JPS63259068A - Production of hard boron nitride film - Google Patents
Production of hard boron nitride filmInfo
- Publication number
- JPS63259068A JPS63259068A JP9370087A JP9370087A JPS63259068A JP S63259068 A JPS63259068 A JP S63259068A JP 9370087 A JP9370087 A JP 9370087A JP 9370087 A JP9370087 A JP 9370087A JP S63259068 A JPS63259068 A JP S63259068A
- Authority
- JP
- Japan
- Prior art keywords
- boron nitride
- film
- purity
- reactor
- hard
- 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 48
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 abstract description 3
- 229910000906 Bronze Inorganic materials 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 2
- 239000010974 bronze Substances 0.000 abstract description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000010894 electron beam technology Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 20
- 238000005240 physical vapour deposition Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- -1 cemented carbide Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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）
本発明は、物理蒸着法による高密度窒化ホウ素を主体に
した硬質窒化ホウ素膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a hard boron nitride film mainly made of high-density boron nitride by physical vapor deposition.
（従来の技術）
物理蒸着法（ＰＶＤ法）は、大別すると、真空蒸着法、
スパッタリング法又はイオンブレーティング法がある。(Prior art) Physical vapor deposition (PVD) can be roughly divided into vacuum evaporation,
There is a sputtering method or an ion blating method.
このＰＶＤ法により窒化ホウ素の膜を形成させることが
行われている。窒化ホウ素は、大別すると、非晶質窒化
ホウ素又は六方晶窒化ホウ素からなる低密度窒化ホウ素
と、立方晶窒化ホウ素又はウルツ鉱型窒化ホウ素からな
る高密度窒化ホウ素がある。ＰＶＤ法により窒化ホウ素
の膜を形成する場合、前者の低密度窒化ホウ素でなる膜
は比較的容易に形成させることができるのに対して、後
者の高密度窒化ホウ素でなる膜を形成させることは非常
に困難であるのが現状である。This PVD method is used to form a boron nitride film. Boron nitride can be broadly classified into low-density boron nitride made of amorphous boron nitride or hexagonal boron nitride, and high-density boron nitride made of cubic boron nitride or wurtzite boron nitride. When forming a boron nitride film using the PVD method, the former low-density boron nitride film can be formed relatively easily, whereas the latter high-density boron nitride film is difficult to form. The current situation is extremely difficult.
ＰＶＤ法を用いた窒化ホウ素の膜又はその製造方法に関
連したものの代表例としては、特開昭５２−８２６９９
号公報及び特開昭５８−１３５１１１号公報がある。A representative example of a boron nitride film using the PVD method or related to its manufacturing method is JP-A-52-82699.
There are Japanese Patent Publication No. 135111/1983.
（発明が解決しようとする問題点）
特開昭５８−１３５１１１号公報は、ホウ素と、該ホウ
素を窒化しうる物質とを別々にして又は混合して、窒素
ガス又はアンモニアガスの少なくとも１種類を含む雰囲
気中ておいて基体に付若させることを特徴とする窒化物
薄膜の形成方法である。この特開昭５８−１３５１１１
号公報の発明は、ホウ素を窒化しうる物質を含有するこ
とにより潤滑性が高く、＃摩耗性や耐食性にすぐれた高
純度の窒化ホウ素膜を形成させることに成功したもので
ある。しかしながら、特開昭５８−１３５１１１号公報
の方法により得られる窒化ホウ素の膜は、低密度窒化ホ
ウ素からなるものである。低密度窒化ホウ素が潤滑性に
すぐれていることから特開昭５８−１３５１１１号公報
の方法による膜は、＃摩耗性にすぐれているが、軟質で
あるために引掻き状の摩耗条件に対しては容易に膜が剥
離してしまうという問題がある。(Problems to be Solved by the Invention) JP-A-58-135111 discloses that boron and a substance capable of nitriding the boron are separated or mixed, and at least one type of nitrogen gas or ammonia gas is added. This is a method for forming a nitride thin film, which is characterized in that it is grown on a substrate in an atmosphere containing nitride. This Japanese Patent Publication No. 58-135111
The invention disclosed in the publication succeeded in forming a high purity boron nitride film which has high lubricity and excellent wear resistance and corrosion resistance by containing a substance capable of nitriding boron. However, the boron nitride film obtained by the method disclosed in JP-A-58-135111 is made of low-density boron nitride. Since low-density boron nitride has excellent lubricity, the film produced by the method of JP-A-58-135111 has excellent abrasion resistance, but since it is soft, it is difficult to resist scratch-like wear conditions. There is a problem that the film easily peels off.
特開昭５２−８２６９９号公報は、蒸着法により被蒸着
基板により施してなる硬質窒化ホウ素膜である。この特
開昭５２−８２６９９号公報には、塊状ホウ素を６ Ｘ
１０ ＝Ｔｏｒｒの窒素ガス中で蒸若させて硬質窒化
ホウ素膜を形成する高周波イオンブレーティング法が開
示されている。この特開昭５２−８２６９９号公報に開
示の方法により得られる窒化ホウ素の膜は、硬質窒化ホ
ウ素膜ではあるけれども、塊状ホウ素の純度、窒素ガス
の純度及び反応容器内のガス雰囲気、特に反応容器内の
酸素分圧の影響により、例えば膜を形成している粒形の
影響により低密度窒化ホウ素の中でも硬質な窒化ホウ素
膜になっている場合、又は低密度窒化ホウ素の中に微量
の高密度窒化ホウ素の混在もしくはその混在量の多少に
より硬質な窒化ホウ素膜になっている場合などと、得ら
れる硬質窒化ホウ素膜の膜質が非常に不安定であるとい
う問題がある。Japanese Unexamined Patent Publication No. 52-82699 discloses a hard boron nitride film formed on a substrate to be deposited by a vapor deposition method. In this Japanese Patent Application Laid-open No. 52-82699, bulk boron is
A high frequency ion blating method is disclosed in which a hard boron nitride film is formed by evaporation in nitrogen gas at 10 Torr. Although the boron nitride film obtained by the method disclosed in JP-A-52-82699 is a hard boron nitride film, the purity of bulk boron, the purity of nitrogen gas, and the gas atmosphere inside the reaction vessel, especially the reaction vessel Due to the influence of the oxygen partial pressure within the film, for example, due to the influence of the particle shape forming the film, the boron nitride film is hard even among low-density boron nitrides, or when there is a trace amount of high-density boron nitride in low-density boron nitride. There is a problem that the film quality of the obtained hard boron nitride film is extremely unstable, such as when the boron nitride film is hard due to the presence of boron nitride or the amount of boron nitride mixed therein.
本発明は、上述のような問題点を解決したもので、具体
的には硬質窒化ホウ素膜を形成するためのホウ素源に高
純度のホウ素を用い、窒素源に高純度の窒素ガスを用い
、さらに反応容器内での酸素含有量を著しく制限するこ
とにより基体との密着性にすぐれた高密度窒化ホウ素を
主体にした安定な膜の形成方法の提供を目的とするもの
である。The present invention solves the above-mentioned problems. Specifically, the present invention uses high-purity boron as a boron source and high-purity nitrogen gas as a nitrogen source to form a hard boron nitride film. Furthermore, it is an object of the present invention to provide a method for forming a stable film mainly made of high-density boron nitride that has excellent adhesion to a substrate by significantly limiting the oxygen content in the reaction vessel.
（問題点を解決するための手段）
本発明者は、イオンプレーテインク法により高密度窒化
ホウ素の膜を形成すべく種々検討していた所、高密度窒
化ホウ素のホウ素源である金属ホウ素の純度と窒素源で
ある窒素ガスの純度が高くなるに従って高密度窒化ホウ
素の含有量の高い膜が得られ、さらに、反応容器内の酸
素含有量が膜中の高密度窒化ホウ素の含有量に著しく影
響を及ぼすという知見を得たものである。(Means for Solving the Problems) The present inventor was conducting various studies to form a high-density boron nitride film using the ion plate ink method, and found that metallic boron, which is the boron source of high-density boron nitride, As the purity and purity of the nitrogen gas that is the nitrogen source increases, a film with a higher content of dense boron nitride can be obtained, and furthermore, the oxygen content in the reaction vessel significantly affects the content of dense boron nitride in the film. We have obtained knowledge that it has an impact.
本発明は、上記知見に基づいて完成するに至ったもので
ある。The present invention has been completed based on the above findings.
すなわち、本発明の硬質窒化ホウ素膜の製造方法は、反
応容器内をＩ Ｘ １０１Ｔｏｒｒ以上の高真空にした
後、該反応容器内で９９．９％以上の高純度ホウ素を加
熱蒸発してイオン化すると共に９９．９９９％以上の高
純度窒素ガスを導入して加熱された基体の表面に硬質窒
化ホウ素膜を形成することを特徴とするものである。That is, the method for producing a hard boron nitride film of the present invention involves creating a high vacuum of I x 101 Torr or more in a reaction vessel, and then heating and evaporating high purity boron of 99.9% or more in the reaction vessel to ionize it. The method is characterized in that a hard boron nitride film is formed on the surface of the heated substrate by introducing high purity nitrogen gas of 99.999% or more.
本発明の硬質窒化示つ素膜の製造方法において、膜の形
成反応中の反応容器内は、含有酸素量を多くとも１ｗｔ
％に制限することが好ましく、このために反応容器内を
ｌ Ｘ Ｉ Ｏ１Ｔｏｒｒ以上の高真空にする必要があ
る。高純度のホウ素の加熱は、電子ビーム、レーザ、高
周波加熱又はアークなど従来の加熱方法を用いることが
できる。また、イオン化する方法は、高周波電場、イオ
ン源、低圧アーク放電などを用いることができる。さら
に、高純度ホウ素をイオン化した後、加速器により加速
すること、又は高純度窒素ガスも同様にイオン化して加
速することは好ましいことである。ここで用いる基体は
、製造条件に耐えるものならば、特別な材質及び形状に
制限がなく、形状的には、粉末、板状体又は塊状体のも
のを用いること、又は材質的にはＷ 、 Ｍ ｏ 、
Ｔ ａ 、 Ｎ ｂ 、 Ｔ ｉ 。In the method for manufacturing a hard nitrided film of the present invention, the amount of oxygen contained in the reaction vessel during the film formation reaction is reduced to at most 1 wt.
%, and for this purpose, it is necessary to maintain a high vacuum of 1 Torr or more in the reaction vessel. High purity boron can be heated using conventional heating methods such as electron beam, laser, high frequency heating, or arc. Further, as the ionization method, a high frequency electric field, an ion source, a low pressure arc discharge, etc. can be used. Furthermore, it is preferable to ionize high-purity boron and then accelerate it using an accelerator, or to similarly ionize and accelerate high-purity nitrogen gas. The substrate used here is not limited to any particular material or shape as long as it can withstand the manufacturing conditions, and in terms of shape, it may be powder, plate-like, or lump-like, or it may be made of W, Mo,
T a , N b , T i .
Ｚｒ、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｕなどの各種金属、青銅、
鋼、サーメット、超硬合金などの各種合金、Ｓｉ３Ｎ４
系セラミックス、ＳｉＣ系セラミックス、ダイヤモンド
含有高圧焼結体、ＣＢＮ含有高圧焼結体などの各種セラ
ミックスや耐熱ガラスなどを用いることができる。これ
らの基体を加熱する場合、それぞれの基体の材質に適し
た加熱温度にする必要がある。金属１合金又はセラミッ
クスからなる基体の加熱温度は、膜の基体への密着性及
び温度による基体の変質防止のために５００℃〜１００
０℃が好ましいものである。膜の基体への密着性を高め
るため又は基体の帯電防止のために基体に高周波などで
電位を印加すること、もしくは熱電子を照射することな
ども好ましいことである。Various metals such as Zr, Fe, Ni, Co, Cu, bronze,
Various alloys such as steel, cermet, cemented carbide, Si3N4
Various types of ceramics, heat-resistant glass, and the like can be used. When heating these substrates, it is necessary to set the heating temperature to be suitable for the material of each substrate. The heating temperature of the substrate made of metal 1 alloy or ceramics is 500°C to 100°C in order to improve the adhesion of the film to the substrate and to prevent deterioration of the substrate due to temperature.
0°C is preferred. In order to increase the adhesion of the film to the substrate or to prevent the substrate from being charged, it is also preferable to apply a potential to the substrate using high frequency waves or the like, or to irradiate the substrate with thermoelectrons.
（作用）
本発明の硬質窒化ホウ素膜の製造方法は、反応容器内を
Ｉ Ｘ １０−７Ｔｏｒｒ以上の高真空にすることによ
り、９９．９％以上の高純度ホウ素の加熱イオン化され
たホウ素イオン及び９９．９９９％以上の高純度窒素ガ
スの窒素イオンの両方を汚染し難くしているものである
。このために、本発明の硬質窒化ホウ素膜の製造方法は
、酸素による汚染及び不純物の少ないホウ素イオンと窒
素イオンにより高密度窒化ホウ素を主体とした膜が形成
されるのである。(Function) The method for producing a hard boron nitride film of the present invention involves creating a high vacuum of I x 10-7 Torr or higher in the reaction vessel to generate heated ionized boron ions of high purity boron of 99.9% or higher. This makes it difficult to contaminate both nitrogen ions of high-purity nitrogen gas of 99.999% or higher. For this reason, in the hard boron nitride film manufacturing method of the present invention, a film mainly composed of high-density boron nitride is formed using boron ions and nitrogen ions with little oxygen contamination and impurities.
実施例
反応容器内に超硬合金（約５Ｘ５Ｘ１３ｍｍ）の基体を
設置し、この反応容器内を１．０Ｘ１０−７Ｔｏｒｒ以
下まで排気した後、９９．９９９％ＡｒガスをＩ Ｘ
１０−２Ｔｏｒｒまで導入した０次いで、基体を８００
℃に加熱しながら直流の電位５００ｖを基体に印加して
５分間基体表面をイオンボンバードした０次に、Ａｒの
導入を止めて再び反応容器内をＩ Ｘ １０−６Ｔｏｒ
ｒにした後、電子銃にて９９．９％金属ホウ素を徐々に
加熱しなから２ＫＷ（１０にマー２００ ｍＡ）で蒸着
を開始した。これと同時に９９．９９９％の窒素ガスを
反応容器内に導入し、（分圧Ｉ Ｘ １０−５Ｔｏｒｒ
） ３５分間保持して基体の表面に２．５ｐｍ厚さの膜
を形成した。Example A substrate made of cemented carbide (approximately 5 x 5 x 13 mm) was placed in a reaction vessel, and after evacuating the inside of this reaction vessel to 1.0 x 10-7 Torr or less, 99.999% Ar gas was blown into IX.
Then, the substrate was heated to 800 Torr.
The substrate surface was ion-bombarded for 5 minutes by applying a direct current potential of 500 V to the substrate while heating at ℃. Next, the introduction of Ar was stopped and the inside of the reaction vessel was heated again to IX 10-6 Tor.
After the temperature was set to r, 99.9% metallic boron was gradually heated using an electron gun and vapor deposition was started at 2 KW (200 mA at 10 mA). At the same time, 99.999% nitrogen gas was introduced into the reaction vessel (partial pressure I
) A film with a thickness of 2.5 pm was formed on the surface of the substrate by holding for 35 minutes.
この膜を調査した所、ヌープ硬さ５７００ ｋｇ／ｍｍ
ｍ２（５０荷重）、比抵抗１．０Ｘ１０１４Ω・ｃｍ。When this film was investigated, the Knoop hardness was 5700 kg/mm.
m2 (50 load), specific resistance 1.0 x 1014 Ω・cm.
ロックウェル硬度計のダイヤモンド圧子を用いた引掻き
試験で８ ｋｇＦまで剥離しなかった。またＸ線回析の
結果は、立方晶窒化ホウ素のピークが明確に表われてい
た。In a scratch test using a diamond indenter of a Rockwell hardness tester, no peeling occurred up to 8 kgF. Furthermore, the results of X-ray diffraction clearly showed the peak of cubic boron nitride.
尚、膜形成におけるンオン化機構は、４極イオンブレー
テイング法を使用し、その条件は、熱電子陰極１０Ｖ
−１５Ａ 、 イオ７化電極５０ｖ−ＬＡ、基体バイア
ス１００ｖであった。The ionization mechanism used in film formation uses the quadrupole ion brating method, and the conditions are: thermionic cathode 10V
-15A, io7ization electrode 50v-LA, and substrate bias 100v.
比較として、上述の条件の内、９５％の金属ホウ素と９
５％の窒素ガスを用いて、６０分間の保持時間の他は全
て同一条件により膜を形成した。For comparison, under the above conditions, 95% metallic boron and 9
A film was formed using 5% nitrogen gas under the same conditions except for a holding time of 60 minutes.
この膜を上述と同様に調査した所、厚さが１．５ｇｍ、
ヌープ硬さ４０００ ｋｇ／■２（５０ｇ荷重）、比抵
抗ｌＸ１ｏ１３Ω・ｃｍ、引掻き試験で２ｋｇｆまで剥
離しなかった。When this film was investigated in the same manner as above, the thickness was 1.5 gm.
It had a Knoop hardness of 4000 kg/■2 (50 g load), a specific resistance of 1×1013 Ω·cm, and did not peel off up to 2 kgf in a scratch test.
（発明の効果）
本発明の硬質窒化ホウ素膜の製造方法は、従来のＰＶＤ
法では高密度窒化ホウ素を主体とした膜の形成が殆んど
不可能であったのに対して、Ｘ線的に立方晶窒化ホウ素
の明確な膜が得られると共に、基体との密着性にすぐれ
た膜が得られる方法である。また１本発明の硬質窒化ホ
ウ素膜の製造方法は、純度の低いホウ素及び純度の低い
窒素ガスを使用する場合に比較して、硬さが約４０％上
昇し、密着強度が約４倍も良好な膜を得ることができる
ものである。これらのことから、本発明の製造方法は、
半導体基板を含めた電子部品、電気機器部品、工具部品
、精密機械部品又は宇宙開発用、医療機器用、化学工業
部品用などの各種産業部品の製造に応用できるものであ
る。(Effects of the Invention) The method for manufacturing a hard boron nitride film of the present invention is similar to the conventional PVD method.
Whereas it was almost impossible to form a film mainly composed of high-density boron nitride using this method, it was possible to obtain a clear film of cubic boron nitride based on X-rays, and the adhesion to the substrate was improved. This method yields an excellent film. In addition, the hard boron nitride film manufacturing method of the present invention increases the hardness by about 40% and has about 4 times better adhesion strength than when using low-purity boron and low-purity nitrogen gas. It is possible to obtain a film with a high quality. From these facts, the manufacturing method of the present invention is as follows:
It can be applied to the production of various industrial parts such as electronic parts including semiconductor substrates, electrical equipment parts, tool parts, precision machine parts, and parts for space development, medical equipment, and chemical industry parts.
Claims (1)
した後、該反応容器内で９９．９％以上の高純度ホウ素
を加熱蒸発してイオン化すると共に ９９．９９９％以上の高純度窒素ガスを導入して加熱さ
れた基体の表面に形成させることを特徴とする硬質窒化
ホウ素膜の製造方法。[Claims] After creating a high vacuum of 1×10^-^7 Torr or more in the reaction vessel, high purity boron of 99.9% or more is ionized by heating in the reaction vessel and 99.999% or more is ionized. 1. A method for producing a hard boron nitride film, which comprises introducing high-purity nitrogen gas of % or more to form it on the surface of a heated substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9370087A JPS63259068A (en) | 1987-04-16 | 1987-04-16 | Production of hard boron nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9370087A JPS63259068A (en) | 1987-04-16 | 1987-04-16 | Production of hard boron nitride film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63259068A true JPS63259068A (en) | 1988-10-26 |
Family
ID=14089678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9370087A Pending JPS63259068A (en) | 1987-04-16 | 1987-04-16 | Production of hard boron nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63259068A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5567227B1 (en) * | 2012-09-21 | 2014-08-06 | Ｊｘ日鉱日石金属株式会社 | Sintered Fe-Pt magnetic material |
| JP5689543B2 (en) * | 2012-08-31 | 2015-03-25 | Jx日鉱日石金属株式会社 | Sintered Fe-based magnetic material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157674A (en) * | 1984-12-29 | 1986-07-17 | Agency Of Ind Science & Technol | Manufacture of high hardness boron nitride film |
-
1987
- 1987-04-16 JP JP9370087A patent/JPS63259068A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157674A (en) * | 1984-12-29 | 1986-07-17 | Agency Of Ind Science & Technol | Manufacture of high hardness boron nitride film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5689543B2 (en) * | 2012-08-31 | 2015-03-25 | Jx日鉱日石金属株式会社 | Sintered Fe-based magnetic material |
| US10090012B2 (en) | 2012-08-31 | 2018-10-02 | Jx Nippon Mining & Metals Corporation | Fe-bases magnetic material sintered compact |
| JP5567227B1 (en) * | 2012-09-21 | 2014-08-06 | Ｊｘ日鉱日石金属株式会社 | Sintered Fe-Pt magnetic material |
| US10755737B2 (en) | 2012-09-21 | 2020-08-25 | Jx Nippon Mining & Metals Corporation | Fe-Pt based magnetic material sintered compact |
| US10937455B2 (en) | 2012-09-21 | 2021-03-02 | Jx Nippon Mining & Metals Corporation | Fe—Pt based magnetic material sintered compact |
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