JP5387815B2 - Cubic boron nitride coating composite - Google Patents

Cubic boron nitride coating composite Download PDF

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JP5387815B2
JP5387815B2 JP2008273051A JP2008273051A JP5387815B2 JP 5387815 B2 JP5387815 B2 JP 5387815B2 JP 2008273051 A JP2008273051 A JP 2008273051A JP 2008273051 A JP2008273051 A JP 2008273051A JP 5387815 B2 JP5387815 B2 JP 5387815B2
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coating film
boron nitride
cubic boron
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精一郎 松本
君元 堤井
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Kyushu University NUC
National Institute for Materials Science
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Description

本発明は、耐摩耗性、低摩擦性、耐熱性、熱伝導性、電気絶縁性等に優れた複合材料に関するもので、より具体的には、切削工具、耐摩耗性治具、高熱伝導性基板、耐熱高絶縁性コーティング、高温電子材料等に応用可能な立方晶窒化ホウ素被覆膜複合材料に関するものである。   The present invention relates to a composite material having excellent wear resistance, low friction, heat resistance, thermal conductivity, electrical insulation, and the like. More specifically, the present invention relates to a cutting tool, an abrasion resistant jig, and a high thermal conductivity. The present invention relates to a cubic boron nitride coating film composite material that can be applied to substrates, heat-resistant and high-insulating coatings, high-temperature electronic materials, and the like.

立方晶窒化ホウ素（以下、ｃ−ＢＮともいう。）は、その高い、硬度、耐摩耗性、しゅう動性、熱伝導性、電気絶縁性のため、難削材研削や高速切削のためのコーティング材、またヒートシンクや耐熱高絶縁性コーティングとしても永年期待されてきた。   Cubic boron nitride (hereinafter also referred to as c-BN) is a coating for grinding difficult-to-cut materials and high-speed cutting because of its high hardness, wear resistance, sliding property, thermal conductivity, and electrical insulation. It has been expected for many years as a material, as a heat sink and as a heat-resistant and highly insulating coating.

しかし、従来のｃ−ＢＮ膜をコーティングする方法は、強いイオンボンバードを用いるため、膜内の内部応力が大きく金属やセラミック等の基体との密着力が十分でなく、密着性の充分な１μｍ以上の膜を得ることは困難であった。また、そのｃ−ＢＮ被覆膜は強いイオン衝撃を用いて作成するため結晶性が悪く、ラマンピークは観察されず、Ｘ線回折でのｃ−ＢＮのピークもブロードであった。   However, the conventional method of coating a c-BN film uses strong ion bombardment, so the internal stress in the film is large and the adhesion with a substrate such as metal or ceramic is not sufficient, and the adhesion is 1 μm or more. It was difficult to obtain a film. Moreover, since the c-BN coating film was formed using strong ion bombardment, the crystallinity was poor, the Raman peak was not observed, and the c-BN peak in X-ray diffraction was also broad.

この密着性を改善するために、ｃ−ＢＮ被覆膜と基体との間に、中間層を介在させる方法も以下の文献のように種々提案されてきた。   In order to improve this adhesion, various methods for interposing an intermediate layer between the c-BN coating film and the substrate have been proposed as in the following documents.

特に、特許文献１〜５、７、１０には、本発明と同じく、周期律表の第４、第５族金属或いはＳｉ、Ａｌとその窒化物、ホウ化物或いはホウ窒化物を中間層として用いている場合がある。
特許第３６７９０４６号公報／第１層（第４族、第５族、第６族金属、Ｓｉ）−（Ｃ、Ｎ、Ｏ）、第２層Ｔｉ−（Ｃ、Ｎ、Ｏ）＋数ナノ〜数十ナノのＢＮ 特開平２００４−３３８０４１号公報／第１層窒化チタン、第２層Ｔｉ−Ｂ−Ｎ、第３層ｃ−ＢＮ（１０−７０ｍｏｌ％）、厚さ０．５〜１．５μｍ 特開平１０−２０４６１８号公報／第１層Ｔｉ、第２層ＴｉＢｘ（Ｘ＝１．５〜２）、第３層ＴｉｙＢｚＮ１−ｚ（Ｙ＝０．６〜１．５、Ｚ＝０．０５〜０．４）、第４層ｃ−ＢＮ 特開平８−１６５５５８号公報／第１層Ｚｒ、Ｈｆ、Ｖ、Ｔａ、Ｎｂ、Ｃｒ、Ｍｏ、Ｗのホウ化物、炭化ホウ素及びそれらの相互固溶体、第２層ｃ−ＢＮ又は硬質窒化ホウ素 特開平４−２４６１６４号公報／第１層窒化チタン、第２層窒化チタン＋窒化ホウ素、第３層ｃ−ＢＮ 特開平４−１６８２６３号公報／第１層金属、（第２層金属間化合物、）第３層ＢｒｉｃｈＢＮ（Ｂ／Ｎ＞１．５）、第４層ｃ−ＢＮ 特開平４−１４７６８２号公報／第１層チタンアルミニウム複窒化物、或いはチタン第４族第５族金属複窒化物、第２層ｃ−ＢＮ 特開平４−１２４２８３号公報／第１層基体のホウ化処理によるホウ化物、第２層窒化ホウ素 特開平３−２６００５４号公報／第１層チタン、第２層傾斜組成構造ホウ素−窒素化合物、第３層ｃ−ＢＮ 特許公報３−１３３０５号公報／第１層Ｔｉ及びＨｆの炭化物、窒化物、炭窒化物、炭酸化物、酸化アルミニウムの１種の単層或いは２種以上の複層（０．５〜５μｍ）、第２層０．３〜４原子％Ｔｉ固溶ｃ−ＢＮ M.Keunecke, E. Wiemann, K.Weigel, S.T. Park, K. Bewilogua, Thin Solid Films 515,967 （2006）. S.F.Wong, C.W. Ong, G.K.H. Pang, Q.Li, W.M. Lau, Diamond and Related Materials 13 （2004） 1632. In particular, in Patent Documents 1 to 5, 7, and 10, as in the present invention, metals of Groups 4 and 5 of the periodic table or Si, Al and nitrides thereof, borides or boronitrides are used as intermediate layers. There may be.
Patent No. 3679046 / First layer (Group 4, Group 5, Group 6 metal, Si)-(C, N, O), second layer Ti- (C, N, O) + several nano- Tens of nano BN JP-A-2004-338041 / first layer titanium nitride, second layer Ti—BN, third layer c-BN (10-70 mol%), thickness 0.5 to 1.5 μm JP-A-10-204618 / first layer Ti, second layer TiBx (X = 1.5 to 2), third layer TiyBzN1-z (Y = 0.6 to 1.5, Z = 0.05 to 0.4), the fourth layer c-BN JP-A-8-165558 / first layer Zr, Hf, V, Ta, Nb, Cr, Mo, W boride, boron carbide and their mutual solid solution, second layer c-BN or hard boron nitride JP-A-4-246164 / first layer titanium nitride, second layer titanium nitride + boron nitride, third layer c-BN JP-A-4-168263 / first layer metal, (second layer intermetallic compound), third layer BrichBN (B / N> 1.5), fourth layer c-BN JP-A-4-147682 / first layer titanium aluminum double nitride, or titanium group 4 and group 5 metal double nitride, second layer c-BN Japanese Patent Application Laid-Open No. 4-124283 / Boride obtained by boriding the first layer substrate, second layer boron nitride JP-A-3-260054 / First layer titanium, second layer gradient composition structure boron-nitrogen compound, third layer c-BN Patent Publication No. 3-13305 / First layer Ti and Hf carbide, nitride, carbonitride, carbonate, aluminum oxide one single layer or two or more types (0.5-5 μm), Second layer 0.3-4 atomic% Ti solid solution c-BN M. Keunecke, E. Wiemann, K. Weigel, ST Park, K. Bewilogua, Thin Solid Films 515,967 (2006). SFWong, CW Ong, GKH Pang, Q.Li, WM Lau, Diamond and Related Materials 13 (2004) 1632.

しかし、これらのいずれの方法でも、従来の結晶性の良くないｃ−ＢＮの作成法を用いているため、基体との密着性は十分でなく、またそのｃ−ＢＮとしての特性は良くなく、実用に供せられるｃ−ＢＮ被覆膜材料は現在まで開発されていない。   However, in any of these methods, since the conventional method for producing c-BN having poor crystallinity is used, the adhesion with the substrate is not sufficient, and the characteristics as c-BN are not good. A c-BN coating material for practical use has not been developed so far.

また、非特許文献１はＴｉＮ或いはＴｉＡｌＮを中間層としているが、さらにその上層の炭化ホウ素、Ｂ−Ｃ−Ｎの傾斜組成層をも中間層としており、またｃ−ＢＮ被覆膜の厚みは１．２μｍにとどまっている。非特許文献１において、その複合素材の機械的性質を評価しているが、これらの構造・膜厚のため、工具としての実用化までには至っていない。   Further, Non-Patent Document 1 uses TiN or TiAlN as an intermediate layer, but further includes an upper layer of boron carbide and a gradient composition layer of B—C—N as an intermediate layer, and the thickness of the c-BN coating film is as follows. It remains at 1.2 μm. Non-Patent Document 1 evaluates the mechanical properties of the composite material, but due to these structures and film thicknesses, it has not been put into practical use as a tool.

非特許文献２は、本発明に用いられる第４族金属のひとつであるＺｒを炭化タングステン基体上にコートし、さらにｃ−ＢＮ膜を被覆後、全体をより高温でアニールすることにより、ｃ−ＢＮ被覆膜と基体との間にＺｒの窒化物、ホウ化物が生成し、密着性が向上すると報告している。しかしながら、ｃ−ＢＮ被覆膜の作成法は、従来法であるイオンアシストの物理的蒸着法であり、結晶性が悪く、残留応力は高いと推定される。また、そのｃ−ＢＮ層は７２ｎｍの厚さに過ぎず、この厚さでは密着性の評価には不十分であり、またそれより厚い密着性のよい表面膜が作成できるかどうか不明である。   Non-Patent Document 2 discloses that by coating Zr, which is one of the Group 4 metals used in the present invention, on a tungsten carbide substrate, and further coating the c-BN film, the whole is annealed at a higher temperature, whereby c- It has been reported that nitrides and borides of Zr are formed between the BN coating film and the substrate, thereby improving the adhesion. However, the preparation method of the c-BN coating film is an ion-assisted physical vapor deposition method that is a conventional method, and is estimated to have poor crystallinity and high residual stress. Further, the c-BN layer is only 72 nm thick, and this thickness is insufficient for evaluation of adhesion, and it is unclear whether a thicker surface film with better adhesion can be produced.

本発明者らは、フッ素を含むガス系からの作成法で、低残留応力で高結晶性のｃ−ＢＮ被覆膜の作成に成功している（非特許文献３）。このｃ−ＢＮ被覆膜の高結晶性は、明瞭なｃ−ＢＮの特性ラマン散乱ピーク及びシャープなｃ−ＢＮのＸ線回折ピークが観察されることで示されている。この作成法による膜は厚く作ることができるため、それまで正しく評価できなかったｃ−ＢＮ膜の硬度や弾性率が、５ミクロンのｃ−ＢＮ膜を用いて初めて正しく求められ、それぞれ７０ＧＰａ、８００ＧＰａと高圧合成のｃ−ＢＮに近い値が得られている（非特許文献４）。これらのバルクの結晶に近い値は現在まで他に報告されていない。しかしながら、この方法によるｃ−ＢＮ膜もＳｉ基体以外では基体との密着性を良くする方法が永年見つからず、応用への障害となっていた。
S.Matsumoto and W.J. Zhang, Japanese Journal of Applied Physics 39, L442 （2000）. C.Y.Chan, W.J. Zhang,, S. Matsumotob, I. Bello, S.T. Lee, Journal of Crystal Growth247 （2003） 438, “A nanoindentation study of thick cBNfilms prepared bychemical vapor deposition”. The present inventors have succeeded in producing a highly crystalline c-BN coating film with a low residual stress by a production method from a gas system containing fluorine (Non-patent Document 3). The high crystallinity of this c-BN coating film is shown by the observation of a clear characteristic Raman scattering peak of c-BN and a sharp x-ray diffraction peak of c-BN. Since the film by this preparation method can be made thick, the hardness and elastic modulus of the c-BN film, which could not be correctly evaluated until now, are correctly obtained for the first time using the c-BN film of 5 microns, and 70 GPa and 800 GPa, respectively. And a value close to c-BN of high-pressure synthesis is obtained (Non-patent Document 4). No other values have been reported to date for these bulk crystals. However, a c-BN film formed by this method has not been found for many years except for a Si substrate, and has been an obstacle to application.
S. Matsumoto and WJ Zhang, Japanese Journal of Applied Physics 39, L442 (2000). CYChan, WJ Zhang ,, S. Matsumotob, I. Bello, ST Lee, Journal of Crystal Growth247 (2003) 438, “A nanoindentation study of thick cBNfilms prepared by chemical vapor deposition”.

そこで、本発明は、このような実情に鑑み、金属やセラミックスの基体との良好な密着性を持ち、耐摩耗性、低摩擦性、耐熱性、熱伝導性、電気絶縁性等に優れた複合材料に関するもので、より具体的には、切削工具、耐摩耗性治具、高熱伝導性基板、耐熱高絶縁性コーティング、高温電子材料等に応用可能なｃ−ＢＮ被覆膜を有する立方晶窒化ホウ素被覆膜複合材料を得ること目的とした。   Therefore, in view of such circumstances, the present invention has a good adhesion to a metal or ceramic substrate and is excellent in wear resistance, low friction, heat resistance, thermal conductivity, electrical insulation, etc. More specifically, it relates to materials, and more specifically, cubic nitriding having a c-BN coating film applicable to cutting tools, wear-resistant jigs, high heat conductive substrates, heat resistant high insulation coatings, high temperature electronic materials, etc. The purpose was to obtain a boron-coated membrane composite.

本発明者らは鋭意研究の結果、第４族、第５族金属板上に、フッ素を含む系からの低残留応力で高結晶性のｃ−ＢＮ膜を被覆した場合、ｃ−ＢＮ被覆膜の密着性が非常によいことを発見した。この場合、基体とｃ−ＢＮ被覆膜の間には、基体を構成する金属の窒化物、ホウ化物、或いはホウ窒化物が中間層として存在していることが明らかになった。さらに研究を進めて、第４族、第５族以外の金属、合金、サーメット、或いはセラミックス基体であっても、基体とｃ−ＢＮの両方に親和性をもつ第４族及び第５族の金属、或いはそれらの金属窒化物、ホウ化物或いはホウ窒化物からなる中間層を介在させることによって、密着性の良好なｃ−ＢＮ被覆膜複合材料を得ることができることを発見してこの発明とした。   As a result of intensive studies, the present inventors have found that when a highly crystalline c-BN film is coated on a Group 4 or 5 metal plate with a low residual stress from a system containing fluorine, a c-BN coating is obtained. It was discovered that the adhesion of the film was very good. In this case, it became clear that a metal nitride, boride, or boronitride constituting the substrate exists as an intermediate layer between the substrate and the c-BN coating film. In further research, even if it is a metal, alloy, cermet, or ceramic substrate other than Group 4 or Group 5, Group 4 and Group 5 metals that have affinity for both the substrate and c-BN Alternatively, the present invention has been made by discovering that a c-BN coating film composite material with good adhesion can be obtained by interposing an intermediate layer made of such metal nitride, boride or boronitride. .

すなわち、第１には、基体表面に立方晶窒化ホウ素を主成分とする表面膜を被覆した複合材料において、該基体と該立方晶窒化ホウ素被覆膜の間に、第４族金属（Ｔｉ、Ｚｒ、Ｈｆ）、第５族金属（Ｖ、Ｎｂ、Ｔａ）、それらの金属の窒化物、ホウ化物或いはホウ窒化物のうちの１種以上の成分よりなる層を１層以上、中間層として形成された立方晶窒化ホウ素被覆複合材料であって、該立方晶窒化ホウ素を主成分とする表面膜の立方晶窒化ホウ素の光学的縦波（ＴＯ）モードのフォノンによるラマン散乱、光学的横波（ＬＯ）モードのフォノンによるラマン散乱のいずれか一方或いは両方の半値幅が５０ｃｍ−１以下のピークを示すか、或いは、薄膜Ｘ線回折で、表面膜が立方晶窒化ホウ素の（１１１）、（２００）、（２２０）、（３１１）の内のいずれか１つの反射ピークの２θの半値幅が、それぞれ、１．５、２．５、２．５、３度以下であることを特徴とする立方晶窒化ホウ素被覆膜複合材料の構成とした。 That is, firstly, in the composite material in which the surface of the base is coated with a surface film mainly composed of cubic boron nitride, a Group 4 metal (Ti, Zr, Hf), Group 5 metals (V, Nb, Ta), nitrides of these metals, borides or one or more layers of boronitrides are formed as one or more layers as an intermediate layer A cubic boron nitride-coated composite material comprising a surface boron-based cubic boron nitride as a main component, and cubic longitudinal scattering (TO) mode Raman scattering by optical longitudinal wave (TO) mode phonons, optical transverse waves (LO) ) A mode in which one or both of Raman scattering by mode phonons shows a peak of 50 cm −1 or less, or thin film X-ray diffraction shows that the surface film is cubic boron nitride (111), (200) , (220), (31 1) The half-width of 2θ of any one of the reflection peaks is 1.5, 2.5, 2.5, or 3 degrees or less, respectively, and the cubic boron nitride coating film composite The material composition was adopted.

前記ラマン散乱の半値幅は、ｃ−ＢＮの結晶性がさらに良い場合は３０ｃｍ−１以下となる。一方、前記薄膜Ｘ線解析の前記半値幅は、ｃ−ＢＮの結晶性がさらに良い場合は、それぞれ、１、１．５、１．５、２度以下となる。 The full width at half maximum of the Raman scattering is 30 cm −1 or less when the crystallinity of c-BN is better. On the other hand, the half width of the thin film X-ray analysis is 1, 1.5, 1.5, 2 degrees or less, respectively, when the crystallinity of c-BN is better.

この中間層はたとえば金属、金属窒化物、金属ホウ化物、或いは金属ホウ窒化物の単独相でもよく、それらの相の混合物でも良い。或いは２種以上の金属或いは合金の、金属窒化物、金属ホウ化物、或いは金属ホウ窒化物の混合物であってもよい。さらに、これらの金属、合金が金属窒化物、金属ホウ化物、或いは金属ホウ窒化物と混ざった層であってもよい。さらに、相構造或いは組成の異なる層を２層以上重ねて、中間層とすることができる。なお、この中間層に、中間層中の窒素、ホウ素全原子数に対し、炭素、酸素が、各々１０ａｔ％以下、合計２０ａｔ％以下の比率で混入されていても、本発明の中間層として用いることができる。   This intermediate layer may be, for example, a single phase of metal, metal nitride, metal boride, or metal boronitride, or a mixture of these phases. Alternatively, a metal nitride, a metal boride, or a mixture of metal boronitrides of two or more metals or alloys may be used. Furthermore, a layer in which these metals and alloys are mixed with metal nitride, metal boride, or metal boronitride may be used. Furthermore, two or more layers having different phase structures or compositions can be stacked to form an intermediate layer. Even if carbon and oxygen are mixed in this intermediate layer at a ratio of 10 at% or less and a total of 20 at% or less with respect to the total number of nitrogen and boron atoms in the intermediate layer, they are used as the intermediate layer of the present invention. be able to.

また、この中間層形成において、第４族金属、第５族金属ともに、窒素と親和性のよいＢ、Ａｌ、Ｓｉを加えることもできる。また、窒化物、ホウ化物を形成し易いランタナイド元素を加えることもできる。さらに比較的、窒化物、ホウ化物を形成し易い、Ｃｒ、Ｍｏ、Ｗを加えることもできる。   In addition, in this intermediate layer formation, B, Al, and Si having a good affinity for nitrogen can be added to both the Group 4 metal and the Group 5 metal. A lanthanide element that easily forms nitrides and borides can also be added. Furthermore, Cr, Mo, and W which can form nitrides and borides relatively easily can also be added.

本発明の立方晶窒化ホウ素を主成分とする表面膜の厚さは、０．１〜２０μｍ範囲で可能で、或いはそれ以上の厚さにも積層することが可能である。０．１μｍの厚さでも、時間をかけて測定すれば上記の明瞭なラマンピーク或いはＸ線回折ピークを得ることができるが、短時間の測定で前記ピークを得るためには厚さ０．５μｍ以上が望ましい。中間層の１層の厚さは０．０２〜１０μｍが適当である。   The thickness of the surface film mainly composed of cubic boron nitride of the present invention can be in the range of 0.1 to 20 μm, or can be laminated to a thickness larger than that. Even if the thickness is 0.1 μm, the above-mentioned clear Raman peak or X-ray diffraction peak can be obtained by measuring over time. To obtain the peak in a short time, the thickness is 0.5 μm. The above is desirable. The thickness of one layer of the intermediate layer is suitably 0.02 to 10 μm.

中間層は、基体に金属、合金、それらの窒化物、ホウ化物、或いはホウ窒化物を、蒸着、スパッタリング、イオンビーム蒸着法、アークイオンプレーティング法等の物理蒸着法（ＰＶＤ）或いはＭＯＣＶＤ、プラズマＣＶＤ法等の化学的堆積法（ＣＶＤ）によって形成することできる。   The intermediate layer is formed by depositing metal, alloy, nitride, boride or boronitride on the substrate, physical vapor deposition (PVD) such as vapor deposition, sputtering, ion beam vapor deposition, arc ion plating, or MOCVD, plasma. It can be formed by chemical deposition (CVD) such as CVD.

金属、合金、或いはそれらの金属、合金の窒化物、ホウ化物、或いはホウ窒化物の中間層は、立方晶窒化ホウ素被覆膜層作成装置以外の装置において事前に被覆しておくこともできるし、立方晶窒化ホウ素被覆膜層作成装置において、立方晶窒化ホウ素被覆膜作成前に被覆することができる。また、それらの金属、合金の被覆層を立方晶窒化ホウ素被覆膜作成中に窒化、ホウ化、或いはホウ窒化することにより中間層とすることをもできる。その際、金属或いは合金層を完全に変化させず残しておくことができる。この場合、金属は独立した薄膜層或いは窒化物、ホウ化物、或いはホウ窒化物と混ざった中間層とすることができる。   Metals, alloys, or nitrides, borides, or boronitride intermediate layers of these metals, alloys, or intermediate layers of boronitrides can be coated in advance in an apparatus other than the cubic boron nitride coating film layer forming apparatus. In the cubic boron nitride coating film layer forming apparatus, coating can be performed before the cubic boron nitride coating film is formed. Further, these metal and alloy coating layers can be made into an intermediate layer by nitriding, boriding, or boriding during the formation of the cubic boron nitride coating film. At that time, the metal or alloy layer can be left unchanged. In this case, the metal can be an independent thin film layer or an intermediate layer mixed with nitride, boride, or boronitride.

第４族金属、第５族金属のいずれか、或いはそれらのいずれかの１種を含む合金を基体とする場合には、あらかじめ中間層を被覆せずに、立方晶窒化ホウ素被覆膜作成中に基体を窒化、ホウ化或いはホウ窒化することにより、中間層とすることができる。   When using a group 4 metal, a group 5 metal, or an alloy containing one of them as a base, a cubic boron nitride coating film is being prepared without previously coating the intermediate layer. The intermediate layer can be formed by nitriding, boriding or boriding the substrate.

本発明である立方晶窒化ホウ素被覆膜複合材料１の概念を図１、２に示す。図１は、基体２とｃ―ＢＮ被覆膜（表面膜）４との間に中間層が一層の場合で、中間層３としては例えば、チタンの窒化物、ホウ化物、ホウ窒化物の混合相を用いることができる。ｃ−ＢＮ層被覆膜は請求項１或いは請求項２に記述した結晶性の良いｃ−ＢＮ被覆膜である。   The concept of the cubic boron nitride coating film composite material 1 according to the present invention is shown in FIGS. FIG. 1 shows a case where the intermediate layer is a single layer between the substrate 2 and the c-BN coating film (surface film) 4. As the intermediate layer 3, for example, a mixture of nitride, boride and boronitride of titanium is used. Phases can be used. The c-BN layer coating film is a c-BN coating film having good crystallinity described in claim 1 or claim 2.

図２は、基体２とｃ―ＢＮ被覆膜４との間に中間層が二層の場合で、例えば第１層の中間層３にチタン金属、第２層の中間層３ａにチタンの窒化物、ホウ化物、ホウ窒化物の混合相を、或いは第１層の中間層３にチタンの窒化物、第２層の中間層３ａにチタンの窒化物、ホウ化物、ホウ窒化物の混合相を用いることができる。この場合もｃ−ＢＮ層被覆膜は請求項１或いは請求項２に記述した結晶性の良いｃ−ＢＮ被覆膜である。   FIG. 2 shows a case where the intermediate layer has two layers between the substrate 2 and the c-BN coating film 4. For example, titanium metal is nitrided in the first intermediate layer 3 and titanium is nitrided in the second intermediate layer 3a. A mixed phase of oxide, boride, and boronitride, or titanium nitride in the first intermediate layer 3 and titanium nitride, boride, and boronitride mixed phase in the second intermediate layer 3a. Can be used. Also in this case, the c-BN layer coating film is the c-BN coating film having good crystallinity described in claim 1 or claim 2.

基体２としては、金属、合金、金属炭化物等のサーメット、窒化珪素や窒化アルミニウム等のセラミックスを用いることができる。本発明によれば、中間層３、３ａの効果により、以前はｓｐ２結合による、六方晶窒化ホウ素（ｈ−ＢＮ）、乱層構造窒化ホウ素（ｔ−ＢＮ）或いは非晶質窒化ホウ素（ａ−ＢＮ）が析出しやすく、ｃ−ＢＮのコーティングが困難であった鉄族元素、鉄族元素を含む合金や、鉄族元素含有超硬合金等上にも密着性のよいｃ−ＢＮを被覆することができることとなる。 As the substrate 2, cermets such as metals, alloys and metal carbides, and ceramics such as silicon nitride and aluminum nitride can be used. According to the present invention, due to the effect of the intermediate layer 3, 3a, by previously sp 2 bond, hexagonal boron nitride (h-BN), turbostratic boron nitride (t-BN) or amorphous boron nitride (a -BN) is easily deposited, and c-BN is difficult to coat with iron group elements, alloys containing iron group elements, iron group element-containing cemented carbides, etc. Will be able to.

本発明者らは以前に高結晶性のｃ−ＢＮ膜の作成法について開示したが（非特許文献３）、その方法を本中間層３、３ａ上の堆積に適するよう応用することによって、本発明のｃ−ＢＮを主成分とする表面膜を作成できることとなった。すなわち、発明１から２に記載の結晶性のよいｃ−ＢＮ被覆膜は、ホウ素源、窒素源及びフッ素源を含むガス種を含む気相からプラズマを用いて基体上に析出させることを特徴としている。   The present inventors have previously disclosed a method for producing a highly crystalline c-BN film (Non-Patent Document 3). By applying this method to be suitable for deposition on the intermediate layers 3 and 3a, the present invention has been disclosed. The surface film which has c-BN of the invention as a main component can be prepared. That is, the c-BN coating film having good crystallinity described in the inventions 1 and 2 is characterized in that it is deposited on a substrate using a plasma from a gas phase containing a gas species including a boron source, a nitrogen source and a fluorine source. It is said.

本発明のｃ−ＢＮ被覆膜の作成法は、非特許文献２に詳しく記しているが、簡単に記述すると、ジボラン、三フッ化ホウ素等のホウ素源、窒素、アンモニア等の窒素源、及び三フッ化ホウ素、フッ素、フッ化水素等のフッ素源を気相中に供給し、気相をプラズマ化により活性化し、立方晶窒化ホウ素を基体上へ析出させる。反応とプラズマの制御のために水素、希ガスのうちどちらか単独を或いは両方を加えることができる。反応容器壁或いは反応容器内に設置した参照電極に対し、基体にバイアス電圧をかける。プラズマの種類としては、プラズマジェット、マイクロ波プラズマ、誘導結合型プラズマ、電子サイクロトロン共鳴プラズマなどのさまざまな高密度プラズマを利用できる。１０−６Ｐａの低圧から数気圧の高い圧力までのプラズマが利用でき、熱プラズマでも非平衡低温プラズマでも可能である。基体バイアスには直流、交流、高周波、或いはそれらの重積、或いはそれらをパルス化した電源のいずれでも用いうる。最適なバイアス電圧は、ガス圧、ガス組成、基体温度等により異なるが、０〜−１５０Ｖ程度、プラズマの種類によっては０〜＋１００Ｖ程度の正のバイアスを用いることも可能である。 The method for producing the c-BN coating film of the present invention is described in detail in Non-Patent Document 2, but briefly described, a boron source such as diborane and boron trifluoride, a nitrogen source such as nitrogen and ammonia, and A fluorine source such as boron trifluoride, fluorine, or hydrogen fluoride is supplied into the gas phase, the gas phase is activated by plasma formation, and cubic boron nitride is deposited on the substrate. One or both of hydrogen and a rare gas can be added for reaction and plasma control. A bias voltage is applied to the substrate with respect to the reaction vessel wall or a reference electrode installed in the reaction vessel. As the type of plasma, various high-density plasmas such as plasma jet, microwave plasma, inductively coupled plasma, and electron cyclotron resonance plasma can be used. Plasma from a low pressure of 10 −6 Pa to a high pressure of several atmospheres can be used, and can be either thermal plasma or non-equilibrium low-temperature plasma. As the substrate bias, any of direct current, alternating current, high frequency, a stack of them, or a power source obtained by pulsing them can be used. The optimum bias voltage varies depending on the gas pressure, gas composition, substrate temperature, etc., but a positive bias of about 0 to −150 V or about 0 to +100 V can be used depending on the type of plasma.

本発明者らは更に鋭意研究した結果、上記中間層３、３ａを被覆した上にさらに当該方法のｃ−ＢＮ被覆膜４を付ける際に、ガス組成、基体２の温度、プラズマ電力、バイアス等の条件を注意深く制御することにより、付着力のよいｃ−ＢＮ被覆膜ができることを発見し、本発明を成した。   As a result of further diligent research, the present inventors have found that when the c-BN coating film 4 of the method is further applied on the intermediate layers 3 and 3a, the gas composition, the temperature of the substrate 2, the plasma power, the bias By carefully controlling such conditions, it was discovered that a c-BN coating film with good adhesion could be formed, and the present invention was made.

その結果、上記構成を実現し、それにより従来Ｓｉ以外の基体上には、限られた場合にしか１μｍ以上の膜厚のｃ−ＢＮ被覆膜は作成できなかったが、多くの種類の基体上に密着性がよく、ｃ−ＢＮを主成分とする表面膜をコーティングすることができるようになった。   As a result, the above-described configuration was realized, and as a result, a c-BN coating film having a film thickness of 1 μm or more could only be formed on a substrate other than Si. Adhesiveness was good on the top, and it became possible to coat a surface film mainly composed of c-BN.

さらに、これらのｃ−ＢＮ被覆膜は明瞭なラマン散乱ピークとシャープなＸ線回析ピークを示すほど結晶性がよく、また高硬度等のｃ−ＢＮ本来の物性を持っている。これらの密着性、厚さ、結晶性、物性を持つｃ−ＢＮ被覆膜複合体は従来にはなかったものである。   Furthermore, these c-BN coating films have good crystallinity so that a clear Raman scattering peak and a sharp X-ray diffraction peak are exhibited, and have the original physical properties of c-BN such as high hardness. A c-BN coating film composite having such adhesion, thickness, crystallinity, and physical properties has never existed in the past.

また、中間層３、３ａをコートした後、ｃ−ＢＮ被覆膜成膜前に水素中でアニール処理をすると、ｃ−ＢＮ被覆膜の残留応力を減らし、密着性を向上させることができることを見出した。水素中の加熱は水素ガス雰囲気中での加熱でも、水素プラズマ雰囲気中での加熱でも有効である。この理由は明らかではないが、中間層３、３ａ中の酸化物の除去、中間層３、３ａの組成変化、中間層３、３ａの基体への拡散促進、中間層３、３ａの格子の緩和等が考えられる。アニール温度、時間は、基体の種類、中間層の種類によって異なるが、５００〜１２００℃（５０℃単位、以下同じ。）、１／６〜１時間が有効である。また、それら雰囲気に希ガス（Ｈｅ、Ｎｅ、Ａｒ、Ｋｒ、Ｘｅ）を混合することもできる。   In addition, if the annealing process is performed in hydrogen after coating the intermediate layers 3 and 3a and before forming the c-BN coating film, the residual stress of the c-BN coating film can be reduced and the adhesion can be improved. I found. Heating in hydrogen is effective both in a hydrogen gas atmosphere or in a hydrogen plasma atmosphere. Although the reason for this is not clear, removal of oxide in the intermediate layers 3 and 3a, change in composition of the intermediate layers 3 and 3a, promotion of diffusion of the intermediate layers 3 and 3a into the substrate, relaxation of the lattice of the intermediate layers 3 and 3a Etc. are considered. Although the annealing temperature and time vary depending on the type of the substrate and the type of the intermediate layer, 500 to 1200 ° C. (50 ° C. unit, the same shall apply hereinafter) and 1/6 to 1 hour are effective. Further, a rare gas (He, Ne, Ar, Kr, Xe) can be mixed in the atmosphere.

この発明でのｃ−ＢＮ被覆膜の密着性のよい理由は次のように考えられる。第一に、フッ素を含むガス系から作成されたｃ−ＢＮ被覆膜は、作成時の基体上へのイオン衝撃が小さく、残留応力が０．５〜２ＧＰａと従来法の１０〜２０ＧＰａに比べて小さく、膜が壊れにくいことである。   The reason why the c-BN coating film has good adhesion in this invention is considered as follows. First, the c-BN coating film prepared from a gas system containing fluorine has a small ion impact on the substrate at the time of preparation, and the residual stress is 0.5 to 2 GPa, which is 10 to 20 GPa of the conventional method. It is small and the membrane is difficult to break.

第二に、中間層に用いる、第４族金属、第５族金属、Ａｌ及びＳｉは窒化物、ホウ化物を形成し易く、さらにこれらの窒化物、ホウ化物は、例えば、Ｚｒの場合、ＺｒＮｘ、ＺｒＢｘと表した場合、ｘ＝０．２〜２の多種類の相が存在することに示されるように、これらの金属、金属窒化物、ホウ化物、ホウ窒化物とＢＮが接した場合は、金属とＢ、Ｎは相互に拡散しやすく、密着しやすくなるためと思われる。これらのｃ−ＢＮ被覆膜の低い残留応力とｃ−ＢＮに親和性のある中間層を用いる両方の効果が相乗的に作用して、密着性のよいｃ−ＢＮ被覆が可能になったと考えられる。第４族金属、第５族金属、Ａｌ及びＳｉが窒化物、ホウ化物を形成し易いことは、例えば次の文献等に記されている。
エス・エス・キバリソフ、ユ・ヴェ・レヴィンスキー著、高融点金属の窒化、日ソ通信社、１９７４年、Ｐ３７の表３中の生成熱の値。 ゲ・ヴェ・サムソノフ、イ・エム・ヴィニッキー著、高融点化合物便覧、日ソ通信社、１９７６年、Ｐ１３８−１８９の表中の生成反応熱の値。 Secondly, the Group 4 metal, Group 5 metal, Al and Si used for the intermediate layer easily form nitrides and borides, and these nitrides and borides are, for example, ZrNx in the case of Zr. When ZrBx is expressed, it is shown that there are many kinds of phases of x = 0.2 to 2, when these metals, metal nitrides, borides, and BN are in contact with BN It seems that metal, B, and N are easily diffused to each other and are easily adhered to each other. It is thought that both the low residual stress of these c-BN coating films and the effect of using an intermediate layer having an affinity for c-BN act synergistically to enable c-BN coating with good adhesion. It is done. The fact that Group 4 metals, Group 5 metals, Al, and Si easily form nitrides and borides is described in, for example, the following documents.
Values of heat of formation in Table 3 of S.S. Kivarisov, Yu We Levinsky, Nitriding of refractory metals, Nisso News Agency, 1974, P37. Values of heat of reaction in the table of Ge We Samsonov, EM Vinnicky, Handbook of High Melting Point Compounds, Nisso News Agency, 1976, P138-189.

この発明によるｃ−ＢＮ被覆膜は密着性がよいため、膜厚を厚くすることができ、また結晶性が高いためｃ−ＢＮ本来の特性が現れ、硬度等の機械的強度が大きくなると考えられる。   The c-BN coating film according to the present invention has a good adhesion, so that the film thickness can be increased, and since the crystallinity is high, the original characteristics of c-BN appear and the mechanical strength such as hardness increases. It is done.

本発明の立方晶窒化ホウ素被覆膜複合材料は、基体との密着性がよくまたｃ−ＢＮの優れた特性を示すので、旋削、切削用のチップ、ドリル、エンドミル等の耐摩耗工具材料や、ポンプ、圧縮機等の軸受けやシール部の対耐磨耗摺動材料として用いることができる。また、高熱伝導性基板、耐熱高絶縁性コーティング、高温電子材料等に用いることができると期待される。   The cubic boron nitride coating film composite material of the present invention has good adhesion to the substrate and exhibits the excellent properties of c-BN, so that wear-resistant tool materials such as turning, cutting tips, drills, end mills, etc. It can be used as a wear-resistant sliding material for bearings and seals of pumps and compressors. It is also expected that it can be used for high thermal conductive substrates, heat resistant and highly insulating coatings, high temperature electronic materials and the like.

本発明の立方晶窒化ホウ素被覆膜複合材料は、基体と、前記基体表面上に形成された周期律表の第４族金属（Ｔｉ、Ｚｒ、Ｈｆ）、第５族金属（Ｖ、Ｎｂ、Ｔａ）、前記第４族金属及び第５族金属の窒化物又はホウ化物或いはホウ窒化物の内から選ばれるいずれか１種以上の成分よりなる中間層と、前記中間層の表面に被膜した立方晶窒化ホウ素を主成分とする表面膜とから形成される立方晶窒化ホウ素被覆膜複合材料であって、前記表面膜の立方晶窒化ホウ素の光学的縦波モードのフォノンによるラマン散乱又は光学的横波モードのフォノンによるラマン散乱のいずれか一方の半値幅が、５０ｃｍ−１以下のピークを示すもの、ｃ−ＢＮの結晶性がさらに良い場合は、３０ｃｍ−１以下であるもの、若しくは、薄膜Ｘ線回折で、前記表面膜の立方晶窒化ホウ素の（１１１）、（２００）、（２２０）、（３１１）の内のいずれか１の反射ピークの２θの半値幅が、それぞれ１．５、２．５、２．５、３度以下となるもの、ｃ−ＢＮの結晶性がさらに良い場合は、それぞれ、１、１．５、１．５、２度以下となるものである。なお、上記上限を超える場合は、結晶性が悪いため、硬度、熱伝導度、電気抵抗等の物性において、ｃ−ＢＮ本来の優れた特性を示さなくなる。 The cubic boron nitride coating film composite material of the present invention comprises a base, a Group 4 metal (Ti, Zr, Hf) and a Group 5 metal (V, Nb, Vf) of the periodic table formed on the surface of the base. Ta), an intermediate layer composed of at least one component selected from the group 4 metal and group 5 metal nitrides or borides or boronitrides, and a cube coated on the surface of the intermediate layer Cubic boron nitride coating film composite material formed from a surface film mainly composed of crystalline boron nitride, and Raman scattering by optical longitudinal wave mode phonon of the cubic boron nitride of the surface film or optical When the half width of either one of the Raman scattering by the phonon in the transverse wave mode shows a peak of 50 cm −1 or less, or when the crystallinity of c-BN is better, it is 30 cm −1 or less, or the thin film X Line diffraction, the surface The half-value width of 2θ of the reflection peak of any one of (111), (200), (220), and (311) of cubic boron nitride is 1.5, 2.5, 2.5, When it becomes 3 degrees or less and when the crystallinity of c-BN is better, it becomes 1, 1.5, 1.5, 2 degrees or less, respectively. In addition, when exceeding the said upper limit, since crystallinity is bad, in the physical properties, such as hardness, thermal conductivity, and electrical resistance, c-BN original excellent characteristics will not be shown.

これらの第４族金属、第５族金属に窒素と親和性のよいＢ、Ａｌ、Ｓｉを加えることもできる。また、窒化物、ホウ化物を形成し易いランタナイド元素を加えることもできる。さらに比較的、窒化物、ホウ化物を形成し易い、Ｃｒ、Ｍｏ、Ｗを加えることもできる。これら元素の添加は、中間層の、結晶粒のサイズ、熱膨張率、弾性率等の制御を容易にし、基体と中間層の密着性の向上および中間層とｃ−ＢＮ被覆膜を合わせた被覆層全体の機械的強度の向上や弾性率等の調節を行うことができる。   B, Al, and Si having a good affinity for nitrogen can be added to these Group 4 metals and Group 5 metals. A lanthanide element that easily forms nitrides and borides can also be added. Furthermore, Cr, Mo, and W which can form nitrides and borides relatively easily can also be added. The addition of these elements facilitates control of the crystal size, thermal expansion coefficient, elastic modulus, etc. of the intermediate layer, improves adhesion between the substrate and the intermediate layer, and combines the intermediate layer with the c-BN coating film. The mechanical strength of the entire coating layer can be improved and the elastic modulus can be adjusted.

さらに、これらの添加元素の添加量は、添加元素の総量において、４０ａｔ%以下、好ましくは３０ａｔ%以下、より好ましくは２０ａｔ%以下とする。これら元素の添加が過剰であると本発明の中間層に用いる第４族金属、第５族金属の、ｃ−ＢＮ被覆膜への拡散の低下に起因する親和性の低下が起こり、ｃ−ＢＮ被覆膜の中間層への、ひいては基体への密着性が低下する。   Furthermore, the addition amount of these additive elements is 40 at% or less, preferably 30 at% or less, more preferably 20 at% or less in the total amount of the additive elements. If these elements are added excessively, the affinity of the Group 4 metal and Group 5 metal used in the intermediate layer of the present invention will decrease due to the decrease in diffusion into the c-BN coating film. Adhesiveness to the intermediate layer of the BN coating film and thus to the substrate is lowered.

本発明の立方晶窒化ホウ素被覆膜複合材料は、前記立方晶窒化ホウ素を生成するにあたり、ホウ素源、窒素源及びフッ素源を含むガスのプラズマを用いて、前記基体上に析出させたもの、さらに、前記中間層を、立方晶窒化ホウ素を主成分とする表面膜作成中に、前記基体の窒化、ホウ化又はホウ窒化、或いは前記基体に被覆した金属又は合金を窒化、ホウ化又はホウ窒化することにより作成したもの、或いは前記基体表面に中間層を形成後、水素ガス或いは水素プラズマ中で基体及び中間層をアニール処理し、立方晶窒化ホウ素を主成分とする表面膜を前記中間層上に被覆したものでもある。なお、ホウ素源、窒素源及びフッ素源を含むガスのプラズマを用いて、前記基体上に析出させたものは、非特許文献３に記載された公知の方法による。   The cubic boron nitride coating film composite material according to the present invention is produced by depositing the cubic boron nitride on the substrate using a plasma of a gas containing a boron source, a nitrogen source, and a fluorine source in producing the cubic boron nitride. Further, the intermediate layer is nitrided, borated, or boronitrided on the substrate, or the metal or alloy coated on the substrate is nitrided, borated, or boronitrided during the creation of a surface film mainly composed of cubic boron nitride. After the intermediate layer is formed on the surface of the substrate, the substrate and the intermediate layer are annealed in hydrogen gas or hydrogen plasma, and a surface film mainly composed of cubic boron nitride is formed on the intermediate layer. Also coated. In addition, what was deposited on the said base | substrate using the plasma of the gas containing a boron source, a nitrogen source, and a fluorine source is based on the well-known method described in the nonpatent literature 3.

また、これら立方晶窒化ホウ素被覆膜複合材料の代表的な用途としては、これを素材として形成された耐摩耗材料、耐摩耗工具が上げられるが、その他にも下記産業上の利用可能性に記載した各種の用途に用いることができる。以下、実施例をもって、本発明を具体的に説明する。   In addition, typical applications of these cubic boron nitride coating film composite materials include wear-resistant materials and wear-resistant tools formed from these materials, but in addition to the following industrial applicability: It can be used for the various applications described. Hereinafter, the present invention will be specifically described with reference to examples.

本作成法は非特許文献２において開示したフッ素を含むガス系からのプラズマジェットＣＶＤ法を用いる方法である。タングステン上にスパッター法でジルコニウムを約７μｍコートしたのち、５０ｍＴｏｒｒの水素プラズマ中で７００℃で１／２時間アニールした。   This preparation method uses the plasma jet CVD method disclosed in Non-Patent Document 2 from a gas system containing fluorine. After about 7 μm of zirconium was coated on tungsten by sputtering, annealing was performed at 700 ° C. for 1/2 hour in a hydrogen plasma of 50 mTorr.

その後ｃ−ＢＮ被覆膜作成膜装置に移し、Ａｒ：２０ｓｌｍ、Ｎ２：１ｓｌｍ、Ｈ２：５ｓｃｃｍを流し、８ｋＷのＤＣアーク放電によりプラズマを発生させ、１０％ＢＦ３／Ｈｅ：３０ｓｃｃｍを流し、直流バイアス電源により−８５Ｖの直流バイアスを基体にかけ、基体温度１０５０℃にて、５０Ｔｏｒｒ下の１／３時間の合成により、タングステン基体上に剥がれていない立方晶窒化ホウ素被覆膜が得られた。 Thereafter, the film was transferred to a c-BN coating film forming apparatus, Ar: 20 slm, N 2 : 1 slm, H 2 : 5 sccm was flown, plasma was generated by DC arc discharge of 8 kW, and 10% BF 3 / He: 30 sccm was flowed. A cubic boron nitride coating film not peeled on the tungsten substrate was obtained by applying a DC bias of −85 V to the substrate with a DC bias power source and synthesizing the substrate at a temperature of 1050 ° C. for 1/3 hour at 50 Torr. .

この方法により得られた立方晶窒化ホウ素被覆複合材料の表面膜側からの薄膜Ｘ線回折図（銅ターゲット）、表面膜のラマンスペクトルを、それぞれ、図３、図４に示す。   The thin film X-ray diffraction diagram (copper target) from the surface film side of the cubic boron nitride-coated composite material obtained by this method and the Raman spectrum of the surface film are shown in FIGS. 3 and 4, respectively.

図３にはｃ−ＢＮ、窒化ジルコニウム、ホウ化ジルコニウム、ホウ窒化ジルコニウムのピークが現れており、最表面層はｃ−ＢＮで、窒化ジルコニウム、ホウ化ジルコニウム、ホウ窒化ジルコニウムが基体とｃ−ＢＮ被覆膜との中間層となっている。   In FIG. 3, peaks of c-BN, zirconium nitride, zirconium boride, and zirconium boronitride appear, and the outermost surface layer is c-BN. Zirconium nitride, zirconium boride, and zirconium boronitride are formed on the base and c-BN. It is an intermediate layer with the coating film.

ｃ−ＢＮ被腹膜の厚みはおよそ４μｍである。ｃ−ＢＮのＸ線回折ピークの２θの半値幅は（１１１）、（２００）、（２２０）のピークについて、それぞれ、０．４９、０．６１、０．６４度である。ただし、（２２０）ピークには弱いＺｒ２Ｎ、ＺｒＢ２のピークが重なっている。（３１１）ピークはＺｒ２Ｎ、ＺｒＢ２のピークが重なっていて半値幅は求めていない。 The thickness of the c-BN peritoneum is approximately 4 μm. The half width of 2θ of the X-ray diffraction peak of c-BN is 0.49, 0.61, and 0.64 degrees for the peaks of (111), (200), and (220), respectively. However, weak (Zr 2 N, ZrB 2 ) peaks overlap with (220) peak. (311) The peaks of Zr 2 N and ZrB 2 overlap, and the half width is not determined.

図４のラマンスペクトルにおいて、ｃ−ＢＮのＴＯ及びＬＯモードのピークはそれぞれ、２９．４、１８．０ｃｍ−１であり、結晶性のよいｃ−ＢＮであることがわかる。Ｘ線回折においては２θ＝２６度付近に現れ、またラマンスペクトルにおいては１３６０ｃｍ−１付近に現れるｈ−ＢＮやｔ−ＢＮのピークはｃ−ＢＮのピークに比べ非常に弱い。ｃ−ＢＮ被覆膜のＸ線の（１１１）ピーク位置（４３．３３度）のバルクｃ−ＢＮ結晶のそれ（４３．３５度）からのシフトからｃ−ＢＮ被覆膜の面内圧縮応力を求めると約０．５ＧＰａとなり、フッ素を用いない従来合成法で一般的な１０〜２０ＧＰａ（非特許文献７）と比べ非常に低いことがわかる。
G.C.A.M.Janssen, Thin Solid Films 515 （2007）6654-6664の第７節（P6661）. In the Raman spectrum of FIG. 4, the TO and LO mode peaks of c-BN are 29.4 and 18.0 cm −1 , respectively, indicating that the c-BN has good crystallinity. In X-ray diffraction, the peak of h-BN and t-BN appearing near 2θ = 26 degrees and the vicinity of 1360 cm −1 in the Raman spectrum is very weak compared to the peak of c-BN. From the shift of the (111) peak position (43.33 degrees) of the X-ray of the c-BN coating film from that of the bulk c-BN crystal (43.35 degrees), the in-plane compressive stress of the c-BN coating film Is about 0.5 GPa, which is very low compared to 10-20 GPa (non-patent document 7) which is general in the conventional synthesis method using no fluorine.
GCAMJanssen, Thin Solid Films 515 (2007) 6654-6664, Section 7 (P6661).

このｃ−ＢＮ被覆膜は６ヶ月経っても剥離せず、この膜をステンレス製の尖ったピンセットで強く引っかいたところ、ピンセットが削られてｃ−ＢＮ被覆膜に融着したが、ｃ−ＢＮ被覆膜は剥離しなかった。   The c-BN coating film did not peel off even after 6 months, and when this film was strongly scratched with pointed stainless steel tweezers, the tweezers were shaved and fused to the c-BN coating film. -The BN coating film did not peel off.

このｃ−ＢＮ被覆膜は十分な硬さと基体との密着力をもっている。ＡＥ（Ａｃｏｕｓｔｉｃ ｅｍｉｓｓｉｏｎ）付スクラッチ試験機によるスクラッチ試験でも密着性が良く、マイクロビッカスース硬度計による硬度測定でも十分な硬度を示した（表１参照）。   This c-BN coating film has sufficient hardness and adhesion to the substrate. Adhesion was good even in a scratch test using an AE (Acoustic Emission) scratch tester, and sufficient hardness was shown by a hardness measurement using a micro-bickus hardness tester (see Table 1).

（比較例１）
中間層を形成せず、タングステン基体上に実施例１と同様の条件でコートしたＢＮ膜は大気中に取り出しと同時にはがれてしまった。 (Comparative Example 1)
The BN film coated on the tungsten substrate under the same conditions as in Example 1 without forming the intermediate layer was peeled off into the atmosphere at the same time.

６％Ｃｏ含有の炭化タングステン基体に３μｍ厚のチタニウム（Ｔｉ）膜を蒸着法によりコートし、アークジェットプラズマＣＶＤ装置において、Ａｒ：２０ｓｌｍ、Ｎ２：１ｓｌｍ、Ｈ２：５ｓｃｃｍ、ＢＦ３／Ｈｅ（１０％）：３０ｓｃｃｍのガス流を用いて、５０Ｔｏｒｒのガス圧下、アーク電力７ｋＷ、基体温度９５０℃、１３．５６MHｚの高周波の自己バイアス電圧−６０Ｖにて、１／６時間反応させ、ｃ−ＢＮ被覆膜を得た。 A 6 μm Co-containing tungsten carbide substrate was coated with a 3 μm thick titanium (Ti) film by a vapor deposition method, and in an arc jet plasma CVD apparatus, Ar: 20 slm, N 2 : 1 slm, H 2 : 5 sccm, BF 3 / He ( 10%): Using a gas flow of 30 sccm, the reaction was carried out for 1/6 hour under a gas pressure of 50 Torr, an arc power of 7 kW, a substrate temperature of 950 ° C., a high frequency self-bias voltage of −60 V of 13.56 MHz, and c-BN. A coating film was obtained.

この被覆膜のＸ線回折図（銅ターゲット）、ラマンスペクトルをそれぞれ図５、図６に示す。図５より、ｃ−ＢＮとＴｉＮのピークが主として現れており、ｃ−ＢＮの（１１１）、（２００）、（２２０）、（３１１）の反射の半値幅は、それぞれ、１．２、１．６、１．８、２．６度である。（１１１）ピークは重なっているＴｉＮのピークを分離して求めた。   The X-ray diffraction pattern (copper target) and Raman spectrum of this coating film are shown in FIGS. 5 and 6, respectively. From FIG. 5, c-BN and TiN peaks mainly appear, and the half widths of reflection of c-BN at (111), (200), (220), and (311) are 1.2, 1 and 1, respectively. .6, 1.8, 2.6 degrees. The (111) peak was obtained by separating the overlapping TiN peaks.

図６より、ラマン散乱ピークの半値幅はＴＯ、ＬＯ各モードについて、４５．０ｃｍ−１、２４．１ｃｍ−１である。これらによりこの膜は結晶性のよいｃ−ＢＮ被覆膜であることがわかる。Ｘ線回折においてはｔ−ＢＮのピークが弱く見られるが、ラマンスペクトルにおいてはｃ−ＢＮのピークに比べてｈ−ＢＮやｔ−ＢＮのピークは非常に弱い。ｃ−ＢＮ被覆膜の平均膜厚はＩＲ吸収スペクトルの干渉フリンジより、２μｍであった。 From FIG. 6, the half-width of the Raman scattering peak TO, for LO modes, 45.0Cm -1, is 24.1 cm -1. These show that this film is a c-BN coating film with good crystallinity. In X-ray diffraction, the t-BN peak is weak, but in the Raman spectrum, the h-BN and t-BN peaks are much weaker than the c-BN peak. The average film thickness of the c-BN coating film was 2 μm from the interference fringe of the IR absorption spectrum.

なお、ｃ−ＢＮ被覆膜のＸ線の（１１１）ピーク位置（４３．２７度）のバルクｃ−ＢＮ結晶のそれ（４３．３５度）からのシフトからｃ−ＢＮ被覆膜の面内圧縮応力を求めると約１．７ＧＰａとなり、この場合も従来合成法の１０〜２０ＧＰａと比べて低いことがわかる。   It should be noted that the in-plane of the c-BN coating film from the shift of the (111) peak position (43.27 degrees) of the c-BN coating film from that of the bulk c-BN crystal (43.35 degrees). When the compressive stress is determined, it is about 1.7 GPa, which is also lower than 10-20 GPa of the conventional synthesis method.

このｃ−ＢＮ被覆膜は６ヶ月経っても剥離しておらず、この膜をステンレス製の尖ったピンセットで強く引っかいたところ、ピンセットが削られてｃ−ＢＮ被覆膜に融着したが、ｃ−ＢＮ被覆膜は剥離しなかった。   The c-BN coating film did not peel off even after 6 months, and when the film was strongly scratched with stainless steel tweezers, the tweezers were shaved and fused to the c-BN coating film. The c-BN coating film did not peel off.

このｃ−ＢＮ被覆膜も十分な硬さと基体との密着力をもっている。ＡＥ付スクラッチ試験機によるスクラッチ試験でも密着性が良く、マイクロビッカスース硬度計（加重２０ｇ）による硬度測定でも十分な硬度を示した（表１参照）。   This c-BN coating film also has sufficient hardness and adhesion to the substrate. Adhesion was good even in a scratch test using an AE scratch tester, and a sufficient hardness was shown by a hardness measurement using a micro-bickus hardness tester (20 g load) (see Table 1).

（比較例２）
中間層なしで６％Ｃｏ含有の炭化タングステン基体に実施例２と同様の条件でコートしたＢＮ膜はｃ−ＢＮよりｓｐ２結合のＢＮ成分が優勢に形成され、また剥がれ易かった。 (Comparative Example 2)
A BN film coated on a tungsten carbide substrate containing 6% Co without an intermediate layer under the same conditions as in Example 2 had a BN component with sp 2 bonds formed more dominantly than c-BN, and was more easily peeled off.

６％Ｃｏ含有の炭化タングステン基体に３μｍ厚のジルコニウム（Ｚｒ）膜をスパッター法によりコート後、３００ｍＴｏｒｒの水素中８００℃にて１／２時間アニール後、アークジェットプラズマＣＶＤ装置において、Ａｒ：２０ｓｌｍ、Ｎ２：１ｓｌｍ、Ｈ２：５ｓｃｃｍ、ＢＦ３／Ｈｅ（１０％）：３０ｓｃｃｍのガス流を用いて、５０Ｔｏｒｒのガス圧下、アーク電力７ｋＷ、基体温度９５０℃、１３．５６MHｚの高周波の自己バイアス電圧−６０Ｖにて、１／６時間反応させ、ｃ−ＢＮ被覆膜を得た。 After a 3 μm-thick zirconium (Zr) film is coated on a tungsten carbide substrate containing 6% Co by a sputtering method, annealing is performed at 800 ° C. for 1/2 hour in 300 mTorr of hydrogen, and in an arc jet plasma CVD apparatus, Ar: 20 slm, N 2 : 1 slm, H 2 : 5 sccm, BF 3 / He (10%): 30 sccm gas pressure, 50 Torr gas pressure, arc power 7 kW, substrate temperature 950 ° C., high frequency self-bias voltage of 13.56 MHz The reaction was carried out at -60 V for 1/6 hour to obtain a c-BN coating film.

この被覆膜のＸ線回折図（銅ターゲット）、図７に示す。図７より、ｃ−ＢＮとＺｒＮのピークが主として現れており、ｃ−ＢＮの（１１１）、（２００）、（２２０）、（３１１）の反射の半値幅は、それぞれ、０．８９、１．２、１．４、１．９５度である。これによりこの膜は結晶性のよいｃ−ＢＮ被覆膜であることがわかる。ｃ−ＢＮ被覆膜の平均膜厚はＩＲ吸収スペクトルの干渉フリンジより、２μｍであった。   An X-ray diffraction pattern (copper target) of this coating film is shown in FIG. From FIG. 7, c-BN and ZrN peaks mainly appear, and the half widths of reflection of c-BN at (111), (200), (220), and (311) are 0.89, 1 and 1, respectively. .2, 1.4, 1.95 degrees. This shows that this film is a c-BN coating film with good crystallinity. The average film thickness of the c-BN coating film was 2 μm from the interference fringe of the IR absorption spectrum.

なお、ｃ−ＢＮ被覆膜のＸ線の（１１１）ピーク位置（４３．３３度）のバルクｃ−ＢＮ結晶のそれ（４３．３５度）からのシフトからｃ−ＢＮ被覆膜の面内圧縮応力を求めると約０．５ＧＰａとなり、この場合も従来合成法の１０〜２０ＧＰａと比べて低いことがわかる。   It should be noted that the in-plane of the c-BN coating film from the shift of the (111) peak position (43.33 degrees) of the c-BN coating film from that of the bulk c-BN crystal (43.35 degrees). When the compressive stress is obtained, it is about 0.5 GPa, which is also lower than 10-20 GPa of the conventional synthesis method.

このｃ−ＢＮ被覆膜は６ヶ月経っても剥離しておらず、この膜をステンレス製の尖ったピンセットで強く引っかいたところ、ピンセットが削られてｃ−ＢＮ被覆膜に融着したが、ｃ−ＢＮ被覆膜は剥離しなかった。   The c-BN coating film did not peel off even after 6 months, and when the film was strongly scratched with stainless steel tweezers, the tweezers were shaved and fused to the c-BN coating film. The c-BN coating film did not peel off.

このｃ−ＢＮ被覆膜も十分な硬さと基体との密着力をもっている。ＡＥ付スクラッチ試験機によるスクラッチ試験でも密着性が良く、マイクロビッカスース硬度計による硬度測定でも十分な硬度を示した（表１参照）。   This c-BN coating film also has sufficient hardness and adhesion to the substrate. Adhesion was good even in a scratch test using an AE scratch tester, and a sufficient hardness was shown even in a hardness measurement using a micro-bickus hardness tester (see Table 1).

基体に中間層であるＺｒをコートした後の水素中アニール処理を行わない他は、実施例３と同様の条件で中間層上にｃ−ＢＮ被覆膜をコートした。その結果、Ｘ線回折でｃ−ＢＮの（１１１）、（２００）の反射の半値幅は、それぞれ、１．１、１．４度であった。なお、（２２０）、（３１１）については測定していない。本実施例によるｃ−ＢＮ被覆膜の残留応力の計算値は、（１１１）ピークのシフトから１．３ＧＰａで、水素アニール処理した場合の残留応力より大きかったものの、本実施例によるｃ−ＢＮ被覆膜も、十分本発明の目的にかなう硬質な被覆膜であった（表１参照）。   A c-BN coating film was coated on the intermediate layer under the same conditions as in Example 3 except that the annealing in hydrogen after coating Zr as the intermediate layer on the substrate was not performed. As a result, the half widths of reflection of c-BN (111) and (200) by X-ray diffraction were 1.1 and 1.4 degrees, respectively. Note that (220) and (311) are not measured. The calculated value of the residual stress of the c-BN coating film according to this example is 1.3 GPa from the shift of the (111) peak, which is larger than the residual stress in the case of the hydrogen annealing treatment, but the c-BN according to this example. The coating film was also a hard coating film that sufficiently fulfilled the object of the present invention (see Table 1).

本実施例は中間層をコートせずにｃ−ＢＮ成膜中に基体表面層を窒化及びホウ化して窒化物、ホウ化物の中間層とした例である。１ｍｍ厚のチタン板を基体としてｃ−ＢＮ被覆膜作成膜装置にセットし、Ａｒ：２０ｓｌｍ、Ｎ２：１．５ｓｌｍ、Ｈ２：５ｓｃｃｍを流し、８ｋＷのＤＣアーク放電によりプラズマを発生させ、１０％ＢＦ３／Ａｒ：３０ｓｃｃｍを流し、直流バイアス電源により−８５Ｖの直流バイアスを基体にかけ、基体温度１０５０℃にて、５０Ｔｏｒｒ下の１／３時間の合成により、基体上に剥がれていない立方晶窒化ホウ素被覆膜が得られた。 In this example, the substrate surface layer is nitrided and borated during c-BN film formation without coating the intermediate layer, thereby forming an intermediate layer of nitride or boride. A titanium plate with a thickness of 1 mm is set as a substrate in a c-BN coating film forming film apparatus, Ar: 20 slm, N 2 : 1.5 slm, H 2 : 5 sccm is flown, and plasma is generated by DC arc discharge of 8 kW. 10% BF 3 / Ar: 30 sccm was passed, a DC bias of −85 V was applied to the substrate by a DC bias power source, and the cubic crystal was not peeled off on the substrate by synthesis for 1/3 hour under 50 Torr at a substrate temperature of 1050 ° C. A boron nitride coating film was obtained.

この方法により得られた立方晶窒化ホウ素の薄膜Ｘ線回折図（銅ターゲット）、ラマンスペクトルを、それぞれ、図８、図９に示す。図８にはｃ−ＢＮ、窒化チタン、ホウ化チタンのピークが現れており、最表面層はｃ−ＢＮで、窒化チタン、ホウ化チタンが基体とｃ−ＢＮ被覆膜との中間層となっている。ｃ−ＢＮ層被覆膜の厚みはおよそ４μｍである。ｃ−ＢＮのＸ線回折ピークの２θの半値幅は（１１１）、（２００）、（２２０）、（３１１）のピークについて、それぞれ、０．５８、０．７５、０．９０、１．４度である。   The thin film X-ray diffraction diagram (copper target) and Raman spectrum of cubic boron nitride obtained by this method are shown in FIGS. 8 and 9, respectively. In FIG. 8, peaks of c-BN, titanium nitride, and titanium boride appear, the outermost surface layer is c-BN, and titanium nitride and titanium boride are intermediate layers between the substrate and the c-BN coating film. It has become. The thickness of the c-BN layer coating film is approximately 4 μm. The half width of 2θ of the X-ray diffraction peak of c-BN is 0.58, 0.75, 0.90, 1.4 for the peaks of (111), (200), (220), and (311), respectively. Degree.

図９のラマンスペクトルにおいて、ｃ−ＢＮのＴＯ及びＬＯモードのピークはそれぞれ、２９．９、１４．９ｃｍ−１であり、結晶性のよいｃ−ＢＮであることがわかる。ｃ−ＢＮ被覆膜のＸ線の（１１１）ピーク位置（４３．３０度）のバルクｃ−ＢＮ結晶のそれ（４３．３５度）からのシフトからｃ−ＢＮ被覆膜の面内圧縮応力を求めると約１．２ＧＰａとなり、フッ素を用いない従来合成法で一般的な１０〜２０ＧＰａ（非特許文献６）と比べ非常に低いことがわかる。 In the Raman spectrum of FIG. 9, the c-BN TO and LO mode peaks are 29.9 and 14.9 cm −1 , respectively, indicating that the c-BN has good crystallinity. From the shift of the (111) peak position (43.30 degrees) of the X-ray of the c-BN coating film from that of the bulk c-BN crystal (43.35 degrees), the in-plane compressive stress of the c-BN coating film Is about 1.2 GPa, which is very low compared to 10-20 GPa (non-patent document 6) that is general in the conventional synthesis method using no fluorine.

このｃ−ＢＮ被覆膜は５年経っても剥離せず、この膜をステンレス製の尖ったピンセットで強く引っかいたところ、ピンセットが削られてｃ−ＢＮ被覆膜に融着したが、ｃ−ＢＮ被覆膜は剥離しなかった。   The c-BN coating film did not peel off even after 5 years, and when this film was strongly scratched with pointed tweezers made of stainless steel, the tweezers were shaved and fused to the c-BN coating film. -The BN coating film did not peel off.

このｃ−ＢＮ被覆膜は十分な硬さと基体との密着力をもっている。ＡＥ付スクラッチ試験機によるスクラッチ試験でも密着性が良く、ナノインデンターとマイクロビッカスース硬度計による硬度測定でも十分な硬度を示した（表１参照）。   This c-BN coating film has sufficient hardness and adhesion to the substrate. Adhesion was good even in a scratch test using an AE scratch tester, and a sufficient hardness was shown even in a hardness measurement using a nanoindenter and a micro-bickus hardness tester (see Table 1).

Figure 0005387815
Figure 0005387815

本発明である立方晶窒化ホウ素被覆膜複合材料は、高結晶性と高膜厚、基体との高密着性のｃ−ＢＮ被覆膜複合体で、高硬度、高耐磨耗性、高耐熱性、高熱伝導度を用いる切削工具、研削工具、ドリル等のコーティングへ、耐摩耗性コーティングに有効である。さらに、高絶縁性、高耐電圧、高耐熱耐酸化性、高熱伝導であるため、高温電子材料素子等への幅広い応用が期待される。   The cubic boron nitride coating film composite material according to the present invention is a c-BN coating film composite having a high crystallinity, a high film thickness, and a high adhesion to a substrate, and has a high hardness, a high wear resistance, a high Effective for wear-resistant coatings for cutting tools, grinding tools, drills, and other coatings that use heat resistance and high thermal conductivity. Furthermore, since it has high insulation, high withstand voltage, high heat and oxidation resistance, and high thermal conductivity, it is expected to be widely applied to high-temperature electronic material elements.

基体上の中間層の上にｃ−ＢＮ膜を被覆した本発明である立方晶窒化ホウ素被覆膜複合材料の断面模式図である。It is a cross-sectional schematic diagram of the cubic boron nitride coating film composite material which is this invention which coat | covered the c-BN film | membrane on the intermediate | middle layer on a base | substrate. 基体上の２層の中間層の上にｃ−ＢＮ膜を被覆した本発明である立方晶窒化ホウ素被覆膜複合材料の断面模式図である。It is a cross-sectional schematic diagram of a cubic boron nitride coating film composite material according to the present invention in which a c-BN film is coated on two intermediate layers on a substrate. 実施例１で作成したジルコニウムのホウ化物、窒化物、ホウ窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜側からの薄膜Ｘ線回折図である。1 is a thin film X-ray diffraction pattern from the surface film side of a cubic boron nitride-coated composite material having zirconium boride, nitride and boronitride as an intermediate layer prepared in Example 1. FIG. 実施例１で作成したジルコニウムのホウ化物、窒化物、ホウ窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜のラマンスペクトルである。2 is a Raman spectrum of a surface film of a cubic boron nitride-coated composite material having an intermediate layer of zirconium boride, nitride and boronitride prepared in Example 1. FIG. 実施例２で得られたチタンの窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜側からの薄膜Ｘ線回折図である。4 is a thin film X-ray diffraction diagram from the surface film side of a cubic boron nitride-coated composite material using titanium nitride obtained in Example 2 as an intermediate layer. FIG. 実施例２で得られたチタンの窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜のラマンスペクトルである。4 is a Raman spectrum of a surface film of a cubic boron nitride-coated composite material having the titanium nitride obtained in Example 2 as an intermediate layer. 実施例３で得られたジルコニウムの窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜側からの薄膜Ｘ線回折図である。FIG. 4 is a thin film X-ray diffraction diagram from the surface film side of a cubic boron nitride-coated composite material having an intermediate layer of zirconium nitride obtained in Example 3. 実施例５で作成したチタンのホウ化物、窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜側からの薄膜Ｘ線回折図である。6 is a thin film X-ray diffraction diagram from the surface film side of a cubic boron nitride-coated composite material having titanium boride and nitride as an intermediate layer prepared in Example 5. FIG. 実施例５で作成したチタンのホウ化物、窒化物を中間層とする立方晶窒化ホウ素被覆複合材料の表面膜のラマンスペクトルである。6 is a Raman spectrum of a surface film of a cubic boron nitride-coated composite material having titanium boride and nitride as an intermediate layer prepared in Example 5. FIG.

符号の説明Explanation of symbols

１ 立方晶窒化ホウ素被覆膜複合材料
２ 基体
３ 中間層
３ａ 第２中間層
４ ｃ−ＢＮ被覆膜（表面膜） DESCRIPTION OF SYMBOLS 1 Cubic boron nitride coating film composite material 2 Base | substrate 3 Intermediate | middle layer 3a 2nd intermediate | middle layer 4 c-BN coating film (surface film)

Claims (2)

基体と、前記基体表面上に形成された周期律表の第４族金属（Ｔｉ、Ｚｒ、Ｈｆ）、第５族金属（Ｖ、Ｎｂ、Ｔａ）、前記第４族金属及び第５族金属の窒化物又はホウ化物或いはホウ窒化物の内から選ばれるいずれか１種以上の成分よりなる中間層と、前記基体表面に中間層を形成後、水素ガス或いは水素プラズマ中で基体及び中間層をアニール処理し、前記中間層の表面に被膜した立方晶窒化ホウ素を主成分とする表面膜とから形成される立方晶窒化ホウ素被覆膜複合材料であって、
前記表面膜の立方晶窒化ホウ素の光学的縦波モードのフォノンによるラマン散乱又は光学的横波モードのフォノンによるラマン散乱のいずれか一方の半値幅が、５０ｃｍ−１以下のピークを示すか、
或いは、
薄膜Ｘ線回折で、前記表面膜の立方晶窒化ホウ素の（１１１）、（２００）、（２２０）、（３１１）の内のいずれか１の反射ピークの２θの半値幅が、それぞれ１．５、２．５、２．５、３度以下であることを特徴とする
立方晶窒化ホウ素被覆膜複合材料。 A base, a Group 4 metal (Ti, Zr, Hf), a Group 5 metal (V, Nb, Ta) of the periodic table formed on the surface of the base, the Group 4 metal and the Group 5 metal. An intermediate layer composed of at least one component selected from nitride, boride or boronitride, and an intermediate layer formed on the surface of the substrate, and then anneal the substrate and the intermediate layer in hydrogen gas or hydrogen plasma A cubic boron nitride coating film composite material formed from a surface film mainly composed of cubic boron nitride that is processed and coated on the surface of the intermediate layer,
The half width of either the Raman scattering by phonons in the optical longitudinal wave mode or the phonons in the optical transverse wave mode of the cubic boron nitride of the surface film shows a peak of 50 cm −1 or less,
Or
In thin film X-ray diffraction, the half-width of 2θ of the reflection peak of any one of (111), (200), (220), and (311) of cubic boron nitride of the surface film is 1.5 respectively. 2.5, 2.5, 3 degrees or less, cubic boron nitride coating film composite material 前記立方晶窒化ホウ素を、ホウ素源、窒素源及びフッ素源を含むガスのプラズマを用いて、前記基体上に析出させたことを特徴とする請求項１に記載の立方晶窒化ホウ素被覆膜複合材料。   2. The cubic boron nitride coating film composite according to claim 1, wherein the cubic boron nitride is deposited on the substrate using a plasma of a gas containing a boron source, a nitrogen source and a fluorine source. material.
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