPH02236269A JPH02236269A JP5667689A JP5667689A JPH02236269A JP H02236269 A JPH02236269 A JP H02236269A JP 5667689 A JP5667689 A JP 5667689A JP 5667689 A JP5667689 A JP 5667689A JP H02236269 A JPH02236269 A JP H02236269A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- boron nitride
- nitride film
- ion
- substrate
- 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.)
- Granted
Links
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 54
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 58
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 238000007740 vapor deposition Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 46
- -1 nitrogen ions Chemical class 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 10
- 238000005520 cutting process Methods 0.000 abstract description 5
- 238000005498 polishing Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 210000001015 abdomen Anatomy 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical group [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
この発明は、たとえば切削工具および研磨工具などの被
覆膜ならびにヒートシンクの材料などとして好適に用い
られる窒化ホウ素膜の形成方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for forming a boron nitride film, which is suitably used as a coating film for cutting tools and polishing tools, and as a material for heat sinks.
（従来の技術〕
窒化ホウ素は、結晶積造によって主に３種類に分けられ
る．それらは、六方品窒化ホウ素（以下ｒｈ−ＢＮＪと
いう．）、六方最密充填窒化ホウ素，および立方晶窒化
ホウ素（以下ｒｃ−ＢＮＪという．）である．このなか
で、ｃ−ＢＮは、熱伝導率．硬度，耐熱性，耐摩耗性．
および絶縁性に優れており、たとえば切削工具および研
磨工具などの被覆膜ならびにヒートシンクの材料などと
して注目されている．これまで、ｃ−ＢＮは高温・高圧
下で合成されてきたが、その用途を拡大するために、最
近では基体上に薄膜化して形成する研究が行われるよう
になってきている．基体表面に窒化ホウ素膜を形成する
方法としては、化学薫着（ＣＶＤ）法および物理蒸着（
ＰＶＤ）法がよく知られている．しかしながら、ｃＶＤ
法では、作製した膜はｈ−ＢＮが主体となり、ｃ−ＢＮ
主体の膜を形成するのが困難であるとともに、膜と基体
との間の密着性が悪いという問題がある，
ＰＶＤ法には、たとえばイオン化された原子を加速，減
速して基体表面に堆積させるイオンビーム・デポジショ
ン法、クラスターイオンを加速して基体上に堆積させる
クラスターイオンブレーティング法、その他イオンビー
ムスパッタリング法などがあるが、これらの方法によっ
てもやはりＣ−ＢＮ主体の膜を形成するのは困難である
．しかも、これらのＰＶＤ法では、基体に照射されるイ
オンの運動エネルギーが数ｅＶ〜数百ｅＶの比較的低い
範囲にあり、このためイオン種の基体内部への注入は期
待し得す、したがって膜と基体との密着性が悪いという
問題がある．
そこで、近年ではエネルギーを数十〜数百ｋｅＶとした
イオン種を用いて成膜を行うイオン注入法やイオンミキ
シング法が注目されている．とくに、ホウ素系の物質の
蕉着と同時または交互に数十〜数百ｋｅＶに加速したイ
オン種を基体に照射するようにして、基体表面に基体の
材料とホウ素とイオンとの混合層を形成するようにした
イオンミキシング法では、ｃ−ＢＮを多く含む膜を基体
に対して強固に密着させて形成できるという報告がなさ
れている．
（発明が解決しようとする諜Ｂ）
しかしながら、上記イオンミキシング法によって形成さ
れる窒化ホウ素膜には、ｃ−ＢＮとともにｈ−ＢＮもま
た含まれており、したがっていわばｃ−ＢＮとｈ−ＢＮ
との混在膜が得られるに過ぎない，ｈ−ＢＮは高潤滑性
および低硬度などのｃ−ＢＮとは相反する性質をいくつ
か有しており、このため上記イオンミキシング法によっ
て形成した窒化ホウ素膜ではｃ−ＢＮの特徴を充分に発
運させることができず、結果として良好な膜質を有する
ことができなかった．
この発明の目的は、上述の技術的課題を解決し、ｌｌ！
質を格段に向上することができる窒化ホウ素膜の形成方
法を提供することである．
〔課題を解決するための手段〕
この発明の窒化ホウ素膜の形成方法は、ホウ素を含む物
質の蒸着と、窒素イオン．窒素化合物イオン．および不
活性ガスイオンのなかの少なくとも１種のイオンの照射
と、水素イオンの照射とを併用して、基体表面に窒化ホ
ウ素膜を形成することを特徴とする．
第１図はこの発明の実施のために用いられる薄膜形成装
置の構成例を示す概念図である．窒化ホウ素膜を形成す
べき基体１はホルダ２表面に固定して配置され、この基
体１に対向して蒸発源３およびイオン源４．５が配置さ
れる．ホルダ２，蒸発源３，およびイオン源４，５など
は図示しない真空槽内に収められており、この真空槽内
は成膜に適した圧力に保たれる．
このような薄膜形成装置によって、蒸発源３からは、ホ
ウ素や窒化ホウ素などのホウ素を含む物質が蒸発させら
れる．このようにして、ホウ素を含む物質の蒸着が行わ
れるのと同時または交互に、イオン源４からは、窒素イ
オン，窒素化合物イオン，および不活性ガスイオンのな
かの少なくとも１種のイオンが基体１に向けて照射され
る．前記窒素化合物とは、たとえばアンモニアなどであ
る．このようにして、基体１の表面に窒化ホウ素膜が堆
積される．ただし、イオン源４からのイオンが不活性ガ
スイオンのみであるときには、蒸発源３からは窒化ホウ
素などの窒素とホウ素とを含む物質が蒸発させられる．
上述のような窒化ホウ素膜の堆積と、同時または交互に
、イオン源５からは水素イオンが照射される．このよう
にして、蒸発源３から蒸発させられる物質の蒸着と、イ
オン源４．５からのイオンの照射とを併用することによ
って基体１上に窒化ホウ素膜が形成される．
このような窒化ホウ素膜の形成は、以下に例示するよう
な種々の形態で行うことができる。(Prior art) Boron nitride is mainly divided into three types depending on the crystal structure. They are hexagonal boron nitride (hereinafter referred to as rh-BNJ), hexagonal close-packed boron nitride, and cubic boron nitride (rh-BNJ). (hereinafter referred to as rc-BNJ).Among these, c-BN has excellent properties such as thermal conductivity, hardness, heat resistance, and abrasion resistance.
Due to its excellent insulation properties, it is attracting attention as a coating film for cutting tools and polishing tools, and as a material for heat sinks. Up until now, c-BN has been synthesized under high temperature and high pressure, but in order to expand its uses, research has recently begun on forming a thin film on a substrate. Methods for forming a boron nitride film on the substrate surface include chemical vapor deposition (CVD) and physical vapor deposition (
PVD) method is well known. However, cVD
In this method, the fabricated film is mainly composed of h-BN and c-BN.
There are problems in that it is difficult to form a film based on the material and that the adhesion between the film and the substrate is poor.The PVD method involves, for example, accelerating and decelerating ionized atoms and depositing them on the surface of the substrate. There are ion beam deposition methods, cluster ion blating methods in which cluster ions are accelerated and deposited on a substrate, and other ion beam sputtering methods, but even with these methods, it is difficult to form a film mainly composed of C-BN. It is difficult. Moreover, in these PVD methods, the kinetic energy of the ions irradiated onto the substrate is in a relatively low range of several eV to several hundred eV, and therefore, the injection of ionic species into the interior of the substrate can be expected. There is a problem with poor adhesion between the material and the substrate. Therefore, in recent years, ion implantation methods and ion mixing methods in which films are formed using ion species with energies of several tens to several hundreds of keV have been attracting attention. In particular, a mixed layer of the substrate material, boron, and ions is formed on the surface of the substrate by irradiating the substrate with ion species accelerated to several tens to hundreds of keV simultaneously or alternately with the deposition of the boron-based substance. It has been reported that the ion mixing method can form a film containing a large amount of c-BN in close contact with the substrate. (Intelligence B to be Solved by the Invention) However, the boron nitride film formed by the above ion mixing method contains h-BN as well as c-BN.
However, h-BN has some properties that are contradictory to c-BN, such as high lubricity and low hardness. The characteristics of c-BN could not be fully expressed in the film, and as a result, the film could not have good film quality. The purpose of this invention is to solve the above-mentioned technical problem and to solve the above-mentioned technical problem.
The purpose of this invention is to provide a method for forming a boron nitride film that can significantly improve its quality. [Means for Solving the Problems] The method for forming a boron nitride film of the present invention includes vapor deposition of a substance containing boron, and nitrogen ion. Nitrogen compound ion. The method is characterized in that a boron nitride film is formed on the surface of the substrate by combining irradiation with at least one kind of ions among inert gas ions and irradiation with hydrogen ions. FIG. 1 is a conceptual diagram showing an example of the configuration of a thin film forming apparatus used for carrying out the present invention. A substrate 1 on which a boron nitride film is to be formed is fixedly placed on the surface of a holder 2, and an evaporation source 3 and an ion source 4.5 are placed opposite this substrate 1. The holder 2, evaporation source 3, ion sources 4, 5, etc. are housed in a vacuum chamber (not shown), and the pressure inside this vacuum chamber is maintained at a pressure suitable for film formation. With such a thin film forming apparatus, boron-containing substances such as boron and boron nitride are evaporated from the evaporation source 3. In this way, at the same time or alternately as the boron-containing substance is deposited, at least one kind of ions among nitrogen ions, nitrogen compound ions, and inert gas ions are supplied to the substrate from the ion source 4. It is irradiated towards. The nitrogen compound is, for example, ammonia. In this way, a boron nitride film is deposited on the surface of the substrate 1. However, when the ions from the ion source 4 are only inert gas ions, a substance containing nitrogen and boron such as boron nitride is evaporated from the evaporation source 3. Simultaneously or alternately with the deposition of the boron nitride film as described above, hydrogen ions are irradiated from the ion source 5. In this way, a boron nitride film is formed on the substrate 1 by combining the deposition of the substance evaporated from the evaporation source 3 and the ion irradiation from the ion source 4.5. Formation of such a boron nitride film can be performed in various forms as exemplified below.
■ 金属ホウ素の蒸着の後に窒素イオンの照射を行い、
この後にさらに水素イオンの照射を行うという一連の操
作を反復して行う。■Nitrogen ion irradiation is performed after metal boron vapor deposition,
After this, the series of operations of further irradiating with hydrogen ions is repeated.
■ 窒化ホウ素の痕着の後に不活性ガスイオンの照射を
行い、この後にさらに水素イオンの照射を行うという一
連の操作を反復して行う。(2) After depositing boron nitride, irradiation with inert gas ions is performed, followed by further irradiation with hydrogen ions, and the series of operations is repeated.
■ 金属ホウ素の萎着と同時に窒素イオンの照射を行っ
て窒化ホウ素膜を堆積させ、この窒化ホウ素膜の堆積後
に水素イオンの照射を行うという一連の操作を反復して
行う。(2) Simultaneously with the withering of metallic boron, nitrogen ion irradiation is performed to deposit a boron nitride film, and after this boron nitride film is deposited, hydrogen ion irradiation is performed.A series of operations is repeated.
■ 窒化ホウ素の蒸着と同時に不活性ガスイオンの照射
を行って窒化ホウ素膜を堆積させ、この窒化ホウ素膜の
堆積後に水素イオンの照射を行うという一連の操作を反
復して行う。(2) A series of operations are repeated in which a boron nitride film is deposited by irradiating inert gas ions at the same time as the boron nitride is deposited, and hydrogen ions are irradiated after the boron nitride film is deposited.
■ 窒化ホウ素の草着と同時に不活性ガスイオンの照射
を行って窒化ホウ素膜を堆積させ、この窒化ホウ素膜の
堆積と同時に水素イオンの照射を行う．
なお、第１図に示された構成では、イオン源が２個設け
られているが、イオン源は１個でもよく、たとえば共通
のイオン源から窒素ガスイオンなどと水素イオンとの照
射を交互に行わせるようにすれば、上記■〜■などの形
態で窒化ホウ素膜を基体表面に形成することができる．
〔作用］
上述のような窒化ホウ素膜の形成方法によれば、基体１
の表面では、蒸発′ａ３からの蒸発物がイオン源４．５
からのイオンにより基体１の内部に押し込まれ、またイ
オン源４．５からのイオンが基体１の内部に侵入するこ
とにより、基体ｌの材料と蒸発源３から蒸発される物質
と前記照射されるイオンとが混合した混合層が形成され
、これによって窒化ホウ素膜は基体１の表面に強固に密
着して形成されることになる．
また、イオンＲ５から照射される水素イオンは、前記窒
化ホウ素腹中に存在するＳＰまたはＳＰ”混成軌道を持
った核（これらは、非立方晶窒化ホウ素を成長させる．
）と反応して、これらをＳＰ”結合の核に変換して、ｃ
−ＢＮの生成を促進する．さらに、前記水素イオンは、
水素一ホウ素化合物や水素一窒化ホウ素を生成すること
により、腹中のｈ−ＢＮを選択的に除去する働きをも脊
している．さらにまた、膜中の未反応ホウ素や窒素原子
を除去して膜を清浄化する役割も果たし、ホウ素と窒素
とが結合する際にＳＰ３結合を生じるに充分な励起状態
となるエネルギーを与える．また水素イオンによって、
膜中のｃ−ＢＮ以外の窒素ホウ素構造物や単体原子１単
体金属が除去され、これによって膜中におけるｃ−ＢＮ
の割合が大きくなり、膿の特性がｃ−ＢＮにより支配さ
れるようになる．
このようにして、熱伝導率，硬度，耐熱性，耐摩耗性．
および絶縁性に優れた窒化ホウ素膜が基体１上に形成さ
れることになる。■ At the same time as boron nitride is deposited, inert gas ions are irradiated to deposit a boron nitride film, and hydrogen ions are irradiated at the same time as this boron nitride film is deposited. In the configuration shown in Fig. 1, two ion sources are provided, but it is also possible to use only one ion source.For example, irradiation with nitrogen gas ions and hydrogen ions from a common ion source can be alternately performed. If this is done, a boron nitride film can be formed on the surface of the substrate in the forms described in (1) to (2) above. [Function] According to the method for forming a boron nitride film as described above, the substrate 1
On the surface of the ion source 4.5, the evaporates from evaporation 'a3
The ions from the ion source 4.5 are pushed into the inside of the substrate 1, and the ions from the ion source 4.5 enter the inside of the substrate 1, so that the material of the substrate 1 and the substance evaporated from the evaporation source 3 are irradiated with each other. A mixed layer containing ions is formed, and as a result, the boron nitride film is firmly adhered to the surface of the substrate 1. In addition, the hydrogen ions irradiated from ion R5 are irradiated with nuclei having SP or SP'' hybrid orbits existing in the boron nitride antipodes (these grow non-cubic boron nitride.
) to convert them into SP” bond nuclei, c
-Promotes the production of BN. Furthermore, the hydrogen ions are
By producing hydrogen monoboron compounds and hydrogen monoboron nitride, it also functions to selectively remove h-BN from the abdomen. Furthermore, it also plays the role of cleaning the film by removing unreacted boron and nitrogen atoms in the film, and provides enough energy to create an excited state when boron and nitrogen bond to form an SP3 bond. Also, due to hydrogen ions,
Nitrogen boron structures other than c-BN in the film and single atom 1 elemental metals are removed, and as a result, c-BN in the film is removed.
The proportion of c-BN increases, and the characteristics of pus become dominated by c-BN. In this way, thermal conductivity, hardness, heat resistance, and wear resistance.
A boron nitride film with excellent insulation properties is then formed on the substrate 1.
なお、窒化ホウ素膜の形成時において、窒素イオン，窒
素化合物イオン．不活性ガスイオン．および水素イオン
の加速エネルギーは、０．１〜５０ｋｅＶとされるのが
好ましく、より好ましくは０．２〜２０ｋｅＶとされる
のがよい．加速エネルギーが０．１ｋｅＶ未満であると
きには、窒化ホウ素膜を基体１に対して充分強固に密着
させることができず、また２ＱｋｅＶ以上の加速工不ル
ギーを有するイオンを照射すると、窒化ホウ素膜中にｃ
−ＢＮが形成されにくくなる．
さらに、窒素イオン，窒素化合物イオン，または不活性
ガスイオンの照射ＩＸに対する水素イオンの照射ｉ１Ｙ
の比（Ｘ／Ｙ）は、０．１〜ｌＯＯに選ばれるのがよく
、より好ましくは０．５〜１０の範囲に選ばれるのがよ
い．この比（Ｘ／Ｙ）が、０．１〜１００の範囲から逸
脱すると、ｃ−ＢＮが形成されにくくなる．
また、蒸発ｌｆＩ３からホウ素を含む吻貿を莫発させ、
イオン源４から窒素イオンを含むイオンを照射する場合
に、基体１の表面におけるホウ素原子と窒素原子との比
（Ｂ／Ｎ）は０． １〜６０の範囲に選ばれるのが好ま
しく、より好ましくは０．５〜４０に選ばれるのがよい
．この比（Ｂ／Ｎ）が、０．１〜６０の範囲から逸脱す
ると、ｃ−ＢＮが形成されにくくなる．
〔実施例１〕
第１図に示された構成において、基体１としてシリコン
基板を用い、このシリコン基板表面に対して蒸発ｆｌ３
からの金属ホウ素の蒸着と同時にイオン源４から窒素イ
オンの照射を行って窒化ホウ素膜を堆積させ、この窒化
ホウ素膜の堆積と同時にイオン源５から水素イオンを照
射して、前記シリコン基板表面に膜厚３０００人の窒化
ホウ素膜を形成した試料を作製した．このとき窒素イオ
ンおよび水素イオンの各加速エネルギーは０．２ｋｅＶ
とし、また基板表面でのホウ素原子と窒素原子との比（
Ｂ／Ｎ）を１とし、水素イオンと窒素イオンとの照射量
の比（水素イオン／窒素イオン）を０．５とした．また
比較のために、水素イオンの照射を行わず、他は前述と
同様な条件で比較用試料を作製した．
上記２つの試料に関して、Ｘ線回折による分析を行った
ところ、上記比較用試料では回折角２θ−４３．９’，
４３．３゜の２点でＸ線回折強度のピークが検出された
．回折角２θ＝ ４ ３． ９°での回折ピークはｈ−
ＢＮの存在を表し、回折角２θ＝４ ３． ３ ”での
回折ピークはｃ−ＢＮの存在を表している．したがって
上記比較用試料ではｃ−ＢＮとｈ−ＢＮとが混在した混
在膜がシリコン基板表面に形成されていることが判る．
これに対して、この実施例に従って作製した試料では、
回折角２θ−４３．３″″でのみＸ線回折強度のピーク
が検出されており、したがってこの実施例に従って作製
した試料では、シリコン基板表面にｃ−ＢＮのみを含む
窒化ホウ素膜が形成されていることが判る．
また、１０ｇ荷重ビッカース硬度は、前記比較用試料で
は４０００Ｈｖであったのに対し、この実施例に従って
作製した試料では５５００Ｈｖであった．したがって、
この実施例によれば硬度が極めて高い窒化ホウ素膜を形
成することができることが理解される．
〔実施例２〕
上記実施例１において、窒素イオンの照射エネルギーを
５ ｋｅＶとし、他は同様の条件でシリコン基板表面に
窒化ホウ素膜を形成した試料を作製した．また、同様な
条件で水素イオンの照射を行わずにシリコン基板表面に
窒化ホウ素膜を形成した比較用試料を作製した．
この２つの試料に関してＸ線回折による分析を行ったと
ころ、上記比較用試料では回折角２θ一４３．９°，４
３．３’の２点でＸ線回折強度のピークが検出されたの
に対し、この実施例に従って作製した試料では、回折角
２θ＝ ４ ３． ３ ”でのみそのピークが検出され
た．また、１０ｇ荷重ビッカース硬度を測定したところ
、上記比較用試料では３９５０Ｈｖであったのに対し、
この実施例に従って作製した試料では５８００Ｈｖであ
った。Note that during the formation of the boron nitride film, nitrogen ions and nitrogen compound ions. Inert gas ion. The acceleration energy of hydrogen ions is preferably 0.1 to 50 keV, more preferably 0.2 to 20 keV. When the acceleration energy is less than 0.1 keV, the boron nitride film cannot be firmly attached to the substrate 1, and when ions having an acceleration energy of 2Q keV or more are irradiated, the boron nitride film will not be bonded firmly enough. c.
- BN is less likely to form. Furthermore, hydrogen ion irradiation i1Y with respect to nitrogen ion, nitrogen compound ion, or inert gas ion irradiation IX
The ratio (X/Y) is preferably selected from 0.1 to lOO, more preferably from 0.5 to 10. If this ratio (X/Y) deviates from the range of 0.1 to 100, c-BN will be difficult to form. In addition, the evaporated lfI3 generates a large amount of stomate containing boron,
When irradiating ions containing nitrogen ions from the ion source 4, the ratio (B/N) of boron atoms to nitrogen atoms on the surface of the substrate 1 is 0. It is preferably selected in the range of 1 to 60, more preferably 0.5 to 40. If this ratio (B/N) deviates from the range of 0.1 to 60, c-BN will be difficult to form. [Example 1] In the configuration shown in FIG. 1, a silicon substrate is used as the base 1, and evaporation fl3 is applied to the surface of the silicon substrate.
Simultaneously with the vapor deposition of metallic boron from the ion source 4, nitrogen ions are irradiated from the ion source 4 to deposit a boron nitride film, and simultaneously with the deposition of this boron nitride film, hydrogen ions are irradiated from the ion source 5 to deposit the silicon substrate surface. A sample was prepared with a boron nitride film of 3000 nm thick. At this time, the acceleration energy of each nitrogen ion and hydrogen ion is 0.2 keV
and the ratio of boron atoms to nitrogen atoms on the substrate surface (
B/N) was set to 1, and the ratio of the irradiation amount of hydrogen ions to nitrogen ions (hydrogen ions/nitrogen ions) was set to 0.5. For comparison, a comparative sample was prepared under the same conditions as above, but without hydrogen ion irradiation. When the above two samples were analyzed by X-ray diffraction, it was found that the above comparison sample had a diffraction angle of 2θ-43.9',
Peaks of X-ray diffraction intensity were detected at two points at 43.3°. Diffraction angle 2θ=4 3. The diffraction peak at 9° is h-
Represents the presence of BN, diffraction angle 2θ=4 3. The diffraction peak at 3'' indicates the presence of c-BN. Therefore, it can be seen that in the comparative sample described above, a mixed film containing c-BN and h-BN is formed on the silicon substrate surface.
In contrast, in the sample prepared according to this example,
The peak of X-ray diffraction intensity was detected only at a diffraction angle of 2θ-43.3″, and therefore, in the sample prepared according to this example, a boron nitride film containing only c-BN was formed on the silicon substrate surface. It turns out that there is. Further, the Vickers hardness under a 10 g load was 4000 Hv for the comparative sample, whereas it was 5500 Hv for the sample prepared according to this example. therefore,
It is understood that according to this example, a boron nitride film with extremely high hardness can be formed. [Example 2] A sample was prepared in which a boron nitride film was formed on the surface of a silicon substrate under the same conditions as in Example 1, except that the nitrogen ion irradiation energy was 5 keV. In addition, a comparison sample was prepared in which a boron nitride film was formed on the surface of a silicon substrate under similar conditions without hydrogen ion irradiation. When these two samples were analyzed by X-ray diffraction, the diffraction angles of the comparative sample were 2θ - 43.9°, 4
While peaks of X-ray diffraction intensity were detected at two points at 3.3', in the sample prepared according to this example, the diffraction angle 2θ=43. The peak was detected only at 3". Also, when the Vickers hardness under a 10g load was measured, it was 3950Hv for the comparative sample, whereas
In the sample prepared according to this example, it was 5800 Hv.
〔発明の効果］
以上のようにこの発明の窒化ホウ素膜の形成方法によれ
ば、基体と窒化ホウ素膜との界面では、基体に蒸着され
るホウ素を含む物質が基体表面に向けて照射されるイオ
ンによって基体の内部に押し込まれ、また前記照射され
るイオンが基体内に．侵入することにより、基体の材料
と前記ホウ素を含む物質と前記照射されるイオンとが混
合した混合層が形成される．この混合層の働きによって
、窒化ホウ素膜は基体に対して強固に密着して形成され
ることになる．
基体表面に堆積された窒化ホウ素膜には、水素イオンが
照射されるが、この水素イオンは、前記窒化ホウ素腹中
でのｃ−ＢＮの生成を促進し、さらに窒化ホウ素膜中に
存在するｃ−ＢＮ以外のものを除去する働きを有し、こ
れによって、基体表面にはｃ−ＢＮの割合が極めて大き
い窒化ホウ素膜が形成されることになる．したがうて、
膜の特性がｃ−ＢＮにより支配されるようになり、熱伝
導率．硬度，耐熱性，耐摩耗性，および絶縁性に優れた
窒化ホウ素膜を基体表面に形成することができるように
なる。[Effects of the Invention] As described above, according to the method for forming a boron nitride film of the present invention, at the interface between the substrate and the boron nitride film, the boron-containing substance deposited on the substrate is irradiated toward the surface of the substrate. The ions are pushed into the substrate, and the irradiated ions are pushed into the substrate. By entering, a mixed layer is formed in which the substrate material, the boron-containing substance, and the irradiated ions are mixed. Due to the action of this mixed layer, the boron nitride film is formed in strong adhesion to the substrate. The boron nitride film deposited on the surface of the substrate is irradiated with hydrogen ions, and these hydrogen ions promote the production of c-BN in the boron nitride abdomen, and further increase the amount of c-BN present in the boron nitride film. It has the function of removing substances other than -BN, and as a result, a boron nitride film containing an extremely large proportion of c-BN is formed on the surface of the substrate. Therefore,
The properties of the film are now dominated by c-BN, and the thermal conductivity. A boron nitride film with excellent hardness, heat resistance, wear resistance, and insulation properties can be formed on the surface of the substrate.
Claims (1)
オン、および不活性ガスイオンのなかの少なくとも１種
のイオンの照射と、水素イオンの照射とを併用して、基
体表面に窒化ホウ素膜を形成することを特徴とする窒化
ホウ素膜の形成方法。A boron nitride film is formed on the surface of the substrate by using a combination of vapor deposition of a substance containing boron, irradiation with at least one type of ion selected from nitrogen ions, nitrogen compound ions, and inert gas ions, and irradiation with hydrogen ions. A method for forming a boron nitride film, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1056676A JP2850352B2 (en) | 1989-03-07 | 1989-03-07 | Method for forming boron nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1056676A JP2850352B2 (en) | 1989-03-07 | 1989-03-07 | Method for forming boron nitride film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02236269A true JPH02236269A (en) | 1990-09-19 |
| JP2850352B2 JP2850352B2 (en) | 1999-01-27 |
Family
ID=13034027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1056676A Expired - Fee Related JP2850352B2 (en) | 1989-03-07 | 1989-03-07 | Method for forming boron nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2850352B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582022A (en) * | 1981-06-27 | 1983-01-07 | Agency Of Ind Science & Technol | Thin film formation |
| JPS60169559A (en) * | 1984-02-13 | 1985-09-03 | Agency Of Ind Science & Technol | Manufacture of high hardness boron nitride film |
-
1989
- 1989-03-07 JP JP1056676A patent/JP2850352B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582022A (en) * | 1981-06-27 | 1983-01-07 | Agency Of Ind Science & Technol | Thin film formation |
| JPS60169559A (en) * | 1984-02-13 | 1985-09-03 | Agency Of Ind Science & Technol | Manufacture of high hardness boron nitride film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2850352B2 (en) | 1999-01-27 |
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